SUPPORTING INFORMATION

Nuclear Magnetic Resonance Spectroscopic Characterization of Legume Exudates

Joseph B. Lambert, *,† Eric A. Heckenback, † Anna E. Hurtley, † Yuyang Wu, † and Jorge

A. Santiago-Blay ‡

Department of Chemistry, Northwestern University, Department of Chemistry, Evanston,

Illinois 60208-3113, and Department of Paleobiology, National Museum of Natural

History, Smithsonian Institution, P. O. Box 37012, Washington, DC 20013-7012, and

Department of Biology, Gallaudet University, 800 Florida Avenue NE, Washington, DC

20002

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Table S1 . Samples of Species a

Subfamily Genus, species, Common Source(s) Carbon- Class subspecies, name(s) 13 (nuclides) varieties, and sample taxonomic number authority Caesalpinoideae Bauhinia carronii northern Oahu, HI, J. A. 487 gum-C F. Muell. beantree, Santiago-Blay Queensland ebony Caesalpinoideae Bauhinia racemosa orchid , (1) Field Museum, (1) 494 (1)kino-C,H Lam. mountain (2) Field Museum (2) 572 (2)kino-C,H ebony Caesalpinoideae Caesalpinia ferrea Brazilian National Tropical 474 gum-C C. Mart. ironwood, Botanical Garden Brazilian Headquarters, leopard tree Kauai, HI, J. A. Santiago-Blay Caesalpinoideae Caesalpinia uhiuhi Captain Cook Amy 576 gum-C, H kavaiensis b H. Greenwall Mann Botanical Gardens, Hawaii, HI, J. A. Santiago-Blay Caesalpinoideae Cercis racemosa chain- U. S. National 508 gum-C Oliv. flowered Arboretum, redbud Washington, DC, J. A. Santiago-Blay Caesalpinoideae Conzattia parotilla , McBryde c kino-H multiflora (B. L. joso , tolole Botanical Garden, Robinson) Standl. Kauai, HI, 830598 002 Caesalpinoideae Copaifera Congo or Field Museum 543 resin-C,H demeusei Harms West African 274249 copal Caesalpinoideae Copaifera Lac Leopold New York 642 resin-C,H mildbraedii Harms Botanical Garden 00079699 JHL 5570 Caesalpinoideae Cryptosepalum mukwe (1) and (2) New (1) 649 (1) resin-C,H pseudotaxus d York Botanical (2) 650 (2) resin-C,H Baker f. or De Garden 00077344 Wild JHL 5709 Caesalpinoideae Daniellia divulungu New York 637 resin-C,H alsteeniana P. A. Botanical Garden Duvign e 01027319 JHL

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5503 Caesalpinoideae Daniellia oliveri African New York 640 other-C,H f (Rolfe) Hutch. & copaiba Botanical Garden Dalziel balsam tree 01027318 JHL 5504 Caesalpinoideae Daniellia ogea faro, Accra New York 644 resin-C,H (Harms) Rolfe ex copal, or gum Botanical Garden Holland g copal tree 01027375 JHL 5512 Caesalpinoideae Delonix regia royal Guaynabo, Puerto 579 gum-C (Bojer ex Hook.) h poinciana, Rico, J. A. flamboyant, Santiago-Blay flame tree Caesalpinoideae sp. etimoe New York 641 gum-C Botanical Garden 00077310 Caesalpinoideae Erythrophleum sassword McBryde 465 gum-C suaveolens (Guill. Botanical Garden, & Perr.) Brennan Kauai, HI, 830189 002, J. A. Santiago-Blay Caesalpinoideae Guibourtia i Sierra Leone (1) Field Museum (1) 495 (1) resin-C,H copallifera Benn. or West 97616, (2) Field (2 )534 (2) resin-C,H African copal Museum 274239, (3) 646 (3) resin-C,H (3) New York Botanical Garden 00077284 JHL 6647 Caesalpinoideae Guibourtia Congo copal, (1) Field Museum (1) 493 (1) resin-C,H demeusei (Harms) East African F21108873, (2) (2) 575 (2) resin-C J. Léonard copal, Department of African Botany, Rutgers rosewood University Caesalpinoideae Guibourtia ehie hyedua, (1) and (2) New (1) 638 (1) resin-C,H (A. Chev.) J. shedua York Botanical (2) 639 (2) resin-C,H Léonard Garden 01027379 JHL 5514 Caesalpinoideae Hymenaea aurea jatobá New York 652 resin-C,H Y. T. Lee & Botanical Garden Langenh. 01027326 Lee 191 Caesalpinoideae Hymenaea jatobá , (1) G. O. Poinar, (1) 63 (1) resin-C courbaril L. stinking toe, Jr., (2) National (2) 473 (2) resin-C,H guapinol Tropical Botanical Garden Headquarters, Kauai, HI, 820229

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002, J. A. Santiago-Blay Caesalpinoideae Hymenaea jatobá New York 656 resin-C,H courbaril var. Botanical Garden altisima (Ducke) 00079615 JHL Lee & Langenh. 5667 Caesalpinoideae Hymenaea jatobá New York 657 resin-C,H courbaril var. Botanical Garden longifolia (Benth.) 00077289 Lee 95 Lee Andrade- Lima. Caesalpinoideae Hymenaea no common New York 647 resin-C,H intermedia Ducke name found Botanical Garden 00079623 JHL 5390 Caesalpinoideae Hymenaea jatobá New York 648 resin-C,H martiana Hayne Botanical Garden 00079628 JHL 5660 Caesalpinoideae Hymenaea azúcar huayo New York 653 resin-C,H oblongifolia var. Botanical Garden latifolia Y. T. Lee 00079612 JHL & Langenh. 5648 Caesalpinoideae Hymenaea no common New York 655 resin-C,H reticulata Ducke name found Botanical Garden 00079616 JHL 5616 Caesalpinoideae Hymenaea jatobá New York 651 resin-C,H rubriflora Ducke Botanical Garden 00077315 JHL 5660 Caesalpinoideae Hymenaea jatobá New York 645 resin-C,H stignocarpa Botanical Garden var. pubescens 00079696 JHL Benth. 5564 Caesalpinoideae Hymenaea velutina no common New York 654 resin-C,H Ducke name found Botanical Garden 00079609 JHL 5642 Caesalpinoideae Hymenaea j Zanzibar or (1) Field Museum (1) 569 (1) resin-C,H verrucosa Gaertn East African F274248, (2) New (2) 635 (2) resin-C,H copal York Botanical Garden 00077345 JHL 5481 Caesalpinoideae Hymenaea sp. copal Field Museum 541 resin-C,H (Tanzania) k 1971608

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Caesalpinoideae Hymenaea sp. Borneo copal Field Museum 570 resin-C,H (Borneo) k 1971568 Caesalpinoideae Macrolobium arapari Field Museum 505 resin-C,H acaciifolium F2108880 (Benth.) Benth. Caesalpinoideae Parkinsonia l palo brea , (1) Field Museum (1) 507 (1) gum-C praecox (Ruiz & Sonoran palo 275060, (2) Field (2) 532 (2) resin-C,H Pav. ex Hook.) J. verde Museum 13365 Hawkins Caesalpinoideae Prioria copaifera cativo Field Museum 501 resin-C,H Griesb. 1971588 Caesalpinoideae Tamarindus indica tamarind Allerton Botanical 468 other-Ca L. Garden, Kauai, HI, J. A. Santiago-Blay biserrata m no common Field Museum 513 gum-C,H name found 271017 Mimosoideae Acacia dealbata silver wattle Field Museum 564 gum-C,H Link 271012 Mimosoideae Acacia decurrens wattle bark, Field Museum 538 gum-C,H Willd. acacia bark, 271009 green wattle Mimosoideae Acacia koa A. koa tree Liliuokalani 498 gum-C Gray Botanical Garden, Oahu, HI, J. A. Santiago-Blay Mimosoideae Acacia koaia koaia tree Limahuli Botanical 462 gum-C Hillebr. Garden, Kauai, HI, J. A. Santiago-Blay and K. Winter Mimosoideae Acacia manna, gum Field Museum 565 gum-C,H microbotrya Benth. wattle 271013 Mimosoideae Acacia penninervis hickory Field Museum 533 gum-C,H Sieber ex DC wattle, 271014 mountain hickory Mimosoideae Acacia vestita Ker hairy wattle, Field Museum 529 gum-C,H Gawl. weeping bore 271016 Mimosoideae Senegalia or black coutch, Field Museum 489 kino-C,H Acacia n catechu cachou 271354 (L. f.) Willd. or (L. f.) P. J. H Hurter & Mabb. Mimosoideae Senegalia or binna Field Museum 536 gum-C,H Acacian ferruginea 273717 DC or (DC) Pedley Mimosoideae Senegalia or cat-clawed San Bernardino c gum-H

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Acacia n greggi A. acacia Co., Mojave Gray Britton & Desert, J. A. Rose or (Wall.) P. Santiago-Blay J. H. Mimosoideae Senegalia or phylaie Field Museum 566 gum-C,H Acacia n modesta 273721 Wall. or (Wall.) P. J. H. Mimosoideae Senegalia or gum acacia, (1) and (2) DOV (1) 488 (1) gum-C,H Acacia n senegal gum arabic Collection of Dried (2) 567 (2) gum-C,H (L.) Willd. or (L.) Botanicals & Britton Wood Mimosoideae Vachellia or whitehorn Las Vegas Springs 454 gum-C Acacian constricta acacia Preserve, NV, J. A. Benth. or (Benth.) Santiago-Blay Seigler & Ebinger Mimosoideae Vachellia or needle bush, (1) Field Museum (1) 537 (1) gum-C,H Acacia n farnesiana sweet acacia, 27340, (2) Koko (2) 577 (2) kino-C,H (L.) Willd. or (L.) husache Crater, Oahu, HI, Wight & Arn. J. A. Santiago-Blay Mimosoideae Vachellia or white bark Field Museum 539 other-Ca Acacia n acacia 273723 leucophloea Roxb. Willd. Mimosoideae Vachellia or gum acacia, (1) Field Museum (1) 512 (1) gum-C,H Acacia n thorn wattle 271353, (2) Deep (2) 574 (2) gum-C,H nilotica o (L.) Foods, Union, NJ Willd. ex Delile Mimosoideae Vachellia or red acacia, Field Museum 535 gum-C,H Acacia n shittim tree 269607 sternocarpa Hochst. ex A. Rich Mimosoideae Vachellia or twisted Miami Fairchild 298 gum-C,H Acacia n tortuosa acacia, Tropical Garden, J. (L.) Seigler & poponax A. Santiago-Blay Ebinger Mimosoideae “Acacia ” sp. p wattle Koko Crater, HI, J. 483 other-C,H f A. Santiago-Blay Mimosoideae “Acacia ” sp. p Talha gum Field Museum 573 gum-C F2108830 Mimosoideae Albizia amara bitter amara Field Museum 499 gum-C (Roxb.) B. Boivin 273743 Mimosoideae Albizia julibrissin Persian silk Las Vegas Springs 492 gum-C,H Durazz. tree, pink Preserve, NV, J. A. siris Santiago-Blay Mimosoideae Albizia lebbek siris, kokko Field Museum 490 gum-C

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Benth. 273736 Mimosoideae Albizia tea shade Field Museum 540 gum-C odoratissima (L. f.) tree, black 273742 Benth. siris Mimosoideae Anadenanthera q Patagonian Field Museum 506 gum-C colubrina (Vell.) rosewood, 11220 Brenan var. cebil curupay , (Griseb.) Altschul vilca , angico Mimosoideae Enterolobium Elephant ear (1) Field Museum (1) 571 (1) gum-C cyclocarpum tree 1971579, (2) New (2) 643 (2) gum-C (Jacq.) Griseb. York Botanical Garden 01027331 JHL 4798 Mimosoideae Inga preussii no common Oahu, HI 81P469F, 491 gum-C Harms name found J. A. Santiago-Blay Mimosoideae Leucaena white leadtree Koko Crater, 329 gum-C leucocephala Oahu, HI, J. A. (Lam.) de Wit Santiago-Blay Mimosoideae Parapiptadenia r angico Field Museum 503 gum-C rigida (Benth.) 1971551 Brenan Mimosoideae Prosopis alba Argentine Ethel M. 455 kino-H Griseb mesquite Henderson Chocolates Cactus Garden, NV, J. A. Santiago-Blay and J. DiMalanta Mimosoideae Prosopis chilensis South (1), (2) Las Vegas (1) 445 (1) gum-C (Molina) Stuntz American or Spring Garden, (2) 446 (2) gum-C Chilean NV, J. A. (3) 451 (3) kino-C,H mesquite Santiago-Blay, (3) Ethel M. Henderson Chocolates Cactus Garden, NV, J. A. Santiago-Blay and J. DiMalanta Mimosoideae Prosopis honey (1) and (3) Vielco, (1) 267 (1) gum-C glandulosa Torr. mesquite Coahuila, Mexico, (2) 443 (2) kino-C,H (2) Mojave (3) 444 (3) gum-C,H National Preserve, (4) 542 (4) gum-C,H Desert Studies Center, CA, J. A. Santiago-Blay, (4) Field Museum F210881

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Mimosoideae Prosopis juliflora bayahonda (1) Miami (1) 289 (1) kino-C,H (Sw.) DC blanca Fairchild Tropical (2) 580 (2) kino-C,H Garden, J. A. Santiago-Blay, (2) Miami Fairchild Tropical Garden, Miami, FL, J. A. Santiago-Blay Mimosoideae Prosopis velutina velvet Las Vegas Spring 442 kino-C,H Wooton mesquite Preserve, J. A. Santiago-Blay Mimosoideae Prosopis sp. Ethel M. 447 gum-C Henderson Chocolates Cactus Garden, NV, J. A. Santiago-Blay and J. DiMalanta Mimosoideae Samanea s saman monkey pod McBryde 496 gum-C (Jacq.) Merr. or rain tree Botanical Garden, Kauai, HI, J. A. Santiago-Blay Alhagi mannifera camelthorn, National Museum 695 gum-C (Papilionoideae) Jaub. & Spach alhagi manna of American History 141,868 Faboideae Astralagus tragacanth Field Museum 509 gum-C,H gummifer Labill. t 271841 Faboideae Astragalus tragacanth Field Museum 563 gum-C,H leioclados u Boiss. 271840 Faboideae Astragalus verus tragacanth, Field Museum 500 gum-C,H Olivier gum dragon 271378 Faboideae Astragalus virens no common Field Museum 530 gum-C Pavlov name found 273707 Faboideae Astragalus sp. tragacanth DOV Collection of 568 gum-C Dried Botanicals & resin-H Wood Faboideae Butea flame of the (1) Field Museum (1) 504 (1) gum monosperma v K. forest, dhak 274162 (India), (2) (2) 691 resin-C D. Koenig ex Field Museum resin-Hw Roxb. 1971548 (Siam) (2) gum resin-C Faboideae Centrolobium arariba (1) and (2) Oahu, (1) 331 (1) kino-C,H tomentosum HI, 76S188, J. A. (2) 439 (2) kino-C,H Guillemin ex Santiago-Blay Benth. Faboideae Enterolobium elephant ear (1) Field Museum (1) 571 (1) gum-C cyclocarpum (Jacq.) tree 1971579, (2) New (2) 643 (2) gum-C

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Griseb. York Botanical Garden 01027331 JHL 4798 Faboideae Myroxylon balsam New York 636 kino-C,H balsamum (L.) Botanical Garden Harms 00079624 JHL 6574 Faboideae Psorothamnus x smokethorn, Mojave National 528 gum resin-C spinosus (A. Gray) smoke tree Preserve, Desert resin-Hw Barneby Studies Center, CA, J. A. Santiago- Blay Faboideae Pterocarpus barwood Field Museum 502 kino-C,H erinaceus Poir. F2108883 Faboideae Pterocarpus Indian kino, Field Museum 531 resin-C,H marsupium Roxb. Malabar kino 273722 Faboideae Pterocarpus sp. mascarene McBryde 470 gum-C Botanical Garden, Kauai, HI, 760249 002, J. A. Santiago-Blay Faboideae Rhynchosia sp. pea vine Los Angeles 581 kino-C County Arboretum, CA, J. A. Santiago- Blay Faboideae Robinia black locust (1) and (2) (1) 423 (1) gum-C,H pseudoacacia L. Gallaudet (2) 467 (2) gum-C University, DC Faboideae Styphnolobium y Japanese (1) J. A. Santiago- (1) 323 (1) gum-C japonicum (L.) pogoda tree, Blay and S. (2) 356 (2) gum-C Schott Chinese Shaffer, (2) scholar tree National Zoo, Washington, DC, J. A. Santiago-Blay Faboideae Tipuana tipu Rosewood, McBryde c kino-H (Benth.) Kuntze pride of Botanical Garden, Bolivia, tipu , Kauai, HI, J. A. yellow Santiago-Blay jacaranda aNomenclature has been updated following Tropicos (http://www.tropicos.org), IPNI

(International Names Index, http://www.ipni.org), ILDIS (International Legume

Database & Information Service, http://www.ildis.org), and GRIN (Germplasm

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Resources Information Network, http://www.ars-grin.gov). Discrepancies between sources that we considered important are noted in the footnotes. bCaesalpinia kauaiensis is an inappropriate spelling variant.

cInsufficient material for the 13 C spectrum, so there is no 13 C sample number.

dThis taxon is considered a species, Cryptosepalum pseudotaxus Baker f., or a subspecies,

Cryptosepalum exfoliatum subsp. pseudotaxus (Baker f.) P.A. Duvign. & Brenannot. eTropicos renders the authorship of this taxon as J. Duvign. fExudates labeled “other” do not have the spectral characteristics of any of the know categories (resin, gum, gum resin, kino). gThe authorship of this species is rendered as Rolfe in IPNI but as (Harms) Holland in

ILDIS. hThe authorship of this species is rendered as (Bojer ex Hook.) in IPNI and Tropicos but as (Hook.) Raf . in ILDIS and GRIN. iCopaifera guibourtiana Benth. is considered a synonym. jSample 569 was labeled Trachylobium hornemannianum . Trachylobium is a synonym for Hymenaea (ref. 2, p. 80), and for this species T. hornemannianum or T. verracosum is common. kThese samples were labeled Trachylobium sp. Trachylobium is a synonym for

Hymenaea (ref. 2, p. 80). lSample (2) was listed as Cercidium viride (H. Karst.) H. Karst., which is considered a synonym for Parkinsonia praecox . mWe have not found this name in any of the nomenclatural sources consulted.

9 S10 nSubdivision of the original genus Acacia into five genera has resulted in new authorship combinations (ref. 13). We have given the authorship for the original genus Acacia , followed by the authorship for the more recent generic classifications. oVachelia nilotica was previously Acacia nilotica . This sample was labeled A. arabica , an apparent synonym for A. nilotica . pThese samples certainly belong to the original genus Acacia , but we cannot assign them to a specific one of the five new genera derived from the original genus (ref. 13). q This sample was labeled Piptadenia macrocarpa Benth., which is considered by GRIN and ILDIS to be a synonym for A. colubrina . rThis sample was labeled Acacia angico Mart., which is considered by GRIN and ILDIS to be a synonym for P. rigida . sWe follow Lewis et al. (ref. 2, pp. 210-211) in assigning saman to the genus Samanea instead of Albizia . tILDIS accepts Astragalus gummifera (Labill.) Podlech as the valid name. uThis sample was labeled Astragalus leiocladus , which is an inappropriate spelling variant. vThis sample was labeled Butea frondosa Roxb. ex Willd, which is considered by GRIN to be a synonym for B. monosperma . wThe gum portion of this exudate probably is insoluble, so that the 1H spectrum misleadingly indicates a resin for this gum resin.

10 S11 xPsorothamnus spinosus will be returned to Psorodendron along with all original members of Psorodendon , but species-level problems remain to be resolved (M. M.

McMahon, personal communication). yThis sample was labeled Sophora japonicum . We follow Lewis et al. (ref. 2, pp. 233,

243) in assigning japonicum to the genus Styphnolobium instead of Sophora .

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Figure S1 . The 100 MHz solid state 13 C spectra of Parkinsonia praecox (sample 2, Field

Museum 13365), (bottom) with normal decoupling and (top) with dipolar dephasing.

Figure S2 . The 100 MHz solid state 13 C spectra of Cryptosepalum pseudotaxus ,

(bottom) with normal decoupling and (top) with dipolar dephasing.

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Figure S3 . The 100 MHz solid state 13 C spectra of Daniellia oliveri , (bottom) with normal decoupling and (top) with dipolar dephasing.

Figure S4. The 100 MHz solid state 13 C spectra of Prioria copaifera , (bottom) with normal decoupling and (top) with dipolar dephasing.

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Figure S5. The 100 MHz solid state 13 C spectra of Tamarindus indica , (bottom) with normal decoupling and (top) with dipolar dephasing.

Figure S6. The 100 MHz solid state 13 C spectra of Acacia biserrata , (bottom) with normal decoupling and (top) with dipolar dephasing.

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Figure S7. The 100 MHz solid state 13 C spectra of Acacia sp. (Koko Crater), (bottom) with normal decoupling and (top) with dipolar dephasing.

Figure S8. The 100 MHz solid state 13 C spectra of Pterocarpus marsupium , (bottom) with normal decoupling and (top) with dipolar dephasing.

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Figure S9. The 100 MHz solid state 13 C spectra of Butea monosperma , (bottom) with normal decoupling and (top) with dipolar dephasing.

Figure S10 . The 100 MHz solid state 13 C spectra of , (bottom) with normal decoupling and (top) with dipolar dephasing.

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