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<mods:title id="C6A6764A24CF51636679A718E0528FE0">Chemotaxonomic investigation of Apocynaceae for retronecine-type pyrrolizidine alkaloids using HPLC-MS / MS</mods:title>
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2.8.
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We sampled 26 species from 10 of 27 genera of tribe
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. Compounds fragmenting to
<emphasis id="BC8C6A253874FFCB026899505096F8DE" bold="true" box="[360,397,1851,1870]" italics="true" pageId="8" pageNumber="9">m/z</emphasis>
120 and 138 were present in samples of
<taxonomicName id="49F8CDB43874FFCB0364993D504AF8FA" authority="R. Br." authorityName="R. Br." box="[100,337,1878,1898]" class="Magnoliopsida" family="Apocynaceae" genus="Marsdenia" kingdom="Plantae" order="Gentianales" pageId="8" pageNumber="9" phylum="Tracheophyta" rank="species" species="tinctoria">
<emphasis id="BC8C6A253874FFCB0364993D500DF8FA" bold="true" box="[100,278,1878,1898]" italics="true" pageId="8" pageNumber="9">Marsdenia tinctoria</emphasis>
R.Br.
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and
<taxonomicName id="49F8CDB43874FFCB0288993D538CF8FA" authority="Constantin" authorityName="Constantin" box="[392,663,1878,1898]" class="Magnoliopsida" family="Apocynaceae" genus="Marsdenia" kingdom="Plantae" order="Gentianales" pageId="8" pageNumber="9" phylum="Tracheophyta" rank="species" species="glabra">
<emphasis id="BC8C6A253874FFCB0288993D5333F8F9" bold="true" box="[392,552,1878,1897]" italics="true" pageId="8" pageNumber="9">Marsdenia glabra</emphasis>
Constantin
</taxonomicName>
(
<tableCitation id="C37A838C3874FFCB01A9993C53EFF8FA" box="[681,756,1879,1898]" 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>
). However, three of these four ions have a molecular mass of 432.5, raising the possibility that these are structurally similar to the aminobenzoyl glycoside previously identified in
<taxonomicName id="49F8CDB43874FFCB012099C1551BFF37" authority="(Srinroch et al., 2019)" baseAuthorityName="Srinroch" baseAuthorityYear="2019" box="[544,1024,148,1981]" class="Magnoliopsida" family="Apocynaceae" genus="Wrightia" kingdom="Plantae" order="Gentianales" pageId="8" pageNumber="9" phylum="Tracheophyta" rank="species" species="antidysenterica">
<emphasis id="BC8C6A253874FFCB012099C15219F82D" bold="true" box="[544,770,1962,1981]" italics="true" pageId="8" pageNumber="9">Wrightia antidysenterica</emphasis>
(
<bibRefCitation id="EA69CBC63874FFCB003A9EFF52E2FF37" author="Srinroch, C. &amp; Sahakitpichan, P. &amp; Techasakul, S. &amp; Chimnoi, N. &amp; Ruchirawat, S. &amp; Kanchanapoom, T." box="[826,1017,148,167]" pageId="8" pageNumber="9" pagination="61 - 64" refId="ref21015" refString="Srinroch, C., Sahakitpichan, P., Techasakul, S., Chimnoi, N., Ruchirawat, S., Kanchanapoom, T., 2019. 2 - Aminobenzoyl and megastigmane glycosides from Wrightia antidysenterica. Phytochem Lett 29, 61 - 64. https: // doi. org / 10.1016 / j. phytol. 2018.11.006." type="journal article" year="2019">Srinroch et al., 2019</bibRefCitation>
)
</taxonomicName>
(
<figureCitation id="16C3AAB23874FFCB070E9EFF5558FF37" box="[1038,1091,148,167]" captionStart="Fig" captionStartId="7.[100,130,1939,1956]" captionTargetBox="[193,1399,1638,1908]" captionTargetId="figure-1008@7.[187,1400,1633,1911]" captionTargetPageId="7" captionText="Fig. 5. Proposed fragmentation scheme for 2-aminobenzoyl O-β-D-apiofuranosyl-(1 → 6)- β-D-glucopyranoside (m/z 432.15 when protonated) in positive ion mode ESI to m/z 300.11, 138.06, and 120.04 fragments." figureDoi="http://doi.org/10.5281/zenodo.8259674" httpUri="https://zenodo.org/record/8259674/files/figure.png" pageId="8" pageNumber="9">Fig. 5</figureCitation>
) rather than PAs. HRMS would need to be used to determine if the
<emphasis id="BC8C6A253874FFCB07349EDB5542FF53" bold="true" box="[1076,1113,176,195]" italics="true" pageId="8" pageNumber="9">m/z</emphasis>
432 ions observed in
<taxonomicName id="49F8CDB43874FFCB06439EC454BAFF52" box="[1347,1441,175,194]" class="Magnoliopsida" family="Apocynaceae" genus="Marsdenia" kingdom="Plantae" order="Gentianales" pageId="8" pageNumber="9" phylum="Tracheophyta" rank="genus">
<emphasis id="BC8C6A253874FFCB06439EC454BAFF52" bold="true" box="[1347,1441,175,194]" italics="true" pageId="8" pageNumber="9">Marsdenia</emphasis>
</taxonomicName>
and
<taxonomicName id="49F8CDB43874FFCB00329EA052DCFF4E" box="[818,967,203,222]" pageId="8" pageNumber="9">
<emphasis id="BC8C6A253874FFCB00329EA05264FF4E" bold="true" box="[818,895,203,222]" italics="true" pageId="8" pageNumber="9">Wrightia</emphasis>
species
</taxonomicName>
are the same compound. Thus we have moderate confidence in the presence of PAs only in the one sample of
<taxonomicName id="49F8CDB43874FFCB063A9E835494FF6A" box="[1338,1423,231,251]" class="Magnoliopsida" family="Apocynaceae" genus="Marsdenia" kingdom="Plantae" order="Gentianales" pageId="8" pageNumber="9" phylum="Tracheophyta" rank="species" species="glabra">
<emphasis id="BC8C6A253874FFCB063A9E835494FF6A" bold="true" box="[1338,1423,231,251]" italics="true" pageId="8" pageNumber="9">M. glabra</emphasis>
</taxonomicName>
, based on the presence of an
<emphasis id="BC8C6A253874FFCB07029F68553CFE86" bold="true" box="[1026,1063,259,278]" italics="true" pageId="8" pageNumber="9">m/z</emphasis>
388.2 ion.
</paragraph>
<paragraph id="8E47B6373874FFCB00519F7455D4FD44" blockId="8.[818,1488,148,725]" pageId="8" pageNumber="9">
The current taxonomic concept of
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<emphasis id="BC8C6A253874FFCB07A49F745419FEA2" bold="true" box="[1188,1282,287,306]" italics="true" pageId="8" pageNumber="9">Marsdenia</emphasis>
R.Br.
</taxonomicName>
is highly polyphyletic (
<bibRefCitation id="EA69CBC63874FFCB00909F505550FEDE" author="Rodda, M. &amp; Simonsson, N. &amp; Ercole, E. &amp; Khew, G. &amp; Niissalo, M. &amp; Rahayu, S. &amp; Livshultz, T." box="[912,1099,315,334]" pageId="8" pageNumber="9" pagination="119 - 138" refId="ref20328" refString="Rodda, M., Simonsson, N., Ercole, E., Khew, G., Niissalo, M., Rahayu, S., Livshultz, T., 2020. Phylogenetic studies in the Hoya group (Apocynaceae, Marsdenieae): the position of anatropanthus and oreosparte. Willdenowia 50, 119 - 138. https: // doi. org / 10.3372 / wi. 50.50112." type="journal article" year="2020">Rodda et al., 2020</bibRefCitation>
), and the segregation of monophyletic genera from
<emphasis id="BC8C6A253874FFCB00A79F3C557BFEFA" bold="true" box="[935,1120,343,362]" italics="true" pageId="8" pageNumber="9">
<taxonomicName id="49F8CDB43874FFCB00A79F3C551EFEFA" box="[935,1029,343,362]" class="Magnoliopsida" family="Apocynaceae" genus="Marsdenia" kingdom="Plantae" order="Gentianales" pageId="8" pageNumber="9" phylum="Tracheophyta" rank="genus" sensu="lato">Marsdenia</taxonomicName>
<taxonomicNameLabel id="A7BFD75E3874FFCB070A9F3C557BFEFA" box="[1034,1120,343,362]" pageId="8" pageNumber="9" sensu="lato">sensu lato</taxonomicNameLabel>
</emphasis>
is ongoing (
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<collectingRegion id="4C3C78D53874FFCB07D29F3C544FFEFA" box="[1234,1364,343,362]" country="Brazil" name="Espirito Santo" pageId="8" pageNumber="9">Espírito Santo</collectingRegion>
et al., 2019
</bibRefCitation>
).
<taxonomicName id="49F8CDB43874FFCB00329F1952FBFE16" box="[818,992,370,390]" class="Magnoliopsida" family="Apocynaceae" genus="Marsdenia" kingdom="Plantae" order="Gentianales" pageId="8" pageNumber="9" phylum="Tracheophyta" rank="species" species="tinctoria">
<emphasis id="BC8C6A253874FFCB00329F1952FBFE16" bold="true" box="[818,992,370,390]" italics="true" pageId="8" pageNumber="9">Marsdenia tinctoria</emphasis>
</taxonomicName>
(the
<typeStatus id="514308953874FFCB07139F185527FE16" box="[1043,1084,371,390]" pageId="8" pageNumber="9">type</typeStatus>
species) and
<taxonomicName id="49F8CDB43874FFCB07BC9F185408FE15" box="[1212,1299,370,390]" class="Magnoliopsida" family="Apocynaceae" genus="Marsdenia" kingdom="Plantae" order="Gentianales" pageId="8" pageNumber="9" phylum="Tracheophyta" rank="species" species="glabra">
<emphasis id="BC8C6A253874FFCB07BC9F185408FE15" bold="true" box="[1212,1299,370,390]" italics="true" pageId="8" pageNumber="9">M. glabra</emphasis>
</taxonomicName>
belong to the small group of species segregated as
<emphasis id="BC8C6A253874FFCB075F9FE5542FFE32" bold="true" box="[1119,1332,398,418]" italics="true" pageId="8" pageNumber="9">
<taxonomicName id="49F8CDB43874FFCB075F9FE555A6FE31" box="[1119,1213,398,417]" class="Magnoliopsida" family="Apocynaceae" genus="Marsdenia" kingdom="Plantae" order="Gentianales" pageId="8" pageNumber="9" phylum="Tracheophyta" rank="genus" sensu="stricto">Marsdenia</taxonomicName>
<taxonomicNameLabel id="A7BFD75E3874FFCB07C69FE4542FFE32" box="[1222,1332,399,418]" pageId="8" pageNumber="9" sensu="stricto">sensu stricto</taxonomicNameLabel>
</emphasis>
(
<bibRefCitation id="EA69CBC63874FFCB06449FE454D2FE32" author="Bullock, A. A." box="[1348,1481,399,418]" pageId="8" pageNumber="9" pagination="503 - 522" refId="ref16187" refString="Bullock, A. A., 1956. Notes on african asclepiadaceae: VIII. Kew Bull. 11, 503 - 522. https: // doi. org / 10.2307 / 4109137." type="journal article" year="1956">Bullock, 1956</bibRefCitation>
;
<bibRefCitation id="EA69CBC63874FFCB00329FC052AFFE2D" author="Forster, P. I." box="[818,948,426,446]" pageId="8" pageNumber="9" pagination="703 - 933" refId="ref17483" refString="Forster, P. I., 1995. Circumscription of Marsdenia (asclepiadaceae, Marsdenieae), with a revision of the genus in Australia and papuasia. Aust. Syst. Bot. 8, 703 - 933. https: // doi. org / 10.1071 / Sb 9950703." type="journal article" year="1995">Forster, 1995</bibRefCitation>
). The most frequently reported natural products from species of
<emphasis id="BC8C6A253874FFCB00999FAD5540FE49" bold="true" box="[921,1115,454,474]" italics="true" pageId="8" pageNumber="9">
<taxonomicName id="49F8CDB43874FFCB00999FAD52ECFE49" box="[921,1015,454,473]" class="Magnoliopsida" family="Apocynaceae" genus="Marsdenia" kingdom="Plantae" order="Gentianales" pageId="8" pageNumber="9" phylum="Tracheophyta" rank="genus" sensu="lato">Marsdenia</taxonomicName>
<taxonomicNameLabel id="A7BFD75E3874FFCB07009FAC5540FE49" box="[1024,1115,454,474]" pageId="8" pageNumber="9" sensu="lato">sensu lato</taxonomicNameLabel>
</emphasis>
and other genera of
<taxonomicName id="49F8CDB43874FFCB06319FAC54B3FE4A" box="[1329,1448,455,474]" class="Magnoliopsida" family="Apocynaceae" kingdom="Plantae" order="Gentianales" pageId="8" pageNumber="9" phylum="Tracheophyta" rank="tribe" tribe="Marsdenieae">Marsdenieae</taxonomicName>
are steroids, steroidal alkaloids, and steroidal glycosides including the antisweet gymnemic acids from the medicinal plant
<taxonomicName id="49F8CDB43874FFCB06249F9552F1FDBD" authority="(Retz.) R. Br. ex Sm." authorityName="Sm." baseAuthorityName="Retz." class="Magnoliopsida" family="Apocynaceae" genus="Gymnema" kingdom="Plantae" order="Gentianales" pageId="8" pageNumber="9" phylum="Tracheophyta" rank="species" species="sylvestre">
<emphasis id="BC8C6A253874FFCB06249F9554CBFD81" bold="true" box="[1316,1488,510,529]" italics="true" pageId="8" pageNumber="9">Gymnema sylvestre</emphasis>
(Retz.) R.Br. ex Sm.
</taxonomicName>
(
<bibRefCitation id="EA69CBC63874FFCB00F79C71559EFDBD" author="Liu, H. M. &amp; Kiuchi, F. &amp; Tsuda, Y." box="[1015,1157,538,558]" pageId="8" pageNumber="9" pagination="1366 - 1375" refId="ref19347" refString="Liu, H. M., Kiuchi, F., Tsuda, Y., 1992. Isolation and structure elucidation of gymnemic acids, antisweet principles of Gymnema sylvestre. Chem. Pharm. Bull. 40, 1366 - 1375." type="journal article" year="1992">Liu et al., 1992</bibRefCitation>
). Phenanthroindolizidine alkaloids are rare, reported only from
<taxonomicName id="49F8CDB43874FFCB073A9C5D545CFDD9" authority="(Roxb.) Craib" authorityName="Craib" baseAuthorityName="Roxb." box="[1082,1351,566,585]" class="Magnoliopsida" family="Apocynaceae" genus="Telosma" kingdom="Plantae" order="Gentianales" pageId="8" pageNumber="9" phylum="Tracheophyta" rank="species" species="pallida">
<emphasis id="BC8C6A253874FFCB073A9C5D55DEFDD9" bold="true" box="[1082,1221,566,585]" italics="true" pageId="8" pageNumber="9">Telosma pallida</emphasis>
(Roxb.) Craib
</taxonomicName>
(
<bibRefCitation id="EA69CBC63874FFCB06549C5D5535FDF5" author="Mulchandani, N. B. &amp; Venkatachalam, S. R." pageId="8" pageNumber="9" pagination="1561 - 1563" refId="ref19960" refString="Mulchandani, N. B., Venkatachalam, S. R., 1976. Alkaloids of Pergularia pallida. Phytochemistry 15, 1561 - 1563. https: // doi. org / 10.1016 / S 0031 - 9422 (00) 88937 - 2." type="journal article" year="1976">Mulchandani and Venkatachalam, 1976</bibRefCitation>
). All three common classes of compounds have been previously reported from
<taxonomicName id="49F8CDB43874FFCB079E9C055410FD11" box="[1182,1291,622,641]" class="Magnoliopsida" family="Apocynaceae" genus="Marsdenia" kingdom="Plantae" order="Gentianales" pageId="8" pageNumber="9" phylum="Tracheophyta" rank="species" species="tinctoria">
<emphasis id="BC8C6A253874FFCB079E9C055410FD11" bold="true" box="[1182,1291,622,641]" italics="true" pageId="8" pageNumber="9">M. tinctoria</emphasis>
</taxonomicName>
(
<bibRefCitation id="EA69CBC63874FFCB061E9C055279FD0D" author="Chowdhury, A. K. A. &amp; Hashim, M. F. &amp; Sen, B. C. &amp; Khan, F. &amp; Ahmed, M." pageId="8" pageNumber="9" pagination="2343 - 2346" refId="ref16423" refString="Chowdhury, A. K. A., Hashim, M. F., Sen, B. C., Khan, F., Ahmed, M., 1994. Antifertility principles from Marsdenia tinctoria - pharmacological and photochemical studies. Pure Appl. Chem. 66, 2343 - 2346. https: // doi. org / 10.1351 / pac 199466102343." type="journal article" year="1994">Chowdhury et al., 1994</bibRefCitation>
;
<bibRefCitation id="EA69CBC63874FFCB00709CE15516FD0D" author="Gao, Z. L. &amp; He, H. P. &amp; Di, Y. T. &amp; Fang, X. &amp; Li, C. S. &amp; Zhang, Q. &amp; Zhao, P. J. &amp; Li, S. L. &amp; Hao, X. J." box="[880,1037,650,669]" pageId="8" pageNumber="9" pagination="1775 - 1781" refId="ref17595" refString="Gao, Z. L., He, H. P., Di, Y. T., Fang, X., Li, C. S., Zhang, Q., Zhao, P. J., Li, S. L., Hao, X. J., 2009. Three new pregnane glycosides from Marsdenia tinctoria. Helv. Chim. Acta 92, 1775 - 1781. https: // doi. org / 10.1002 / hlca. 200900072." type="journal article" year="2009">Gao et al., 2009</bibRefCitation>
).
<taxonomicName id="49F8CDB43874FFCB07239CE255C8FD0D" box="[1059,1235,649,669]" class="Magnoliopsida" family="Apocynaceae" genus="Marsdenia" kingdom="Plantae" order="Gentianales" pageId="8" pageNumber="9" phylum="Tracheophyta" rank="species" species="tinctoria">
<emphasis id="BC8C6A253874FFCB07239CE255C8FD0D" bold="true" box="[1059,1235,649,669]" italics="true" pageId="8" pageNumber="9">Marsdenia tinctoria</emphasis>
</taxonomicName>
is also a source of indigo (
<bibRefCitation id="EA69CBC63874FFCB003A9CCD557AFD29" author="Mohd Nasuha, N. A. &amp; Choo, Y. M." box="[826,1121,678,697]" pageId="8" pageNumber="9" pagination="1532 - 1536" refId="ref19739" refString="Mohd Nasuha, N. A., Choo, Y. M., 2016. A new flavone from Malaysia Borneo Marsdenia tinctoria. Nat. Prod. Res. 30, 1532 - 1536. https: // doi. org / 10.1080 / 14786419.2015. 1118629." type="journal article" year="2016">Mohd Nasuha and Choo, 2016</bibRefCitation>
), although the chemical origin of the stain has not been identified in this species.
</paragraph>
</subSubSection>
</treatment>
</document>