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<document id="C92827C6ACA037A084BECAFEFD80F8F8" ID-CLB-Dataset="55368" ID-DOI="10.1016/j.phytochem.2021.112662" ID-GBIF-Dataset="c2a0cd6a-4d45-4488-9357-509b5fa38fc8" ID-ISSN="1873-3700" ID-Zenodo-Dep="8259664" IM.bibliography_approvedBy="carolina" IM.illustrations_approvedBy="carolina" IM.materialsCitations_approvedBy="felipe" IM.metadata_approvedBy="felipe" IM.tables_approvedBy="carolina" IM.taxonomicNames_approvedBy="carolina" IM.treatments_approvedBy="carolina" checkinTime="1692309280030" checkinUser="felipe" docAuthor="Barny, Lea A., Tasca, Julia A., Sanchez, Hugo A., Smith, Chelsea R., Koptur, Suzanne, Livshultz, Tatyana &amp; Minbiole, Kevin P. C." docDate="2021" docId="065107213874FFCB03649D7D51EBF952" docLanguage="en" docName="Phytochemistry.185.112662.pdf" docOrigin="Phytochemistry (112662) 185" docSource="http://dx.doi.org/10.1016/j.phytochem.2021.112662" docStyle="DocumentStyle:F36D69FC8B198FBE91029DF9C24697D3.5:Phytochemistry.2020-.journal_article" docStyleId="F36D69FC8B198FBE91029DF9C24697D3" docStyleName="Phytochemistry.2020-.journal_article" docStyleVersion="5" docTitle="Apocynaceae" docType="treatment" docVersion="3" lastPageNumber="9" masterDocId="FA687F59387CFFC303009E6B511BFF90" masterDocTitle="Chemotaxonomic investigation of Apocynaceae for retronecine-type pyrrolizidine alkaloids using HPLC-MS / MS" masterLastPageNumber="15" masterPageNumber="1" pageNumber="9" updateTime="1692713795367" updateUser="ExternalLinkService">
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<mods:title id="31672887F3371D33F5CD8BE12F1481F2">Chemotaxonomic investigation of Apocynaceae for retronecine-type pyrrolizidine alkaloids using HPLC-MS / MS</mods:title>
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<mods:namePart id="265EC0ECD4BBCB939B32ADB82F2900EA">Tasca, Julia A.</mods:namePart>
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2.7.
<taxonomicName id="49F8CDB43874FFCB03959D7D51EEFCB9" box="[149,245,790,809]" class="Magnoliopsida" family="Apocynaceae" kingdom="Plantae" order="Gentianales" pageId="8" pageNumber="9" phylum="Tracheophyta" rank="tribe">Apocyneae</taxonomicName>
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We sampled 36 species from 17 of 21 genera of Apocyneae. In this tribe, PAs had been previously reported from
<taxonomicName id="49F8CDB43874FFCB011C9D025219FCED" authority="Druce" authorityName="Druce" box="[540,770,873,893]" class="Magnoliopsida" family="Apocynaceae" genus="Anodendron" kingdom="Plantae" order="Gentianales" pageId="8" pageNumber="9" phylum="Tracheophyta" rank="species" species="affine">
<emphasis id="BC8C6A253874FFCB011C9D0253D8FCEC" bold="true" box="[540,707,873,892]" italics="true" pageId="8" pageNumber="9">Anodendron affine</emphasis>
Druce
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(
<bibRefCitation id="EA69CBC63874FFCB036C9DED504CFC09" author="Sasaki, K. &amp; Hirata, Y." box="[108,343,902,921]" pageId="8" pageNumber="9" pagination="2119 - 2126" refId="ref20552" refString="Sasaki, K., Hirata, Y., 1970. The alkaloids of Anodendron affine Druce. Tetrahedron 26, 2119 - 2126. https: // doi. org / 10.1016 / S 0040 - 4020 (01) 92789 - 9." type="journal article" year="1970">Sasaki and Hirata, 1970</bibRefCitation>
) and
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<emphasis id="BC8C6A253874FFCB02939DEE539EFC09" bold="true" box="[403,645,901,921]" italics="true" pageId="8" pageNumber="9">Amphineurion marginatum</emphasis>
(Roxb.) D.J. Middleton
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(
<bibRefCitation id="EA69CBC63874FFCB03D69DC950BAFC25" author="Colegate, S. M. &amp; Gardner, D. R. &amp; Betz, J. M. &amp; Fischer, O. W. &amp; Liede-Schumann, S." box="[214,417,930,949]" pageId="8" pageNumber="9" pagination="257 - 276" refId="ref16564" refString="Colegate, S. M., Gardner, D. R., Betz, J. M., Fischer, O. W., Liede-Schumann, S., Boppr´e, M., 2016. Pro-toxic 1, 2 - dehydropyrrolizidine alkaloid esters, including unprecedented 10 - membered macrocyclic diesters, in the medicinally-used Alafia cf. caudata and Amphineurion marginatum (Apocynaceae: apocynoideae: Nerieae and Apocyneae). Phytochem. Anal. 27, 257 - 276. https: // doi. org / 10.1002 / pca. 2624." type="journal article" year="2016">Colegate et al., 2016</bibRefCitation>
). These species belong to two early diverging lineages of Apocyneae (subtribes Papuechitinae and Amphineurinae, respectively) and
<bibRefCitation id="EA69CBC63874FFCB026C9DB25351FC7C" author="Livshultz, T. &amp; Middleton, D. J. &amp; van der Ham, R. W. J. M. &amp; Khew, G." box="[364,586,985,1005]" pageId="8" pageNumber="9" pagination="341 - 358" refId="ref19552" refString="Livshultz, T., Middleton, D. J., van der Ham, R. W. J. M., Khew, G., 2018 b. Generic delimitation in Apocyneae (Apocynaceae). Taxon 67, 341 - 358. https: // doi. org / 10.12705 / 672.5." type="journal article" year="2018">Livshultz et al. (2018b)</bibRefCitation>
suggested that PAs were potentially a chemotaxonomic character for delimiting these early diverging lineages from the rest of the radiation.
</paragraph>
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No PAs were detected with high confidence in any sample of Apocyneae. Two of three accessions of
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<emphasis id="BC8C6A253874FFCB02C89A2253A7FBCC" bold="true" box="[456,700,1097,1116]" italics="true" pageId="8" pageNumber="9">Amphineurion marginatum</emphasis>
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leaves possessed a molecular ion of
<emphasis id="BC8C6A253874FFCB02749A0E5082FBE8" bold="true" box="[372,409,1125,1144]" italics="true" pageId="8" pageNumber="9">m/z</emphasis>
320 which appeared only in the
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120 scan with associated chromatography at a late retention time of ~15 min (
<emphasis id="BC8C6A253874FFCB03C69AF651CDFB20" box="[198,214,1181,1200]" italics="true" pageId="8" pageNumber="9">&gt;</emphasis>
3 to 1
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/N) (
<tableCitation id="C37A838C3874FFCB02519AF65083FB20" box="[337,408,1181,1200]" captionStart="Table 2" captionStartId="5.[100,150,150,166]" captionTargetBox="[116,1426,264,1935]" captionText="Table 2 Samples analyzed on all PREC scans (m/z 120, 138, 156). Samples determined as N: no candidate ions detected, Y (low): low confidence, candidate ions detected only in PREC 120, Y (mod):moderate confidence, candidate ions detected in PREC 120 and PREC 138; Y (low): only candidate ion with mass 432.4432.5 detected in PREC 120 and PREC 138; Y (high): high confidence, candidate ions detected in PREC 120, 138, and 156. ND: not detected. Vouchers in Table S2. Tribe Species Author sample organ Determination PREC PREC PREC Uncorrected Relative # 120 138 156 Retention Time (min) Vinceae Ochrosia poweri F.M.Bailey 28097 leaf N ND ND ND Rauvolfia balansae (Baill.) Boiteau 28131 leaf N ND ND ND Rauvolfia verticillata (Lour.) Baill. 28099 leaf N ND ND ND Rauvolfia vomitoria Afzel. 28116 leaf N ND ND ND Melodineae Craspidospermum Bojer ex Decne. 630 leaf N ND ND ND verticillatum Wrightieae Wrightia antidysenterica (L.) R. Br. 28422 leaf Y (low) 432.5 a 432.5 ND 11.43 Wrightia dubia (Sims) Spreng. 28418 leaf Y (low) 432.5a 432.5 ND 11.4 Wrightia dubia (Sims) Spreng. 28421 leaf Y (low) 432.5a 432.5 ND 11.39 Wrightia karaketii D.J. Middleton 28451 leaf Y (low) 432.5 a 432.5 ND 11.48 Wrightia tinctoria R.Br. 29370 seed Y (mod) 210.2 ND ND 7.56 328.5 ND ND 9.99 460 ND ND 10.16 300.2 300.2 ND ~10.36 432.4 a 432.4 ND ~10.36 328.5 328.5 ND ~10.36 270.3 270.3 ND ~10.36 352.1 ND ND 11.4 Wrightia tinctoria R.Br. 29371 seed Y (mod) 210.2 ND ND 7.32 328.5 ND ND 9.96 460 ND ND 10.19 300.2 300.2 ND ~10.36 328.5 328.5 ND ~10.36 270.3 270.3 ND ~10.36 432.4 a 432.4 ND ~10.36 352.1 ND ND 11.36 Wrightia versicolor S.T. Blake 28423 leaf Y (mod) 432.4 a 432.4 ND 11.33 300.2 300.2 ND 11.66 Malouetieae Eucorymbia alba Stapf 28111 leaf Y (mod) 238.3 238.3 ND 11.79 354.4 354.4 ND 11.93 396.4 ND ND 12.96 436.5 ND ND 14.72 Eucorymbia alba Stapf 28112 leaf Y (mod) 238.3 238.3 ND 11.798 354.4 354.4 ND 11.932 436.5 ND ND 14.67 Galactophora Woodson 116 leaf Y (mod) 270.4 270.4 ND 9.76 schomburgkiana 238.2 238.2 ND 11.92 Holarrhena pubescens Wall. ex G. Don 231 leaf N ND ND ND Holarrhena pubescens Wall. ex G. Don 233 leaf N ND ND ND Holarrhena pubescens Wall. ex G. Don 234 leaf N ND ND ND Holarrhena pubescens Wall. ex G.Don 29372 seed Y (low) 474.4 ND ND 9.52 498.4 ND ND 9.83 Malouetia calva Markgr. 28965 leaf N ND ND ND Malouetia cestroides Müll.Arg. 28966 leaf N ND ND ND Apocyneae Amphineurion (Roxb.) G. Don 23 leaf Y (low) 320.4 ND ND 15.16 marginatum Amphineurion (Roxb.) G. Don 52 leaf N ND ND ND marginatum Amphineurion (Roxb.) G. Don 270 leaf Y (low) 320.4 ND ND 15.16 marginatum Apocynum cannabinum L. 28918 leaf N ND ND ND Beaumontia murtonii Craib 267 leaf N ND ND ND Beaumontia murtonii Craib 268 leaf N ND ND ND Trachelospermum Nakai 81 leaf N ND ND ND asiaticum Vallaris solanacea (Roth) O. Kuntze 90 leaf N ND ND ND Odontadenieae Pentalinon luteum (L.) B.F.Hansen &amp; 28673 leaf N ND ND ND Wunderlin Pentalinon luteum (L.) B.F.Hansen &amp; 28676 leaf N ND ND ND Wunderlin Mesechiteae Mandevilla boliviensis (Hook. f.) Woodson 76 leaf Y (low) 444.2 ND ND 9.76 458.5 ND ND 9.96 Echiteae Bahiella infundibuliflora J.F.Morales 28143 leaf Y (high) 300.1 300.1 300.1 10.22 Echites panduratus A. DC. 28459 leaf N ND ND ND Echites umbellatus Jacq. 28516 leaf Y (high) 318.4 318.4 318.4 10.43 300.5 300.5 300.5 10.73 456.2 456.2 456.2 11.93 470.5 470.5 470.5 12.57 444.4 444.4 444.4 12.73 458.3 458.3 ND 12.87 (continued on next page)" pageId="8" pageNumber="9">Table 2</tableCitation>
). Fragmentation of a
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with an
<emphasis id="BC8C6A253874FFCB01DD9AF65219FB20" bold="true" box="[733,770,1181,1200]" italics="true" pageId="8" pageNumber="9">m/z</emphasis>
320 via product ion scan (PIS) by
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was consistent with our
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120 findings, as that compound was found to only result in
<emphasis id="BC8C6A253874FFCB03809A9B51BFFA93" bold="true" box="[128,164,1264,1283]" italics="true" pageId="8" pageNumber="9">m/z</emphasis>
120 fragment with no
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138 or 156 fragments.
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was utilized to propose a molecular formula for the
<emphasis id="BC8C6A253874FFCB011A9B675324FA8F" bold="true" box="[538,575,1292,1311]" italics="true" pageId="8" pageNumber="9">m/z</emphasis>
320 ion, C
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H
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NO
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and therefore it was tentatively identified as an open-chain diester (
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).
<bibRefCitation id="EA69CBC63874FFCB024C9B2F5304FAC7" author="Colegate, S. M. &amp; Gardner, D. R. &amp; Betz, J. M. &amp; Fischer, O. W. &amp; Liede-Schumann, S." box="[332,543,1348,1367]" pageId="8" pageNumber="9" pagination="257 - 276" refId="ref16564" refString="Colegate, S. M., Gardner, D. R., Betz, J. M., Fischer, O. W., Liede-Schumann, S., Boppr´e, M., 2016. Pro-toxic 1, 2 - dehydropyrrolizidine alkaloid esters, including unprecedented 10 - membered macrocyclic diesters, in the medicinally-used Alafia cf. caudata and Amphineurion marginatum (Apocynaceae: apocynoideae: Nerieae and Apocyneae). Phytochem. Anal. 27, 257 - 276. https: // doi. org / 10.1002 / pca. 2624." type="journal article" year="2016">Colegate et al. (2016)</bibRefCitation>
reported that leaves of
<taxonomicName id="49F8CDB43874FFCB03649B345040FAE3" box="[100,347,1375,1395]" class="Magnoliopsida" family="Apocynaceae" genus="Amphineurion" kingdom="Plantae" order="Gentianales" pageId="8" pageNumber="9" phylum="Tracheophyta" rank="species" species="marginatum">
<emphasis id="BC8C6A253874FFCB03649B345040FAE3" bold="true" box="[100,347,1375,1395]" italics="true" pageId="8" pageNumber="9">Amphineurion marginatum</emphasis>
</taxonomicName>
contained the lowest percentage by dry weight of PAs (0.02%) compared to roots (0.13%) and stems (0.09%). This may account for the lack of
<collectionCode id="E8E92EF23874FFCB029A9BF350AEFA3B" box="[410,437,1432,1451]" country="Brazil" name="Universidade Federal do Oeste do Pará" pageId="8" pageNumber="9" type="Herbarium">PA</collectionCode>
structural diversity and abundance observed in our leaf samples but other factors, environmentally induced plasticity, genetic variation, cannot be ruled out in the present study. A product scan and/or
<collectionCode id="E8E92EF23874FFCB02279B875079FA6F" box="[295,354,1516,1535]" pageId="8" pageNumber="9">HRMS</collectionCode>
would need to be completed on the
<emphasis id="BC8C6A253874FFCB01B49B8053C2FA6E" bold="true" box="[692,729,1515,1534]" italics="true" pageId="8" pageNumber="9">m/z</emphasis>
320 molecular ion in our
<taxonomicName id="49F8CDB43874FFCB0233986C533FF98A" box="[307,548,1543,1562]" class="Magnoliopsida" family="Apocynaceae" genus="Amphineurion" kingdom="Plantae" order="Gentianales" pageId="8" pageNumber="9" phylum="Tracheophyta" rank="species" species="marginatum">
<emphasis id="BC8C6A253874FFCB0233986C533FF98A" bold="true" box="[307,548,1543,1562]" italics="true" pageId="8" pageNumber="9">Amphineurion marginatum</emphasis>
</taxonomicName>
leaf samples to understand fully the fragmentation pattern and identity of this compound.
</paragraph>
<paragraph id="8E47B6373874FFCB0384985451EBF952" blockId="8.[100,771,846,1730]" pageId="8" pageNumber="9">
The unusual PAs previously identified in
<taxonomicName id="49F8CDB43874FFCB0113985453A0F9C2" box="[531,699,1599,1618]" class="Magnoliopsida" family="Apocynaceae" genus="Anodendron" kingdom="Plantae" order="Gentianales" pageId="8" pageNumber="9" phylum="Tracheophyta" rank="species" species="affine">
<emphasis id="BC8C6A253874FFCB0113985453A0F9C2" bold="true" box="[531,699,1599,1618]" italics="true" pageId="8" pageNumber="9">Anodendron affine</emphasis>
</taxonomicName>
have a platynecine core (
<bibRefCitation id="EA69CBC63874FFCB020C983050F1F9FE" author="Sasaki, K. &amp; Hirata, Y." box="[268,490,1627,1646]" pageId="8" pageNumber="9" pagination="2119 - 2126" refId="ref20552" refString="Sasaki, K., Hirata, Y., 1970. The alkaloids of Anodendron affine Druce. Tetrahedron 26, 2119 - 2126. https: // doi. org / 10.1016 / S 0040 - 4020 (01) 92789 - 9." type="journal article" year="1970">Sasaki and Hirata, 1970</bibRefCitation>
) that would not be detectable with our strategy. Thus, the occurrence and distribution of platynecine-derived PAs in other Apocyneae species also remains an open question.
</paragraph>
</subSubSection>
</treatment>
</document>