1501 lines
161 KiB
XML
1501 lines
161 KiB
XML
<document id="85B98392A4171B90D25D38C87EF1F045" ID-DOI="10.1016/j.phytochem.2022.113256" ID-ISSN="1873-3700" ID-Zenodo-Dep="8235322" IM.bibliography_approvedBy="carolina" IM.illustrations_approvedBy="carolina" IM.materialsCitations_approvedBy="felipe" IM.metadata_approvedBy="felipe" IM.tables_approvedBy="carolina" IM.taxonomicNames_approvedBy="felipe" IM.treatments_approvedBy="carolina" checkinTime="1691690115347" checkinUser="felipe" docAuthor="Grignon-Dubois, Micheline, Rezzonico, Bernadette & Blanchet, Hugues" docDate="2022" docId="A2143D69FFE9FFD7FC89F9075ABFFDCD" docLanguage="en" docName="Phytochemistry.201.113256.pdf" docOrigin="Phytochemistry (113256) 201" docSource="http://dx.doi.org/10.1016/j.phytochem.2022.113256" docStyle="DocumentStyle:F36D69FC8B198FBE91029DF9C24697D3.5:Phytochemistry.2020-.journal_article" docStyleId="F36D69FC8B198FBE91029DF9C24697D3" docStyleName="Phytochemistry.2020-.journal_article" docStyleVersion="5" docTitle="Phyllospadix torreyi" docType="treatment" docVersion="1" lastPageNumber="6" masterDocId="5E2D4511FFEBFFD1FFBBFFFA5A78FFA8" masterDocTitle="Phenolic fingerprints of the Pacific seagrass Phyllospadix torreyi - Structural characterization and quantification of undescribed flavonoid sulfates" masterLastPageNumber="15" masterPageNumber="1" pageNumber="3" updateTime="1692303185427" updateUser="carolina">
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<mods:mods id="0FE9798692E9BD01C0F29A1C8E6DEB65" xmlns:mods="http://www.loc.gov/mods/v3">
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<mods:title id="65B3673BA68873916B422D505AAECDD1">Phenolic fingerprints of the Pacific seagrass Phyllospadix torreyi - Structural characterization and quantification of undescribed flavonoid sulfates</mods:title>
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<mods:namePart id="9EAEED1D6201176FCFCB6DBB6956487C">Grignon-Dubois, Micheline</mods:namePart>
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<mods:namePart id="098887EBB4861D8C364FD88652F95E56">Rezzonico, Bernadette</mods:namePart>
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<mods:namePart id="5D13353662B7AD144D91EF26F38C6A02">Blanchet, Hugues</mods:namePart>
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<mods:typeOfResource id="F45F725B442076B529C4C61159F1B6FD">text</mods:typeOfResource>
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<mods:title id="05F3DB0D99AEC0C0E5C701DEEC521E47">Phytochemistry</mods:title>
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<mods:part id="FB1DDC5F4E40D43501FAE99C93258FDA">
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<mods:date id="5B99ABD8A53A8CE001630825E7BEA2E9">2022</mods:date>
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<mods:title id="DD4BCA617EBB750B27E5363D35314567">113256</mods:title>
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<mods:number id="2AF8B81818E755B4815DAC1707DE6583">2022-09-30</mods:number>
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<mods:number id="7C681A652419575E39E8F6A86311916C">201</mods:number>
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<mods:url id="4166DEF0073DCB0612ED92BDC353A86E">http://dx.doi.org/10.1016/j.phytochem.2022.113256</mods:url>
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<mods:classification id="AFBC105280579CBBF39A0BA97B47A97B">journal article</mods:classification>
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<mods:identifier id="46C928F642130D4755C724B6E5D2ADC3" type="DOI">10.1016/j.phytochem.2022.113256</mods:identifier>
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<mods:identifier id="78F22BEA18C6F2B12B77994F6B87402C" type="ISSN">1873-3700</mods:identifier>
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<mods:identifier id="0F56014C8D44EC1BE48F604180B8D23B" type="Zenodo-Dep">8235322</mods:identifier>
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</mods:mods>
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<treatment id="A2143D69FFE9FFD7FC89F9075ABFFDCD" LSID="urn:lsid:plazi:treatment:A2143D69FFE9FFD7FC89F9075ABFFDCD" httpUri="http://treatment.plazi.org/id/A2143D69FFE9FFD7FC89F9075ABFFDCD" lastPageId="6" lastPageNumber="6" pageId="2" pageNumber="3">
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<subSubSection id="62A7DFF4FFE9FFD3FC89F90759E2F884" pageId="2" pageNumber="3" type="nomenclature">
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<paragraph id="2A028C7FFFE9FFD3FC89F90759E2F884" blockId="2.[818,1471,1789,1808]" lastBlockId="2.[818,922,1816,1836]" pageId="2" pageNumber="3">
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<emphasis id="18C9506DFFE9FFD3FC89F90759E2F884" bold="true" italics="true" pageId="2" pageNumber="3">
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<heading id="714A3B13FFE9FFD3FC89F9075FC7F8B8" bold="true" box="[818,1471,1789,1808]" centered="true" fontSize="36" level="1" pageId="2" pageNumber="3" reason="1">
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||
2.1. Determination of the phenolic fingerprints of
|
||
<taxonomicName id="EDBDF7FCFFE9FFD3FB52F9075F42F8B8" ID-CoL="6VFPT" ID-ENA="55486" baseAuthorityName="Zapata and McMillan" baseAuthorityYear="1979" box="[1257,1338,1789,1808]" class="Liliopsida" family="Zosteraceae" genus="Phyllospadix" kingdom="Plantae" order="Alismatales" pageId="2" pageNumber="3" phylum="Tracheophyta" rank="species" species="torreyi">P. torreyi</taxonomicName>
|
||
by HPLC-DAD
|
||
</heading>
|
||
<heading id="714A3B13FFE9FFD3FC89F8E259E2F884" box="[818,922,1816,1836]" fontSize="8" level="3" pageId="2" pageNumber="3" reason="8">and LC/MS</heading>
|
||
</emphasis>
|
||
</paragraph>
|
||
</subSubSection>
|
||
<subSubSection id="62A7DFF4FFE9FFD7FCEAF8AA5ABFFDCD" lastPageId="6" lastPageNumber="7" pageId="2" pageNumber="3" type="description">
|
||
<paragraph id="2A028C7FFFE9FFD2FCEAF8AA58CFFC2D" blockId="2.[818,1488,1872,1976]" lastBlockId="3.[101,771,659,1599]" lastPageId="3" lastPageNumber="4" pageId="2" pageNumber="3">
|
||
The crude extracts of
|
||
<taxonomicName id="EDBDF7FCFFE9FFD3FB91F8AB5E07F8CB" baseAuthorityName="Zapata and McMillan" baseAuthorityYear="1979" box="[1066,1151,1872,1892]" class="Liliopsida" family="Zosteraceae" genus="Phyllospadix" kingdom="Plantae" order="Alismatales" pageId="2" pageNumber="3" phylum="Tracheophyta" rank="species" species="torreyi">
|
||
<emphasis id="18C9506DFFE9FFD3FB91F8AB5E07F8CB" bold="true" box="[1066,1151,1872,1892]" italics="true" pageId="2" pageNumber="3">P. torreyi</emphasis>
|
||
</taxonomicName>
|
||
were analyzed by HPLC-DAD and HPLC/ESI-MS in positive mode to obtain their chromatographic profiles, on-line UV spectra and mass spectral information regarding their components. Sixteen peaks of variable intensity were detected (
|
||
<tableCitation id="673FB9C4FFE9FFD3FAC4F85E5FB1F81F" box="[1407,1481,1956,1975]" captionStart="Table 1" captionStartId="1.[101,151,993,1009]" captionTargetPageId="1" captionText="Table 1 Peak number, HPLC retention time (Rt), sampling dates and sample names, concentration (mg g 1 dw of plant tissue, mean values SD) of phenolic compounds from ± Phyllospadix torreyi." pageId="2" pageNumber="3">Table 1</tableCitation>
|
||
, Fig. 2). Comparison of retention time and UV spectra with those of flavonoid standards indicated the absence of flavonols and flavanones. Examination of on-line UV spectra enabled the identification of three phenolic acids and thirteen flavonoids (Fig. S31). The phenolic acids were identified as caffeic- (
|
||
<emphasis id="18C9506DFFE8FFD2FEDFFCF95B0FFCBE" bold="true" box="[356,375,771,790]" pageId="3" pageNumber="4">1,</emphasis>
|
||
Rt 12.1 min), coumaric- (
|
||
<emphasis id="18C9506DFFE8FFD2FDD7FCF95800FCBE" bold="true" box="[620,632,771,790]" pageId="3" pageNumber="4">5</emphasis>
|
||
, Rt 16.7 min), and rosmarinic acid (
|
||
<emphasis id="18C9506DFFE8FFD2FE8FFCE55B35FC9A" bold="true" box="[308,333,799,818]" pageId="3" pageNumber="4">10</emphasis>
|
||
, Rt 23.2 min), of which rosmarinic acid was predominant (Figs. 2 and 3). The flavonoid pattern was largely dominated by three flavonoids (
|
||
<emphasis id="18C9506DFFE8FFD2FEDFFCAC5B08FCC1" bold="true" box="[356,368,854,873]" pageId="3" pageNumber="4">3</emphasis>
|
||
,
|
||
<emphasis id="18C9506DFFE8FFD2FEC6FCAC5BF1FCC1" bold="true" box="[381,393,854,873]" pageId="3" pageNumber="4">6</emphasis>
|
||
and
|
||
<emphasis id="18C9506DFFE8FFD2FE01FCAD5BBEFCC2" bold="true" box="[442,454,855,874]" pageId="3" pageNumber="4">7</emphasis>
|
||
), along with compounds in moderate amounts (
|
||
<emphasis id="18C9506DFFE8FFD2FF42FC885B7DFC2D" bold="true" box="[249,261,882,901]" pageId="3" pageNumber="4">8</emphasis>
|
||
,
|
||
<emphasis id="18C9506DFFE8FFD2FEA9FC885B36FC2D" bold="true" box="[274,334,882,902]" pageId="3" pageNumber="4">11–16</emphasis>
|
||
), or in low to trace amounts (
|
||
<emphasis id="18C9506DFFE8FFD2FDD0FC88580FFC2D" bold="true" box="[619,631,882,901]" pageId="3" pageNumber="4">2</emphasis>
|
||
,
|
||
<emphasis id="18C9506DFFE8FFD2FD3FFC8858E8FC2D" bold="true" box="[644,656,882,901]" pageId="3" pageNumber="4">4</emphasis>
|
||
,
|
||
<emphasis id="18C9506DFFE8FFD2FD26FC8858D1FC2D" bold="true" box="[669,681,882,901]" pageId="3" pageNumber="4">9</emphasis>
|
||
).
|
||
</paragraph>
|
||
<caption id="7EC2DCF7FFE8FFD2FFDEFF6D5970FF69" pageId="3" pageNumber="4" startId="3.[101,151,151,167]" targetBox="[117,1461,211,605]" targetIsTable="true" targetPageId="3" targetType="table">
|
||
<paragraph id="2A028C7FFFE8FFD2FFDEFF6D5970FF69" blockId="3.[101,776,150,195]" pageId="3" pageNumber="4">
|
||
<emphasis id="18C9506DFFE8FFD2FFDEFF6D5ADFFF0F" bold="true" box="[101,167,150,167]" pageId="3" pageNumber="4">Table 2</emphasis>
|
||
<superScript id="DDC82137FFE8FFD2FFDEFF515A15FF1F" attach="right" box="[101,109,171,183]" fontSize="5" pageId="3" pageNumber="4">1</superScript>
|
||
H-NMR data for flavonoid sulfates
|
||
<emphasis id="18C9506DFFE8FFD2FE2EFF4A5868FF69" bold="true" box="[405,528,176,193]" pageId="3" pageNumber="4">3, 6, 7, 11 15</emphasis>
|
||
in DMSO‑
|
||
<emphasis id="18C9506DFFE8FFD2FDD0FF4A580DFF69" bold="true" box="[619,629,176,193]" italics="true" pageId="3" pageNumber="4">d</emphasis>
|
||
(δ
|
||
<emphasis id="18C9506DFFE8FFD2FD22FF4A58B7FF68" bold="true" box="[665,719,176,192]" italics="true" pageId="3" pageNumber="4">ppm, J</emphasis>
|
||
(Hz)).
|
||
</paragraph>
|
||
</caption>
|
||
<paragraph id="2A028C7FFFE8FFD2FE4AFF485805FF6B" blockId="3.[101,776,150,195]" box="[497,637,178,195]" pageId="3" pageNumber="4">
|
||
–
|
||
<subScript id="B6398E3AFFE8FFD2FDCEFF4D5805FF6B" attach="left" box="[629,637,183,195]" fontSize="5" pageId="3" pageNumber="4">6</subScript>
|
||
</paragraph>
|
||
<paragraph id="2A028C7FFFE8FFD2FFCEFF2F5F0DFDF5" pageId="3" pageNumber="4">
|
||
<table id="58BD7EDFFFE8002EFFCEFF295FCDFDF5" box="[117,1461,211,605]" gridcols="9" gridrows="17" pageId="3" pageNumber="4">
|
||
<tr id="948D8E3DFFE8002EFFCEFF295FCDFF4B" box="[117,1461,211,227]" gridrow="0" pageId="3" pageNumber="4">
|
||
<th id="D75CE741FFE8002EFFCEFF295ABFFF4B" box="[117,199,211,227]" gridcol="0" gridrow="0" pageId="3" pageNumber="4">Compound</th>
|
||
<th id="D75CE741FFE8002EFF5EFF295B3BFF4B" box="[229,323,211,227]" gridcol="1" gridrow="0" pageId="3" pageNumber="4">3</th>
|
||
<th id="D75CE741FFE8002EFEDAFF295BBAFF4B" box="[353,450,211,227]" gridcol="2" gridrow="0" pageId="3" pageNumber="4">6</th>
|
||
<th id="D75CE741FFE8002EFDB9FF29581BFF4B" box="[514,611,211,227]" gridcol="3" gridrow="0" pageId="3" pageNumber="4">8</th>
|
||
<th id="D75CE741FFE8002EFD19FF295956FF4B" box="[674,814,211,227]" gridcol="4" gridrow="0" pageId="3" pageNumber="4">2′</th>
|
||
<th id="D75CE741FFE8002EFCF7FF2959E3FF4B" box="[844,923,211,227]" gridcol="5" gridrow="0" pageId="3" pageNumber="4">3′</th>
|
||
<th id="D75CE741FFE8002EFC4DFF295EFAFF4B" box="[1014,1154,211,227]" gridcol="6" gridrow="0" pageId="3" pageNumber="4">5′</th>
|
||
<th id="D75CE741FFE8002EFB1BFF295F4FFF4B" box="[1184,1335,211,227]" gridcol="7" gridrow="0" pageId="3" pageNumber="4">6′</th>
|
||
<th id="D75CE741FFE8002EFADCFF295FCDFF4B" box="[1383,1461,211,227]" gridcol="8" gridrow="0" pageId="3" pageNumber="4">OMe</th>
|
||
</tr>
|
||
<tr id="948D8E3DFFE8002EFFCEFF025FCDFEAE" box="[117,1461,248,262]" gridrow="1" pageId="3" pageNumber="4" rowspan-5="1">
|
||
<th id="D75CE741FFE8002EFFCEFF025ABFFEAE" box="[117,199,248,262]" gridcol="0" gridrow="1" pageId="3" pageNumber="4">
|
||
<emphasis id="18C9506DFFE8FFD2FFCEFF025A07FEAE" bold="true" box="[117,127,248,262]" pageId="3" pageNumber="4">3</emphasis>
|
||
</th>
|
||
<td id="D75CE741FFE8002EFF5EFF025B3BFEAE" box="[229,323,248,262]" gridcol="1" gridrow="1" pageId="3" pageNumber="4">6.50 [1 H, s]</td>
|
||
<td id="D75CE741FFE8002EFEDAFF025BBAFEAE" box="[353,450,248,262]" gridcol="2" gridrow="1" pageId="3" pageNumber="4">6.70 [1 H,</td>
|
||
<td id="D75CE741FFE8002EFDB9FF02581BFEAE" box="[514,611,248,262]" gridcol="3" gridrow="1" pageId="3" pageNumber="4">7.12 [1 H,</td>
|
||
<td id="D75CE741FFE8002EFD19FF025956FEAE" box="[674,814,248,262]" gridcol="4" gridrow="1" pageId="3" pageNumber="4">7.84 [1 H, d (2.3)]</td>
|
||
<td id="D75CE741FFE8002EFC4DFF025EFAFEAE" box="[1014,1154,248,262]" gridcol="6" gridrow="1" pageId="3" pageNumber="4">6.97 [1 H, d [8.5])</td>
|
||
<td id="D75CE741FFE8002EFB1BFF025F4FFEAE" box="[1184,1335,248,262]" gridcol="7" gridrow="1" pageId="3" pageNumber="4">7.63 [1 H, dd (2.3,</td>
|
||
<td id="D75CE741FFE8002EFADCFF025FCDFEAE" box="[1383,1461,248,262]" gridcol="8" gridrow="1" pageId="3" pageNumber="4">3.81 [3 H,</td>
|
||
</tr>
|
||
<tr id="948D8E3DFFE8002EFFCEFEF55FCDFEB5" box="[117,1461,271,285]" gridrow="2" pageId="3" pageNumber="4" rowspan-0="1" rowspan-1="1" rowspan-4="1" rowspan-5="1" rowspan-6="1">
|
||
<td id="D75CE741FFE8002EFEDAFEF55BBAFEB5" box="[353,450,271,285]" gridcol="2" gridrow="2" pageId="3" pageNumber="4">d (2.2)]</td>
|
||
<td id="D75CE741FFE8002EFDB9FEF5581BFEB5" box="[514,611,271,285]" gridcol="3" gridrow="2" pageId="3" pageNumber="4">d (2.2)]</td>
|
||
<td id="D75CE741FFE8002EFB1BFEF55F4FFEB5" box="[1184,1335,271,285]" gridcol="7" gridrow="2" pageId="3" pageNumber="4">8.5)]</td>
|
||
<td id="D75CE741FFE8002EFADCFEF55FCDFEB5" box="[1383,1461,271,285]" gridcol="8" gridrow="2" pageId="3" pageNumber="4">s]</td>
|
||
</tr>
|
||
<tr id="948D8E3DFFE8002EFFCEFEDC5FCDFE9C" box="[117,1461,294,308]" gridrow="3" pageId="3" pageNumber="4" rowspan-5="1" rowspan-8="1">
|
||
<th id="D75CE741FFE8002EFFCEFEDC5ABFFE9C" box="[117,199,294,308]" gridcol="0" gridrow="3" pageId="3" pageNumber="4">
|
||
<emphasis id="18C9506DFFE8FFD2FFCEFEDC5A07FE9C" bold="true" box="[117,127,294,308]" pageId="3" pageNumber="4">6</emphasis>
|
||
</th>
|
||
<td id="D75CE741FFE8002EFF5EFEDC5B3BFE9C" box="[229,323,294,308]" gridcol="1" gridrow="3" pageId="3" pageNumber="4">6.75 [1 H, s]</td>
|
||
<td id="D75CE741FFE8002EFEDAFEDC5BBAFE9C" box="[353,450,294,308]" gridcol="2" gridrow="3" pageId="3" pageNumber="4">6.57 [1 H,</td>
|
||
<td id="D75CE741FFE8002EFDB9FEDC581BFE9C" box="[514,611,294,308]" gridcol="3" gridrow="3" pageId="3" pageNumber="4">6.98 [1 H,</td>
|
||
<td id="D75CE741FFE8002EFD19FEDC5956FE9C" box="[674,814,294,308]" gridcol="4" gridrow="3" pageId="3" pageNumber="4">7.92 [1 H, d (2.3)]</td>
|
||
<td id="D75CE741FFE8002EFC4DFEDC5EFAFE9C" box="[1014,1154,294,308]" gridcol="6" gridrow="3" pageId="3" pageNumber="4">6.99 [1 H, d [8.6])</td>
|
||
<td id="D75CE741FFE8002EFB1BFEDC5F4FFE9C" box="[1184,1335,294,308]" gridcol="7" gridrow="3" pageId="3" pageNumber="4">7.71 [1 H, dd (2.3,</td>
|
||
</tr>
|
||
<tr id="948D8E3DFFE8002EFFCEFEC65FCDFEE3" box="[117,1461,316,331]" gridrow="4" pageId="3" pageNumber="4" rowspan-0="1" rowspan-1="1" rowspan-4="1" rowspan-5="1" rowspan-6="1" rowspan-8="1">
|
||
<td id="D75CE741FFE8002EFEDAFEC65BBAFEE3" box="[353,450,316,331]" gridcol="2" gridrow="4" pageId="3" pageNumber="4">d (2.1)]</td>
|
||
<td id="D75CE741FFE8002EFDB9FEC6581BFEE3" box="[514,611,316,331]" gridcol="3" gridrow="4" pageId="3" pageNumber="4">d (2.1)]</td>
|
||
<td id="D75CE741FFE8002EFB1BFEC65F4FFEE3" box="[1184,1335,316,331]" gridcol="7" gridrow="4" pageId="3" pageNumber="4">8.6)]</td>
|
||
</tr>
|
||
<tr id="948D8E3DFFE8002EFFCEFEA95FCDFECA" box="[117,1461,339,354]" gridrow="5" pageId="3" pageNumber="4" rowspan-2="1" rowspan-5="1">
|
||
<th id="D75CE741FFE8002EFFCEFEA95ABFFECA" box="[117,199,339,354]" gridcol="0" gridrow="5" pageId="3" pageNumber="4">
|
||
<emphasis id="18C9506DFFE8FFD2FFCEFEA95A07FEC9" bold="true" box="[117,127,339,353]" pageId="3" pageNumber="4">7</emphasis>
|
||
</th>
|
||
<td id="D75CE741FFE8002EFF5EFEA95B3BFECA" box="[229,323,339,354]" gridcol="1" gridrow="5" pageId="3" pageNumber="4">6.73 [1 H,</td>
|
||
<td id="D75CE741FFE8002EFDB9FEA9581BFECA" box="[514,611,339,354]" gridcol="3" gridrow="5" pageId="3" pageNumber="4">7.32 [1 H, s]</td>
|
||
<td id="D75CE741FFE8002EFD19FEA95956FECA" box="[674,814,339,354]" gridcol="4" gridrow="5" pageId="3" pageNumber="4">7.93 [1 H, d (2.3)]</td>
|
||
<td id="D75CE741FFE8002EFC4DFEA95EFAFECA" box="[1014,1154,339,354]" gridcol="6" gridrow="5" pageId="3" pageNumber="4">6.96 [1 H, d (8.6)]</td>
|
||
<td id="D75CE741FFE8002EFB1BFEA95F4FFECA" box="[1184,1335,339,354]" gridcol="7" gridrow="5" pageId="3" pageNumber="4">7.71 [1 H, dd (2.3,</td>
|
||
<td id="D75CE741FFE8002EFADCFEA95FCDFECA" box="[1383,1461,339,354]" gridcol="8" gridrow="5" pageId="3" pageNumber="4">3.76 [3 H,</td>
|
||
</tr>
|
||
<tr id="948D8E3DFFE8002EFFCEFE905FCDFED1" box="[117,1461,362,377]" gridrow="6" pageId="3" pageNumber="4" rowspan-0="1" rowspan-2="1" rowspan-3="1" rowspan-4="1" rowspan-5="1" rowspan-6="1">
|
||
<td id="D75CE741FFE8002EFF5EFE905B3BFED1" box="[229,323,362,377]" gridcol="1" gridrow="6" pageId="3" pageNumber="4">s)]</td>
|
||
<td id="D75CE741FFE8002EFB1BFE905F4FFED1" box="[1184,1335,362,377]" gridcol="7" gridrow="6" pageId="3" pageNumber="4">8.6)]</td>
|
||
<td id="D75CE741FFE8002EFADCFE905FCDFED1" box="[1383,1461,362,377]" gridcol="8" gridrow="6" pageId="3" pageNumber="4">s]</td>
|
||
</tr>
|
||
<tr id="948D8E3DFFE8002EFFCEFE7B5FCDFE38" box="[117,1461,385,400]" gridrow="7" pageId="3" pageNumber="4" rowspan-5="1" rowspan-8="1">
|
||
<th id="D75CE741FFE8002EFFCEFE7B5ABFFE38" box="[117,199,385,400]" gridcol="0" gridrow="7" pageId="3" pageNumber="4">
|
||
<emphasis id="18C9506DFFE8FFD2FFCEFE7B5AF1FE27" bold="true" box="[117,137,385,399]" pageId="3" pageNumber="4">11</emphasis>
|
||
</th>
|
||
<td id="D75CE741FFE8002EFF5EFE7B5B3BFE38" box="[229,323,385,400]" gridcol="1" gridrow="7" pageId="3" pageNumber="4">6.74 [1 H, s]</td>
|
||
<td id="D75CE741FFE8002EFEDAFE7B5BBAFE38" box="[353,450,385,400]" gridcol="2" gridrow="7" pageId="3" pageNumber="4">6.51 [1 H,</td>
|
||
<td id="D75CE741FFE8002EFDB9FE7B581BFE38" box="[514,611,385,400]" gridcol="3" gridrow="7" pageId="3" pageNumber="4">7.01 [1 H,</td>
|
||
<td id="D75CE741FFE8002EFD19FE7B5956FE38" box="[674,814,385,400]" gridcol="4" gridrow="7" pageId="3" pageNumber="4">7.44 [1 H, d (2.1)]</td>
|
||
<td id="D75CE741FFE8002EFC4DFE7B5EFAFE38" box="[1014,1154,385,400]" gridcol="6" gridrow="7" pageId="3" pageNumber="4">6.87 [1 H, d [8.9])</td>
|
||
<td id="D75CE741FFE8002EFB1BFE7B5F4FFE38" box="[1184,1335,385,400]" gridcol="7" gridrow="7" pageId="3" pageNumber="4">7.44 [1 H, dd (2.1,</td>
|
||
</tr>
|
||
<tr id="948D8E3DFFE8002EFFCEFE625FCDFE0E" box="[117,1461,408,422]" gridrow="8" pageId="3" pageNumber="4" rowspan-0="1" rowspan-1="1" rowspan-4="1" rowspan-5="1" rowspan-6="1" rowspan-8="1">
|
||
<td id="D75CE741FFE8002EFEDAFE625BBAFE0E" box="[353,450,408,422]" gridcol="2" gridrow="8" pageId="3" pageNumber="4">d (2.1)]</td>
|
||
<td id="D75CE741FFE8002EFDB9FE62581BFE0E" box="[514,611,408,422]" gridcol="3" gridrow="8" pageId="3" pageNumber="4">d (2.1)]</td>
|
||
<td id="D75CE741FFE8002EFB1BFE625F4FFE0E" box="[1184,1335,408,422]" gridcol="7" gridrow="8" pageId="3" pageNumber="4">8.9)]</td>
|
||
</tr>
|
||
<tr id="948D8E3DFFE8002EFFCEFE555FCDFE15" box="[117,1461,431,445]" gridrow="9" pageId="3" pageNumber="4" rowspan-2="1" rowspan-5="1">
|
||
<th id="D75CE741FFE8002EFFCEFE555ABFFE15" box="[117,199,431,445]" gridcol="0" gridrow="9" pageId="3" pageNumber="4">
|
||
<emphasis id="18C9506DFFE8FFD2FFCEFE555AF1FE15" bold="true" box="[117,137,431,445]" pageId="3" pageNumber="4">12</emphasis>
|
||
</th>
|
||
<td id="D75CE741FFE8002EFF5EFE555B3BFE15" box="[229,323,431,445]" gridcol="1" gridrow="9" pageId="3" pageNumber="4">6.75 [1 H, s]</td>
|
||
<td id="D75CE741FFE8002EFDB9FE55581BFE15" box="[514,611,431,445]" gridcol="3" gridrow="9" pageId="3" pageNumber="4">7.32 [1 H, s]</td>
|
||
<td id="D75CE741FFE8002EFD19FE555956FE15" box="[674,814,431,445]" gridcol="4" gridrow="9" pageId="3" pageNumber="4">7.46 [1 H, d (2.0)]</td>
|
||
<td id="D75CE741FFE8002EFC4DFE555EFAFE15" box="[1014,1154,431,445]" gridcol="6" gridrow="9" pageId="3" pageNumber="4">6.86 [1 H, d [8.8])</td>
|
||
<td id="D75CE741FFE8002EFB1BFE555F4FFE15" box="[1184,1335,431,445]" gridcol="7" gridrow="9" pageId="3" pageNumber="4">7.45 [1 H, dd (2.0,</td>
|
||
<td id="D75CE741FFE8002EFADCFE555FCDFE15" box="[1383,1461,431,445]" gridcol="8" gridrow="9" pageId="3" pageNumber="4">3.72 [3 H,</td>
|
||
</tr>
|
||
<tr id="948D8E3DFFE8002EFFCEFE3C5FCDFE7C" box="[117,1461,454,468]" gridrow="10" pageId="3" pageNumber="4" rowspan-0="1" rowspan-1="1" rowspan-2="1" rowspan-3="1" rowspan-4="1" rowspan-5="1" rowspan-6="1">
|
||
<td id="D75CE741FFE8002EFB1BFE3C5F4FFE7C" box="[1184,1335,454,468]" gridcol="7" gridrow="10" pageId="3" pageNumber="4">8.8)]</td>
|
||
<td id="D75CE741FFE8002EFADCFE3C5FCDFE7C" box="[1383,1461,454,468]" gridcol="8" gridrow="10" pageId="3" pageNumber="4">s]</td>
|
||
</tr>
|
||
<tr id="948D8E3DFFE8002EFFCEFE265FCDFE43" box="[117,1461,476,491]" gridrow="11" pageId="3" pageNumber="4" rowspan-5="1" rowspan-8="1">
|
||
<th id="D75CE741FFE8002EFFCEFE265ABFFE43" box="[117,199,476,491]" gridcol="0" gridrow="11" pageId="3" pageNumber="4">
|
||
<emphasis id="18C9506DFFE8FFD2FFCEFE265AF1FE42" bold="true" box="[117,137,476,490]" pageId="3" pageNumber="4">13</emphasis>
|
||
</th>
|
||
<td id="D75CE741FFE8002EFF5EFE265B3BFE43" box="[229,323,476,491]" gridcol="1" gridrow="11" pageId="3" pageNumber="4">6.69 [1 H,</td>
|
||
<td id="D75CE741FFE8002EFEDAFE265BBAFE43" box="[353,450,476,491]" gridcol="2" gridrow="11" pageId="3" pageNumber="4">6.18 [1 H,</td>
|
||
<td id="D75CE741FFE8002EFDB9FE26581BFE43" box="[514,611,476,491]" gridcol="3" gridrow="11" pageId="3" pageNumber="4">6.49 [1 H,</td>
|
||
<td id="D75CE741FFE8002EFD19FE265956FE43" box="[674,814,476,491]" gridcol="4" gridrow="11" pageId="3" pageNumber="4">7.89 [1 H, d (2.3)]</td>
|
||
<td id="D75CE741FFE8002EFC4DFE265EFAFE43" box="[1014,1154,476,491]" gridcol="6" gridrow="11" pageId="3" pageNumber="4">6.96 [1 H, d [8.6])</td>
|
||
<td id="D75CE741FFE8002EFB1BFE265F4FFE43" box="[1184,1335,476,491]" gridcol="7" gridrow="11" pageId="3" pageNumber="4">7.68 [1 H, dd (2.3,</td>
|
||
</tr>
|
||
<tr id="948D8E3DFFE8002EFFCEFE095FCDFDA9" box="[117,1461,499,513]" gridrow="12" pageId="3" pageNumber="4" rowspan-0="1" rowspan-4="1" rowspan-5="1" rowspan-6="1" rowspan-8="1">
|
||
<td id="D75CE741FFE8002EFF5EFE095B3BFDA9" box="[229,323,499,513]" gridcol="1" gridrow="12" pageId="3" pageNumber="4">s)]</td>
|
||
<td id="D75CE741FFE8002EFEDAFE095BBAFDA9" box="[353,450,499,513]" gridcol="2" gridrow="12" pageId="3" pageNumber="4">d (2.1)]</td>
|
||
<td id="D75CE741FFE8002EFDB9FE09581BFDA9" box="[514,611,499,513]" gridcol="3" gridrow="12" pageId="3" pageNumber="4">d (2.1)]</td>
|
||
<td id="D75CE741FFE8002EFB1BFE095F4FFDA9" box="[1184,1335,499,513]" gridcol="7" gridrow="12" pageId="3" pageNumber="4">8.6)]</td>
|
||
</tr>
|
||
<tr id="948D8E3DFFE8002EFFCEFDF05FCDFDB0" box="[117,1461,522,536]" gridrow="13" pageId="3" pageNumber="4" rowspan-2="1" rowspan-5="1">
|
||
<th id="D75CE741FFE8002EFFCEFDF05ABFFDB0" box="[117,199,522,536]" gridcol="0" gridrow="13" pageId="3" pageNumber="4">
|
||
<emphasis id="18C9506DFFE8FFD2FFCEFDF05AF1FDB0" bold="true" box="[117,137,522,536]" pageId="3" pageNumber="4">14</emphasis>
|
||
</th>
|
||
<td id="D75CE741FFE8002EFF5EFDF05B3BFDB0" box="[229,323,522,536]" gridcol="1" gridrow="13" pageId="3" pageNumber="4">6.44 [1 H,</td>
|
||
<td id="D75CE741FFE8002EFDB9FDF0581BFDB0" box="[514,611,522,536]" gridcol="3" gridrow="13" pageId="3" pageNumber="4">6.15 [1 H, s]</td>
|
||
<td id="D75CE741FFE8002EFD19FDF05956FDB0" box="[674,814,522,536]" gridcol="4" gridrow="13" pageId="3" pageNumber="4">7.79 [1 H, d (2.3)]</td>
|
||
<td id="D75CE741FFE8002EFC4DFDF05EFAFDB0" box="[1014,1154,522,536]" gridcol="6" gridrow="13" pageId="3" pageNumber="4">6.93 [1 H, d (8.6)]</td>
|
||
<td id="D75CE741FFE8002EFB1BFDF05F4FFDB0" box="[1184,1335,522,536]" gridcol="7" gridrow="13" pageId="3" pageNumber="4">7.58 [1 H, dd (2.3,</td>
|
||
<td id="D75CE741FFE8002EFADCFDF05FCDFDB0" box="[1383,1461,522,536]" gridcol="8" gridrow="13" pageId="3" pageNumber="4">3.67 [3 H,</td>
|
||
</tr>
|
||
<tr id="948D8E3DFFE8002EFFCEFDDB5FCDFD87" box="[117,1461,545,559]" gridrow="14" pageId="3" pageNumber="4" rowspan-0="1" rowspan-2="1" rowspan-3="1" rowspan-4="1" rowspan-5="1" rowspan-6="1">
|
||
<td id="D75CE741FFE8002EFF5EFDDB5B3BFD87" box="[229,323,545,559]" gridcol="1" gridrow="14" pageId="3" pageNumber="4">s)]</td>
|
||
<td id="D75CE741FFE8002EFB1BFDDB5F4FFD87" box="[1184,1335,545,559]" gridcol="7" gridrow="14" pageId="3" pageNumber="4">8.6)]</td>
|
||
<td id="D75CE741FFE8002EFADCFDDB5FCDFD87" box="[1383,1461,545,559]" gridcol="8" gridrow="14" pageId="3" pageNumber="4">s]</td>
|
||
</tr>
|
||
<tr id="948D8E3DFFE8002EFFCEFDC25FCDFDEE" box="[117,1461,568,582]" gridrow="15" pageId="3" pageNumber="4" rowspan-1="1">
|
||
<th id="D75CE741FFE8002EFFCEFDC25ABFFDEE" box="[117,199,568,582]" gridcol="0" gridrow="15" pageId="3" pageNumber="4">
|
||
<emphasis id="18C9506DFFE8FFD2FFCEFDC25AF1FDEE" bold="true" box="[117,137,568,582]" pageId="3" pageNumber="4">15</emphasis>
|
||
</th>
|
||
<td id="D75CE741FFE8002EFEDAFDC25BBAFDEE" box="[353,450,568,582]" gridcol="2" gridrow="15" pageId="3" pageNumber="4">6.81 [1 H, s]</td>
|
||
<td id="D75CE741FFE8002EFDB9FDC2581BFDEE" box="[514,611,568,582]" gridcol="3" gridrow="15" pageId="3" pageNumber="4">7.33 [1 H, s]</td>
|
||
<td id="D75CE741FFE8002EFD19FDC25956FDEE" box="[674,814,568,582]" gridcol="4" gridrow="15" pageId="3" pageNumber="4">7.91 [1 H,</td>
|
||
<td id="D75CE741FFE8002EFCF7FDC259E3FDEE" box="[844,923,568,582]" gridcol="5" gridrow="15" pageId="3" pageNumber="4">6.89 [1 H,</td>
|
||
<td id="D75CE741FFE8002EFC4DFDC25EFAFDEE" box="[1014,1154,568,582]" gridcol="6" gridrow="15" pageId="3" pageNumber="4">6.89 [1 H,</td>
|
||
<td id="D75CE741FFE8002EFB1BFDC25F4FFDEE" box="[1184,1335,568,582]" gridcol="7" gridrow="15" pageId="3" pageNumber="4">7.91 [1 H, d (8.78)]</td>
|
||
<td id="D75CE741FFE8002EFADCFDC25FCDFDEE" box="[1383,1461,568,582]" gridcol="8" gridrow="15" pageId="3" pageNumber="4">3.73 [3 H,</td>
|
||
</tr>
|
||
<tr id="948D8E3DFFE8002EFFCEFDB55FCDFDF5" box="[117,1461,591,605]" gridrow="16" pageId="3" pageNumber="4" rowspan-0="1" rowspan-1="1" rowspan-2="1" rowspan-3="1" rowspan-7="1">
|
||
<td id="D75CE741FFE8002EFD19FDB55956FDF5" box="[674,814,591,605]" gridcol="4" gridrow="16" pageId="3" pageNumber="4">d (8.78)]</td>
|
||
<td id="D75CE741FFE8002EFCF7FDB559E3FDF5" box="[844,923,591,605]" gridcol="5" gridrow="16" pageId="3" pageNumber="4">d (8.78)]</td>
|
||
<td id="D75CE741FFE8002EFC4DFDB55EFAFDF5" box="[1014,1154,591,605]" gridcol="6" gridrow="16" pageId="3" pageNumber="4">d (8.78)]</td>
|
||
<td id="D75CE741FFE8002EFADCFDB55FCDFDF5" box="[1383,1461,591,605]" gridcol="8" gridrow="16" pageId="3" pageNumber="4">s]</td>
|
||
</tr>
|
||
</table>
|
||
</paragraph>
|
||
<caption id="7EC2DCF7FFE8FFD2FC89FD5D5FBBFD7C" pageId="3" pageNumber="4" startId="3.[818,868,679,695]" targetBox="[834,1471,742,1134]" targetIsTable="true" targetPageId="3" targetType="table">
|
||
<paragraph id="2A028C7FFFE8FFD2FC89FD5D590DFD10" blockId="3.[818,1488,679,724]" box="[818,885,679,696]" pageId="3" pageNumber="4">
|
||
<emphasis id="18C9506DFFE8FFD2FC89FD5D590DFD10" bold="true" box="[818,885,679,696]" pageId="3" pageNumber="4">Table 3</emphasis>
|
||
</paragraph>
|
||
<paragraph id="2A028C7FFFE8FFD2FC89FD465FA8FD7A" blockId="3.[818,1488,679,724]" box="[818,1488,700,722]" pageId="3" pageNumber="4">
|
||
<superScript id="DDC82137FFE8FFD2FC89FD46593AFD60" attach="right" box="[818,834,700,712]" fontSize="5" pageId="3" pageNumber="4">13</superScript>
|
||
C-NMR chemical shifts for flavonoid sulfates
|
||
<emphasis id="18C9506DFFE8FFD2FB02FD3B5EBCFD7A" bold="true" box="[1209,1220,705,722]" pageId="3" pageNumber="4">3</emphasis>
|
||
,
|
||
<emphasis id="18C9506DFFE8FFD2FB75FD3B5EA1FD7A" bold="true" box="[1230,1241,705,722]" pageId="3" pageNumber="4">6</emphasis>
|
||
,
|
||
<emphasis id="18C9506DFFE8FFD2FB58FD3B5E96FD79" bold="true" box="[1251,1262,705,721]" pageId="3" pageNumber="4">7</emphasis>
|
||
,
|
||
<emphasis id="18C9506DFFE8FFD2FB43FD3B5F56FD7A" bold="true" box="[1272,1326,705,722]" pageId="3" pageNumber="4">11–14</emphasis>
|
||
(δ
|
||
<emphasis id="18C9506DFFE8FFD2FAF3FD3B5F17FD79" bold="true" box="[1352,1391,705,721]" italics="true" pageId="3" pageNumber="4">ppm,</emphasis>
|
||
DMSO‑
|
||
<emphasis id="18C9506DFFE8FFD2FA0AFD3A5FC3FD79" bold="true" box="[1457,1467,704,721]" italics="true" pageId="3" pageNumber="4">d</emphasis>
|
||
).
|
||
</paragraph>
|
||
<paragraph id="2A028C7FFFE8FFD2FA00FD325FBBFD7C" blockId="3.[818,1488,679,724]" box="[1467,1475,712,724]" pageId="3" pageNumber="4">
|
||
<subScript id="B6398E3AFFE8FFD2FA00FD325FBBFD7C" attach="left" box="[1467,1475,712,724]" fontSize="5" pageId="3" pageNumber="4">6</subScript>
|
||
</paragraph>
|
||
</caption>
|
||
<paragraph id="2A028C7FFFE8FFD2FCF9FD1C5FCDFBC5" pageId="3" pageNumber="4">
|
||
<table id="58BD7EDFFFE8002EFCF9FD1C5FC7FBC6" box="[834,1471,742,1134]" gridcols="8" gridrows="17" pageId="3" pageNumber="4">
|
||
<tr id="948D8E3DFFE8002EFCF9FD1C5FC7FD5C" box="[834,1471,742,756]" gridrow="0" pageId="3" pageNumber="4">
|
||
<th id="D75CE741FFE8002EFCF9FD1C59F4FD5C" box="[834,908,742,756]" gridcol="0" gridrow="0" pageId="3" pageNumber="4">C number</th>
|
||
<th id="D75CE741FFE8002EFC0BFD1C599DFD5C" box="[944,997,742,756]" gridcol="1" gridrow="0" pageId="3" pageNumber="4">3</th>
|
||
<th id="D75CE741FFE8002EFBB2FD1C5E4CFD5C" box="[1033,1076,742,756]" gridcol="2" gridrow="0" pageId="3" pageNumber="4">6</th>
|
||
<th id="D75CE741FFE8002EFBE3FD1C5EFBFD5C" box="[1112,1155,742,756]" gridcol="3" gridrow="0" pageId="3" pageNumber="4">7</th>
|
||
<th id="D75CE741FFE8002EFB1CFD1C5EAAFD5C" box="[1191,1234,742,756]" gridcol="4" gridrow="0" pageId="3" pageNumber="4">11</th>
|
||
<th id="D75CE741FFE8002EFB4DFD1C5F59FD5C" box="[1270,1313,742,756]" gridcol="5" gridrow="0" pageId="3" pageNumber="4">12</th>
|
||
<th id="D75CE741FFE8002EFAFEFD1C5F08FD5C" box="[1349,1392,742,756]" gridcol="6" gridrow="0" pageId="3" pageNumber="4">13</th>
|
||
<th id="D75CE741FFE8002EFA2FFD1C5FC7FD5C" box="[1428,1471,742,756]" gridcol="7" gridrow="0" pageId="3" pageNumber="4">14</th>
|
||
</tr>
|
||
<tr id="948D8E3DFFE8002EFCF9FCF35FC7FCBF" box="[834,1471,777,791]" gridrow="1" pageId="3" pageNumber="4">
|
||
<th id="D75CE741FFE8002EFCF9FCF359F4FCBF" box="[834,908,777,791]" gridcol="0" gridrow="1" pageId="3" pageNumber="4">2</th>
|
||
<td id="D75CE741FFE8002EFC0BFCF3599DFCBF" box="[944,997,777,791]" gridcol="1" gridrow="1" pageId="3" pageNumber="4">160.3</td>
|
||
<td id="D75CE741FFE8002EFBB2FCF35E4CFCBF" box="[1033,1076,777,791]" gridcol="2" gridrow="1" pageId="3" pageNumber="4">164.2</td>
|
||
<td id="D75CE741FFE8002EFBE3FCF35EFBFCBF" box="[1112,1155,777,791]" gridcol="3" gridrow="1" pageId="3" pageNumber="4">165.0</td>
|
||
<td id="D75CE741FFE8002EFB1CFCF35EAAFCBF" box="[1191,1234,777,791]" gridcol="4" gridrow="1" pageId="3" pageNumber="4">164.5</td>
|
||
<td id="D75CE741FFE8002EFB4DFCF35F59FCBF" box="[1270,1313,777,791]" gridcol="5" gridrow="1" pageId="3" pageNumber="4">164.4</td>
|
||
<td id="D75CE741FFE8002EFAFEFCF35F08FCBF" box="[1349,1392,777,791]" gridcol="6" gridrow="1" pageId="3" pageNumber="4">163.6</td>
|
||
<td id="D75CE741FFE8002EFA2FFCF35FC7FCBF" box="[1428,1471,777,791]" gridcol="7" gridrow="1" pageId="3" pageNumber="4">162.0</td>
|
||
</tr>
|
||
<tr id="948D8E3DFFE8002EFCF9FCDA5FC7FC86" box="[834,1471,800,814]" gridrow="2" pageId="3" pageNumber="4">
|
||
<th id="D75CE741FFE8002EFCF9FCDA59F4FC86" box="[834,908,800,814]" gridcol="0" gridrow="2" pageId="3" pageNumber="4">3</th>
|
||
<td id="D75CE741FFE8002EFC0BFCDA599DFC86" box="[944,997,800,814]" gridcol="1" gridrow="2" pageId="3" pageNumber="4">106.66</td>
|
||
<td id="D75CE741FFE8002EFBB2FCDA5E4CFC86" box="[1033,1076,800,814]" gridcol="2" gridrow="2" pageId="3" pageNumber="4">103.3</td>
|
||
<td id="D75CE741FFE8002EFBE3FCDA5EFBFC86" box="[1112,1155,800,814]" gridcol="3" gridrow="2" pageId="3" pageNumber="4">102.9</td>
|
||
<td id="D75CE741FFE8002EFB1CFCDA5EAAFC86" box="[1191,1234,800,814]" gridcol="4" gridrow="2" pageId="3" pageNumber="4">103.2</td>
|
||
<td id="D75CE741FFE8002EFB4DFCDA5F59FC86" box="[1270,1313,800,814]" gridcol="5" gridrow="2" pageId="3" pageNumber="4">102.4</td>
|
||
<td id="D75CE741FFE8002EFAFEFCDA5F08FC86" box="[1349,1392,800,814]" gridcol="6" gridrow="2" pageId="3" pageNumber="4">103.2</td>
|
||
<td id="D75CE741FFE8002EFA2FFCDA5FC7FC86" box="[1428,1471,800,814]" gridcol="7" gridrow="2" pageId="3" pageNumber="4">102.3</td>
|
||
</tr>
|
||
<tr id="948D8E3DFFE8002EFCF9FCCC5FC7FCEC" box="[834,1471,822,836]" gridrow="3" pageId="3" pageNumber="4">
|
||
<th id="D75CE741FFE8002EFCF9FCCC59F4FCEC" box="[834,908,822,836]" gridcol="0" gridrow="3" pageId="3" pageNumber="4">4</th>
|
||
<td id="D75CE741FFE8002EFC0BFCCC599DFCEC" box="[944,997,822,836]" gridcol="1" gridrow="3" pageId="3" pageNumber="4">176.1</td>
|
||
<td id="D75CE741FFE8002EFBB2FCCC5E4CFCEC" box="[1033,1076,822,836]" gridcol="2" gridrow="3" pageId="3" pageNumber="4">182.3</td>
|
||
<td id="D75CE741FFE8002EFBE3FCCC5EFBFCEC" box="[1112,1155,822,836]" gridcol="3" gridrow="3" pageId="3" pageNumber="4">182.6</td>
|
||
<td id="D75CE741FFE8002EFB1CFCCC5EAAFCEC" box="[1191,1234,822,836]" gridcol="4" gridrow="3" pageId="3" pageNumber="4">182.1</td>
|
||
<td id="D75CE741FFE8002EFB4DFCCC5F59FCEC" box="[1270,1313,822,836]" gridcol="5" gridrow="3" pageId="3" pageNumber="4">182.3</td>
|
||
<td id="D75CE741FFE8002EFAFEFCCC5F08FCEC" box="[1349,1392,822,836]" gridcol="6" gridrow="3" pageId="3" pageNumber="4">181.9</td>
|
||
<td id="D75CE741FFE8002EFA2FFCCC5FC7FCEC" box="[1428,1471,822,836]" gridcol="7" gridrow="3" pageId="3" pageNumber="4">180.6</td>
|
||
</tr>
|
||
<tr id="948D8E3DFFE8002EFCF9FCB75FC7FCF3" box="[834,1471,845,859]" gridrow="4" pageId="3" pageNumber="4">
|
||
<th id="D75CE741FFE8002EFCF9FCB759F4FCF3" box="[834,908,845,859]" gridcol="0" gridrow="4" pageId="3" pageNumber="4">5</th>
|
||
<td id="D75CE741FFE8002EFC0BFCB7599DFCF3" box="[944,997,845,859]" gridcol="1" gridrow="4" pageId="3" pageNumber="4">160.0</td>
|
||
<td id="D75CE741FFE8002EFBB2FCB75E4CFCF3" box="[1033,1076,845,859]" gridcol="2" gridrow="4" pageId="3" pageNumber="4">159.6</td>
|
||
<td id="D75CE741FFE8002EFBE3FCB75EFBFCF3" box="[1112,1155,845,859]" gridcol="3" gridrow="4" pageId="3" pageNumber="4">151.5</td>
|
||
<td id="D75CE741FFE8002EFB1CFCB75EAAFCF3" box="[1191,1234,845,859]" gridcol="4" gridrow="4" pageId="3" pageNumber="4">160.6</td>
|
||
<td id="D75CE741FFE8002EFB4DFCB75F59FCF3" box="[1270,1313,845,859]" gridcol="5" gridrow="4" pageId="3" pageNumber="4">151.4</td>
|
||
<td id="D75CE741FFE8002EFAFEFCB75F08FCF3" box="[1349,1392,845,859]" gridcol="6" gridrow="4" pageId="3" pageNumber="4">161.8</td>
|
||
<td id="D75CE741FFE8002EFA2FFCB75FC7FCF3" box="[1428,1471,845,859]" gridcol="7" gridrow="4" pageId="3" pageNumber="4">152.8</td>
|
||
</tr>
|
||
<tr id="948D8E3DFFE8002EFCF9FC9E5FC7FCDA" box="[834,1471,868,882]" gridrow="5" pageId="3" pageNumber="4">
|
||
<th id="D75CE741FFE8002EFCF9FC9E59F4FCDA" box="[834,908,868,882]" gridcol="0" gridrow="5" pageId="3" pageNumber="4">6</th>
|
||
<td id="D75CE741FFE8002EFC0BFC9E599DFCDA" box="[944,997,868,882]" gridcol="1" gridrow="5" pageId="3" pageNumber="4">99.9</td>
|
||
<td id="D75CE741FFE8002EFBB2FC9E5E4CFCDA" box="[1033,1076,868,882]" gridcol="2" gridrow="5" pageId="3" pageNumber="4">102.3</td>
|
||
<td id="D75CE741FFE8002EFBE3FC9E5EFBFCDA" box="[1112,1155,868,882]" gridcol="3" gridrow="5" pageId="3" pageNumber="4">134.1</td>
|
||
<td id="D75CE741FFE8002EFB1CFC9E5EAAFCDA" box="[1191,1234,868,882]" gridcol="4" gridrow="5" pageId="3" pageNumber="4">102.2</td>
|
||
<td id="D75CE741FFE8002EFB4DFC9E5F59FCDA" box="[1270,1313,868,882]" gridcol="5" gridrow="5" pageId="3" pageNumber="4">133.2</td>
|
||
<td id="D75CE741FFE8002EFAFEFC9E5F08FCDA" box="[1349,1392,868,882]" gridcol="6" gridrow="5" pageId="3" pageNumber="4">99.1</td>
|
||
<td id="D75CE741FFE8002EFA2FFC9E5FC7FCDA" box="[1428,1471,868,882]" gridcol="7" gridrow="5" pageId="3" pageNumber="4">133.5</td>
|
||
</tr>
|
||
<tr id="948D8E3DFFE8002EFCF9FC815FC7FC21" box="[834,1471,891,905]" gridrow="6" pageId="3" pageNumber="4">
|
||
<th id="D75CE741FFE8002EFCF9FC8159F4FC21" box="[834,908,891,905]" gridcol="0" gridrow="6" pageId="3" pageNumber="4">7</th>
|
||
<td id="D75CE741FFE8002EFC0BFC81599DFC21" box="[944,997,891,905]" gridcol="1" gridrow="6" pageId="3" pageNumber="4">158.4</td>
|
||
<td id="D75CE741FFE8002EFBB2FC815E4CFC21" box="[1033,1076,891,905]" gridcol="2" gridrow="6" pageId="3" pageNumber="4">159.4</td>
|
||
<td id="D75CE741FFE8002EFBE3FC815EFBFC21" box="[1112,1155,891,905]" gridcol="3" gridrow="6" pageId="3" pageNumber="4">153.9</td>
|
||
<td id="D75CE741FFE8002EFB1CFC815EAAFC21" box="[1191,1234,891,905]" gridcol="4" gridrow="6" pageId="3" pageNumber="4">159.6</td>
|
||
<td id="D75CE741FFE8002EFB4DFC815F59FC21" box="[1270,1313,891,905]" gridcol="5" gridrow="6" pageId="3" pageNumber="4">152.8</td>
|
||
<td id="D75CE741FFE8002EFAFEFC815F08FC21" box="[1349,1392,891,905]" gridcol="6" gridrow="6" pageId="3" pageNumber="4">164.5</td>
|
||
<td id="D75CE741FFE8002EFA2FFC815FC7FC21" box="[1428,1471,891,905]" gridcol="7" gridrow="6" pageId="3" pageNumber="4">154.0</td>
|
||
</tr>
|
||
<tr id="948D8E3DFFE8002EFCF9FC685FC7FC08" box="[834,1471,914,928]" gridrow="7" pageId="3" pageNumber="4">
|
||
<th id="D75CE741FFE8002EFCF9FC6859F4FC08" box="[834,908,914,928]" gridcol="0" gridrow="7" pageId="3" pageNumber="4">8</th>
|
||
<td id="D75CE741FFE8002EFC0BFC68599DFC08" box="[944,997,914,928]" gridcol="1" gridrow="7" pageId="3" pageNumber="4">99.8</td>
|
||
<td id="D75CE741FFE8002EFBB2FC685E4CFC08" box="[1033,1076,914,928]" gridcol="2" gridrow="7" pageId="3" pageNumber="4">97.7</td>
|
||
<td id="D75CE741FFE8002EFBE3FC685EFBFC08" box="[1112,1155,914,928]" gridcol="3" gridrow="7" pageId="3" pageNumber="4">98.5</td>
|
||
<td id="D75CE741FFE8002EFB1CFC685EAAFC08" box="[1191,1234,914,928]" gridcol="4" gridrow="7" pageId="3" pageNumber="4">97.7</td>
|
||
<td id="D75CE741FFE8002EFB4DFC685F59FC08" box="[1270,1313,914,928]" gridcol="5" gridrow="7" pageId="3" pageNumber="4">98.3</td>
|
||
<td id="D75CE741FFE8002EFAFEFC685F08FC08" box="[1349,1392,914,928]" gridcol="6" gridrow="7" pageId="3" pageNumber="4">94.1</td>
|
||
<td id="D75CE741FFE8002EFA2FFC685FC7FC08" box="[1428,1471,914,928]" gridcol="7" gridrow="7" pageId="3" pageNumber="4">95.5</td>
|
||
</tr>
|
||
<tr id="948D8E3DFFE8002EFCF9FC535FC7FC1F" box="[834,1471,937,951]" gridrow="8" pageId="3" pageNumber="4">
|
||
<th id="D75CE741FFE8002EFCF9FC5359F4FC1F" box="[834,908,937,951]" gridcol="0" gridrow="8" pageId="3" pageNumber="4">9</th>
|
||
<td id="D75CE741FFE8002EFC0BFC53599DFC1F" box="[944,997,937,951]" gridcol="1" gridrow="8" pageId="3" pageNumber="4">158.4</td>
|
||
<td id="D75CE741FFE8002EFBB2FC535E4CFC1F" box="[1033,1076,937,951]" gridcol="2" gridrow="8" pageId="3" pageNumber="4">156.6</td>
|
||
<td id="D75CE741FFE8002EFBE3FC535EFBFC1F" box="[1112,1155,937,951]" gridcol="3" gridrow="8" pageId="3" pageNumber="4">152.7</td>
|
||
<td id="D75CE741FFE8002EFB1CFC535EAAFC1F" box="[1191,1234,937,951]" gridcol="4" gridrow="8" pageId="3" pageNumber="4">156.4</td>
|
||
<td id="D75CE741FFE8002EFB4DFC535F59FC1F" box="[1270,1313,937,951]" gridcol="5" gridrow="8" pageId="3" pageNumber="4">152.6</td>
|
||
<td id="D75CE741FFE8002EFAFEFC535F08FC1F" box="[1349,1392,937,951]" gridcol="6" gridrow="8" pageId="3" pageNumber="4">157.4</td>
|
||
<td id="D75CE741FFE8002EFA2FFC535FC7FC1F" box="[1428,1471,937,951]" gridcol="7" gridrow="8" pageId="3" pageNumber="4">153.0</td>
|
||
</tr>
|
||
<tr id="948D8E3DFFE8002EFCF9FC455FC7FC66" box="[834,1471,959,974]" gridrow="9" pageId="3" pageNumber="4">
|
||
<th id="D75CE741FFE8002EFCF9FC4559F4FC66" box="[834,908,959,974]" gridcol="0" gridrow="9" pageId="3" pageNumber="4">10</th>
|
||
<td id="D75CE741FFE8002EFC0BFC45599DFC66" box="[944,997,959,974]" gridcol="1" gridrow="9" pageId="3" pageNumber="4">109.5</td>
|
||
<td id="D75CE741FFE8002EFBB2FC455E4CFC66" box="[1033,1076,959,974]" gridcol="2" gridrow="9" pageId="3" pageNumber="4">105.9</td>
|
||
<td id="D75CE741FFE8002EFBE3FC455EFBFC66" box="[1112,1155,959,974]" gridcol="3" gridrow="9" pageId="3" pageNumber="4">106.4</td>
|
||
<td id="D75CE741FFE8002EFB1CFC455EAAFC66" box="[1191,1234,959,974]" gridcol="4" gridrow="9" pageId="3" pageNumber="4">105.3</td>
|
||
<td id="D75CE741FFE8002EFB4DFC455F59FC66" box="[1270,1313,959,974]" gridcol="5" gridrow="9" pageId="3" pageNumber="4">106.2</td>
|
||
<td id="D75CE741FFE8002EFAFEFC455F08FC66" box="[1349,1392,959,974]" gridcol="6" gridrow="9" pageId="3" pageNumber="4">104.0</td>
|
||
<td id="D75CE741FFE8002EFA2FFC455FC7FC66" box="[1428,1471,959,974]" gridcol="7" gridrow="9" pageId="3" pageNumber="4">101.2</td>
|
||
</tr>
|
||
<tr id="948D8E3DFFE8002EFCF9FC2F5FC7FC4C" box="[834,1471,981,996]" gridrow="10" pageId="3" pageNumber="4">
|
||
<th id="D75CE741FFE8002EFCF9FC2F59F4FC4C" box="[834,908,981,996]" gridcol="0" gridrow="10" pageId="3" pageNumber="4">1′</th>
|
||
<td id="D75CE741FFE8002EFC0BFC2F599DFC4C" box="[944,997,981,996]" gridcol="1" gridrow="10" pageId="3" pageNumber="4">121.8</td>
|
||
<td id="D75CE741FFE8002EFBB2FC2F5E4CFC4C" box="[1033,1076,981,996]" gridcol="2" gridrow="10" pageId="3" pageNumber="4">123.6</td>
|
||
<td id="D75CE741FFE8002EFBE3FC2F5EFBFC4C" box="[1112,1155,981,996]" gridcol="3" gridrow="10" pageId="3" pageNumber="4">121.0</td>
|
||
<td id="D75CE741FFE8002EFB1CFC2F5EAAFC4C" box="[1191,1234,981,996]" gridcol="4" gridrow="10" pageId="3" pageNumber="4">121.1</td>
|
||
<td id="D75CE741FFE8002EFB4DFC2F5F59FC4C" box="[1270,1313,981,996]" gridcol="5" gridrow="10" pageId="3" pageNumber="4">120.5</td>
|
||
<td id="D75CE741FFE8002EFAFEFC2F5F08FC4C" box="[1349,1392,981,996]" gridcol="6" gridrow="10" pageId="3" pageNumber="4">121.6</td>
|
||
<td id="D75CE741FFE8002EFA2FFC2F5FC7FC4C" box="[1428,1471,981,996]" gridcol="7" gridrow="10" pageId="3" pageNumber="4">122.3</td>
|
||
</tr>
|
||
<tr id="948D8E3DFFE8002EFCF9FC165FC7FC53" box="[834,1471,1004,1019]" gridrow="11" pageId="3" pageNumber="4">
|
||
<th id="D75CE741FFE8002EFCF9FC1659F4FC53" box="[834,908,1004,1019]" gridcol="0" gridrow="11" pageId="3" pageNumber="4">2′</th>
|
||
<td id="D75CE741FFE8002EFC0BFC16599DFC53" box="[944,997,1004,1019]" gridcol="1" gridrow="11" pageId="3" pageNumber="4">120.3</td>
|
||
<td id="D75CE741FFE8002EFBB2FC165E4CFC53" box="[1033,1076,1004,1019]" gridcol="2" gridrow="11" pageId="3" pageNumber="4">120.6</td>
|
||
<td id="D75CE741FFE8002EFBE3FC165EFBFC53" box="[1112,1155,1004,1019]" gridcol="3" gridrow="11" pageId="3" pageNumber="4">120.6</td>
|
||
<td id="D75CE741FFE8002EFB1CFC165EAAFC53" box="[1191,1234,1004,1019]" gridcol="4" gridrow="11" pageId="3" pageNumber="4">113.3</td>
|
||
<td id="D75CE741FFE8002EFB4DFC165F59FC53" box="[1270,1313,1004,1019]" gridcol="5" gridrow="11" pageId="3" pageNumber="4">116.3</td>
|
||
<td id="D75CE741FFE8002EFAFEFC165F08FC53" box="[1349,1392,1004,1019]" gridcol="6" gridrow="11" pageId="3" pageNumber="4">120.8</td>
|
||
<td id="D75CE741FFE8002EFA2FFC165FC7FC53" box="[1428,1471,1004,1019]" gridcol="7" gridrow="11" pageId="3" pageNumber="4">120.1</td>
|
||
</tr>
|
||
<tr id="948D8E3DFFE8002EFCF9FBF85FC7FBBA" box="[834,1471,1026,1042]" gridrow="12" pageId="3" pageNumber="4">
|
||
<th id="D75CE741FFE8002EFCF9FBF859F4FBBA" box="[834,908,1026,1042]" gridcol="0" gridrow="12" pageId="3" pageNumber="4">3′</th>
|
||
<td id="D75CE741FFE8002EFC0BFBF8599DFBBA" box="[944,997,1026,1042]" gridcol="1" gridrow="12" pageId="3" pageNumber="4">141.7</td>
|
||
<td id="D75CE741FFE8002EFBB2FBF85E4CFBBA" box="[1033,1076,1026,1042]" gridcol="2" gridrow="12" pageId="3" pageNumber="4">141.5</td>
|
||
<td id="D75CE741FFE8002EFBE3FBF85EFBFBBA" box="[1112,1155,1026,1042]" gridcol="3" gridrow="12" pageId="3" pageNumber="4">141.8</td>
|
||
<td id="D75CE741FFE8002EFB1CFBF85EAAFBBA" box="[1191,1234,1026,1042]" gridcol="4" gridrow="12" pageId="3" pageNumber="4">145.1</td>
|
||
<td id="D75CE741FFE8002EFB4DFBF85F59FBBA" box="[1270,1313,1026,1042]" gridcol="5" gridrow="12" pageId="3" pageNumber="4">146.4</td>
|
||
<td id="D75CE741FFE8002EFAFEFBF85F08FBBA" box="[1349,1392,1026,1042]" gridcol="6" gridrow="12" pageId="3" pageNumber="4">141.6</td>
|
||
<td id="D75CE741FFE8002EFA2FFBF85FC7FBBA" box="[1428,1471,1026,1042]" gridcol="7" gridrow="12" pageId="3" pageNumber="4">141.7</td>
|
||
</tr>
|
||
<tr id="948D8E3DFFE8002EFCF9FBE35FC7FB81" box="[834,1471,1049,1065]" gridrow="13" pageId="3" pageNumber="4">
|
||
<th id="D75CE741FFE8002EFCF9FBE359F4FB81" box="[834,908,1049,1065]" gridcol="0" gridrow="13" pageId="3" pageNumber="4">4′</th>
|
||
<td id="D75CE741FFE8002EFC0BFBE3599DFB81" box="[944,997,1049,1065]" gridcol="1" gridrow="13" pageId="3" pageNumber="4">152.5</td>
|
||
<td id="D75CE741FFE8002EFBB2FBE35E4CFB81" box="[1033,1076,1049,1065]" gridcol="2" gridrow="13" pageId="3" pageNumber="4">153.5</td>
|
||
<td id="D75CE741FFE8002EFBE3FBE35EFBFB81" box="[1112,1155,1049,1065]" gridcol="3" gridrow="13" pageId="3" pageNumber="4">153.1</td>
|
||
<td id="D75CE741FFE8002EFB1CFBE35EAAFB81" box="[1191,1234,1049,1065]" gridcol="4" gridrow="13" pageId="3" pageNumber="4">150.3</td>
|
||
<td id="D75CE741FFE8002EFB4DFBE35F59FB81" box="[1270,1313,1049,1065]" gridcol="5" gridrow="13" pageId="3" pageNumber="4">151.3</td>
|
||
<td id="D75CE741FFE8002EFAFEFBE35F08FB81" box="[1349,1392,1049,1065]" gridcol="6" gridrow="13" pageId="3" pageNumber="4">152.8</td>
|
||
<td id="D75CE741FFE8002EFA2FFBE35FC7FB81" box="[1428,1471,1049,1065]" gridcol="7" gridrow="13" pageId="3" pageNumber="4">154.0</td>
|
||
</tr>
|
||
<tr id="948D8E3DFFE8002EFCF9FBCA5FC7FBE8" box="[834,1471,1072,1088]" gridrow="14" pageId="3" pageNumber="4">
|
||
<th id="D75CE741FFE8002EFCF9FBCA59F4FBE8" box="[834,908,1072,1088]" gridcol="0" gridrow="14" pageId="3" pageNumber="4">5′</th>
|
||
<td id="D75CE741FFE8002EFC0BFBCA599DFBE8" box="[944,997,1072,1088]" gridcol="1" gridrow="14" pageId="3" pageNumber="4">117.7</td>
|
||
<td id="D75CE741FFE8002EFBB2FBCA5E4CFBE8" box="[1033,1076,1072,1088]" gridcol="2" gridrow="14" pageId="3" pageNumber="4">117.4</td>
|
||
<td id="D75CE741FFE8002EFBE3FBCA5EFBFBE8" box="[1112,1155,1072,1088]" gridcol="3" gridrow="14" pageId="3" pageNumber="4">117.8</td>
|
||
<td id="D75CE741FFE8002EFB1CFBCA5EAAFBE8" box="[1191,1234,1072,1088]" gridcol="4" gridrow="14" pageId="3" pageNumber="4">116.2</td>
|
||
<td id="D75CE741FFE8002EFB4DFBCA5F59FBE8" box="[1270,1313,1072,1088]" gridcol="5" gridrow="14" pageId="3" pageNumber="4">113.1</td>
|
||
<td id="D75CE741FFE8002EFAFEFBCA5F08FBE8" box="[1349,1392,1072,1088]" gridcol="6" gridrow="14" pageId="3" pageNumber="4">117.5</td>
|
||
<td id="D75CE741FFE8002EFA2FFBCA5FC7FBE8" box="[1428,1471,1072,1088]" gridcol="7" gridrow="14" pageId="3" pageNumber="4">117.6</td>
|
||
</tr>
|
||
<tr id="948D8E3DFFE8002EFCF9FBBD5FC7FBFF" box="[834,1471,1095,1111]" gridrow="15" pageId="3" pageNumber="4">
|
||
<th id="D75CE741FFE8002EFCF9FBBD59F4FBFF" box="[834,908,1095,1111]" gridcol="0" gridrow="15" pageId="3" pageNumber="4">6′</th>
|
||
<td id="D75CE741FFE8002EFC0BFBBD599DFBFF" box="[944,997,1095,1111]" gridcol="1" gridrow="15" pageId="3" pageNumber="4">123.1</td>
|
||
<td id="D75CE741FFE8002EFBB2FBBD5E4CFBFF" box="[1033,1076,1095,1111]" gridcol="2" gridrow="15" pageId="3" pageNumber="4">123.5</td>
|
||
<td id="D75CE741FFE8002EFBE3FBBD5EFBFBFF" box="[1112,1155,1095,1111]" gridcol="3" gridrow="15" pageId="3" pageNumber="4">123.8</td>
|
||
<td id="D75CE741FFE8002EFB1CFBBD5EAAFBFF" box="[1191,1234,1095,1111]" gridcol="4" gridrow="15" pageId="3" pageNumber="4">119.3</td>
|
||
<td id="D75CE741FFE8002EFB4DFBBD5F59FBFF" box="[1270,1313,1095,1111]" gridcol="5" gridrow="15" pageId="3" pageNumber="4">119.3</td>
|
||
<td id="D75CE741FFE8002EFAFEFBBD5F08FBFF" box="[1349,1392,1095,1111]" gridcol="6" gridrow="15" pageId="3" pageNumber="4">123.5</td>
|
||
<td id="D75CE741FFE8002EFA2FFBBD5FC7FBFF" box="[1428,1471,1095,1111]" gridcol="7" gridrow="15" pageId="3" pageNumber="4">123.0</td>
|
||
</tr>
|
||
<tr id="948D8E3DFFE8002EFCF9FBA55FC7FBC6" box="[834,1471,1119,1134]" gridrow="16" pageId="3" pageNumber="4" rowspan-2="1" rowspan-6="1">
|
||
<th id="D75CE741FFE8002EFCF9FBA559F4FBC6" box="[834,908,1119,1134]" gridcol="0" gridrow="16" pageId="3" pageNumber="4">OMe</th>
|
||
<td id="D75CE741FFE8002EFC0BFBA5599DFBC6" box="[944,997,1119,1134]" gridcol="1" gridrow="16" pageId="3" pageNumber="4">56.4</td>
|
||
<td id="D75CE741FFE8002EFBE3FBA55EFBFBC6" box="[1112,1155,1119,1134]" gridcol="3" gridrow="16" pageId="3" pageNumber="4">60.5</td>
|
||
<td id="D75CE741FFE8002EFB1CFBA55EAAFBC6" box="[1191,1234,1119,1134]" gridcol="4" gridrow="16" pageId="3" pageNumber="4">–</td>
|
||
<td id="D75CE741FFE8002EFB4DFBA55F59FBC6" box="[1270,1313,1119,1134]" gridcol="5" gridrow="16" pageId="3" pageNumber="4">60.2</td>
|
||
<td id="D75CE741FFE8002EFA2FFBA55FC7FBC6" box="[1428,1471,1119,1134]" gridcol="7" gridrow="16" pageId="3" pageNumber="4">59.2</td>
|
||
</tr>
|
||
</table>
|
||
</paragraph>
|
||
<paragraph id="2A028C7FFFE8FFD2FF3FFC745BFCF997" blockId="3.[101,771,659,1599]" pageId="3" pageNumber="4">
|
||
Total acid hydrolysis of the crude extract resulted in the complete disappearance of the 13 peaks assigned as flavonoid (
|
||
<emphasis id="18C9506DFFE8FFD2FDC5FC5058D9FC15" bold="true" box="[638,673,938,958]" pageId="3" pageNumber="4">2–4</emphasis>
|
||
,
|
||
<emphasis id="18C9506DFFE8FFD2FD0AFC5058ACFC15" bold="true" box="[689,724,938,958]" pageId="3" pageNumber="4">6–9</emphasis>
|
||
and
|
||
<emphasis id="18C9506DFFE8FFD2FFDEFC3C5AD9FC71" bold="true" box="[101,161,966,985]" pageId="3" pageNumber="4">11–16</emphasis>
|
||
), and the appearance of six aglycones (
|
||
<emphasis id="18C9506DFFE8FFD2FDB6FC3C585EFC71" bold="true" box="[525,550,966,985]" pageId="3" pageNumber="4">a -f</emphasis>
|
||
, Fig. 2). Peaks assigned to phenolic acids (
|
||
<emphasis id="18C9506DFFE8FFD2FEAFFC185B58FC5D" bold="true" box="[276,288,994,1013]" pageId="3" pageNumber="4">1</emphasis>
|
||
,
|
||
<emphasis id="18C9506DFFE8FFD2FE96FC185B41FC5D" bold="true" box="[301,313,994,1013]" pageId="3" pageNumber="4">5</emphasis>
|
||
,
|
||
<emphasis id="18C9506DFFE8FFD2FEFCFC185B18FC5D" bold="true" box="[327,352,994,1013]" pageId="3" pageNumber="4">10</emphasis>
|
||
) were recovered unchanged. Based on their UV spectra and comparison to standards and data from literature, the aglycones were identified as 6-hydroxyluteolin (
|
||
<emphasis id="18C9506DFFE8FFD2FD85FBE05832FB85" bold="true" box="[574,586,1050,1069]" pageId="3" pageNumber="4">a</emphasis>
|
||
, Rt, 24.1 min), 5- methoxyluteolin (
|
||
<emphasis id="18C9506DFFE8FFD2FEA8FBCC5B58FBE1" bold="true" box="[275,288,1078,1097]" pageId="3" pageNumber="4">b</emphasis>
|
||
, 25.1 min), luteolin (
|
||
<emphasis id="18C9506DFFE8FFD2FDB8FBCC5876FBE1" bold="true" box="[515,526,1078,1097]" pageId="3" pageNumber="4">c</emphasis>
|
||
, 30.2 min), nepetin (
|
||
<emphasis id="18C9506DFFE8FFD2FD54FBCC5884FBE1" bold="true" box="[751,764,1078,1097]" pageId="3" pageNumber="4">d</emphasis>
|
||
, 30.9 min), hispidulin (
|
||
<emphasis id="18C9506DFFE8FFD2FE85FBA85B31FBCD" bold="true" box="[318,329,1106,1125]" pageId="3" pageNumber="4">e</emphasis>
|
||
, 33.6 min), and jaceosidin (
|
||
<emphasis id="18C9506DFFE8FFD2FDE2FBAB5810FBCC" bold="true" box="[601,616,1105,1124]" pageId="3" pageNumber="4">f,</emphasis>
|
||
34.0 min). This order of elution on C18 column and UV
|
||
<emphasis id="18C9506DFFE8FFD2FE5EFB945B97FB29" bold="true" box="[485,495,1134,1153]" italics="true" pageId="3" pageNumber="4">λ</emphasis>
|
||
<subScript id="B6398E3AFFE8FFD2FE54FB8F5875FB2B" attach="left" box="[495,525,1141,1155]" fontSize="6" pageId="3" pageNumber="4">max</subScript>
|
||
values of these aglycones are in agreement with literature data (
|
||
<bibRefCitation id="4E2CF18EFFE8FFD2FE61FB7358EBFB34" author="Bojilov, D. & Dagnon, S. & Ivanov, I." box="[474,659,1161,1181]" pageId="3" pageNumber="4" pagination="316 - 321" refId="ref16240" refString="Bojilov, D., Dagnon, S., Ivanov, I., 2017. New insight into the flavonoid composition of Chenopodium botrys. Phytochem. Lett. 20, 316 - 321. https: // doi. org / 10.1016 / j. phytol. 2017.01.015." type="journal article" year="2017">Bojilov et al., 2017</bibRefCitation>
|
||
;
|
||
<bibRefCitation id="4E2CF18EFFE8FFD2FD1AFB735AA2FB10" author="Greenham, J. & Harborne, J. B. & Williams, C. A." pageId="3" pageNumber="4" pagination="100 - 118" refId="ref16929" refString="Greenham, J., Harborne, J. B., Williams, C. A., 2003. Identification of lipophilic flavones and flavonols by comparative HPLC, TLC and UV. Spectral analysis. Phytochem. Anal. 14, 100 - 118. https: // doi. org / 10.1002 / pca. 693." type="journal article" year="2003">Greenham et al., 2003</bibRefCitation>
|
||
). It should be noted that whilst the introduction of a methoxyl group generally makes the product more lipophilic, resulting in a higher retention time, this is not the case for 5-methoxyluteolin, which was eluted earlier than luteolin due to the absence of internal hydrogen bond with the carbonyl group (
|
||
<bibRefCitation id="4E2CF18EFFE8FFD2FDABFAEF588CFA80" author="Greenham, J. & Harborne, J. B. & Williams, C. A." box="[528,756,1301,1320]" pageId="3" pageNumber="4" pagination="100 - 118" refId="ref16929" refString="Greenham, J., Harborne, J. B., Williams, C. A., 2003. Identification of lipophilic flavones and flavonols by comparative HPLC, TLC and UV. Spectral analysis. Phytochem. Anal. 14, 100 - 118. https: // doi. org / 10.1002 / pca. 693." type="journal article" year="2003">Greenham et al., 2003</bibRefCitation>
|
||
). 5-Methoxyluteolin, luteolin, nepetin, hispidulin were unambiguously assigned by spectroscopic data (NMR, UV, and MS). Elution order and on-line UV spectra for 6-hydroxyluteolin and jaceosidin were in agreement with literature data (
|
||
<bibRefCitation id="4E2CF18EFFE8FFD2FEDFFA7E5862FA3F" author="Bojilov, D. & Dagnon, S. & Ivanov, I." box="[356,538,1412,1432]" pageId="3" pageNumber="4" pagination="316 - 321" refId="ref16240" refString="Bojilov, D., Dagnon, S., Ivanov, I., 2017. New insight into the flavonoid composition of Chenopodium botrys. Phytochem. Lett. 20, 316 - 321. https: // doi. org / 10.1016 / j. phytol. 2017.01.015." type="journal article" year="2017">Bojilov et al., 2017</bibRefCitation>
|
||
;
|
||
<bibRefCitation id="4E2CF18EFFE8FFD2FD9CFA7E5884FA3F" author="Greenham, J. & Harborne, J. B. & Williams, C. A." box="[551,764,1412,1432]" pageId="3" pageNumber="4" pagination="100 - 118" refId="ref16929" refString="Greenham, J., Harborne, J. B., Williams, C. A., 2003. Identification of lipophilic flavones and flavonols by comparative HPLC, TLC and UV. Spectral analysis. Phytochem. Anal. 14, 100 - 118. https: // doi. org / 10.1002 / pca. 693." type="journal article" year="2003">Greenham et al., 2003</bibRefCitation>
|
||
; Tom´as-Barber´an et al., 1987). Controlled hydrolysis in mild condition released flavonoids
|
||
<emphasis id="18C9506DFFE8FFD2FE93FA465B39FA67" bold="true" box="[296,321,1468,1487]" pageId="3" pageNumber="4">13</emphasis>
|
||
and
|
||
<emphasis id="18C9506DFFE8FFD2FEC3FA465BE9FA67" bold="true" box="[376,401,1468,1487]" pageId="3" pageNumber="4">14</emphasis>
|
||
, whose peak intensity has increased, along with two additional compounds (
|
||
<emphasis id="18C9506DFFE8FFD2FE74FA225B90FA43" bold="true" box="[463,488,1496,1515]" pageId="3" pageNumber="4">17</emphasis>
|
||
and
|
||
<emphasis id="18C9506DFFE8FFD2FDAFFA225855FA43" bold="true" box="[532,557,1496,1515]" pageId="3" pageNumber="4">18</emphasis>
|
||
), and the six aglycones
|
||
<emphasis id="18C9506DFFE8FFD2FFDEFA0E5A06F9AF" bold="true" box="[101,126,1524,1543]" pageId="3" pageNumber="4">a -f</emphasis>
|
||
(Figs. 2 and 3, and S31). This suggests that compounds
|
||
<emphasis id="18C9506DFFE8FFD2FD27FA0E58A0F9AF" bold="true" box="[668,728,1524,1544]" pageId="3" pageNumber="4">13–14</emphasis>
|
||
and
|
||
<emphasis id="18C9506DFFE8FFD2FFDEF9EA5AD9F98B" bold="true" box="[101,161,1552,1571]" pageId="3" pageNumber="4">17–18</emphasis>
|
||
are intermediates with respect to the level of sulfation of their respective flavonoid aglycone.
|
||
</paragraph>
|
||
<paragraph id="2A028C7FFFE8FFD2FFDEF9825AB0F90F" blockId="3.[101,751,1656,1675]" lastBlockId="3.[101,200,1684,1703]" pageId="3" pageNumber="4">
|
||
<emphasis id="18C9506DFFE8FFD2FFDEF9825AB0F90F" bold="true" italics="true" pageId="3" pageNumber="4">
|
||
<heading id="714A3B13FFE8FFD2FFDEF9825897F923" bold="true" box="[101,751,1656,1675]" centered="true" fontSize="36" level="1" pageId="3" pageNumber="4" reason="1">
|
||
<tableCitation id="673FB9C4FFE8FFD2FFDEF9825AFDF923" box="[101,133,1656,1675]" captionStart="Table 2" captionStartId="3.[101,151,151,167]" captionTargetPageId="3" captionText="Table 2 1H-NMR data for flavonoid sulfates 3, 6, 7, 11 15 in DMSO‑d (δ ppm, J (Hz))." pageId="3" pageNumber="4">2.2</tableCitation>
|
||
. Purification of the extracts and structure identification of flavonoid
|
||
</heading>
|
||
<heading id="714A3B13FFE8FFD2FFDEF96E5AB0F90F" box="[101,200,1684,1703]" fontSize="8" level="3" pageId="3" pageNumber="4" reason="8">compounds</heading>
|
||
</emphasis>
|
||
</paragraph>
|
||
<paragraph id="2A028C7FFFE8FFD2FF3FF9365FDEFB7B" blockId="3.[101,770,1740,1982]" lastBlockId="3.[818,1491,1188,1961]" pageId="3" pageNumber="4">
|
||
The crude aqueous-methanolic extract was serially partitioned between water and organic solvent of increasing polarity,
|
||
<emphasis id="18C9506DFFE8FFD2FDC6F91D58E0F952" bold="true" box="[637,664,1767,1786]" italics="true" pageId="3" pageNumber="4">i.e.</emphasis>
|
||
methylene chloride (F1, 0.2% yield), ethyl acetate (F2, 0.6% yield), and then
|
||
<emphasis id="18C9506DFFE8FFD2FD4BF8FE5AD5F89A" bold="true" italics="true" pageId="3" pageNumber="4">nbutanol</emphasis>
|
||
(F3, 11.2% yield). Of these, only F3 was found to contain significant amounts of flavonoid. HPLC analysis of F2 showed a complex mixture of apolar products dominated by 3, 4-dihydroxy benzaldehyde (5% of the total), caffeic acid (18%), coumaric acid (7%) and rosmarinic acid (13%). They were identified by UV, comparison to authentic standards, and
|
||
<collectionCode id="4CAC14BAFFE8FFD2FF4FF8515B5FF816" box="[244,295,1963,1982]" pageId="3" pageNumber="4">NMR</collectionCode>
|
||
. This is the first report of rosmarinic acid from the genus
|
||
<emphasis id="18C9506DFFE8FFD2FCCEFB5E5994FB1F" bold="true" box="[885,1004,1188,1207]" italics="true" pageId="3" pageNumber="4">
|
||
<taxonomicName id="EDBDF7FCFFE8FFD2FCCEFB5E5991FB1F" box="[885,1001,1188,1207]" class="Liliopsida" family="Zosteraceae" genus="Phyllospadix" kingdom="Plantae" order="Alismatales" pageId="3" pageNumber="4" phylum="Tracheophyta" rank="genus">Phyllospadix</taxonomicName>
|
||
.
|
||
</emphasis>
|
||
The presence of caffeic- and coumaric acid in
|
||
<taxonomicName id="EDBDF7FCFFE8FFD2FC89FB3A59FCFB7B" baseAuthorityName="Zapata and McMillan" baseAuthorityYear="1979" box="[818,900,1216,1235]" class="Liliopsida" family="Zosteraceae" genus="Phyllospadix" kingdom="Plantae" order="Alismatales" pageId="3" pageNumber="4" phylum="Tracheophyta" rank="species" species="torreyi">
|
||
<emphasis id="18C9506DFFE8FFD2FC89FB3A59FCFB7B" bold="true" box="[818,900,1216,1235]" italics="true" pageId="3" pageNumber="4">P. torreyi</emphasis>
|
||
</taxonomicName>
|
||
was previously reported by
|
||
<bibRefCitation id="4E2CF18EFFE8FFD2FB29FB3A5FD8FB7B" author="Zapata, O. & McMillan, C." box="[1170,1440,1216,1235]" pageId="3" pageNumber="4" pagination="307 - 317" refId="ref21343" refString="Zapata, O., McMillan, C., 1979. Phenolic acids in seagrasses. Aquat. Bot. 7, 307 - 317. https: // doi. org / 10.1016 / 0304 - 3770 (79) 90032 - 9." type="journal article" year="1979">Zapata and McMillan (1979)</bibRefCitation>
|
||
.
|
||
</paragraph>
|
||
<paragraph id="2A028C7FFFE8FFD2FCE9FB265F13FA8E" blockId="3.[818,1491,1188,1961]" pageId="3" pageNumber="4">
|
||
Fractionation of F3 by successive chromatography on C18 reverse phase silica gel led to the isolation of seven pure flavonoids (
|
||
<emphasis id="18C9506DFFE8FFD2FA30FB0D5FEFFAA2" bold="true" box="[1419,1431,1271,1290]" pageId="3" pageNumber="4">3</emphasis>
|
||
,
|
||
<emphasis id="18C9506DFFE8FFD2FA1DFB0D5FB1FAA3" bold="true" box="[1446,1481,1271,1292]" pageId="3" pageNumber="4">6–7</emphasis>
|
||
,
|
||
<emphasis id="18C9506DFFE8FFD2FC89FAE95916FA8E" bold="true" box="[818,878,1299,1319]" pageId="3" pageNumber="4">11–14</emphasis>
|
||
), of which
|
||
<emphasis id="18C9506DFFE8FFD2FC60FAE9599FFA8E" bold="true" box="[987,999,1299,1318]" pageId="3" pageNumber="4">3</emphasis>
|
||
,
|
||
<emphasis id="18C9506DFFE8FFD2FC4FFAEE5E78FA8F" bold="true" box="[1012,1024,1300,1319]" pageId="3" pageNumber="4">7</emphasis>
|
||
, and
|
||
<emphasis id="18C9506DFFE8FFD2FB8DFAE95E37FA8E" bold="true" box="[1078,1103,1299,1318]" pageId="3" pageNumber="4">14</emphasis>
|
||
were previously undescribed.
|
||
</paragraph>
|
||
<paragraph id="2A028C7FFFE8FFD5FCE9FAD55A86FCAC" blockId="3.[818,1491,1188,1961]" lastBlockId="4.[100,773,502,1972]" lastPageId="4" lastPageNumber="5" pageId="3" pageNumber="4">
|
||
Compound
|
||
<emphasis id="18C9506DFFE8FFD2FC7AFAD559B5FAEA" bold="true" box="[961,973,1327,1346]" pageId="3" pageNumber="4">3</emphasis>
|
||
eluted at 14.4 min in the chromatographic run. The positive ESI-MS spectrum gave a quasimolecular peak [M+H]
|
||
<superScript id="DDC82137FFE8FFD2FAC4FABD5FF6FAFB" attach="left" box="[1407,1422,1351,1363]" fontSize="6" pageId="3" pageNumber="4">+</superScript>
|
||
at
|
||
<quantity id="ED45219AFFE8FFD2FA10FAB1593BFAD2" metricMagnitude="2" metricUnit="m" metricValue="4.61" pageId="3" pageNumber="4" unit="m" value="461.0">
|
||
461
|
||
<emphasis id="18C9506DFFE8FFD2FC89FA9D593BFAD2" bold="true" box="[818,835,1383,1402]" italics="true" pageId="3" pageNumber="4">m</emphasis>
|
||
</quantity>
|
||
/z, which was compatible with the molecular formula C
|
||
<subScript id="B6398E3AFFE8FFD2FADBFA945F0AFAD4" attach="both" box="[1376,1394,1390,1404]" fontSize="6" pageId="3" pageNumber="4">16</subScript>
|
||
H
|
||
<subScript id="B6398E3AFFE8FFD2FA39FA945FECFAD4" attach="both" box="[1410,1428,1390,1404]" fontSize="6" pageId="3" pageNumber="4">12</subScript>
|
||
O
|
||
<subScript id="B6398E3AFFE8FFD2FA18FA945FCDFAD4" attach="both" box="[1443,1461,1390,1404]" fontSize="6" pageId="3" pageNumber="4">12</subScript>
|
||
S
|
||
<subScript id="B6398E3AFFE8FFD2FA7AFA945FB2FAD4" attach="right" box="[1473,1482,1390,1404]" fontSize="6" pageId="3" pageNumber="4">2</subScript>
|
||
. Two pairs of another significant ions at
|
||
<emphasis id="18C9506DFFE8FFD2FB25FA795EBBFA3E" bold="true" box="[1182,1219,1411,1430]" italics="true" pageId="3" pageNumber="4">m/z</emphasis>
|
||
403 ([M-80 +Na]
|
||
<superScript id="DDC82137FFE8FFD2FAD5FA855F02FA23" attach="right" box="[1390,1402,1407,1419]" fontSize="6" pageId="3" pageNumber="4">+</superScript>
|
||
, 381 [M-80 + H]
|
||
<superScript id="DDC82137FFE8FFD2FC3AFA6159F5FA0F" attach="none" box="[897,909,1435,1447]" fontSize="6" pageId="3" pageNumber="4">+</superScript>
|
||
, and 323 [M-160 + Na]
|
||
<superScript id="DDC82137FFE8FFD2FBCDFA615EFAFA0F" attach="none" box="[1142,1154,1435,1447]" fontSize="6" pageId="3" pageNumber="4">+</superScript>
|
||
, 301 [M-160 + H]
|
||
<superScript id="DDC82137FFE8FFD2FA83FA615F3FFA0F" attach="left" box="[1336,1351,1435,1447]" fontSize="6" pageId="3" pageNumber="4">+</superScript>
|
||
confirmed the presence of two sulfate groups. The
|
||
<superScript id="DDC82137FFE8FFD2FB22FA4F5ED3FA6B" attach="right" box="[1177,1195,1461,1475]" fontSize="6" pageId="3" pageNumber="4">13</superScript>
|
||
C
|
||
<collectionCode id="4CAC14BAFFE8FFD2FB79FA415E8AFA66" box="[1218,1266,1467,1486]" pageId="3" pageNumber="4">NMR</collectionCode>
|
||
spectrum in DMSO‑
|
||
<emphasis id="18C9506DFFE8FFD2FA00FA415FBEFA66" bold="true" box="[1467,1478,1467,1486]" italics="true" pageId="3" pageNumber="4">d</emphasis>
|
||
<subScript id="B6398E3AFFE8FFD2FA7DFA385FB7FA78" attach="left" box="[1478,1487,1474,1488]" fontSize="6" pageId="3" pageNumber="4">6</subScript>
|
||
showed 16 resonances (1 methoxy, 6
|
||
<collectingCountry id="52AACCEFFFE8FFD2FB31FA2D5ED2FA42" box="[1162,1194,1495,1514]" name="Switzerland" pageId="3" pageNumber="4">CH</collectingCountry>
|
||
, and 9 quaternary C including a carbonyl). The
|
||
<superScript id="DDC82137FFE8FFD2FC79FA1759B3FA53" attach="right" box="[962,971,1517,1531]" fontSize="6" pageId="3" pageNumber="4">1</superScript>
|
||
H
|
||
<collectionCode id="4CAC14BAFFE8FFD2FC5AFA095E69F9AE" box="[993,1041,1523,1542]" pageId="3" pageNumber="4">NMR</collectionCode>
|
||
spectrum showed six proton signals in the aromatic region in accordance with a luteolin derivative,
|
||
<emphasis id="18C9506DFFE8FFD2FA94F9F45F32F989" bold="true" box="[1327,1354,1550,1569]" italics="true" pageId="3" pageNumber="4">i.e.</emphasis>
|
||
a pair of
|
||
<emphasis id="18C9506DFFE8FFD2FA1FF9F55FB7F98A" bold="true" box="[1444,1487,1551,1570]" italics="true" pageId="3" pageNumber="4">meta</emphasis>
|
||
coupled protons at
|
||
<emphasis id="18C9506DFFE8FFD2FC58F9D05995F995" bold="true" box="[995,1005,1578,1597]" italics="true" pageId="3" pageNumber="4">δ</emphasis>
|
||
6.70 (1 H,
|
||
<emphasis id="18C9506DFFE8FFD2FBE8F9D05E26F995" bold="true" box="[1107,1118,1578,1597]" italics="true" pageId="3" pageNumber="4">d</emphasis>
|
||
,
|
||
<emphasis id="18C9506DFFE8FFD2FBD2F9D15E0BF996" bold="true" box="[1129,1139,1579,1598]" italics="true" pageId="3" pageNumber="4">J</emphasis>
|
||
=2.2 Hz, H-6) and
|
||
<emphasis id="18C9506DFFE8FFD2FA90F9D05F4DF995" bold="true" box="[1323,1333,1578,1597]" italics="true" pageId="3" pageNumber="4">δ</emphasis>
|
||
7.12 (1 H,
|
||
<emphasis id="18C9506DFFE8FFD2FA20F9D05FDEF995" bold="true" box="[1435,1446,1578,1597]" italics="true" pageId="3" pageNumber="4">d</emphasis>
|
||
,
|
||
<emphasis id="18C9506DFFE8FFD2FA0BF9D15FC2F996" bold="true" box="[1456,1466,1579,1598]" italics="true" pageId="3" pageNumber="4">J</emphasis>
|
||
= 2.2 Hz, H-8), a one proton singlet at
|
||
<emphasis id="18C9506DFFE8FFD2FB1AF9BC5ED3F9F1" bold="true" box="[1185,1195,1606,1625]" italics="true" pageId="3" pageNumber="4">δ</emphasis>
|
||
6.50 (H-3), and an AMX spin system at
|
||
<emphasis id="18C9506DFFE8FFD2FC37F99859EEF9DD" bold="true" box="[908,918,1634,1653]" italics="true" pageId="3" pageNumber="4">δ</emphasis>
|
||
7.84 (1 H,
|
||
<emphasis id="18C9506DFFE8FFD2FC40F9985E7EF9DD" bold="true" box="[1019,1030,1634,1653]" italics="true" pageId="3" pageNumber="4">d</emphasis>
|
||
,
|
||
<emphasis id="18C9506DFFE8FFD2FBABF9985E62F9DD" bold="true" box="[1040,1050,1634,1653]" italics="true" pageId="3" pageNumber="4">J</emphasis>
|
||
=2.3 Hz, H-2
|
||
<superScript id="DDC82137FFE8FFD2FB27F9A55ED9F9C4" attach="none" box="[1180,1185,1631,1644]" fontSize="6" pageId="3" pageNumber="4">′</superScript>
|
||
),
|
||
<emphasis id="18C9506DFFE8FFD2FB0FF9985EC6F9DD" bold="true" box="[1204,1214,1634,1653]" italics="true" pageId="3" pageNumber="4">δ</emphasis>
|
||
7.63 (1 H,
|
||
<emphasis id="18C9506DFFE8FFD2FA99F9985F40F9DD" bold="true" box="[1314,1336,1634,1653]" italics="true" pageId="3" pageNumber="4">dd</emphasis>
|
||
,
|
||
<emphasis id="18C9506DFFE8FFD2FAF8F9985F35F9DD" bold="true" box="[1347,1357,1634,1653]" italics="true" pageId="3" pageNumber="4">J</emphasis>
|
||
=2.3, 8.5 Hz, H-6
|
||
<superScript id="DDC82137FFE8FFD2FCEEF9815922F920" attach="none" box="[853,858,1659,1672]" fontSize="6" pageId="3" pageNumber="4">′</superScript>
|
||
),
|
||
<emphasis id="18C9506DFFE8FFD2FCD5F9845900F939" bold="true" box="[878,888,1662,1681]" italics="true" pageId="3" pageNumber="4">δ</emphasis>
|
||
6.97 (1 H,
|
||
<emphasis id="18C9506DFFE8FFD2FC5FF9845997F939" bold="true" box="[996,1007,1662,1681]" italics="true" pageId="3" pageNumber="4">d</emphasis>
|
||
,
|
||
<emphasis id="18C9506DFFE8FFD2FC40F9845E7DF939" bold="true" box="[1019,1029,1662,1681]" italics="true" pageId="3" pageNumber="4">J</emphasis>
|
||
= 8.5 Hz, H-5
|
||
<superScript id="DDC82137FFE8FFD2FB35F9815EEBF920" attach="none" box="[1166,1171,1659,1672]" fontSize="6" pageId="3" pageNumber="4">′</superScript>
|
||
) (
|
||
<tableCitation id="673FB9C4FFE8FFD2FB11F9845E88F939" box="[1194,1264,1662,1681]" captionStart="Table 2" captionStartId="3.[101,151,151,167]" captionTargetPageId="3" captionText="Table 2 1H-NMR data for flavonoid sulfates 3, 6, 7, 11 15 in DMSO‑d (δ ppm, J (Hz))." pageId="3" pageNumber="4">Table 2</tableCitation>
|
||
). Resonances of carbon and proton showed the typical
|
||
<emphasis id="18C9506DFFE8FFD2FBF5F9605E09F905" bold="true" box="[1102,1137,1690,1709]" italics="true" pageId="3" pageNumber="4">ipso</emphasis>
|
||
and
|
||
<emphasis id="18C9506DFFE8FFD2FB26F9605EB4F905" bold="true" box="[1181,1228,1690,1709]" italics="true" pageId="3" pageNumber="4">ortho</emphasis>
|
||
shifts due to the presence of a sulfate group at position 7 (strong deshielding of H-8 and C-8; shielding of C-7), and 3’ (strong deshielding of H-2
|
||
<superScript id="DDC82137FFE8FFD2FA8AF9355F4EF974" attach="none" box="[1329,1334,1743,1756]" fontSize="6" pageId="3" pageNumber="4">′</superScript>
|
||
, C-2
|
||
<superScript id="DDC82137FFE8FFD2FADDF9355F13F974" attach="left" box="[1382,1387,1743,1756]" fontSize="6" pageId="3" pageNumber="4">′</superScript>
|
||
and C-4’; shielding of C-3
|
||
<superScript id="DDC82137FFE8FFD2FC7EF91059B2F95F" attach="none" box="[965,970,1770,1783]" fontSize="6" pageId="3" pageNumber="4">′</superScript>
|
||
) (
|
||
<tableCitation id="673FB9C4FFE8FFD2FC5BF9145E56F8A9" box="[992,1070,1774,1793]" captionStart="Table 3" captionStartId="3.[818,868,679,695]" captionTargetPageId="3" captionText="Table 3 13C-NMR chemical shifts for flavonoid sulfates 3, 6, 7, 11–14 (δ ppm, DMSO‑d). 6" pageId="3" pageNumber="4">Tables 3</tableCitation>
|
||
and
|
||
<tableCitation id="673FB9C4FFE8FFD2FBE0F9145E1FF8A9" box="[1115,1127,1774,1793]" captionStart="Table 4" captionStartId="4.[100,150,150,166]" captionTargetPageId="4" captionText="Table 4 Diagnostic 1H and13C NMR sulfation shifts for flavonoid sulfates 3, 6, 7, 11–15 (DMSO‑d); values are expressed in ppm as δ (flavonoid sulfate) - δ (flavonoid)." pageId="3" pageNumber="4">4</tableCitation>
|
||
), (
|
||
<bibRefCitation id="4E2CF18EFFE8FFD2FB38F9145F4AF8A9" author="Barron, D. & Varin, L. & Ibrahim, R. K. & Harborne, J. B. & Williams, C. A." box="[1155,1330,1774,1793]" pageId="3" pageNumber="4" pagination="2375 - 2395" refId="ref16118" refString="Barron, D., Varin, L., Ibrahim, R. K., Harborne, J. B., Williams, C. A., 1988. Sulphated flavonoids: an update. Phytochemistry 27, 2375 - 2395. https: // doi. org / 10.1016 / 0031 - 9422 (88) 87003 - 1." type="journal article" year="1988">Barron et al., 1988</bibRefCitation>
|
||
). The absence of phenol –OH group signal around
|
||
<emphasis id="18C9506DFFE8FFD2FBC4F8F35EF1F8B4" bold="true" box="[1151,1161,1801,1820]" italics="true" pageId="3" pageNumber="4">δ</emphasis>
|
||
13 ppm was consistent with the methoxy group linked to C-5. This was confirmed by the HMBC correlation observed between C-5 and the methoxy protons, the crosspeak observed between the methoxyl and H-6 resonances in the NOESY spectrum, the shielding of the carbonyl (176.1 ppm versus 181.9 ppm for luteolin) and the deshielding of C-3 (106.7 ppm versus 103.1 ppm) due to the absence of the strong internal hydrogen bond with a hydroxyl group at C-5. UV spectra (DAD on-line 266 and
|
||
<quantity id="ED45219AFFEFFFD5FDA1FDE8581AFD8D" box="[538,610,530,549]" metricMagnitude="-7" metricUnit="m" metricValue="3.32" pageId="4" pageNumber="5" unit="nm" value="332.0">332 nm</quantity>
|
||
; UV (MeOH) 266 and
|
||
<quantity id="ED45219AFFEFFFD5FF34FDD45AA3FDE9" box="[143,219,558,577]" metricMagnitude="-7" metricUnit="m" metricValue="3.27" pageId="4" pageNumber="5" unit="nm" value="327.0">327 nm</quantity>
|
||
) are in agreement with the hypsochromic shift of Band I induced by sulfation at position 3’ (
|
||
<bibRefCitation id="4E2CF18EFFEFFFD5FE02FDB05813FDF4" author="Barron, D. & Varin, L. & Ibrahim, R. K. & Harborne, J. B. & Williams, C. A." box="[441,619,585,605]" pageId="4" pageNumber="5" pagination="2375 - 2395" refId="ref16118" refString="Barron, D., Varin, L., Ibrahim, R. K., Harborne, J. B., Williams, C. A., 1988. Sulphated flavonoids: an update. Phytochemistry 27, 2375 - 2395. https: // doi. org / 10.1016 / 0031 - 9422 (88) 87003 - 1." type="journal article" year="1988">Barron et al., 1988</bibRefCitation>
|
||
). After acid hydrolysis, compound
|
||
<emphasis id="18C9506DFFEFFFD5FE9FFD9F5B48FDD0" bold="true" box="[292,304,613,632]" pageId="4" pageNumber="5">3</emphasis>
|
||
yielded 5-methoxyluteolin, which was identified by UV and
|
||
<collectionCode id="4CAC14BAFFEFFFD5FF70FD7B5A83FD3C" box="[203,251,641,660]" pageId="4" pageNumber="5">NMR</collectionCode>
|
||
(
|
||
<figureCitation id="B28690FAFFEFFFD5FEB2FD7B5B45FD3C" box="[265,317,641,660]" captionStart="Fig" captionStartId="5.[100,130,736,753]" captionTargetBox="[264,1323,149,707]" captionTargetId="figure-940@5.[263,1324,148,708]" captionTargetPageId="5" captionText="Fig. 4. Inter-annual variation in the amounts of phenolic compound in fresh (samples Phy1-F to Phy5-F) and detrital (sample Phy-3 D). Concentrations values on ordinate are given as mg g ¡1 dw of plant tissue, mean values SD (n 3). Products are given in order of elution: Caff: 1; Nep7,4’: 2; OMeLu2S: 3; 6OHLu2S: 4; ± = Coum: 5; Lu2S: 6; Nep2S: 7; 5OMeLu7S: 8; 6OHLu7S: 9; RA: 10; L7S: 11; Nep7S: 12; Lu3′S: 13; Nep3′S: 14; Hispi7S: 15; Jaceo7S: 16. See Fig. 3 for formulae and Table 1 for full data." figureDoi="http://doi.org/10.5281/zenodo.8235330" httpUri="https://zenodo.org/record/8235330/files/figure.png" pageId="4" pageNumber="5">Fig. 4</figureCitation>
|
||
and S31,
|
||
<tableCitation id="673FB9C4FFEFFFD5FE22FD7B5B9FFD3C" box="[409,487,641,660]" captionStart="Table 2" captionStartId="3.[101,151,151,167]" captionTargetPageId="3" captionText="Table 2 1H-NMR data for flavonoid sulfates 3, 6, 7, 11 15 in DMSO‑d (δ ppm, J (Hz))." pageId="4" pageNumber="5">Tables 2</tableCitation>
|
||
and
|
||
<tableCitation id="673FB9C4FFEFFFD5FDAFFD7B5858FD3C" box="[532,544,641,660]" captionStart="Table 3" captionStartId="3.[818,868,679,695]" captionTargetPageId="3" captionText="Table 3 13C-NMR chemical shifts for flavonoid sulfates 3, 6, 7, 11–14 (δ ppm, DMSO‑d). 6" pageId="4" pageNumber="5">3</tableCitation>
|
||
). All these data allowed identification of
|
||
<emphasis id="18C9506DFFEFFFD5FEB8FD675B77FD18" bold="true" box="[259,271,669,688]" pageId="4" pageNumber="5">3</emphasis>
|
||
as 5-methoxyluteolin 7, 3
|
||
<superScript id="DDC82137FFEFFFD5FDB0FD605868FD0F" attach="none" box="[523,528,666,679]" fontSize="6" pageId="4" pageNumber="5">′</superScript>
|
||
-disulfate. Analysis of the 2D
|
||
<collectionCode id="4CAC14BAFFEFFFD5FF3FFD435ACCFD64" box="[132,180,697,716]" pageId="4" pageNumber="5">NMR</collectionCode>
|
||
data from the COSY, HSQC and HMBC spectra and querying of the SciFinder database confirmed the structure of
|
||
<emphasis id="18C9506DFFEFFFD5FDF8FD2F5837FD40" bold="true" box="[579,591,725,744]" pageId="4" pageNumber="5">3</emphasis>
|
||
as an undescribed natural product.
|
||
</paragraph>
|
||
<caption id="7EC2DCF7FFEFFFD5FFDFFF6C5FD6FF69" pageId="4" pageNumber="5" startId="4.[100,150,150,166]" targetBox="[116,1471,211,422]" targetIsTable="true" targetPageId="4" targetType="table">
|
||
<paragraph id="2A028C7FFFEFFFD5FFDFFF6C5FD6FF69" blockId="4.[100,1454,150,195]" pageId="4" pageNumber="5">
|
||
<emphasis id="18C9506DFFEFFFD5FFDFFF6C5ADFFF0F" bold="true" box="[100,167,150,167]" pageId="4" pageNumber="5">Table 4</emphasis>
|
||
Diagnostic
|
||
<superScript id="DDC82137FFEFFFD5FF78FF515AB3FF1F" attach="right" box="[195,203,171,183]" fontSize="5" pageId="4" pageNumber="5">1</superScript>
|
||
H and
|
||
<superScript id="DDC82137FFEFFFD5FF45FF515B76FF1F" attach="both" box="[254,270,171,183]" fontSize="5" pageId="4" pageNumber="5">13</superScript>
|
||
C NMR sulfation shifts for flavonoid sulfates
|
||
<emphasis id="18C9506DFFEFFFD5FD37FF4A58EFFF69" bold="true" box="[652,663,176,193]" pageId="4" pageNumber="5">3</emphasis>
|
||
,
|
||
<emphasis id="18C9506DFFEFFFD5FD19FF4A58D5FF69" bold="true" box="[674,685,176,193]" pageId="4" pageNumber="5">6</emphasis>
|
||
,
|
||
<emphasis id="18C9506DFFEFFFD5FD03FF4A58BBFF68" bold="true" box="[696,707,176,192]" pageId="4" pageNumber="5">7</emphasis>
|
||
,
|
||
<emphasis id="18C9506DFFEFFFD5FD74FF4A597DFF69" bold="true" box="[719,773,176,193]" pageId="4" pageNumber="5">11–15</emphasis>
|
||
(DMSO‑
|
||
<emphasis id="18C9506DFFEFFFD5FCEBFF555922FF68" bold="true" box="[848,858,175,192]" italics="true" pageId="4" pageNumber="5">d</emphasis>
|
||
); values are expressed in
|
||
<emphasis id="18C9506DFFEFFFD5FB85FF4A5E18FF68" bold="true" box="[1086,1120,176,192]" italics="true" pageId="4" pageNumber="5">ppm</emphasis>
|
||
as δ (flavonoid sulfate) - δ (flavonoid).
|
||
</paragraph>
|
||
</caption>
|
||
<paragraph id="2A028C7FFFEFFFD5FCE1FF4D591AFF6B" blockId="4.[100,1454,150,195]" box="[858,866,183,195]" pageId="4" pageNumber="5">
|
||
<subScript id="B6398E3AFFEFFFD5FCE1FF4D591AFF6B" attach="left" box="[858,866,183,195]" fontSize="5" pageId="4" pageNumber="5">6</subScript>
|
||
</paragraph>
|
||
<paragraph id="2A028C7FFFEFFFD5FFCFFF2F5E89FE35" pageId="4" pageNumber="5">
|
||
<table id="58BD7EDFFFEF002EFFCFFF295FC7FE0E" box="[116,1471,211,422]" gridcols="11" gridrows="9" pageId="4" pageNumber="5">
|
||
<tr id="948D8E3DFFEF002EFFCFFF295FC7FF4B" box="[116,1471,211,227]" gridrow="0" pageId="4" pageNumber="5">
|
||
<th id="D75CE741FFEF002EFFCFFF295B5BFF4B" box="[116,291,211,227]" gridcol="0" gridrow="0" pageId="4" pageNumber="5">Aglycon</th>
|
||
<th id="D75CE741FFEF002EFEDFFF295B97FF4B" box="[356,495,211,227]" gridcol="1" gridrow="0" pageId="4" pageNumber="5">Sulfate derivatives</th>
|
||
<th id="D75CE741FFEF002EFD8AFF295827FF4B" box="[561,607,211,227]" gridcol="2" gridrow="0" pageId="4" pageNumber="5">H-8</th>
|
||
<th id="D75CE741FFEF002EFD19FF2958A8FF4B" box="[674,720,211,227]" gridcol="3" gridrow="0" pageId="4" pageNumber="5">H-2′</th>
|
||
<th id="D75CE741FFEF002EFCA9FF295938FF4B" box="[786,832,211,227]" gridcol="4" gridrow="0" pageId="4" pageNumber="5">H-5′</th>
|
||
<th id="D75CE741FFEF002EFC39FF2959C8FF4B" box="[898,944,211,227]" gridcol="5" gridrow="0" pageId="4" pageNumber="5">H-6′</th>
|
||
<th id="D75CE741FFEF002EFC49FF295E6FFF4B" box="[1010,1047,211,227]" gridcol="6" gridrow="0" pageId="4" pageNumber="5">C-7</th>
|
||
<th id="D75CE741FFEF002EFBE2FF295EFCFF4B" box="[1113,1156,211,227]" gridcol="7" gridrow="0" pageId="4" pageNumber="5">C-8</th>
|
||
<th id="D75CE741FFEF002EFB7DFF295E89FF4B" box="[1222,1265,211,227]" gridcol="8" gridrow="0" pageId="4" pageNumber="5">C-2′</th>
|
||
<th id="D75CE741FFEF002EFA88FF295F21FF4B" box="[1331,1369,211,227]" gridcol="9" gridrow="0" pageId="4" pageNumber="5">C-3′</th>
|
||
<th id="D75CE741FFEF002EFA21FF295FC7FF4B" box="[1434,1471,211,227]" gridcol="10" gridrow="0" pageId="4" pageNumber="5">C-4′</th>
|
||
</tr>
|
||
<tr id="948D8E3DFFEF002EFFCFFF0C5FC7FEAF" box="[116,1471,246,263]" gridrow="1" pageId="4" pageNumber="5">
|
||
<th id="D75CE741FFEF002EFFCFFF0C5B5BFEAF" box="[116,291,246,263]" gridcol="0" gridrow="1" pageId="4" pageNumber="5">luteolin 5-methyl ether</th>
|
||
<td id="D75CE741FFEF002EFEDFFF0C5B97FEAF" box="[356,495,246,263]" gridcol="1" gridrow="1" pageId="4" pageNumber="5">
|
||
7,3′-disulfate:
|
||
<emphasis id="18C9506DFFEFFFD5FE6AFF025BA3FEAE" bold="true" box="[465,475,248,262]" pageId="4" pageNumber="5">3</emphasis>
|
||
</td>
|
||
<td id="D75CE741FFEF002EFD8AFF0C5827FEAF" box="[561,607,246,263]" gridcol="2" gridrow="1" pageId="4" pageNumber="5">+0.66</td>
|
||
<td id="D75CE741FFEF002EFD19FF0C58A8FEAF" box="[674,720,246,263]" gridcol="3" gridrow="1" pageId="4" pageNumber="5">+0.53</td>
|
||
<td id="D75CE741FFEF002EFCA9FF0C5938FEAF" box="[786,832,246,263]" gridcol="4" gridrow="1" pageId="4" pageNumber="5">+0.12</td>
|
||
<td id="D75CE741FFEF002EFC39FF0C59C8FEAF" box="[898,944,246,263]" gridcol="5" gridrow="1" pageId="4" pageNumber="5">+0.34</td>
|
||
<td id="D75CE741FFEF002EFC49FF0C5E6FFEAF" box="[1010,1047,246,263]" gridcol="6" gridrow="1" pageId="4" pageNumber="5">4.3</td>
|
||
<td id="D75CE741FFEF002EFBE2FF0C5EFCFEAF" box="[1113,1156,246,263]" gridcol="7" gridrow="1" pageId="4" pageNumber="5">+3.1</td>
|
||
<td id="D75CE741FFEF002EFB7DFF0C5E89FEAF" box="[1222,1265,246,263]" gridcol="8" gridrow="1" pageId="4" pageNumber="5">+7.2</td>
|
||
<td id="D75CE741FFEF002EFA88FF0C5F21FEAF" box="[1331,1369,246,263]" gridcol="9" gridrow="1" pageId="4" pageNumber="5">4.2</td>
|
||
<td id="D75CE741FFEF002EFA21FF0C5FC7FEAF" box="[1434,1471,246,263]" gridcol="10" gridrow="1" pageId="4" pageNumber="5">+3.4</td>
|
||
</tr>
|
||
<tr id="948D8E3DFFEF002EFFCFFEF45FC7FEB5" box="[116,1471,270,285]" gridrow="2" pageId="4" pageNumber="5">
|
||
<th id="D75CE741FFEF002EFFCFFEF45B5BFEB5" box="[116,291,270,285]" gridcol="0" gridrow="2" pageId="4" pageNumber="5">luteolin</th>
|
||
<td id="D75CE741FFEF002EFEDFFEF45B97FEB5" box="[356,495,270,285]" gridcol="1" gridrow="2" pageId="4" pageNumber="5">
|
||
7-sulfate:
|
||
<emphasis id="18C9506DFFEFFFD5FE14FEF45BBBFEB4" bold="true" box="[431,451,270,284]" pageId="4" pageNumber="5">11</emphasis>
|
||
</td>
|
||
<td id="D75CE741FFEF002EFD8AFEF45827FEB5" box="[561,607,270,285]" gridcol="2" gridrow="2" pageId="4" pageNumber="5">+0.58</td>
|
||
<td id="D75CE741FFEF002EFD19FEF458A8FEB5" box="[674,720,270,285]" gridcol="3" gridrow="2" pageId="4" pageNumber="5">+0.06</td>
|
||
<td id="D75CE741FFEF002EFCA9FEF45938FEB5" box="[786,832,270,285]" gridcol="4" gridrow="2" pageId="4" pageNumber="5">0.01</td>
|
||
<td id="D75CE741FFEF002EFC39FEF459C8FEB5" box="[898,944,270,285]" gridcol="5" gridrow="2" pageId="4" pageNumber="5">+0.04</td>
|
||
<td id="D75CE741FFEF002EFC49FEF45E6FFEB5" box="[1010,1047,270,285]" gridcol="6" gridrow="2" pageId="4" pageNumber="5">4.7</td>
|
||
<td id="D75CE741FFEF002EFBE2FEF45EFCFEB5" box="[1113,1156,270,285]" gridcol="7" gridrow="2" pageId="4" pageNumber="5">+3.6</td>
|
||
<td id="D75CE741FFEF002EFB7DFEF45E89FEB5" box="[1222,1265,270,285]" gridcol="8" gridrow="2" pageId="4" pageNumber="5">0.3</td>
|
||
<td id="D75CE741FFEF002EFA88FEF45F21FEB5" box="[1331,1369,270,285]" gridcol="9" gridrow="2" pageId="4" pageNumber="5">0.8</td>
|
||
<td id="D75CE741FFEF002EFA21FEF45FC7FEB5" box="[1434,1471,270,285]" gridcol="10" gridrow="2" pageId="4" pageNumber="5">+0.4</td>
|
||
</tr>
|
||
<tr id="948D8E3DFFEF002EFFCFFEDE5FC7FE9B" box="[116,1471,292,307]" gridrow="3" pageId="4" pageNumber="5" rowspan-0="1">
|
||
<td id="D75CE741FFEF002EFEDFFEDE5B97FE9B" box="[356,495,292,307]" gridcol="1" gridrow="3" pageId="4" pageNumber="5">
|
||
3′-sulfate:
|
||
<emphasis id="18C9506DFFEFFFD5FE0FFEDF5BB0FE9B" bold="true" box="[436,456,293,307]" pageId="4" pageNumber="5">13</emphasis>
|
||
</td>
|
||
<td id="D75CE741FFEF002EFD8AFEDE5827FE9B" box="[561,607,292,307]" gridcol="2" gridrow="3" pageId="4" pageNumber="5">+0.06</td>
|
||
<td id="D75CE741FFEF002EFD19FEDE58A8FE9B" box="[674,720,292,307]" gridcol="3" gridrow="3" pageId="4" pageNumber="5">+0.49</td>
|
||
<td id="D75CE741FFEF002EFCA9FEDE5938FE9B" box="[786,832,292,307]" gridcol="4" gridrow="3" pageId="4" pageNumber="5">+0.08</td>
|
||
<td id="D75CE741FFEF002EFC39FEDE59C8FE9B" box="[898,944,292,307]" gridcol="5" gridrow="3" pageId="4" pageNumber="5">+0.28</td>
|
||
<td id="D75CE741FFEF002EFC49FEDE5E6FFE9B" box="[1010,1047,292,307]" gridcol="6" gridrow="3" pageId="4" pageNumber="5">+0.2</td>
|
||
<td id="D75CE741FFEF002EFBE2FEDE5EFCFE9B" box="[1113,1156,292,307]" gridcol="7" gridrow="3" pageId="4" pageNumber="5">0</td>
|
||
<td id="D75CE741FFEF002EFB7DFEDE5E89FE9B" box="[1222,1265,292,307]" gridcol="8" gridrow="3" pageId="4" pageNumber="5">+7.2</td>
|
||
<td id="D75CE741FFEF002EFA88FEDE5F21FE9B" box="[1331,1369,292,307]" gridcol="9" gridrow="3" pageId="4" pageNumber="5">4.3</td>
|
||
<td id="D75CE741FFEF002EFA21FEDE5FC7FE9B" box="[1434,1471,292,307]" gridcol="10" gridrow="3" pageId="4" pageNumber="5">+3.0</td>
|
||
</tr>
|
||
<tr id="948D8E3DFFEF002EFFCFFEC05FC7FEE2" box="[116,1471,314,330]" gridrow="4" pageId="4" pageNumber="5" rowspan-0="1">
|
||
<td id="D75CE741FFEF002EFEDFFEC05B97FEE2" box="[356,495,314,330]" gridcol="1" gridrow="4" pageId="4" pageNumber="5">
|
||
7,3′-disulfate:
|
||
<emphasis id="18C9506DFFEFFFD5FE6AFEC65BA3FEE2" bold="true" box="[465,475,316,330]" pageId="4" pageNumber="5">6</emphasis>
|
||
</td>
|
||
<td id="D75CE741FFEF002EFD8AFEC05827FEE2" box="[561,607,314,330]" gridcol="2" gridrow="4" pageId="4" pageNumber="5">+0.55</td>
|
||
<td id="D75CE741FFEF002EFD19FEC058A8FEE2" box="[674,720,314,330]" gridcol="3" gridrow="4" pageId="4" pageNumber="5">+0.54</td>
|
||
<td id="D75CE741FFEF002EFCA9FEC05938FEE2" box="[786,832,314,330]" gridcol="4" gridrow="4" pageId="4" pageNumber="5">+0.11</td>
|
||
<td id="D75CE741FFEF002EFC39FEC059C8FEE2" box="[898,944,314,330]" gridcol="5" gridrow="4" pageId="4" pageNumber="5">+0.31</td>
|
||
<td id="D75CE741FFEF002EFC49FEC05E6FFEE2" box="[1010,1047,314,330]" gridcol="6" gridrow="4" pageId="4" pageNumber="5">4.9</td>
|
||
<td id="D75CE741FFEF002EFBE2FEC05EFCFEE2" box="[1113,1156,314,330]" gridcol="7" gridrow="4" pageId="4" pageNumber="5">+3.6</td>
|
||
<td id="D75CE741FFEF002EFB7DFEC05E89FEE2" box="[1222,1265,314,330]" gridcol="8" gridrow="4" pageId="4" pageNumber="5">+7.0</td>
|
||
<td id="D75CE741FFEF002EFA88FEC05F21FEE2" box="[1331,1369,314,330]" gridcol="9" gridrow="4" pageId="4" pageNumber="5">4.4</td>
|
||
<td id="D75CE741FFEF002EFA21FEC05FC7FEE2" box="[1434,1471,314,330]" gridcol="10" gridrow="4" pageId="4" pageNumber="5">+3.6</td>
|
||
</tr>
|
||
<tr id="948D8E3DFFEF002EFFCFFEA95FC7FEC9" box="[116,1471,339,353]" gridrow="5" pageId="4" pageNumber="5">
|
||
<th id="D75CE741FFEF002EFFCFFEA95B5BFEC9" box="[116,291,339,353]" gridcol="0" gridrow="5" pageId="4" pageNumber="5">nepetin</th>
|
||
<td id="D75CE741FFEF002EFEDFFEA95B97FEC9" box="[356,495,339,353]" gridcol="1" gridrow="5" pageId="4" pageNumber="5">
|
||
7-sulfate:
|
||
<emphasis id="18C9506DFFEFFFD5FE14FEA95BBBFEC9" bold="true" box="[431,451,339,353]" pageId="4" pageNumber="5">12</emphasis>
|
||
</td>
|
||
<td id="D75CE741FFEF002EFD8AFEA95827FEC9" box="[561,607,339,353]" gridcol="2" gridrow="5" pageId="4" pageNumber="5">+0.85</td>
|
||
<td id="D75CE741FFEF002EFD19FEA958A8FEC9" box="[674,720,339,353]" gridcol="3" gridrow="5" pageId="4" pageNumber="5">+0.06</td>
|
||
<td id="D75CE741FFEF002EFCA9FEA95938FEC9" box="[786,832,339,353]" gridcol="4" gridrow="5" pageId="4" pageNumber="5">+0.01</td>
|
||
<td id="D75CE741FFEF002EFC39FEA959C8FEC9" box="[898,944,339,353]" gridcol="5" gridrow="5" pageId="4" pageNumber="5">0</td>
|
||
<td id="D75CE741FFEF002EFC49FEA95E6FFEC9" box="[1010,1047,339,353]" gridcol="6" gridrow="5" pageId="4" pageNumber="5">0.1</td>
|
||
<td id="D75CE741FFEF002EFBE2FEA95EFCFEC9" box="[1113,1156,339,353]" gridcol="7" gridrow="5" pageId="4" pageNumber="5">+4.0</td>
|
||
<td id="D75CE741FFEF002EFB7DFEA95E89FEC9" box="[1222,1265,339,353]" gridcol="8" gridrow="5" pageId="4" pageNumber="5">+0.1</td>
|
||
<td id="D75CE741FFEF002EFA88FEA95F21FEC9" box="[1331,1369,339,353]" gridcol="9" gridrow="5" pageId="4" pageNumber="5">+0.5</td>
|
||
<td id="D75CE741FFEF002EFA21FEA95FC7FEC9" box="[1434,1471,339,353]" gridcol="10" gridrow="5" pageId="4" pageNumber="5">+1.5</td>
|
||
</tr>
|
||
<tr id="948D8E3DFFEF002EFFCFFE925FC7FED0" box="[116,1471,360,376]" gridrow="6" pageId="4" pageNumber="5" rowspan-0="1">
|
||
<td id="D75CE741FFEF002EFEDFFE925B97FED0" box="[356,495,360,376]" gridcol="1" gridrow="6" pageId="4" pageNumber="5">
|
||
3′-sulfate:
|
||
<emphasis id="18C9506DFFEFFFD5FE0FFE905BB0FED0" bold="true" box="[436,456,362,376]" pageId="4" pageNumber="5">14</emphasis>
|
||
</td>
|
||
<td id="D75CE741FFEF002EFD8AFE925827FED0" box="[561,607,360,376]" gridcol="2" gridrow="6" pageId="4" pageNumber="5">0.32</td>
|
||
<td id="D75CE741FFEF002EFD19FE9258A8FED0" box="[674,720,360,376]" gridcol="3" gridrow="6" pageId="4" pageNumber="5">+0.39</td>
|
||
<td id="D75CE741FFEF002EFCA9FE925938FED0" box="[786,832,360,376]" gridcol="4" gridrow="6" pageId="4" pageNumber="5">+0.08</td>
|
||
<td id="D75CE741FFEF002EFC39FE9259C8FED0" box="[898,944,360,376]" gridcol="5" gridrow="6" pageId="4" pageNumber="5">+0.13</td>
|
||
<td id="D75CE741FFEF002EFC49FE925E6FFED0" box="[1010,1047,360,376]" gridcol="6" gridrow="6" pageId="4" pageNumber="5">+1.1</td>
|
||
<td id="D75CE741FFEF002EFBE2FE925EFCFED0" box="[1113,1156,360,376]" gridcol="7" gridrow="6" pageId="4" pageNumber="5">+1.2</td>
|
||
<td id="D75CE741FFEF002EFB7DFE925E89FED0" box="[1222,1265,360,376]" gridcol="8" gridrow="6" pageId="4" pageNumber="5">+3.9</td>
|
||
<td id="D75CE741FFEF002EFA88FE925F21FED0" box="[1331,1369,360,376]" gridcol="9" gridrow="6" pageId="4" pageNumber="5">4.2</td>
|
||
<td id="D75CE741FFEF002EFA21FE925FC7FED0" box="[1434,1471,360,376]" gridcol="10" gridrow="6" pageId="4" pageNumber="5">+5.1</td>
|
||
</tr>
|
||
<tr id="948D8E3DFFEF002EFFCFFE855FC7FE27" box="[116,1471,383,399]" gridrow="7" pageId="4" pageNumber="5" rowspan-0="1">
|
||
<td id="D75CE741FFEF002EFEDFFE855B97FE27" box="[356,495,383,399]" gridcol="1" gridrow="7" pageId="4" pageNumber="5">
|
||
7,3′-disulfate:
|
||
<emphasis id="18C9506DFFEFFFD5FE6AFE7B5BA3FE27" bold="true" box="[465,475,385,399]" pageId="4" pageNumber="5">7</emphasis>
|
||
</td>
|
||
<td id="D75CE741FFEF002EFD8AFE855827FE27" box="[561,607,383,399]" gridcol="2" gridrow="7" pageId="4" pageNumber="5">+071</td>
|
||
<td id="D75CE741FFEF002EFD19FE8558A8FE27" box="[674,720,383,399]" gridcol="3" gridrow="7" pageId="4" pageNumber="5">+0.57</td>
|
||
<td id="D75CE741FFEF002EFCA9FE855938FE27" box="[786,832,383,399]" gridcol="4" gridrow="7" pageId="4" pageNumber="5">0.11</td>
|
||
<td id="D75CE741FFEF002EFC39FE8559C8FE27" box="[898,944,383,399]" gridcol="5" gridrow="7" pageId="4" pageNumber="5">+0.33</td>
|
||
<td id="D75CE741FFEF002EFC49FE855E6FFE27" box="[1010,1047,383,399]" gridcol="6" gridrow="7" pageId="4" pageNumber="5">0.1</td>
|
||
<td id="D75CE741FFEF002EFBE2FE855EFCFE27" box="[1113,1156,383,399]" gridcol="7" gridrow="7" pageId="4" pageNumber="5">+4.2</td>
|
||
<td id="D75CE741FFEF002EFB7DFE855E89FE27" box="[1222,1265,383,399]" gridcol="8" gridrow="7" pageId="4" pageNumber="5">+4.2</td>
|
||
<td id="D75CE741FFEF002EFA88FE855F21FE27" box="[1331,1369,383,399]" gridcol="9" gridrow="7" pageId="4" pageNumber="5">4.1</td>
|
||
<td id="D75CE741FFEF002EFA21FE855FC7FE27" box="[1434,1471,383,399]" gridcol="10" gridrow="7" pageId="4" pageNumber="5">+3.3</td>
|
||
</tr>
|
||
<tr id="948D8E3DFFEF002EFFCFFE6E5FC7FE0E" box="[116,1471,404,422]" gridrow="8" pageId="4" pageNumber="5" rowspan-10="1" rowspan-6="1" rowspan-9="1">
|
||
<th id="D75CE741FFEF002EFFCFFE6E5B5BFE0E" box="[116,291,404,422]" gridcol="0" gridrow="8" pageId="4" pageNumber="5">hispiduline</th>
|
||
<td id="D75CE741FFEF002EFEDFFE6E5B97FE0E" box="[356,495,404,422]" gridcol="1" gridrow="8" pageId="4" pageNumber="5">
|
||
7-sulfate:
|
||
<emphasis id="18C9506DFFEFFFD5FE14FE625BBBFE0E" bold="true" box="[431,451,408,422]" pageId="4" pageNumber="5">15</emphasis>
|
||
</td>
|
||
<td id="D75CE741FFEF002EFD8AFE6E5827FE0E" box="[561,607,404,422]" gridcol="2" gridrow="8" pageId="4" pageNumber="5">+075</td>
|
||
<td id="D75CE741FFEF002EFD19FE6E58A8FE0E" box="[674,720,404,422]" gridcol="3" gridrow="8" pageId="4" pageNumber="5">0.01</td>
|
||
<td id="D75CE741FFEF002EFCA9FE6E5938FE0E" box="[786,832,404,422]" gridcol="4" gridrow="8" pageId="4" pageNumber="5">+0.04</td>
|
||
<td id="D75CE741FFEF002EFC39FE6E59C8FE0E" box="[898,944,404,422]" gridcol="5" gridrow="8" pageId="4" pageNumber="5">0.01</td>
|
||
<td id="D75CE741FFEF002EFBE2FE6E5EFCFE0E" box="[1113,1156,404,422]" gridcol="7" gridrow="8" pageId="4" pageNumber="5">4.8 a +</td>
|
||
<td id="D75CE741FFEF002EFB7DFE6E5E89FE0E" box="[1222,1265,404,422]" gridcol="8" gridrow="8" pageId="4" pageNumber="5">0.4 a</td>
|
||
</tr>
|
||
</table>
|
||
</paragraph>
|
||
<paragraph id="2A028C7FFFEFFFD5FFC8FE4D5BF7FE65" blockId="4.[115,399,439,461]" box="[115,399,439,461]" pageId="4" pageNumber="5">
|
||
<tableNote id="D75B8DF1FFEFFFD5FFC8FE4D5BF7FE65" box="[115,399,439,461]" pageId="4" pageNumber="5" targetBox="[116,1471,211,422]" targetPageId="4">
|
||
<superScript id="DDC82137FFEFFFD5FFC8FE4D5A02FE6B" attach="left" box="[115,122,439,451]" fontSize="5" pageId="4" pageNumber="5">a</superScript>
|
||
Values determined from HSQC.
|
||
</tableNote>
|
||
</paragraph>
|
||
<paragraph id="2A028C7FFFEFFFD5FF3FFCF65BF7FA71" blockId="4.[100,773,502,1972]" pageId="4" pageNumber="5">
|
||
Compound
|
||
<emphasis id="18C9506DFFEFFFD5FF4BFCF75A84FC88" bold="true" box="[240,252,781,800]" pageId="4" pageNumber="5">7</emphasis>
|
||
eluted at 19.2 min. The positive ESI-MS spectrum gave a quasimolecular peak [M+H]
|
||
<superScript id="DDC82137FFEFFFD5FE3BFCDF5BF7FC99" attach="right" box="[384,399,805,817]" fontSize="6" pageId="4" pageNumber="5">+</superScript>
|
||
at
|
||
<quantity id="ED45219AFFEFFFD5FE12FCD35B9BFC93" box="[425,483,808,828]" metricMagnitude="2" metricUnit="m" metricValue="4.77" pageId="4" pageNumber="5" unit="m" value="477.0">
|
||
477
|
||
<emphasis id="18C9506DFFEFFFD5FE69FCD25B9BFC93" bold="true" box="[466,483,808,827]" italics="true" pageId="4" pageNumber="5">m</emphasis>
|
||
</quantity>
|
||
/z, which was compatible with the molecular formula C
|
||
<subScript id="B6398E3AFFEFFFD5FEFDFCB15B20FCF1" attach="both" box="[326,344,843,857]" fontSize="6" pageId="4" pageNumber="5">16</subScript>
|
||
H
|
||
<subScript id="B6398E3AFFEFFFD5FED3FCB15B02FCF1" attach="both" box="[360,378,843,857]" fontSize="6" pageId="4" pageNumber="5">12</subScript>
|
||
O
|
||
<subScript id="B6398E3AFFEFFFD5FE32FCB15BE3FCF1" attach="both" box="[393,411,843,857]" fontSize="6" pageId="4" pageNumber="5">13</subScript>
|
||
S
|
||
<subScript id="B6398E3AFFEFFFD5FE1DFCB15BD7FCF1" attach="left" box="[422,431,843,857]" fontSize="6" pageId="4" pageNumber="5">2</subScript>
|
||
. Another significant ions at
|
||
<emphasis id="18C9506DFFEFFFD5FD0EFCBE58A1FCFF" bold="true" box="[693,729,836,855]" italics="true" pageId="4" pageNumber="5">m/z</emphasis>
|
||
397 [M-80 + H]
|
||
<superScript id="DDC82137FFEFFFD5FF62FCA65A90FCC0" attach="left" box="[217,232,860,872]" fontSize="6" pageId="4" pageNumber="5">+</superScript>
|
||
and 317 [M-160 + H]
|
||
<superScript id="DDC82137FFEFFFD5FE7DFCA65BADFCC0" attach="left" box="[454,469,860,872]" fontSize="6" pageId="4" pageNumber="5">+</superScript>
|
||
confirmed the presence of two sulfate groups. The
|
||
<superScript id="DDC82137FFEFFFD5FE9DFC8C5B40FC2C" attach="right" box="[294,312,886,900]" fontSize="6" pageId="4" pageNumber="5">13</superScript>
|
||
C
|
||
<collectionCode id="4CAC14BAFFEFFFD5FEF5FC875B06FC38" box="[334,382,893,912]" pageId="4" pageNumber="5">NMR</collectionCode>
|
||
spectrum in DMSO‑
|
||
<emphasis id="18C9506DFFEFFFD5FDFDFC865829FC27" bold="true" box="[582,593,892,911]" italics="true" pageId="4" pageNumber="5">d</emphasis>
|
||
<subScript id="B6398E3AFFEFFFD5FDEAFC795822FC39" attach="left" box="[593,602,899,913]" fontSize="6" pageId="4" pageNumber="5">6</subScript>
|
||
showed 16 resonances (1 methoxy, 5
|
||
<collectingCountry id="52AACCEFFFEFFFD5FE83FC625B20FC03" box="[312,344,920,939]" name="Switzerland" pageId="4" pageNumber="5">CH</collectingCountry>
|
||
, and 10 quaternary C including 1 carbonyl). The
|
||
<superScript id="DDC82137FFEFFFD5FF35FC545AEFFC14" attach="right" box="[142,151,942,956]" fontSize="6" pageId="4" pageNumber="5">1</superScript>
|
||
H
|
||
<collectionCode id="4CAC14BAFFEFFFD5FF15FC4E5AA6FC6F" box="[174,222,948,967]" pageId="4" pageNumber="5">NMR</collectionCode>
|
||
spectrum showed a singlet (3H) at
|
||
<emphasis id="18C9506DFFEFFFD5FD8BFC4E5842FC6F" bold="true" box="[560,570,948,967]" italics="true" pageId="4" pageNumber="5">δ</emphasis>
|
||
3.76 and five proton signals at
|
||
<emphasis id="18C9506DFFEFFFD5FF78FC2A5AB5FC4B" bold="true" box="[195,205,976,995]" italics="true" pageId="4" pageNumber="5">δ</emphasis>
|
||
6.73 (s, H-3), 6.96 (1 H,
|
||
<emphasis id="18C9506DFFEFFFD5FE05FC355BB1FC4A" bold="true" box="[446,457,975,994]" italics="true" pageId="4" pageNumber="5">d</emphasis>
|
||
,
|
||
<emphasis id="18C9506DFFEFFFD5FE6DFC2A5B98FC4B" bold="true" box="[470,480,976,995]" italics="true" pageId="4" pageNumber="5">J</emphasis>
|
||
= 8.6 Hz, H-5
|
||
<superScript id="DDC82137FFEFFFD5FDD1FC375817FC72" attach="none" box="[618,623,973,986]" fontSize="6" pageId="4" pageNumber="5">′</superScript>
|
||
), 7.32 (s, H-8), system at 7.71 (1 H,
|
||
<emphasis id="18C9506DFFEFFFD5FE9BFC115B4EFC56" bold="true" box="[288,310,1003,1022]" italics="true" pageId="4" pageNumber="5">dd</emphasis>
|
||
,
|
||
<emphasis id="18C9506DFFEFFFD5FEFBFC165B32FC57" bold="true" box="[320,330,1004,1023]" italics="true" pageId="4" pageNumber="5">J</emphasis>
|
||
=2.3, 8.6 Hz, H-6
|
||
<superScript id="DDC82137FFEFFFD5FE4FFC135B81FC5E" attach="none" box="[500,505,1001,1014]" fontSize="6" pageId="4" pageNumber="5">′</superScript>
|
||
), 7.93 (1 H,
|
||
<emphasis id="18C9506DFFEFFFD5FDD7FC11580FFC56" bold="true" box="[620,631,1003,1022]" italics="true" pageId="4" pageNumber="5">d</emphasis>
|
||
,
|
||
<emphasis id="18C9506DFFEFFFD5FD39FC1658F4FC57" bold="true" box="[642,652,1004,1023]" italics="true" pageId="4" pageNumber="5">J</emphasis>
|
||
=2.3 Hz, H- 2
|
||
<superScript id="DDC82137FFEFFFD5FFCBFBFE5A0DFBB9" attach="none" box="[112,117,1028,1041]" fontSize="6" pageId="4" pageNumber="5">′</superScript>
|
||
) (
|
||
<tableCitation id="673FB9C4FFEFFFD5FF36FBF25AA5FBB3" box="[141,221,1032,1051]" captionStart="Table 2" captionStartId="3.[101,151,151,167]" captionTargetPageId="3" captionText="Table 2 1H-NMR data for flavonoid sulfates 3, 6, 7, 11 15 in DMSO‑d (δ ppm, J (Hz))." pageId="4" pageNumber="5">Tables 2</tableCitation>
|
||
and
|
||
<tableCitation id="673FB9C4FFEFFFD5FEB5FBF25B62FBB3" box="[270,282,1032,1051]" captionStart="Table 3" captionStartId="3.[818,868,679,695]" captionTargetPageId="3" captionText="Table 3 13C-NMR chemical shifts for flavonoid sulfates 3, 6, 7, 11–14 (δ ppm, DMSO‑d). 6" pageId="4" pageNumber="5">3</tableCitation>
|
||
). The
|
||
<superScript id="DDC82137FFEFFFD5FEE1FBF85B1BFBB8" attach="right" box="[346,355,1026,1040]" fontSize="6" pageId="4" pageNumber="5">1</superScript>
|
||
H and COSY data also indicated the lack of coupling for ring A and the absence of H-6 signal in the aromatic region, suggesting the methoxy group to be attached to C-6. The methoxy position was confirmed by the HMBC correlation between
|
||
<superScript id="DDC82137FFEFFFD5FD36FBAC58EEFBCC" attach="right" box="[653,662,1110,1124]" fontSize="6" pageId="4" pageNumber="5">1</superScript>
|
||
H signal at 3.76 ppm and C-6 at 134.1 ppm. Resonances of carbons and protons showed the typical shifts due to the presence of a sulfate group at position 7 (strong deshielding of H-8 and C-8; shielding of C-7) and 3
|
||
<superScript id="DDC82137FFEFFFD5FD47FB565979FB11" attach="none" box="[764,769,1196,1209]" fontSize="6" pageId="4" pageNumber="5">′</superScript>
|
||
(strong deshielding of H-2
|
||
<superScript id="DDC82137FFEFFFD5FEDFFB325B11FB7D" attach="none" box="[356,361,1224,1237]" fontSize="6" pageId="4" pageNumber="5">′</superScript>
|
||
, C-2
|
||
<superScript id="DDC82137FFEFFFD5FE23FB325BE5FB7D" attach="left" box="[408,413,1224,1237]" fontSize="6" pageId="4" pageNumber="5">′</superScript>
|
||
and C-4’; shielding of C-3
|
||
<superScript id="DDC82137FFEFFFD5FD18FB3258D0FB7D" attach="none" box="[675,680,1224,1237]" fontSize="6" pageId="4" pageNumber="5">′</superScript>
|
||
) (
|
||
<bibRefCitation id="4E2CF18EFFEFFFD5FD79FB315AB6FB52" author="Barron, D. & Varin, L. & Ibrahim, R. K. & Harborne, J. B. & Williams, C. A." pageId="4" pageNumber="5" pagination="2375 - 2395" refId="ref16118" refString="Barron, D., Varin, L., Ibrahim, R. K., Harborne, J. B., Williams, C. A., 1988. Sulphated flavonoids: an update. Phytochemistry 27, 2375 - 2395. https: // doi. org / 10.1016 / 0031 - 9422 (88) 87003 - 1." type="journal article" year="1988">Barron et al., 1988</bibRefCitation>
|
||
). UV spectra of compound
|
||
<emphasis id="18C9506DFFEFFFD5FE74FB1D5BA3FB52" bold="true" box="[463,475,1255,1274]" pageId="4" pageNumber="5">7</emphasis>
|
||
(DAD on-line 264 and
|
||
<quantity id="ED45219AFFEFFFD5FD0FFB1D5886FB52" box="[692,766,1255,1274]" metricMagnitude="-7" metricUnit="m" metricValue="3.32" pageId="4" pageNumber="5" unit="nm" value="332.0">332 nm</quantity>
|
||
; UV (MeOH) 266 and
|
||
<quantity id="ED45219AFFEFFFD5FE93FAF95B08FABE" box="[296,368,1283,1302]" metricMagnitude="-7" metricUnit="m" metricValue="3.27" pageId="4" pageNumber="5" unit="nm" value="327.0">327 nm</quantity>
|
||
) were in agreement with the hypsochromic shift of Band I induced by sulfation at position 3’ (
|
||
<bibRefCitation id="4E2CF18EFFEFFFD5FDF8FAE5588CFA9A" author="Barron, D. & Varin, L. & Ibrahim, R. K. & Harborne, J. B. & Williams, C. A." box="[579,756,1311,1330]" pageId="4" pageNumber="5" pagination="2375 - 2395" refId="ref16118" refString="Barron, D., Varin, L., Ibrahim, R. K., Harborne, J. B., Williams, C. A., 1988. Sulphated flavonoids: an update. Phytochemistry 27, 2375 - 2395. https: // doi. org / 10.1016 / 0031 - 9422 (88) 87003 - 1." type="journal article" year="1988">Barron et al., 1988</bibRefCitation>
|
||
). After acid hydrolysis, compound
|
||
<emphasis id="18C9506DFFEFFFD5FE2DFAC15BDAFAE6" bold="true" box="[406,418,1339,1358]" pageId="4" pageNumber="5">7</emphasis>
|
||
yielded nepetin, which was identified by UV,
|
||
<collectionCode id="4CAC14BAFFEFFFD5FF15FAAD5AA6FAC2" box="[174,222,1367,1386]" pageId="4" pageNumber="5">NMR</collectionCode>
|
||
and comparison against an authentic standard (Fig. S31,
|
||
<tableCitation id="673FB9C4FFEFFFD5FFDFFA885ACBFA2D" box="[100,179,1394,1413]" captionStart="Table 2" captionStartId="3.[101,151,151,167]" captionTargetPageId="3" captionText="Table 2 1H-NMR data for flavonoid sulfates 3, 6, 7, 11 15 in DMSO‑d (δ ppm, J (Hz))." pageId="4" pageNumber="5">Tables 2</tableCitation>
|
||
and
|
||
<tableCitation id="673FB9C4FFEFFFD5FF59FA885A96FA2D" box="[226,238,1394,1413]" captionStart="Table 3" captionStartId="3.[818,868,679,695]" captionTargetPageId="3" captionText="Table 3 13C-NMR chemical shifts for flavonoid sulfates 3, 6, 7, 11–14 (δ ppm, DMSO‑d). 6" pageId="4" pageNumber="5">3</tableCitation>
|
||
). All these data allowed identification of
|
||
<emphasis id="18C9506DFFEFFFD5FDCCFA8858FBFA2D" bold="true" box="[631,643,1394,1413]" pageId="4" pageNumber="5">7</emphasis>
|
||
as nepetin 7, 3
|
||
<superScript id="DDC82137FFEFFFD5FFCBFA715A0DFA30" attach="none" box="[112,117,1419,1432]" fontSize="6" pageId="4" pageNumber="5">′</superScript>
|
||
-disulfate. The analysis of the 2D
|
||
<collectionCode id="4CAC14BAFFEFFFD5FE11FA755BA2FA0A" box="[426,474,1423,1442]" pageId="4" pageNumber="5">NMR</collectionCode>
|
||
data from the HSQC and HMBC spectra and querying of the SciFinder database confirmed the structure of
|
||
<emphasis id="18C9506DFFEFFFD5FFC6FA3C5AF1FA71" bold="true" box="[125,137,1478,1497]" pageId="4" pageNumber="5">7</emphasis>
|
||
as an undescribed product.
|
||
</paragraph>
|
||
<paragraph id="2A028C7FFFEFFFD5FF3FFA1859BCFCAC" blockId="4.[100,773,502,1972]" lastBlockId="4.[818,1488,498,995]" pageId="4" pageNumber="5">
|
||
Compound
|
||
<emphasis id="18C9506DFFEFFFD5FF54FA185B70FA5D" bold="true" box="[239,264,1506,1525]" pageId="4" pageNumber="5">14</emphasis>
|
||
eluted at 27.4 min. The positive ESI-MS spectrum gave a quasimolecular peak [M+H]
|
||
<superScript id="DDC82137FFEFFFD5FE3BFA005BF7F9AE" attach="right" box="[384,399,1530,1542]" fontSize="6" pageId="4" pageNumber="5">+</superScript>
|
||
at
|
||
<quantity id="ED45219AFFEFFFD5FE12FA045B9BF9B9" box="[425,483,1534,1553]" metricMagnitude="2" metricUnit="m" metricValue="3.97" pageId="4" pageNumber="5" unit="m" value="397.0">
|
||
397
|
||
<emphasis id="18C9506DFFEFFFD5FE69FA045B9BF9B9" bold="true" box="[466,483,1534,1553]" italics="true" pageId="4" pageNumber="5">m</emphasis>
|
||
</quantity>
|
||
/z, which was compatible with the molecular formula C
|
||
<subScript id="B6398E3AFFEFFFD5FEF2F9DB5B23F987" attach="both" box="[329,347,1569,1583]" fontSize="6" pageId="4" pageNumber="5">16</subScript>
|
||
H
|
||
<subScript id="B6398E3AFFEFFFD5FED0F9DB5B05F987" attach="both" box="[363,381,1569,1583]" fontSize="6" pageId="4" pageNumber="5">12</subScript>
|
||
O
|
||
<subScript id="B6398E3AFFEFFFD5FE37F9DB5BE6F987" attach="both" box="[396,414,1569,1583]" fontSize="6" pageId="4" pageNumber="5">10</subScript>
|
||
S. Another significant ions at
|
||
<emphasis id="18C9506DFFEFFFD5FD0FF9E358A0F984" bold="true" box="[692,728,1561,1580]" italics="true" pageId="4" pageNumber="5">m/z</emphasis>
|
||
317 [M-80 + H]
|
||
<superScript id="DDC82137FFEFFFD5FF60F9C85A92F996" attach="left" box="[219,234,1586,1598]" fontSize="6" pageId="4" pageNumber="5">+</superScript>
|
||
and 339 [M-80 +Na]
|
||
<superScript id="DDC82137FFEFFFD5FE79F9C85BA9F996" attach="left" box="[450,465,1586,1598]" fontSize="6" pageId="4" pageNumber="5">+</superScript>
|
||
confirmed the presence of one sulfate group. The
|
||
<superScript id="DDC82137FFEFFFD5FE9BF9B65B4AF9F2" attach="right" box="[288,306,1612,1626]" fontSize="6" pageId="4" pageNumber="5">13</superScript>
|
||
C
|
||
<collectionCode id="4CAC14BAFFEFFFD5FEF2F9A85B01F9CD" box="[329,377,1618,1637]" pageId="4" pageNumber="5">NMR</collectionCode>
|
||
spectrum in DMSO‑
|
||
<emphasis id="18C9506DFFEFFFD5FDFFF9AB5837F9CC" bold="true" box="[580,591,1617,1636]" italics="true" pageId="4" pageNumber="5">d</emphasis>
|
||
<subScript id="B6398E3AFFEFFFD5FDF4F9A35820F9CF" attach="left" box="[591,600,1625,1639]" fontSize="6" pageId="4" pageNumber="5">6</subScript>
|
||
showed 16 resonances (1 methoxy, 5
|
||
<collectingCountry id="52AACCEFFFEFFFD5FE80F9975B23F928" box="[315,347,1645,1664]" name="Switzerland" pageId="4" pageNumber="5">CH</collectingCountry>
|
||
, and 10 quaternary C including 1 carbonyl) (
|
||
<tableCitation id="673FB9C4FFEFFFD5FFD7F9735AC2F934" box="[108,186,1673,1692]" captionStart="Table 2" captionStartId="3.[101,151,151,167]" captionTargetPageId="3" captionText="Table 2 1H-NMR data for flavonoid sulfates 3, 6, 7, 11 15 in DMSO‑d (δ ppm, J (Hz))." pageId="4" pageNumber="5">Tables 2</tableCitation>
|
||
and
|
||
<tableCitation id="673FB9C4FFEFFFD5FF53F9735A8CF934" box="[232,244,1673,1692]" captionStart="Table 3" captionStartId="3.[818,868,679,695]" captionTargetPageId="3" captionText="Table 3 13C-NMR chemical shifts for flavonoid sulfates 3, 6, 7, 11–14 (δ ppm, DMSO‑d). 6" pageId="4" pageNumber="5">3</tableCitation>
|
||
). The
|
||
<superScript id="DDC82137FFEFFFD5FE8BF9795B41F939" attach="right" box="[304,313,1667,1681]" fontSize="6" pageId="4" pageNumber="5">1</superScript>
|
||
H
|
||
<collectionCode id="4CAC14BAFFEFFFD5FEF5F9705B06F935" box="[334,382,1674,1693]" pageId="4" pageNumber="5">NMR</collectionCode>
|
||
spectrum showed a singlet (3H) at
|
||
<emphasis id="18C9506DFFEFFFD5FD72F97358ABF934" bold="true" box="[713,723,1673,1692]" italics="true" pageId="4" pageNumber="5">δ</emphasis>
|
||
3.75 and five proton signals at
|
||
<emphasis id="18C9506DFFEFFFD5FEEDF95F5B18F910" bold="true" box="[342,352,1701,1720]" italics="true" pageId="4" pageNumber="5">δ</emphasis>
|
||
6.15 (s, H-8), 6.44 (s, H-3), 6.93 (1 H,
|
||
<emphasis id="18C9506DFFEFFFD5FD70F95F58AEF910" bold="true" box="[715,726,1701,1720]" italics="true" pageId="4" pageNumber="5">d</emphasis>
|
||
,
|
||
<emphasis id="18C9506DFFEFFFD5FD59F95F5894F910" bold="true" box="[738,748,1701,1720]" italics="true" pageId="4" pageNumber="5">J</emphasis>
|
||
= 8.6 Hz, H-5
|
||
<superScript id="DDC82137FFEFFFD5FF6BF9445AADF963" attach="none" box="[208,213,1726,1739]" fontSize="6" pageId="4" pageNumber="5">′</superScript>
|
||
), 7.58 (1 H,
|
||
<emphasis id="18C9506DFFEFFFD5FEF6F93B5B1BF97C" bold="true" box="[333,355,1729,1748]" italics="true" pageId="4" pageNumber="5">dd</emphasis>
|
||
,
|
||
<emphasis id="18C9506DFFEFFFD5FED4F93B5B01F97C" bold="true" box="[367,377,1729,1748]" italics="true" pageId="4" pageNumber="5">J</emphasis>
|
||
=2.3, 8.6 Hz, H-6
|
||
<superScript id="DDC82137FFEFFFD5FD91F9445857F963" attach="none" box="[554,559,1726,1739]" fontSize="6" pageId="4" pageNumber="5">′</superScript>
|
||
), 7.79 (1 H,
|
||
<emphasis id="18C9506DFFEFFFD5FD1CF93B58CAF97C" bold="true" box="[679,690,1729,1748]" italics="true" pageId="4" pageNumber="5">d</emphasis>
|
||
,
|
||
<emphasis id="18C9506DFFEFFFD5FD05F93B58B0F97C" bold="true" box="[702,712,1729,1748]" italics="true" pageId="4" pageNumber="5">J</emphasis>
|
||
=2.3 Hz, H-2
|
||
<superScript id="DDC82137FFEFFFD5FF10F9205AC8F94F" attach="none" box="[171,176,1754,1767]" fontSize="6" pageId="4" pageNumber="5">′</superScript>
|
||
). The weak effect observed on H-8 (+0.17) while strong effect is still observed on H-2’ (+0.37) is in agreement with the sulfate group linked at position 3’. The
|
||
<superScript id="DDC82137FFEFFFD5FEE9F8F55B23F8B5" attach="right" box="[338,347,1807,1821]" fontSize="6" pageId="4" pageNumber="5">1</superScript>
|
||
H and COSY spectra also indicated the lack of coupling for ring A and the absence of H-6 signal in the aromatic region, suggesting the methoxy group to be attached to C-6. The methoxy position was confirmed by the HMBC correlation between
|
||
<superScript id="DDC82137FFEFFFD5FD36F89958EEF8D9" attach="right" box="[653,662,1891,1905]" fontSize="6" pageId="4" pageNumber="5">1</superScript>
|
||
H signal at 3.75 ppm and C-6 at 133.5 ppm. Resonances of carbon showed the typical shifts due to the presence of a sulfate group at position 3’ (strong deshielding of H-2
|
||
<superScript id="DDC82137FFEFFFD5FC5CFE085994FE57" attach="none" box="[999,1004,498,511]" fontSize="6" pageId="4" pageNumber="5">′</superScript>
|
||
, C-2
|
||
<superScript id="DDC82137FFEFFFD5FBA6FE085E5AFE57" attach="left" box="[1053,1058,498,511]" fontSize="6" pageId="4" pageNumber="5">′</superScript>
|
||
and C-4’; shielding of C-3’ (
|
||
<tableCitation id="673FB9C4FFEFFFD5FAFCFE0C5FEAFDA1" box="[1351,1426,502,521]" captionStart="Table 4" captionStartId="4.[100,150,150,166]" captionTargetPageId="4" captionText="Table 4 Diagnostic 1H and13C NMR sulfation shifts for flavonoid sulfates 3, 6, 7, 11–15 (DMSO‑d); values are expressed in ppm as δ (flavonoid sulfate) - δ (flavonoid)." pageId="4" pageNumber="5">Table 4</tableCitation>
|
||
)). UV spectra of compound
|
||
<emphasis id="18C9506DFFEFFFD5FC47FDEB5E6DFD8C" bold="true" box="[1020,1045,529,548]" pageId="4" pageNumber="5">14</emphasis>
|
||
(DAD on-line (nm) 237, 273, 335; UV (MeOH) 239, 276, 333) are in agreement with the hypsochromic shift of Band I induced by sulfation at position 3’ (
|
||
<bibRefCitation id="4E2CF18EFFEFFFD5FB3DFDB05F41FDF4" author="Barron, D. & Varin, L. & Ibrahim, R. K. & Harborne, J. B. & Williams, C. A." box="[1158,1337,585,605]" pageId="4" pageNumber="5" pagination="2375 - 2395" refId="ref16118" refString="Barron, D., Varin, L., Ibrahim, R. K., Harborne, J. B., Williams, C. A., 1988. Sulphated flavonoids: an update. Phytochemistry 27, 2375 - 2395. https: // doi. org / 10.1016 / 0031 - 9422 (88) 87003 - 1." type="journal article" year="1988">Barron et al., 1988</bibRefCitation>
|
||
). After acid hydrolysis, compound
|
||
<emphasis id="18C9506DFFEFFFD5FC4EFD9F5E76FDD0" bold="true" box="[1013,1038,613,632]" pageId="4" pageNumber="5">14</emphasis>
|
||
yielded nepetin, which was identified by UV,
|
||
<collectionCode id="4CAC14BAFFEFFFD5FC89FD7B591AFD3C" box="[818,866,641,660]" pageId="4" pageNumber="5">NMR</collectionCode>
|
||
and comparison against an authentic standard (Fig. S31,
|
||
<tableCitation id="673FB9C4FFEFFFD5FA3BFD7B5FB7FD3C" box="[1408,1487,641,660]" captionStart="Table 2" captionStartId="3.[101,151,151,167]" captionTargetPageId="3" captionText="Table 2 1H-NMR data for flavonoid sulfates 3, 6, 7, 11 15 in DMSO‑d (δ ppm, J (Hz))." pageId="4" pageNumber="5">Tables 2</tableCitation>
|
||
and
|
||
<tableCitation id="673FB9C4FFEFFFD5FCE0FD67591FFD18" box="[859,871,669,688]" captionStart="Table 3" captionStartId="3.[818,868,679,695]" captionTargetPageId="3" captionText="Table 3 13C-NMR chemical shifts for flavonoid sulfates 3, 6, 7, 11–14 (δ ppm, DMSO‑d). 6" pageId="4" pageNumber="5">3</tableCitation>
|
||
). Altogether, these data identified
|
||
<emphasis id="18C9506DFFEFFFD5FB08FD675EB4FD18" bold="true" box="[1203,1228,669,688]" pageId="4" pageNumber="5">14</emphasis>
|
||
as nepetin 3
|
||
<superScript id="DDC82137FFEFFFD5FAFDFD605F33FD0F" attach="none" box="[1350,1355,666,679]" fontSize="6" pageId="4" pageNumber="5">′</superScript>
|
||
-sulfate. Analysis of HSQC and HMBC spectra confirmed the structure of
|
||
<emphasis id="18C9506DFFEFFFD5FAD1FD435FFBFD64" bold="true" box="[1386,1411,697,716]" pageId="4" pageNumber="5">14</emphasis>
|
||
. To our knowledge, this compound has not been reported as a plant natural product before.
|
||
</paragraph>
|
||
<paragraph id="2A028C7FFFEFFFD5FCEAFCF65E86FC4B" blockId="4.[818,1488,498,995]" pageId="4" pageNumber="5">
|
||
Comparison of UV, SM and
|
||
<collectionCode id="4CAC14BAFFEFFFD5FBEFFCF75EFCFC88" box="[1108,1156,781,800]" pageId="4" pageNumber="5">NMR</collectionCode>
|
||
spectroscopic data of compound
|
||
<emphasis id="18C9506DFFEFFFD5FA06FCF65FB1FCB7" bold="true" box="[1469,1481,780,799]" pageId="4" pageNumber="5">6</emphasis>
|
||
,
|
||
<emphasis id="18C9506DFFEFFFD5FC89FCD25933FC93" bold="true" box="[818,843,808,827]" pageId="4" pageNumber="5">11</emphasis>
|
||
,
|
||
<emphasis id="18C9506DFFEFFFD5FCECFCD25908FC93" bold="true" box="[855,880,808,827]" pageId="4" pageNumber="5">12</emphasis>
|
||
and
|
||
<emphasis id="18C9506DFFEFFFD5FC1BFCD259C1FC93" bold="true" box="[928,953,808,827]" pageId="4" pageNumber="5">13</emphasis>
|
||
with those reported in the literature allowed their identification as luteolin 7, 3
|
||
<superScript id="DDC82137FFEFFFD5FBA7FCBB5E59FCE6" attach="none" box="[1052,1057,833,846]" fontSize="6" pageId="4" pageNumber="5">′</superScript>
|
||
-disulfate (
|
||
<emphasis id="18C9506DFFEFFFD5FB33FCBE5EECFCFF" bold="true" box="[1160,1172,836,855]" pageId="4" pageNumber="5">6</emphasis>
|
||
) (
|
||
<bibRefCitation id="4E2CF18EFFEFFFD5FB10FCBF5F27FCFF" author="Barron, D. & Varin, L. & Ibrahim, R. K. & Harborne, J. B. & Williams, C. A." box="[1195,1375,836,856]" pageId="4" pageNumber="5" pagination="2375 - 2395" refId="ref16118" refString="Barron, D., Varin, L., Ibrahim, R. K., Harborne, J. B., Williams, C. A., 1988. Sulphated flavonoids: an update. Phytochemistry 27, 2375 - 2395. https: // doi. org / 10.1016 / 0031 - 9422 (88) 87003 - 1." type="journal article" year="1988">Barron et al., 1988</bibRefCitation>
|
||
;
|
||
<bibRefCitation id="4E2CF18EFFEFFFD5FAD0FCBE59E2FCDB" author="Enerstvedt, K. H. & Lundberg, A. & Sjotun, K. & Fadnes, P. & Jordheim, M." pageId="4" pageNumber="5" pagination="42 - 50" refId="ref16657" refString="Enerstvedt, K. H., Lundberg, A., Sjotun, K., Fadnes, P., Jordheim, M., 2017. Characterization and seasonal variation of individual flavonoids in Zostera marina and Zostera noltii from Norwegian coastal waters. Biochem. Syst. Ecol. 74, 42 - 50. https: // doi. org / 10.1016 / j. bse. 2017.08.003." type="journal article" year="2017">Enerstvedt et al., 2017</bibRefCitation>
|
||
), luteolin 7-sulfate (
|
||
<emphasis id="18C9506DFFEFFFD5FBECFC9A5E08FCDB" bold="true" box="[1111,1136,864,883]" pageId="4" pageNumber="5">11</emphasis>
|
||
) (
|
||
<bibRefCitation id="4E2CF18EFFEFFFD5FB3FFC9B5F48FCDB" author="Barron, D. & Varin, L. & Ibrahim, R. K. & Harborne, J. B. & Williams, C. A." box="[1156,1328,864,884]" pageId="4" pageNumber="5" pagination="2375 - 2395" refId="ref16118" refString="Barron, D., Varin, L., Ibrahim, R. K., Harborne, J. B., Williams, C. A., 1988. Sulphated flavonoids: an update. Phytochemistry 27, 2375 - 2395. https: // doi. org / 10.1016 / 0031 - 9422 (88) 87003 - 1." type="journal article" year="1988">Barron et al., 1988</bibRefCitation>
|
||
;
|
||
<bibRefCitation id="4E2CF18EFFEFFFD5FA80FC9A5E78FC27" author="Grignon-Dubois, M. & Rezzonico, B." pageId="4" pageNumber="5" pagination="91 - 101" refId="ref17041" refString="Grignon-Dubois, M., Rezzonico, B., 2018. Phenolic chemistry of the seagrass Zostera noltei Hornem. Part 1: first evidence of three infraspecific flavonoid chemotypes in three distinctive geographical regions. Phytochemistry 146, 91 - 101. https: // doi. org / 10.1016 / j. phytochem. 2017.12.006." type="journal article" year="2018">Grignon-Dubois and Rezzonico, 2018</bibRefCitation>
|
||
), nepetin 7-sulfate (
|
||
<emphasis id="18C9506DFFEFFFD5FB75FC865E9FFC27" bold="true" box="[1230,1255,892,911]" pageId="4" pageNumber="5">12</emphasis>
|
||
) (
|
||
<bibRefCitation id="4E2CF18EFFEFFFD5FAB9FC865FB1FC27" author="Flamini, G. & Pardini, M. & Morell, I." box="[1282,1481,892,912]" pageId="4" pageNumber="5" pagination="1229 - 1233" refId="ref16872" refString="Flamini, G., Pardini, M., Morell, I., 2001. A flavonoid sulphate and other compounds from the roots of Centaurea bracteata. Phytochemistry 58, 1229 - 1233. https: // doi. org / 10.1016 / s 0031 - 9422 (01) 00345 - 4." type="journal article" year="2001">Flamini et al., 2001</bibRefCitation>
|
||
; Tom´as-Barber´an et al., 1987), and luteolin 3
|
||
<superScript id="DDC82137FFEFFFD5FB6BFC6F5EADFC0A" attach="none" box="[1232,1237,917,930]" fontSize="6" pageId="4" pageNumber="5">′</superScript>
|
||
-sulfate (
|
||
<emphasis id="18C9506DFFEFFFD5FA9CFC625F38FC03" bold="true" box="[1319,1344,920,939]" pageId="4" pageNumber="5">13</emphasis>
|
||
) (
|
||
<bibRefCitation id="4E2CF18EFFEFFFD5FAEDFC62591AFC6F" author="Barron, D. & Varin, L. & Ibrahim, R. K. & Harborne, J. B. & Williams, C. A." pageId="4" pageNumber="5" pagination="2375 - 2395" refId="ref16118" refString="Barron, D., Varin, L., Ibrahim, R. K., Harborne, J. B., Williams, C. A., 1988. Sulphated flavonoids: an update. Phytochemistry 27, 2375 - 2395. https: // doi. org / 10.1016 / 0031 - 9422 (88) 87003 - 1." type="journal article" year="1988">Barron et al., 1988</bibRefCitation>
|
||
;
|
||
<bibRefCitation id="4E2CF18EFFEFFFD5FCCFFC4E5E22FC6F" author="Enerstvedt, K. H. & Lundberg, A. & Sjotun, K. & Fadnes, P. & Jordheim, M." box="[884,1114,948,967]" pageId="4" pageNumber="5" pagination="42 - 50" refId="ref16657" refString="Enerstvedt, K. H., Lundberg, A., Sjotun, K., Fadnes, P., Jordheim, M., 2017. Characterization and seasonal variation of individual flavonoids in Zostera marina and Zostera noltii from Norwegian coastal waters. Biochem. Syst. Ecol. 74, 42 - 50. https: // doi. org / 10.1016 / j. bse. 2017.08.003." type="journal article" year="2017">Enerstvedt et al., 2017</bibRefCitation>
|
||
;
|
||
<bibRefCitation id="4E2CF18EFFEFFFD5FBD7FC4E5F6CFC6F" author="Kim, H. & Jeong, H. & Hong, J. W. & Ju, E. K. & Chang-Suk, K. & Youngwan, S." box="[1132,1300,948,967]" pageId="4" pageNumber="5" pagination="823 - 829" refId="ref17700" refString="Kim, H., Jeong, H., Hong, J. W., Ju, E. K., Chang-Suk, K., Youngwan, S., 2016. Evaluation of flavonoids from Zostera asiatica as antioxidants and nitric oxide inhibitors. Biotechnol. Bioproc. Eng. 21 (6), 823 - 829. https: // doi. org / 10.1007 / s 12257 - 016 - 0567 - 9." type="journal article" year="2016">Kim et al., 2016</bibRefCitation>
|
||
) (
|
||
<figureCitation id="B28690FAFFEFFFD5FA8BFC4E5F13FC6F" box="[1328,1387,948,967]" captionStart="Fig" captionStartId="2.[278,308,1675,1692]" captionTargetBox="[266,1317,840,1647]" captionTargetPageId="2" captionText="Fig. 3. Structural formulae of compounds 1–18 and a-e. Underlined names indicate the previously unreported products." figureDoi="http://doi.org/10.5281/zenodo.8235328" httpUri="https://zenodo.org/record/8235328/files/figure.png" pageId="4" pageNumber="5">Fig. 3</figureCitation>
|
||
and S31,
|
||
<tableCitation id="673FB9C4FFEFFFD5FC89FC2A59EFFC4B" box="[818,919,976,995]" captionStart-0="Table 2" captionStart-1="Table 3" captionStart-2="Table 4" captionStartId-0="3.[101,151,151,167]" captionStartId-1="3.[818,868,679,695]" captionStartId-2="4.[100,150,150,166]" captionTargetPageId-0="3" captionTargetPageId-1="3" captionTargetPageId-2="4" captionText-0="Table 2 1H-NMR data for flavonoid sulfates 3, 6, 7, 11 15 in DMSO‑d (δ ppm, J (Hz))." captionText-1="Table 3 13C-NMR chemical shifts for flavonoid sulfates 3, 6, 7, 11–14 (δ ppm, DMSO‑d). 6" captionText-2="Table 4 Diagnostic 1H and13C NMR sulfation shifts for flavonoid sulfates 3, 6, 7, 11–15 (DMSO‑d); values are expressed in ppm as δ (flavonoid sulfate) - δ (flavonoid)." pageId="4" pageNumber="5">Tables 2–4</tableCitation>
|
||
, and Supplementary data for details).
|
||
</paragraph>
|
||
<paragraph id="2A028C7FFFEFFFD5FC89FBF25F11FBB3" blockId="4.[818,1385,1031,1051]" box="[818,1385,1031,1051]" pageId="4" pageNumber="5">
|
||
<heading id="714A3B13FFEFFFD5FC89FBF25F11FBB3" bold="true" box="[818,1385,1031,1051]" fontSize="36" level="1" pageId="4" pageNumber="5" reason="1">
|
||
<emphasis id="18C9506DFFEFFFD5FC89FBF25F11FBB3" bold="true" box="[818,1385,1031,1051]" italics="true" pageId="4" pageNumber="5">2.2.1. Identification of minor flavonoids 2, 4, 8, 9, 15 and 16</emphasis>
|
||
</heading>
|
||
</paragraph>
|
||
<paragraph id="2A028C7FFFEFFFD5FCEAFBDE59E2FB6A" blockId="4.[818,1488,1059,1972]" pageId="4" pageNumber="5">
|
||
Attempts to isolate as pure compound the flavonoids only present in low amounts (
|
||
<emphasis id="18C9506DFFEFFFD5FC04FBC559B3FBFA" bold="true" box="[959,971,1087,1106]" pageId="4" pageNumber="5">2</emphasis>
|
||
,
|
||
<emphasis id="18C9506DFFEFFFD5FC61FBC5599EFBFA" bold="true" box="[986,998,1087,1106]" pageId="4" pageNumber="5">4</emphasis>
|
||
,
|
||
<emphasis id="18C9506DFFEFFFD5FC4DFBC55E7AFBFA" bold="true" box="[1014,1026,1087,1106]" pageId="4" pageNumber="5">8</emphasis>
|
||
,
|
||
<emphasis id="18C9506DFFEFFFD5FBAAFBC55E65FBFA" bold="true" box="[1041,1053,1087,1106]" pageId="4" pageNumber="5">9</emphasis>
|
||
,
|
||
<emphasis id="18C9506DFFEFFFD5FB96FBC55E3EFBFA" bold="true" box="[1069,1094,1087,1106]" pageId="4" pageNumber="5">15</emphasis>
|
||
, and 16) were unsuccessful. Insufficient sample quantities did not allow further purification and their identity could not be fully confirmed by
|
||
<collectionCode id="4CAC14BAFFEFFFD5FBE5FB825EE9FB23" box="[1118,1169,1144,1163]" pageId="4" pageNumber="5">NMR</collectionCode>
|
||
. However, these minor flavonoids were found structurally related to each other and to the major flavonoids.
|
||
</paragraph>
|
||
<paragraph id="2A028C7FFFEFFFD5FCEAFB315FBCF83F" blockId="4.[818,1488,1059,1972]" pageId="4" pageNumber="5">
|
||
Compound
|
||
<emphasis id="18C9506DFFEFFFD5FC04FB3159B3FB76" bold="true" box="[959,971,1227,1246]" pageId="4" pageNumber="5">2</emphasis>
|
||
was the first flavonoid eluted in the chromatographic run (13.3 min; earlier than all the identified disulfates (
|
||
<emphasis id="18C9506DFFEFFFD5FA81FB1D5F3EFB52" bold="true" box="[1338,1350,1255,1274]" pageId="4" pageNumber="5">3</emphasis>
|
||
,
|
||
<emphasis id="18C9506DFFEFFFD5FAE9FB1D5F26FB52" bold="true" box="[1362,1374,1255,1274]" pageId="4" pageNumber="5">4</emphasis>
|
||
,
|
||
<emphasis id="18C9506DFFEFFFD5FAD1FB1D5F0EFB52" bold="true" box="[1386,1398,1255,1274]" pageId="4" pageNumber="5">6</emphasis>
|
||
,
|
||
<emphasis id="18C9506DFFEFFFD5FA39FB1D5FF6FB52" bold="true" box="[1410,1422,1255,1274]" pageId="4" pageNumber="5">7</emphasis>
|
||
). Only present in low amount, it makes it impossible to isolate and it was not detected in the LC/MS spectra. However, some data were available from its chemical behavior. Its HPLC retention time (the lowest observed in the flavonoid series), and on-line UV spectra (
|
||
<quantity id="ED45219AFFEFFFD5FABBFAAC5FFCFAC1" box="[1280,1412,1366,1385]" metricMagnitude="-4" metricUnit="m" metricValue="2.7332799999999997" pageId="4" pageNumber="5" unit="nm" value="273328.0">273, 328 nm</quantity>
|
||
) are in agreement with a 6-methoxy flavone substituted by at least two electron
|
||
<emphasis id="18C9506DFFEFFFD5FCE2FA745918FA09" bold="true" box="[857,864,1422,1441]" italics="true" pageId="4" pageNumber="5">-</emphasis>
|
||
withdrawing groups. Only three 6-methoxy aglycones were obtained after acid hydrolysis of the crude extract, namely nepetin, hispidulin and jaceosidin. Of the three, only nepetin was compatible with retention time of compound
|
||
<emphasis id="18C9506DFFEFFFD5FBD0FA185E06FA5D" bold="true" box="[1131,1150,1506,1525]" pageId="4" pageNumber="5">2.</emphasis>
|
||
The polarity of compound
|
||
<emphasis id="18C9506DFFEFFFD5FAC0FA185FFFFA5D" bold="true" box="[1403,1415,1506,1525]" pageId="4" pageNumber="5">2</emphasis>
|
||
, higher than that of nepetin 7, 3
|
||
<superScript id="DDC82137FFEFFFD5FBA5FA015E5BF9A0" attach="none" box="[1054,1059,1531,1544]" fontSize="6" pageId="4" pageNumber="5">′</superScript>
|
||
-disulfate could lead to identify it with a trisulfated derivative. We found no mention of nepetin trisulfate in the SciFinder database. UV spectral studies of several naturally occurring and synthetic sulfated compounds indicated that sulfation at ring B induce an important hypsochromic shift in Band I due to the electron withdrawing effect of the sulfate group (
|
||
<bibRefCitation id="4E2CF18EFFEFFFD5FB03F9705F15F934" author="Barron, D. & Varin, L. & Ibrahim, R. K. & Harborne, J. B. & Williams, C. A." box="[1208,1389,1673,1693]" pageId="4" pageNumber="5" pagination="2375 - 2395" refId="ref16118" refString="Barron, D., Varin, L., Ibrahim, R. K., Harborne, J. B., Williams, C. A., 1988. Sulphated flavonoids: an update. Phytochemistry 27, 2375 - 2395. https: // doi. org / 10.1016 / 0031 - 9422 (88) 87003 - 1." type="journal article" year="1988">Barron et al., 1988</bibRefCitation>
|
||
), whereas sulfation at ring A does not influence the UV absorption significantly. In the case of luteolin, Band I UV (
|
||
<emphasis id="18C9506DFFEFFFD5FBE3F9385E1AF97D" bold="true" box="[1112,1122,1730,1749]" italics="true" pageId="4" pageNumber="5">λ</emphasis>
|
||
<subScript id="B6398E3AFFEFFFD5FBDCF9325EFDF97E" attach="right" box="[1127,1157,1736,1750]" fontSize="6" pageId="4" pageNumber="5">max</subScript>
|
||
) values were as follows (nm): 7, 3
|
||
<superScript id="DDC82137FFEFFFD5FA7FF9445FB1F963" attach="none" box="[1476,1481,1726,1739]" fontSize="6" pageId="4" pageNumber="5">′</superScript>
|
||
, 4
|
||
<superScript id="DDC82137FFEFFFD5FC85F920593BF94F" attach="none" box="[830,835,1754,1767]" fontSize="6" pageId="4" pageNumber="5">′</superScript>
|
||
-trisulfate (305), 7, 4’- (320), 7, 3
|
||
<superScript id="DDC82137FFEFFFD5FB34F9205EECF94F" attach="none" box="[1167,1172,1754,1767]" fontSize="6" pageId="4" pageNumber="5">′</superScript>
|
||
-disulfate (333), 4
|
||
<superScript id="DDC82137FFEFFFD5FAF9F9205F3FF94F" attach="none" box="[1346,1351,1754,1767]" fontSize="6" pageId="4" pageNumber="5">′</superScript>
|
||
-sulfate (325), 3
|
||
<superScript id="DDC82137FFEFFFD5FC85F90C593BF8AB" attach="none" box="[830,835,1782,1795]" fontSize="6" pageId="4" pageNumber="5">′</superScript>
|
||
-sulfate (330), 7-sulfate (348) and luteolin (350). Our results with nepetin show the same tendency: 7, 3
|
||
<superScript id="DDC82137FFEFFFD5FB2EF8EB5EE2F8B6" attach="none" box="[1173,1178,1809,1822]" fontSize="6" pageId="4" pageNumber="5">′</superScript>
|
||
-disulfate (330), 3
|
||
<superScript id="DDC82137FFEFFFD5FAFEF8EB5F32F8B6" attach="none" box="[1349,1354,1809,1822]" fontSize="6" pageId="4" pageNumber="5">′</superScript>
|
||
-sulfate (334), 7-sulfate (348), and nepetin (348). From these values it appears that Band I UV (
|
||
<emphasis id="18C9506DFFEFFFD5FC27F8B759DEF8C8" bold="true" box="[924,934,1869,1888]" italics="true" pageId="4" pageNumber="5">λ</emphasis>
|
||
<subScript id="B6398E3AFFEFFFD5FC10F8AE59B1F8CA" attach="right" box="[939,969,1876,1890]" fontSize="6" pageId="4" pageNumber="5">max</subScript>
|
||
) value for compound
|
||
<emphasis id="18C9506DFFEFFFD5FB2EF8B65ED9F8F7" bold="true" box="[1173,1185,1868,1887]" pageId="4" pageNumber="5">2</emphasis>
|
||
(
|
||
<quantity id="ED45219AFFEFFFD5FB16F8B75E8EF8C8" box="[1197,1270,1869,1888]" metricMagnitude="-7" metricUnit="m" metricValue="3.28" pageId="4" pageNumber="5" unit="nm" value="328.0">328 nm</quantity>
|
||
) is incompatible with a trisulfate, which led us to tentatively assign compound
|
||
<emphasis id="18C9506DFFEFFFD5FAF9F8925F36F8D3" bold="true" box="[1346,1358,1896,1915]" pageId="4" pageNumber="5">2</emphasis>
|
||
as nepetin 7, 4
|
||
<superScript id="DDC82137FFEFFFD5FC85F87B593BF826" attach="none" box="[830,835,1921,1934]" fontSize="6" pageId="4" pageNumber="5">′</superScript>
|
||
-disulfate. To our knowledge, this product had never been reported.
|
||
</paragraph>
|
||
<paragraph id="2A028C7FFFEFFFD4FCEAF85A5B2EFB94" blockId="4.[818,1488,1059,1972]" lastBlockId="5.[100,770,866,1280]" lastPageId="5" lastPageNumber="6" pageId="4" pageNumber="5">
|
||
Compound
|
||
<emphasis id="18C9506DFFEFFFD5FC72F85A59ADF81B" bold="true" box="[969,981,1952,1971]" pageId="4" pageNumber="5">8</emphasis>
|
||
eluted at 19.6 min. ESI-MS spectrum gave a quasimolecular peak [M+H]
|
||
<superScript id="DDC82137FFEEFFD4FEC8FC985BFAFCC6" attach="left" box="[371,386,866,878]" fontSize="6" pageId="5" pageNumber="6">+</superScript>
|
||
at
|
||
<quantity id="ED45219AFFEEFFD4FE1BFC9C5BA4FCD1" box="[416,476,870,889]" metricMagnitude="2" metricUnit="m" metricValue="3.81" pageId="5" pageNumber="6" unit="m" value="381.0">
|
||
381
|
||
<emphasis id="18C9506DFFEEFFD4FE70FC9C5BA4FCD1" bold="true" box="[459,476,870,889]" italics="true" pageId="5" pageNumber="6">m</emphasis>
|
||
</quantity>
|
||
/z, which was compatible with the molecular formula C
|
||
<subScript id="B6398E3AFFEEFFD4FEF4FC735B19FC3F" attach="both" box="[335,353,905,919]" fontSize="6" pageId="5" pageNumber="6">16</subScript>
|
||
H
|
||
<subScript id="B6398E3AFFEEFFD4FECAFC735BFBFC3F" attach="both" box="[369,387,905,919]" fontSize="6" pageId="5" pageNumber="6">12</subScript>
|
||
O
|
||
<subScript id="B6398E3AFFEEFFD4FE29FC735BE3FC3F" attach="both" box="[402,411,905,919]" fontSize="6" pageId="5" pageNumber="6">9</subScript>
|
||
S. Another significant ion at
|
||
<emphasis id="18C9506DFFEEFFD4FD09FC7858AEFC3D" bold="true" box="[690,726,898,917]" italics="true" pageId="5" pageNumber="6">m/z</emphasis>
|
||
301 [M-80 +H]
|
||
<superScript id="DDC82137FFEEFFD4FF69FC605A99FC0E" attach="left" box="[210,225,922,934]" fontSize="6" pageId="5" pageNumber="6">+</superScript>
|
||
confirmed the presence of one sulfate group. UV spectrum (DAD on-line 266 and
|
||
<quantity id="ED45219AFFEEFFD4FE87FC405BFEFC65" box="[316,390,954,973]" metricMagnitude="-7" metricUnit="m" metricValue="3.41" pageId="5" pageNumber="6" unit="nm" value="341.0">341 nm</quantity>
|
||
) was in agreement with sulfation at position 7 (
|
||
<bibRefCitation id="4E2CF18EFFEEFFD4FF0CFC2C5B1CFC41" author="Barron, D. & Varin, L. & Ibrahim, R. K. & Harborne, J. B. & Williams, C. A." box="[183,356,982,1001]" pageId="5" pageNumber="6" pagination="2375 - 2395" refId="ref16118" refString="Barron, D., Varin, L., Ibrahim, R. K., Harborne, J. B., Williams, C. A., 1988. Sulphated flavonoids: an update. Phytochemistry 27, 2375 - 2395. https: // doi. org / 10.1016 / 0031 - 9422 (88) 87003 - 1." type="journal article" year="1988">Barron et al., 1988</bibRefCitation>
|
||
). After acid hydrolysis, compound
|
||
<emphasis id="18C9506DFFEEFFD4FD10FC2C58CFFC41" bold="true" box="[683,695,982,1001]" pageId="5" pageNumber="6">8</emphasis>
|
||
yielded 5-methoxyluteolin. These results allowed identification of compound
|
||
<emphasis id="18C9506DFFEEFFD4FD4EFC085979FBAD" bold="true" box="[757,769,1010,1029]" pageId="5" pageNumber="6">8</emphasis>
|
||
as 5-methoxyluteolin 7-sulfate. To our knowledge, this compound has not been reported before.
|
||
</paragraph>
|
||
<caption id="7EC2DCF7FFEEFFD4FFDFFD1A5B6FFC95" ID-DOI="http://doi.org/10.5281/zenodo.8235330" ID-Zenodo-Dep="8235330" httpUri="https://zenodo.org/record/8235330/files/figure.png" pageId="5" pageNumber="6" startId="5.[100,130,736,753]" targetBox="[264,1323,149,707]" targetPageId="5" targetType="figure">
|
||
<paragraph id="2A028C7FFFEEFFD4FFDFFD1A5B6FFC95" blockId="5.[100,1487,736,829]" pageId="5" pageNumber="6">
|
||
<emphasis id="18C9506DFFEEFFD4FFDFFD1A5AE6FD59" bold="true" box="[100,158,736,753]" pageId="5" pageNumber="6">Fig. 4.</emphasis>
|
||
Inter-annual variation in the amounts of phenolic compound in fresh (samples Phy1-F to Phy5-F) and detrital (sample Phy-3 D). Concentrations values on ordinate are given as mg g
|
||
<superScript id="DDC82137FFEEFFD4FEF2FD0E5B26FCA8" attach="left" box="[329,350,756,768]" fontSize="5" pageId="5" pageNumber="6">
|
||
<emphasis id="18C9506DFFEEFFD4FEF2FD0E5B2EFCA8" bold="true" box="[329,342,756,768]" pageId="5" pageNumber="6">¡</emphasis>
|
||
1
|
||
</superScript>
|
||
dw of plant tissue, mean values SD (n 3). Products are given in order of elution: Caff:
|
||
<emphasis id="18C9506DFFEEFFD4FBCAFD035E04FCA2" bold="true" box="[1137,1148,761,778]" pageId="5" pageNumber="6">1</emphasis>
|
||
; Nep7,4’:
|
||
<emphasis id="18C9506DFFEEFFD4FB6CFD035E9AFCA2" bold="true" box="[1239,1250,761,778]" pageId="5" pageNumber="6">2</emphasis>
|
||
; OMeLu2S:
|
||
<emphasis id="18C9506DFFEEFFD4FAF0FD035F2EFCA2" bold="true" box="[1355,1366,761,778]" pageId="5" pageNumber="6">3</emphasis>
|
||
; 6OHLu2S:
|
||
<emphasis id="18C9506DFFEEFFD4FA04FD035FB2FCA2" bold="true" box="[1471,1482,761,778]" pageId="5" pageNumber="6">4</emphasis>
|
||
; ± = Coum:
|
||
<emphasis id="18C9506DFFEEFFD4FF1AFCE95AD4FC8B" bold="true" box="[161,172,787,803]" pageId="5" pageNumber="6">5</emphasis>
|
||
; Lu2S:
|
||
<emphasis id="18C9506DFFEEFFD4FF56FCE95A80FC8C" bold="true" box="[237,248,787,804]" pageId="5" pageNumber="6">6</emphasis>
|
||
; Nep2S:
|
||
<emphasis id="18C9506DFFEEFFD4FEFEFCE95B28FC8B" bold="true" box="[325,336,787,803]" pageId="5" pageNumber="6">7</emphasis>
|
||
; 5OMeLu7S:
|
||
<emphasis id="18C9506DFFEEFFD4FE7FFCE95BB7FC8C" bold="true" box="[452,463,787,804]" pageId="5" pageNumber="6">8</emphasis>
|
||
; 6OHLu7S:
|
||
<emphasis id="18C9506DFFEEFFD4FD8DFCE95839FC8C" bold="true" box="[566,577,787,804]" pageId="5" pageNumber="6">9</emphasis>
|
||
; RA:
|
||
<emphasis id="18C9506DFFEEFFD4FDCAFCE958FFFC8C" bold="true" box="[625,647,787,804]" pageId="5" pageNumber="6">10</emphasis>
|
||
; L7S:
|
||
<emphasis id="18C9506DFFEEFFD4FD06FCE958ABFC8C" bold="true" box="[701,723,787,804]" pageId="5" pageNumber="6">11</emphasis>
|
||
; Nep7S:
|
||
<emphasis id="18C9506DFFEEFFD4FC9AFCE9594FFC8C" bold="true" box="[801,823,787,804]" pageId="5" pageNumber="6">12</emphasis>
|
||
; Lu3
|
||
<superScript id="DDC82137FFEEFFD4FCD8FCEA591FFCB3" attach="right" box="[867,871,784,795]" fontSize="5" pageId="5" pageNumber="6">′</superScript>
|
||
S:
|
||
<emphasis id="18C9506DFFEEFFD4FCC6FCE959EBFC8C" bold="true" box="[893,915,787,804]" pageId="5" pageNumber="6">13</emphasis>
|
||
; Nep3
|
||
<superScript id="DDC82137FFEEFFD4FC70FCEA59B7FCB3" attach="right" box="[971,975,784,795]" fontSize="5" pageId="5" pageNumber="6">′</superScript>
|
||
S:
|
||
<emphasis id="18C9506DFFEEFFD4FC5EFCE95983FC8C" bold="true" box="[997,1019,787,804]" pageId="5" pageNumber="6">14</emphasis>
|
||
; Hispi7S:
|
||
<emphasis id="18C9506DFFEEFFD4FBE8FCE95E11FC8C" bold="true" box="[1107,1129,787,804]" pageId="5" pageNumber="6">15</emphasis>
|
||
; Jaceo7S:
|
||
<emphasis id="18C9506DFFEEFFD4FB7EFCE95EA3FC8C" bold="true" box="[1221,1243,787,804]" pageId="5" pageNumber="6">16</emphasis>
|
||
. See Fig. 3 for formulae and Table 1 for full data.
|
||
</paragraph>
|
||
</caption>
|
||
<paragraph id="2A028C7FFFEEFFD4FF3FFBBF5BEDFAA8" blockId="5.[100,770,866,1280]" pageId="5" pageNumber="6">
|
||
Comparison of spectroscopic data and chemical behavior of compound
|
||
<emphasis id="18C9506DFFEEFFD4FF1EFB9B5AC9FBDC" bold="true" box="[165,177,1121,1140]" pageId="5" pageNumber="6">4</emphasis>
|
||
,
|
||
<emphasis id="18C9506DFFEEFFD4FF07FB9B5AB0FBDC" bold="true" box="[188,200,1121,1140]" pageId="5" pageNumber="6">9</emphasis>
|
||
,
|
||
<emphasis id="18C9506DFFEEFFD4FF68FB9B5A94FBDC" bold="true" box="[211,236,1121,1140]" pageId="5" pageNumber="6">15</emphasis>
|
||
and
|
||
<emphasis id="18C9506DFFEEFFD4FEA3FB9B5B49FBDC" bold="true" box="[280,305,1121,1140]" pageId="5" pageNumber="6">16</emphasis>
|
||
with those reported in the literature allowed their identification as 6-hydroxyluteolin disulfate and monosulfate (
|
||
<emphasis id="18C9506DFFEEFFD4FD09FB8758C6FB38" bold="true" box="[690,702,1149,1168]" pageId="5" pageNumber="6">4</emphasis>
|
||
and
|
||
<emphasis id="18C9506DFFEEFFD4FD56FB875881FB38" bold="true" box="[749,761,1149,1168]" pageId="5" pageNumber="6">9</emphasis>
|
||
) (
|
||
<bibRefCitation id="4E2CF18EFFEEFFD4FFD7FB635B46FB04" author="Greenham, J. & Harborne, J. B. & Williams, C. A." box="[108,318,1177,1196]" pageId="5" pageNumber="6" pagination="100 - 118" refId="ref16929" refString="Greenham, J., Harborne, J. B., Williams, C. A., 2003. Identification of lipophilic flavones and flavonols by comparative HPLC, TLC and UV. Spectral analysis. Phytochem. Anal. 14, 100 - 118. https: // doi. org / 10.1002 / pca. 693." type="journal article" year="2003">Greenham et al., 2003</bibRefCitation>
|
||
; Tom´as-Barber´an et al., 1987), hispidulin 7-sulfate (
|
||
<emphasis id="18C9506DFFEEFFD4FF2DFB4F5AD7FB60" bold="true" box="[150,175,1205,1224]" pageId="5" pageNumber="6">15</emphasis>
|
||
) (
|
||
<bibRefCitation id="4E2CF18EFFEEFFD4FF7FFB4F5B04FB60" author="Flamini, G. & Pardini, M. & Morell, I." box="[196,380,1205,1224]" pageId="5" pageNumber="6" pagination="1229 - 1233" refId="ref16872" refString="Flamini, G., Pardini, M., Morell, I., 2001. A flavonoid sulphate and other compounds from the roots of Centaurea bracteata. Phytochemistry 58, 1229 - 1233. https: // doi. org / 10.1016 / s 0031 - 9422 (01) 00345 - 4." type="journal article" year="2001">Flamini et al., 2001</bibRefCitation>
|
||
;
|
||
<bibRefCitation id="4E2CF18EFFEEFFD4FE33FB4F5855FB60" author="Kwak, J. Y. & Seok, J. K. & Suh, H. J. & Choi, Y. H. & Hong, S. S. & Kim, D. S. & Boo, Y. C." box="[392,557,1205,1224]" pageId="5" pageNumber="6" pagination="501 - 511" refId="ref18011" refString="Kwak, J. Y., Seok, J. K., Suh, H. J., Choi, Y. H., Hong, S. S., Kim, D. S., Boo, Y. C., 2016. Antimelanogenic effects of luteolin 7 - sulfate isolated from Phyllospadix iwatensis Makino. Br. J. Dermatol. 175, 501 - 511. https: // doi. org / 10.1111 / bjd. 14496." type="journal article" year="2016">Kwak et al., 2016</bibRefCitation>
|
||
), and jaceosidin 7-sulfate (
|
||
<emphasis id="18C9506DFFEEFFD4FF26FB2B5ACEFB4C" bold="true" box="[157,182,1233,1252]" pageId="5" pageNumber="6">16</emphasis>
|
||
) (Tom´as-Barber´an et al., 1987;
|
||
<bibRefCitation id="4E2CF18EFFEEFFD4FDBCFB2B58BFFB4C" author="Zhang, L. & Tu, Z. - C. & Wang, H. Z. - F. & Fu, F. & Wen, Q. - H. & Fan, D." box="[519,711,1233,1252]" pageId="5" pageNumber="6" pagination="123 - 132" refId="ref21389" refString="Zhang, L., Tu, Z. - C., Wang, H. Z. - F., Fu, F., Wen, Q. - H., Fan, D., 2015. Metabolic profiling of antioxidants constituents in Artemisia selengensis leaves. Food Chem. 186, 123 - 132. https: // doi. org / 10.1016 / j. foodchem. 2015.03.068." type="journal article" year="2015">Zhang et al., 2015</bibRefCitation>
|
||
) (see Supplementary data for details).
|
||
</paragraph>
|
||
<paragraph id="2A028C7FFFEEFFD4FFDFFADF5825FA9F" blockId="5.[100,605,1316,1336]" box="[100,605,1316,1336]" pageId="5" pageNumber="6">
|
||
<heading id="714A3B13FFEEFFD4FFDFFADF5825FA9F" bold="true" box="[100,605,1316,1336]" fontSize="36" level="1" pageId="5" pageNumber="6" reason="1">
|
||
<emphasis id="18C9506DFFEEFFD4FFDFFADF5825FA9F" bold="true" box="[100,605,1316,1336]" italics="true" pageId="5" pageNumber="6">2.2.2. Comments on the structural identities as assigned</emphasis>
|
||
</heading>
|
||
</paragraph>
|
||
<paragraph id="2A028C7FFFEEFFD4FFD4FAA75890F9E7" blockId="5.[111,770,1372,1978]" pageId="5" pageNumber="6">
|
||
1 Care should be taken when assigning HPLC peaks
|
||
<emphasis id="18C9506DFFEEFFD4FDE5FAA6580FFAC7" bold="true" box="[606,631,1372,1391]" pageId="5" pageNumber="6">14</emphasis>
|
||
and
|
||
<emphasis id="18C9506DFFEEFFD4FD1CFAA658B8FAC7" bold="true" box="[679,704,1372,1391]" pageId="5" pageNumber="6">15</emphasis>
|
||
on the only basis of their on-line UV spectra maxima. They present, indeed, very close maxima values (
|
||
<emphasis id="18C9506DFFEEFFD4FE31FA6E5BDBFA0F" bold="true" box="[394,419,1428,1447]" pageId="5" pageNumber="6">14</emphasis>
|
||
: 273 and
|
||
<quantity id="ED45219AFFEEFFD4FDB3FA6E582CFA00" box="[520,596,1428,1448]" metricMagnitude="-7" metricUnit="m" metricValue="3.35" pageId="5" pageNumber="6" unit="nm" value="335.0">335 nm</quantity>
|
||
;
|
||
<emphasis id="18C9506DFFEEFFD4FDDBFA6E5801FA0F" bold="true" box="[608,633,1428,1447]" pageId="5" pageNumber="6">15</emphasis>
|
||
: 274 and
|
||
<quantity id="ED45219AFFEEFFD4FD65FA6E5ADEFA6B" metricMagnitude="-7" metricUnit="m" metricValue="3.36" pageId="5" pageNumber="6" unit="nm" value="336.0">336 nm</quantity>
|
||
). Careful examination of the UV minima of band II and the shape of the absorbance profiles is necessary in this case to achieve a correct assignment as nepetin 3
|
||
<superScript id="DDC82137FFEEFFD4FE36FA1F5BEAFA5A" attach="none" box="[397,402,1509,1522]" fontSize="6" pageId="5" pageNumber="6">′</superScript>
|
||
-sulfate (
|
||
<emphasis id="18C9506DFFEEFFD4FE5EFA125B86FA53" bold="true" box="[485,510,1512,1531]" pageId="5" pageNumber="6">14</emphasis>
|
||
) and as hispidulin 7-sulfate (
|
||
<emphasis id="18C9506DFFEEFFD4FF37F9FE5ADDF9BF" bold="true" box="[140,165,1540,1559]" pageId="5" pageNumber="6">15</emphasis>
|
||
). Compound
|
||
<emphasis id="18C9506DFFEEFFD4FE9DF9FE5B47F9BF" bold="true" box="[294,319,1540,1559]" pageId="5" pageNumber="6">14</emphasis>
|
||
shows a band II
|
||
<emphasis id="18C9506DFFEEFFD4FE5AF9FE5B93F9BF" bold="true" box="[481,491,1540,1559]" italics="true" pageId="5" pageNumber="6">λ</emphasis>
|
||
<subScript id="B6398E3AFFEEFFD4FE51F9F1587DF9B1" attach="left" box="[490,517,1547,1561]" fontSize="6" pageId="5" pageNumber="6">min</subScript>
|
||
at
|
||
<quantity id="ED45219AFFEEFFD4FD9EF9FE5815F9BF" box="[549,621,1540,1559]" metricMagnitude="-7" metricUnit="m" metricValue="2.52" pageId="5" pageNumber="6" unit="nm" value="252.0">252 nm</quantity>
|
||
with a concave inflexion on both sides, while compound
|
||
<emphasis id="18C9506DFFEEFFD4FDB0F9DA585CF99B" bold="true" box="[523,548,1568,1587]" pageId="5" pageNumber="6">15</emphasis>
|
||
shows a band II
|
||
<emphasis id="18C9506DFFEEFFD4FD7FF9DA58B6F99B" bold="true" box="[708,718,1568,1587]" italics="true" pageId="5" pageNumber="6">λ</emphasis>
|
||
<subScript id="B6398E3AFFEEFFD4FD75F9DD5891F99D" attach="left" box="[718,745,1575,1589]" fontSize="6" pageId="5" pageNumber="6">min</subScript>
|
||
at
|
||
<quantity id="ED45219AFFEEFFD4FF3FF9C65AB4F9E7" box="[132,204,1596,1615]" metricMagnitude="-7" metricUnit="m" metricValue="2.4699999999999998" pageId="5" pageNumber="6" unit="nm" value="247.0">247 nm</quantity>
|
||
with a convex inflexion on both sides (Fig. S21and S31).
|
||
</paragraph>
|
||
<paragraph id="2A028C7FFFEEFFD4FFD4F9A25BDAF8BA" blockId="5.[111,770,1372,1978]" pageId="5" pageNumber="6">
|
||
2 A purification sub-fraction containing a mixture of disulfate derivatives (
|
||
<emphasis id="18C9506DFFEEFFD4FF5DF9895A8AF92E" bold="true" box="[230,242,1651,1670]" pageId="5" pageNumber="6">3</emphasis>
|
||
,
|
||
<emphasis id="18C9506DFFEEFFD4FEB8F9895B77F92E" bold="true" box="[259,271,1651,1670]" pageId="5" pageNumber="6">6</emphasis>
|
||
,
|
||
<emphasis id="18C9506DFFEEFFD4FEA4F9895B53F92E" bold="true" box="[287,299,1651,1670]" pageId="5" pageNumber="6">7</emphasis>
|
||
) showed a minor compound eluted between 5- methoxyluteolin 7, 3
|
||
<superScript id="DDC82137FFEEFFD4FEF6F9765B2AF931" attach="none" box="[333,338,1676,1689]" fontSize="6" pageId="5" pageNumber="6">′</superScript>
|
||
-disulfate (
|
||
<emphasis id="18C9506DFFEEFFD4FE01F9755BBEF90A" bold="true" box="[442,454,1679,1698]" pageId="5" pageNumber="6">3</emphasis>
|
||
) and luteolin 7, 3
|
||
<superScript id="DDC82137FFEEFFD4FDC1F9765807F931" attach="none" box="[634,639,1676,1689]" fontSize="6" pageId="5" pageNumber="6">′</superScript>
|
||
-disulfate (
|
||
<emphasis id="18C9506DFFEEFFD4FD5CF975588BF90A" bold="true" box="[743,755,1679,1698]" pageId="5" pageNumber="6">6</emphasis>
|
||
), which was below the detection level in the crude extract. Its on-line UV spectra (269 and
|
||
<quantity id="ED45219AFFEEFFD4FEFEF93D5BF5F972" box="[325,397,1735,1754]" metricMagnitude="-7" metricUnit="m" metricValue="3.2" pageId="5" pageNumber="6" unit="nm" value="320.0">320 nm</quantity>
|
||
) and order of elution are consistent with the presence in the crude extract of traces amounts of luteolin 7, 4
|
||
<superScript id="DDC82137FFEEFFD4FD4DF91A5883F945" attach="none" box="[758,763,1760,1773]" fontSize="6" pageId="5" pageNumber="6">′</superScript>
|
||
- disulfate (
|
||
<bibRefCitation id="4E2CF18EFFEEFFD4FF58F9055BEDF8BA" author="Barron, D. & Varin, L. & Ibrahim, R. K. & Harborne, J. B. & Williams, C. A." box="[227,405,1791,1810]" pageId="5" pageNumber="6" pagination="2375 - 2395" refId="ref16118" refString="Barron, D., Varin, L., Ibrahim, R. K., Harborne, J. B., Williams, C. A., 1988. Sulphated flavonoids: an update. Phytochemistry 27, 2375 - 2395. https: // doi. org / 10.1016 / 0031 - 9422 (88) 87003 - 1." type="journal article" year="1988">Barron et al., 1988</bibRefCitation>
|
||
).
|
||
</paragraph>
|
||
<paragraph id="2A028C7FFFEEFFD4FFD4F8E15E9BFA77" blockId="5.[111,770,1372,1978]" lastBlockId="5.[849,1488,870,1503]" pageId="5" pageNumber="6">
|
||
3 Two chromatographic peaks of low intensity and poor resolution were detected in LC/MS. Their spectra showed odd [M+H]
|
||
<superScript id="DDC82137FFEEFFD4FD0FF8C958BBF897" attach="left" box="[692,707,1843,1855]" fontSize="6" pageId="5" pageNumber="6">+</superScript>
|
||
values at 450 and 480, typical of organic substances containing one nitrogen atom, and odd [M-80 + H]
|
||
<superScript id="DDC82137FFEEFFD4FE11F8905BC1F8DE" attach="left" box="[426,441,1898,1910]" fontSize="6" pageId="5" pageNumber="6">+</superScript>
|
||
ions at 370 and 400 indicating the presence of one sulfate group, but the low signal-to-noise ratio did not allow exploitation of other fragmentations (Fig. S29 and S30). These data support the presence of traces of flavoalkaloid monosulfates with molecular weight of 449 (Rt ~25 min) and 479 (Rt ~26 min), but their concentration was too low to obtain useable on-line UV spectra.
|
||
<bibRefCitation id="4E2CF18EFFEEFFD4FC7DFC405EFBFC65" author="Takagi, M. & Funahashi, S. & Ohta, K. & Nakabayashi, T." box="[966,1155,954,973]" pageId="5" pageNumber="6" pagination="3019 - 3020" refId="ref20571" refString="Takagi, M., Funahashi, S., Ohta, K., Nakabayashi, T., 1980. Phyllospadine, a new flavonoidal alkaloid from the sea-grass Phyllosphadix iwatensis. Agric. Biol. Chem. 44 (12), 3019 - 3020. https: // doi. org / 10.1271 / bbb 1961.44.3019." type="journal article" year="1980">Takagi et al. (1980)</bibRefCitation>
|
||
had isolated low amounts of a flavoalkaloid derivative from
|
||
<taxonomicName id="EDBDF7FCFFEEFFD4FBE2FC2C5EBBFC41" box="[1113,1219,982,1001]" class="Liliopsida" family="Zosteraceae" genus="Phyllospadix" kingdom="Plantae" order="Alismatales" pageId="5" pageNumber="6" phylum="Tracheophyta" rank="species" species="iwatensis">
|
||
<emphasis id="18C9506DFFEEFFD4FBE2FC2C5EBBFC41" bold="true" box="[1113,1219,982,1001]" italics="true" pageId="5" pageNumber="6">P. iwatensis</emphasis>
|
||
</taxonomicName>
|
||
, which they named phyllospadine (C
|
||
<subScript id="B6398E3AFFEEFFD4FC7AFC0359ABFBAF" attach="both" box="[961,979,1017,1031]" fontSize="6" pageId="5" pageNumber="6">21</subScript>
|
||
H
|
||
<subScript id="B6398E3AFFEEFFD4FC58FC03598DFBAF" attach="both" box="[995,1013,1017,1031]" fontSize="6" pageId="5" pageNumber="6">21</subScript>
|
||
NO
|
||
<subScript id="B6398E3AFFEEFFD4FBAFFC035E65FBAF" attach="left" box="[1044,1053,1017,1031]" fontSize="6" pageId="5" pageNumber="6">6</subScript>
|
||
, MW = 383). Its purification required acetylation with acetic anhydride and it was isolated as triacetate of hispidulin 8-(1-methyl-2-pyrrolidinyl) (C
|
||
<subScript id="B6398E3AFFEEFFD4FB64FBCB5E89FB97" attach="both" box="[1247,1265,1073,1087]" fontSize="6" pageId="5" pageNumber="6">27</subScript>
|
||
H
|
||
<subScript id="B6398E3AFFEEFFD4FABAFBCB5F6BFB97" attach="both" box="[1281,1299,1073,1087]" fontSize="6" pageId="5" pageNumber="6">27</subScript>
|
||
NO
|
||
<subScript id="B6398E3AFFEEFFD4FA89FBCB5F43FB97" attach="left" box="[1330,1339,1073,1087]" fontSize="6" pageId="5" pageNumber="6">9</subScript>
|
||
, MW = 509). Forty mg of phyllospadine tri-acetate were obtained from two kg of dried plant, accounting for 15 μg gdw
|
||
<superScript id="DDC82137FFEEFFD4FB6AFBA65EA2FBC2" attach="right" box="[1233,1242,1116,1130]" fontSize="6" pageId="5" pageNumber="6">1</superScript>
|
||
of phyllospadine.
|
||
<bibRefCitation id="4E2CF18EFFEEFFD4FA2BFB9B59BEFB38" author="Takagi, M. & Funahashi, S. & Ohta, K. & Nakabayashi, T." pageId="5" pageNumber="6" pagination="2417 - 2418" refId="ref20516" refString="Takagi, M., Funahashi, S., Ohta, K., Nakabayashi, T., 1979. Flavonoids in the sea-grass Phyllospadix japonica. Agric. Biol. Chem. 43 (11), 2417 - 2418. https: // doi. org / 10.1080 / 00021369.1979.10863833." type="journal article" year="1979">Takagi et al. (1979)</bibRefCitation>
|
||
also analyzed the flavonoid content of
|
||
<taxonomicName id="EDBDF7FCFFEEFFD4FA82FB845FDCFB38" box="[1337,1444,1149,1169]" class="Liliopsida" family="Zosteraceae" genus="Phyllospadix" kingdom="Plantae" order="Alismatales" pageId="5" pageNumber="6" phylum="Tracheophyta" rank="species" species="japonicus">
|
||
<emphasis id="18C9506DFFEEFFD4FA82FB845FDCFB38" bold="true" box="[1337,1444,1149,1169]" italics="true" pageId="5" pageNumber="6">P. japonicus</emphasis>
|
||
</taxonomicName>
|
||
, but phyllospadine was not found in this species. Neither phyllospadine nor its hypothetical sulfate was found in our extracts, but the two nitrogeneous compounds detected in the present study would probably share a number of similarities with this substance. Flavonoid alkaloids are of interest due to their rarity, their amphoteric nature, and the biological activity of some of their natural sources. They result from the convergence of two distinct biosynthetic pathways, affording natural products with a wide range of interesting biological activities that would not be expected for flavonoids or alkaloids alone (
|
||
<bibRefCitation id="4E2CF18EFFEEFFD4FC2EFA6E5E43FA0F" author="Blair, L. M. & Calvert, M. B. & Sperry, J." box="[917,1083,1428,1448]" pageId="5" pageNumber="6" pagination="85 - 115" refId="ref16183" refString="Blair, L. M., Calvert, M. B., Sperry, J., 2017. Flavoalkaloids-isolation, biological activity, and total synthesis. Alkaloids - Chem. Biol. 77, 85 - 115. https: // doi. org / 10.1016 / bs. alkal. 2016.04.001." type="journal article" year="2017">Blair et al., 2017</bibRefCitation>
|
||
). Our next step in this respect will be to collect the large amounts of plant material needed to isolate and characterize these very minor compounds.
|
||
</paragraph>
|
||
<paragraph id="2A028C7FFFEEFFD4FC89F9F25F0EF9B3" blockId="5.[818,1398,1544,1563]" box="[818,1398,1544,1563]" pageId="5" pageNumber="6">
|
||
<heading id="714A3B13FFEEFFD4FC89F9F25F0EF9B3" bold="true" box="[818,1398,1544,1563]" fontSize="36" level="1" pageId="5" pageNumber="6" reason="1">
|
||
<emphasis id="18C9506DFFEEFFD4FC89F9F25F0EF9B3" bold="true" box="[818,1398,1544,1563]" italics="true" pageId="5" pageNumber="6">
|
||
2.3. Inter-annual variability in the phenolic content of
|
||
<taxonomicName id="EDBDF7FCFFEEFFD4FA98F9F25F0EF9B3" ID-CoL="6VFPT" ID-ENA="55486" baseAuthorityName="Zapata and McMillan" baseAuthorityYear="1979" box="[1315,1398,1544,1563]" class="Liliopsida" family="Zosteraceae" genus="Phyllospadix" kingdom="Plantae" order="Alismatales" pageId="5" pageNumber="6" phylum="Tracheophyta" rank="species" species="torreyi">P. torreyi</taxonomicName>
|
||
</emphasis>
|
||
</heading>
|
||
</paragraph>
|
||
<paragraph id="2A028C7FFFEEFFD7FCEAF9BA5ABFFDCD" blockId="5.[818,1487,1600,1982]" lastBlockId="6.[100,770,142,613]" lastPageId="6" lastPageNumber="7" pageId="5" pageNumber="6">
|
||
A total of five sampling campaigns of fresh samples of the aerial part of
|
||
<taxonomicName id="EDBDF7FCFFEEFFD4FCF7F9A659D8F9C7" baseAuthorityName="Zapata and McMillan" baseAuthorityYear="1979" box="[844,928,1628,1647]" class="Liliopsida" family="Zosteraceae" genus="Phyllospadix" kingdom="Plantae" order="Alismatales" pageId="5" pageNumber="6" phylum="Tracheophyta" rank="species" species="torreyi">
|
||
<emphasis id="18C9506DFFEEFFD4FCF7F9A659D8F9C7" bold="true" box="[844,928,1628,1647]" italics="true" pageId="5" pageNumber="6">P. torreyi</emphasis>
|
||
</taxonomicName>
|
||
(batch number: PhyF 1–5, each constituted of three independent samples) were conducted in La Jolla (
|
||
<figureCitation id="B28690FAFFEEFFD4FB60F9825F77F923" box="[1243,1295,1656,1675]" captionStart="Fig" captionStartId="1.[101,131,917,934]" captionTargetBox="[266,1321,151,886]" captionTargetId="figure-164@1.[263,1324,148,889]" captionTargetPageId="1" captionText="Fig. 1. Schematic map showing the location of the sampling sites in La Jolla, San Diego County, California, USA. 1: site for fresh material. 2: site for detrital material." figureDoi="http://doi.org/10.5281/zenodo.8235324" httpUri="https://zenodo.org/record/8235324/files/figure.png" pageId="5" pageNumber="6">Fig. 1</figureCitation>
|
||
) over different years (2015–2017) and seasons (summer and winter). Aqueous-methanolic extracts were prepared from each collection and individual phenolic compounds were quantified by HPLC in each of the fifteen crude extracts. The quantitative variation of flavonoids and phenolic acids was found to be relatively consistent from year to year. Comparison of the summer extracts showed similar HPLC profile and a weak variability in the phenolic concentrations. For all samples, the flavonoid pattern was found largely dominated by the disulfates (
|
||
<emphasis id="18C9506DFFEEFFD4FB6AF8AD5EA5F8C2" bold="true" box="[1233,1245,1879,1898]" pageId="5" pageNumber="6">3</emphasis>
|
||
,
|
||
<emphasis id="18C9506DFFEEFFD4FB50F8AD5E8FF8C2" bold="true" box="[1259,1271,1879,1898]" pageId="5" pageNumber="6">6</emphasis>
|
||
and
|
||
<emphasis id="18C9506DFFEEFFD4FA91F8AD5F4EF8C2" bold="true" box="[1322,1334,1879,1898]" pageId="5" pageNumber="6">7</emphasis>
|
||
). Nepetin 7, 3
|
||
<superScript id="DDC82137FFEEFFD4FA78F8AE5FB0F8C9" attach="none" box="[1475,1480,1876,1889]" fontSize="6" pageId="5" pageNumber="6">′</superScript>
|
||
- disulfate (
|
||
<emphasis id="18C9506DFFEEFFD4FC2BF88959E4F82E" bold="true" box="[912,924,1907,1926]" pageId="5" pageNumber="6">7</emphasis>
|
||
) had the highest content among all compounds in all tested samples (
|
||
<quantity id="ED45219AFFEEFFD4FC31F8755E76F80A" box="[906,1038,1935,1954]" metricMagnitude="-6" metricUnit="kg" metricValue="6.9399999999999995" metricValueMax="7.81" metricValueMin="6.07" pageId="5" pageNumber="6" unit="mg" value="6.9399999999999995" valueMax="7.81" valueMin="6.07">6.07–7.81 mg</quantity>
|
||
g
|
||
<superScript id="DDC82137FFEEFFD4FB97F8735E4DF83F" attach="right" box="[1068,1077,1929,1943]" fontSize="6" pageId="5" pageNumber="6">1</superScript>
|
||
) and represented 41–52% of the flavonoid pool. The second most abundant product was 5-methoxyluteolin 7, 3
|
||
<superScript id="DDC82137FFEEFFD4FA78F85D5FB0F81C" attach="none" box="[1475,1480,1959,1972]" fontSize="6" pageId="5" pageNumber="6">′</superScript>
|
||
- disulfate (
|
||
<emphasis id="18C9506DFFEDFFD7FF7DFF6E5AAAFF0F" bold="true" box="[198,210,148,167]" pageId="6" pageNumber="7">3</emphasis>
|
||
,
|
||
<quantity id="ED45219AFFEDFFD7FF59FF6E5B1EFF0F" box="[226,358,148,167]" metricMagnitude="-6" metricUnit="kg" metricValue="2.795" metricValueMax="3.86" metricValueMin="1.73" pageId="6" pageNumber="7" unit="mg" value="2.795" valueMax="3.86" valueMin="1.73">1.73–3.86 mg</quantity>
|
||
g
|
||
<superScript id="DDC82137FFEDFFD7FE3CFF745BE8FF34" attach="right" box="[391,400,142,156]" fontSize="6" pageId="6" pageNumber="7">1</superScript>
|
||
; 12–29%), followed by luteolin 7, 3
|
||
<superScript id="DDC82137FFEDFFD7FD4DFF6B5883FF36" attach="none" box="[758,763,145,158]" fontSize="6" pageId="6" pageNumber="7">′</superScript>
|
||
- disulfate (
|
||
<emphasis id="18C9506DFFEDFFD7FF79FF4A5AB6FF6B" bold="true" box="[194,206,176,195]" pageId="6" pageNumber="7">6</emphasis>
|
||
;
|
||
<quantity id="ED45219AFFEDFFD7FF62FF4A5B22FF6B" box="[217,346,176,195]" metricMagnitude="-6" metricUnit="kg" metricValue="1.8699999999999999" metricValueMax="2.32" metricValueMin="1.42" pageId="6" pageNumber="7" unit="mg" value="1.8699999999999999" valueMax="2.32" valueMin="1.42">1.42–2.32 mg</quantity>
|
||
g
|
||
<superScript id="DDC82137FFEDFFD7FECDFF505B07FF10" attach="right" box="[374,383,170,184]" fontSize="6" pageId="6" pageNumber="7">1</superScript>
|
||
; 10–13%). The minor flavonoids
|
||
<emphasis id="18C9506DFFEDFFD7FD0DFF4A58BAFF6B" bold="true" box="[694,706,176,195]" pageId="6" pageNumber="7">2</emphasis>
|
||
,
|
||
<emphasis id="18C9506DFFEDFFD7FD75FF4A58A2FF6B" bold="true" box="[718,730,176,195]" pageId="6" pageNumber="7">4</emphasis>
|
||
and
|
||
<emphasis id="18C9506DFFEDFFD7FFDFFF315A08FF76" bold="true" box="[100,112,203,222]" pageId="6" pageNumber="7">9</emphasis>
|
||
were only detected in the summer samples. The flavonoid 7-sulfates (
|
||
<emphasis id="18C9506DFFEDFFD7FFD7FF1D5A00FF52" bold="true" box="[108,120,231,250]" pageId="6" pageNumber="7">8</emphasis>
|
||
,
|
||
<emphasis id="18C9506DFFEDFFD7FF33FF1D5AD9FF52" bold="true" box="[136,161,231,250]" pageId="6" pageNumber="7">11</emphasis>
|
||
,
|
||
<emphasis id="18C9506DFFEDFFD7FF0AFF1D5AB2FF52" bold="true" box="[177,202,231,250]" pageId="6" pageNumber="7">12</emphasis>
|
||
, and
|
||
<emphasis id="18C9506DFFEDFFD7FEBDFF1D5B67FF52" bold="true" box="[262,287,231,250]" pageId="6" pageNumber="7">15</emphasis>
|
||
) and 3
|
||
<superScript id="DDC82137FFEDFFD7FED2FF1E5B16FF59" attach="none" box="[361,366,228,241]" fontSize="6" pageId="6" pageNumber="7">′</superScript>
|
||
-sulfates (
|
||
<emphasis id="18C9506DFFEDFFD7FE75FF1D5B9FFF52" bold="true" box="[462,487,231,250]" pageId="6" pageNumber="7">13</emphasis>
|
||
,
|
||
<emphasis id="18C9506DFFEDFFD7FE4DFF1D5877FF52" bold="true" box="[502,527,231,250]" pageId="6" pageNumber="7">14</emphasis>
|
||
) were present in all the samples in moderate amounts, while jaceosidin 7-sulfate (
|
||
<emphasis id="18C9506DFFEDFFD7FD0AFEF958B2FEBE" bold="true" box="[689,714,259,278]" pageId="6" pageNumber="7">16</emphasis>
|
||
) was detected only in summer. Low amounts of caffeic- (
|
||
<emphasis id="18C9506DFFEDFFD7FD85FEE55832FE9A" bold="true" box="[574,586,287,306]" pageId="6" pageNumber="7">1</emphasis>
|
||
) and coumaric acid (
|
||
<emphasis id="18C9506DFFEDFFD7FFD7FEC15A00FEE6" bold="true" box="[108,120,315,334]" pageId="6" pageNumber="7">5</emphasis>
|
||
) were found in all the samples (
|
||
<quantity id="ED45219AFFEDFFD7FE1BFEC15841FEE6" box="[416,569,315,334]" metricMagnitude="-7" metricUnit="kg" metricValue="1.165" metricValueMax="1.58" metricValueMin="0.75" pageId="6" pageNumber="7" unit="mg" value="0.11649999999999999" valueMax="0.158" valueMin="0.075">
|
||
<geoCoordinate id="4F89EAB8FFEDFFD7FE1BFEC15BAFFEE6" box="[416,471,315,334]" degrees="0.075" direction="north" orientation="latitude" pageId="6" pageNumber="7" precision="55" value="0.075">0.075</geoCoordinate>
|
||
<geoCoordinate id="4F89EAB8FFEDFFD7FE6CFEC15860FEE6" box="[471,536,315,334]" degrees="0.158" direction="west" orientation="longitude" pageId="6" pageNumber="7" precision="55" value="-0.158">–0.158</geoCoordinate>
|
||
mg
|
||
</quantity>
|
||
g
|
||
<superScript id="DDC82137FFEDFFD7FDEDFECF5827FEEB" attach="right" box="[598,607,309,323]" fontSize="6" pageId="6" pageNumber="7">1</superScript>
|
||
and
|
||
<quantity id="ED45219AFFEDFFD7FD37FEC15AF9FEC2" metricMagnitude="-8" metricUnit="kg" metricValue="3.4" metricValueMax="4.1" metricValueMin="2.7" pageId="6" pageNumber="7" unit="mg" value="0.034" valueMax="0.041" valueMin="0.027">
|
||
<geoCoordinate id="4F89EAB8FFEDFFD7FD37FEC158BAFEE6" box="[652,706,315,334]" degrees="0.027" direction="north" orientation="latitude" pageId="6" pageNumber="7" precision="55" value="0.027">0.027</geoCoordinate>
|
||
<geoCoordinate id="4F89EAB8FFEDFFD7FD7AFEC1597AFEE6" box="[705,770,315,334]" degrees="0.041" direction="west" orientation="longitude" pageId="6" pageNumber="7" precision="55" value="-0.041">–0.041</geoCoordinate>
|
||
mg
|
||
</quantity>
|
||
g
|
||
<superScript id="DDC82137FFEDFFD7FF19FEAB5AD3FEF7" attach="right" box="[162,171,337,351]" fontSize="6" pageId="6" pageNumber="7">1</superScript>
|
||
respectively). These two phenolic acids are very common in seagrasses (
|
||
<bibRefCitation id="4E2CF18EFFEDFFD7FF68FE895BA2FE2E" author="Zapata, O. & McMillan, C." box="[211,474,371,390]" pageId="6" pageNumber="7" pagination="307 - 317" refId="ref21343" refString="Zapata, O., McMillan, C., 1979. Phenolic acids in seagrasses. Aquat. Bot. 7, 307 - 317. https: // doi. org / 10.1016 / 0304 - 3770 (79) 90032 - 9." type="journal article" year="1979">Zapata and McMillan, 1979</bibRefCitation>
|
||
). Seasonality was observed for rosmarinic acid (
|
||
<emphasis id="18C9506DFFEDFFD7FEA8FE755B54FE0A" bold="true" box="[275,300,399,418]" pageId="6" pageNumber="7">10</emphasis>
|
||
) whose concentration was higher in summer (
|
||
<quantity id="ED45219AFFEDFFD7FFD0FE505B70FE16" box="[107,264,426,446]" metricMagnitude="-6" metricUnit="kg" metricValue="1.6604999999999999" metricValueMax="2.264" metricValueMin="1.057" pageId="6" pageNumber="7" unit="mg" value="1.6604999999999999" valueMax="2.264" valueMin="1.057">
|
||
<geoCoordinate id="4F89EAB8FFEDFFD7FFD0FE505ADAFE15" box="[107,162,426,445]" degrees="1.057" direction="north" orientation="latitude" pageId="6" pageNumber="7" precision="55" value="1.057">1.057</geoCoordinate>
|
||
<geoCoordinate id="4F89EAB8FFEDFFD7FF19FE515A9BFE16" box="[162,227,427,446]" degrees="2.264" direction="west" orientation="longitude" pageId="6" pageNumber="7" precision="55" value="-2.264">–2.264</geoCoordinate>
|
||
mg
|
||
</quantity>
|
||
g
|
||
<superScript id="DDC82137FFEDFFD7FE93FE5F5B49FE1B" attach="right" box="[296,305,421,435]" fontSize="6" pageId="6" pageNumber="7">1</superScript>
|
||
) than in winter (
|
||
<quantity id="ED45219AFFEDFFD7FE60FE515801FE16" box="[475,633,427,446]" metricMagnitude="-7" metricUnit="kg" metricValue="4.26" metricValueMax="4.91" metricValueMin="3.61" pageId="6" pageNumber="7" unit="mg" value="0.426" valueMax="0.491" valueMin="0.361">
|
||
<geoCoordinate id="4F89EAB8FFEDFFD7FE60FE51586AFE16" box="[475,530,427,446]" degrees="0.361" direction="north" orientation="latitude" pageId="6" pageNumber="7" precision="55" value="0.361">0.361</geoCoordinate>
|
||
<geoCoordinate id="4F89EAB8FFEDFFD7FDA8FE51582BFE16" box="[531,595,427,446]" degrees="0.491" direction="west" orientation="longitude" pageId="6" pageNumber="7" precision="55" value="-0.491">–0.491</geoCoordinate>
|
||
mg
|
||
</quantity>
|
||
g
|
||
<superScript id="DDC82137FFEDFFD7FD22FE5F58DAFE1B" attach="right" box="[665,674,421,435]" fontSize="6" pageId="6" pageNumber="7">1</superScript>
|
||
). We had previously isolated rosmarinic acid from
|
||
<taxonomicName id="EDBDF7FCFFEDFFD7FE51FE3D583AFE71" box="[490,578,454,474]" class="Liliopsida" family="Zosteraceae" genus="Zostera" kingdom="Plantae" order="Alismatales" pageId="6" pageNumber="7" phylum="Tracheophyta" rank="species" species="marina">
|
||
<emphasis id="18C9506DFFEDFFD7FE51FE3D583AFE71" bold="true" box="[490,578,454,474]" italics="true" pageId="6" pageNumber="7">Z. marina</emphasis>
|
||
</taxonomicName>
|
||
and
|
||
<emphasis id="18C9506DFFEDFFD7FDC9FE3D58C4FE71" bold="true" box="[626,700,454,474]" italics="true" pageId="6" pageNumber="7">Z. noltei</emphasis>
|
||
, which also belong to the
|
||
<taxonomicName id="EDBDF7FCFFEDFFD7FEADFE195BFDFE5E" box="[278,389,483,502]" class="Liliopsida" family="Zosteraceae" kingdom="Plantae" order="Alismatales" pageId="6" pageNumber="7" phylum="Tracheophyta" rank="family">Zosteraceae</taxonomicName>
|
||
family (
|
||
<bibRefCitation id="4E2CF18EFFEDFFD7FE6CFE1858D7FE5E" author="Achamlale, S. & Rezzonico, B. & Grignon-Dubois, M." box="[471,687,482,502]" pageId="6" pageNumber="7" pagination="878 - 883" refId="ref16005" refString="Achamlale, S., Rezzonico, B., Grignon-Dubois, M., 2009. Rosmarinic acid from beach waste: isolation and HPLC quantification in Zostera detritus from Arcachon lagoon. Food Chem. 113, 878 - 883 https // doi. org / 10.1016 / j. foodchem. 2008.07.040." type="journal article" year="2009">Achamlale et al., 2009</bibRefCitation>
|
||
). This is the first report of rosmarinic acid in a member of the genus
|
||
<emphasis id="18C9506DFFEDFFD7FD30FE04597AFDB9" bold="true" box="[651,770,510,529]" italics="true" pageId="6" pageNumber="7">
|
||
<taxonomicName id="EDBDF7FCFFEDFFD7FD30FE045887FDB9" box="[651,767,510,529]" class="Liliopsida" family="Zosteraceae" genus="Phyllospadix" kingdom="Plantae" order="Alismatales" pageId="6" pageNumber="7" phylum="Tracheophyta" rank="genus">Phyllospadix</taxonomicName>
|
||
.
|
||
</emphasis>
|
||
The results are summarized in
|
||
<tableCitation id="673FB9C4FFEDFFD7FE21FDE05B9DFD85" box="[410,485,538,557]" captionStart="Table 1" captionStartId="1.[101,151,993,1009]" captionTargetPageId="1" captionText="Table 1 Peak number, HPLC retention time (Rt), sampling dates and sample names, concentration (mg g 1 dw of plant tissue, mean values SD) of phenolic compounds from ± Phyllospadix torreyi." pageId="6" pageNumber="7">Table 1</tableCitation>
|
||
and
|
||
<figureCitation id="B28690FAFFEDFFD7FDA7FDE0582DFD85" box="[540,597,538,557]" captionStart="Fig" captionStartId="5.[100,130,736,753]" captionTargetBox="[264,1323,149,707]" captionTargetId="figure-940@5.[263,1324,148,708]" captionTargetPageId="5" captionText="Fig. 4. Inter-annual variation in the amounts of phenolic compound in fresh (samples Phy1-F to Phy5-F) and detrital (sample Phy-3 D). Concentrations values on ordinate are given as mg g ¡1 dw of plant tissue, mean values SD (n 3). Products are given in order of elution: Caff: 1; Nep7,4’: 2; OMeLu2S: 3; 6OHLu2S: 4; ± = Coum: 5; Lu2S: 6; Nep2S: 7; 5OMeLu7S: 8; 6OHLu7S: 9; RA: 10; L7S: 11; Nep7S: 12; Lu3′S: 13; Nep3′S: 14; Hispi7S: 15; Jaceo7S: 16. See Fig. 3 for formulae and Table 1 for full data." figureDoi="http://doi.org/10.5281/zenodo.8235330" httpUri="https://zenodo.org/record/8235330/files/figure.png" pageId="6" pageNumber="7">Fig. 4</figureCitation>
|
||
, which show the average concentrations of the three harvest replicates for each sampling campaign.
|
||
</paragraph>
|
||
</subSubSection>
|
||
</treatment>
|
||
</document> |