On the probable composition of ‘Jamaican stone’ aphrodisiac

On he p obable composi ion o ‘Jamaican s one’ aph odisiac Pablo Ma ín-Ramos a, *, Paula Ca ión-P ie o b , Iosody Sil a-Cas o b , No lan M. Ruiz-Po osme c , Sal ado He nández-Na a o b , Jesús Ma ín-Gil b a EPSH, Uni e sidad de Za agoza, Ca e e a de Cua e s/n, 22071 Huesca, Spain b ETSIIAA, Uni e sidad de Valladolid, A enida de Mad id 44, 34004 Palencia, Spain c Uni e sidad Eu opea Miguel de Ce an es. C/Pad e Julio Che alie 2, 47012 Valladolid, Spain A R T I C L E I N F O A icle his o y: Recei ed 26 Sep embe 2016 Recei ed in e ised o m 1 No embe 2016 Accep ed 7 No embe 2016 A ailable online 14 No embe 2016 Keywo ds: Bu adienolides Ca ’s claw FTIR Gambi Jamaican s one Squill A B S T R A C T A dange ous aph odisiac, commonly known as ‘Jamaican s one’, banned by he U.S. Food and D ug Adminis a ion, has been s udied by ib a ional spec oscopy in o de o sol e he con o e sy on i s composi ion. The esul s o he ATR-FTIR analysis e ealed he p esence o he a -py one ing, which is cha ac e is ic o bu adienolides om oad enom and bulbs o squill (D imia ma i ima (L.) S ea n). This conclusion was eached a e a compa a i e s udy wi h he spec a o phy ochemicals de i ed om gambi and ca ’s claw, wo Unca ia species also p econized as aph odisiacs and deemed as possible cons i uen s o he ‘s one’. Owing o hei physiologic simila i ies o digoxin, bu adienolides ha e been shown o p oduce a oxic p ofile simila o ha o digoxin, al hough he lack one o he side chains ound on digoxin should allow he use o hemodialysis o ea ‘Jamaican s one’ o e dose. ã 2016 Phy ochemical Socie y o Eu ope. Published by Else ie L d. All igh s ese ed. 1. In oduc ion ‘Jamaican s one’ (also e e ed o as ‘Pied a china’, ‘lo e s one’, ‘black s one’ o ‘China ock’) is a ha d, da k b own d ug, sold as a solid chunk (pills o dice). In he US, in spi e o being banned by he Food and D ug Adminis a ion (FDA) and e en when i s impo a- ion and dis ibu ion a e p osecu ed, i can s ill be ound in some adul s o es and in neighbo hood s o es in some Hispanic dis ic s. I is usually packaged in a clea plas ic bag wi h some labeling and an in o ma ion leafle , wa ning ha i s use should be es ic ed o opical applica ions (Fig. 1). The ‘s one’ can cause se ious hea p oblems o e en dea h when inges ed. E en when applied on he skin, which is i s mos equen use, i can s ill be dange ous. Symp oms o poisoning include omi ing and ches and abdominal pain. Al hough i has been used o yea s, he e is s ill e y li le esea ch done on he composi ion o he ‘Jamaican s one’. The manu ac u e indica ions on i s o igin simply s a e ha i is made om he concen a ed sap o a ee which only g ows in Asia and Jamaica and gi e elusi e e e ences o i s anes he ics-like e ec s among he local people om whe e i is o igina ed. In 1967, a s udy by Das and G i fi hs (1967) claimed ha i s main cons i uen would be Unca ia gambi Roxb. ex ac (gambie o gambi ) and led o he iden ifica ion o e hyl ace a e as he chemical esponsible o i s bi e as e. O he plan species ha ha e been sugges ed as componen s o he ‘Jamaican S one’ a e he Ca ibbean ca 's claw (Unca ia omen osa (Willd. ex Schul .) DC), some species o seaweed (e.g., I ish moss seaweed, Chond us c ispus S ackh.) and squill (D imia ma i ima (L.) S ea n; syn. U ginea ma i ima (L.) Bake ). Gambi is an as ingen ba k om a sh ub g owing in Bo neo which has been adi ionally used o handle he pain om oo h aches and as a chew when combined wi h nu s ( o ood). Gambi is mainly composed o ca echu- anic acid (a annin), (+)-ca echin (see Fig. 2), (+)-epica echin, dime ic p oan hocyanidins, p ocya- nidins B1 and B3, and gambi iins A1, A2, B1, B2 and C (Taniguchi e al., 2007), much o hem 3 0 ,4 0 ,5,7- e ahyd oxysubs i u ed de i a i es o 3,4-dihyd o-2-phenyl-2H-1-benzopy an. Gambi , in a simila ashion o cocoa and chocola e, has been epo ed o exe an e ec on human sexuali y, ac ing as an e ec i e aph odisiac, inc easing sexual desi e and imp o ing sexual pleasu e (Salonia e al., 2006). Cocoa p oduc s, apa om phenyle hylamide (PEA), which has been epo ed s imula e he hypo halamus inducing pleasu e sensa ions (Maxwell, 1996), also include (+)-ca echin, (+)-epica echin and p ocyanidins (Todo o ic e al., 2015), which a e p esen in gambi oo. Thus, gambi ’s aph odisiac p ope ies may be e e ed o i s fla onoid * Co esponding au ho . E-mail add ess: pm @uniza .es (P. Ma ín-Ramos). h p://dx.doi.o g/10.1016/j.phy ol.2016.11.005 1874-3900/ã 2016 Phy ochemical Socie y o Eu ope. Published by Else ie L d. All igh s ese ed. Phy ochemis y Le e s 19 (2017) 30–33 Con en s lis s a ailable a ScienceDi ec Phy ochemis y Le e s jou nal homepa ge: www.else ie .com/loca e/phy ol composi ion. I is wo h no ing ha i has also enjoyed a spu o popula i y in a comme cialized o m (Gambi Sa awak) because i can be u ned in o a solu ion ha is abso bed by he skin o he penis and delays he o gasm eflex. Ca ’s claw is a plan whose ba k con ains quino ic acid glycosides, i e penes, s e ols and phenolic compounds and sha es oxindole alkaloids wi h o he Unca ia (Wahid e al., 2013) (Fig. 3). Ne e heless, a low doses, a om showing oxic e ec s, i has been epo ed o ha e an i-inflama o y and inmunos imulan p ope ies (Quin ela and Lock de Ugaz, 2003). The ac ha Bo neo and Malaysian ade s ecommend a p oduc (Gambi Sa awak o ambah powe ), which is di e en (and be e ) han he ‘Jamaican s one’ (Lim e al., 2016), led us o conside an al e na i e composi ion: bu adienolides, sugges ed by he U.S. Food and D ug Adminis a ion on he basis o he a hy hmia p oblems epo ed by ‘s one’ use s (Si e lin, 2015). Bu adienolides and hei glycosides, which a e compounds wi h s e oid s uc u e (Fig. 4), a e de i ed om oad enom and bulbs o squill, and a e ca dio onic s e oids ha cause symp oms simila o digoxin (CDC, 1995; Iizuka e al., 2001; Kamano e al., 1998; Meng e al., 2016). Specifically, hey can cause an a io en icula block, b adyca dia, en icula achyca dia, and possibly le hal ca diac a es (CDC, 1995). In he wo k p esen ed he ein, a apid and accu a e me hod o he as and simul aneous quali a i e and quan i a i e cha ac e i- za ion o na u al p oduc s and hei cons i uen s (Huck, 2015), namely A enua ed To al Reflec ance Fou ie -T ans o m In a ed (ATR-FTIR) spec oscopy, has been used o disc imina e among fla an and diphenol ings (in gambi ), oxindole alkaloids (in ca ’s claw) and a-py one ing ( ypical o bu adienolides) in o de o asce ain he ac ual composi ion o he ‘Jamaican s one’ (Fig. 5). Fig. 1. Pho og aphs o a comme cial sample o ‘Jamaican s one’. Fig. 2. Some cons i uen s o gambi . Fig. 3. Examples o oxindole alkaloid componen s o Unca ia omen osa (Wahid e al., 2013). Fig. 4. Examples o bu adienolides (Miyashi o e al., 2008). P. Ma ín-Ramos e al. / Phy ochemis y Le e s 19 (2017) 30–33 31 2. Ma e ials and me hods A dice o Jamaican s one was supplied, o esea ch pu poses, du ing a esea ch s ay a Columbia Uni e si y. The sample was pu chased a a neighbo hood ma ke a Eas Ha lem (New Yo k, NY, USA). The ib a ional spec a o he ma e ial in he 400–4000 cm 1 spec al ange was measu ed using a The mo Scien ific (Wal ham, MA, USA) Nicole iS50 FT-IR Spec ome e , equipped wi h an in- buil diamond a enua ed o al eflec ion (ATR) sys em. 3. Resul s and discussion The p esence o fla an-3-ol and ca echol ings in he s udied sample would be associa ed o h ee cha ac e is ic abso p ion bands: a oma ic CH g oup (nCH g oup, in-plane dCH and ou -o -plane dCH); a oma ic C¼C g oup (nC¼C g oup a 1469 and 1619 cm 1 ); and COH phenolic g oup (nOH, in-plane dOH a 1360 cm 1 and a oma ic nCO a 1279 and 1238 cm 1 ) (Cha le , 2012). A s ong NH abso p ion peak would appea a 3368 cm 1 i oxindole alkaloids occu ed ins ead (Wahid e al., 2013). Al e na i ely, i py one s uc u es ( om bu o oxin and bu alin bu odienolides) we e ound in he ‘Jamaican s one’, he enol e he a omic g ouping (OC¼C) would abso b because o he CH g oup, he olefinic C¼C bond, and he e he COC bond (Ba oso- Bogea e al., 2014). Mo eo e , i in pa icula bu o enine (a hallucinogenic congene o se o onin) in e ened in he composi- ion, he abso p ion bands o he indole ing would be obse ed. The ATR-FTIR spec um o he sample unde conside a ion (Fig. 6) showed fi e bands ha could be a ibu ed o ca echol: he one ha appea ed a 1156 cm 1 (p o ided ha 5,7-dihyd oxysub- s i u ed fla onoids abso b a 1165 cm 1 ) and ou mo e (a 1521, 1507, 1419 and 1086 cm 1 ), all o low in ensi y. Ne e heless, he sp 2 CO s e ching band a a ound 1280 cm 1 , ypical o phenols; he CO s e ching band in phenolic compounds a 1620 cm 1 ; and he ¼COC g oups s e ching band a 1265 cm 1 we e missing. Likewise, he s ong NH abso p ion peak, which would appea a 3368 cm 1 i oxindole alkaloids occu ed, was no p esen ei he . O he is he case o he a-py one (Py) ing, associa ed wi h a leas hal o he bands o highe abso bance in he spec um, including hose associa ed o e he a omic g ouping OC¼C (see Table 1). On he basis o he ib a ional cha ac e iza ion, a composi ion ich in bu o oxin and bu alin bu odienolides appea s o be he mos p obable. Howe e , bu o enine ( om bu o oad skin and glands), an ac i e ing edien in Wes Indian lo e s one and in chan su Chinese medica ion, has no be iden ified: he expec ed abso p ion a 1064 cm 1 om he indole ib a ions (nNC, dCH, nCC) does no appea s in he spec um. Bu adienolides a e usual componen s o aph odisiacs, bo h in adi ional Chinese medica ions (B essman e al., 2016) and in Ca ibbean coun ies. Owing o hei physiologic simila i ies o digoxin, bu adienolides ha e been shown o p oduce a oxic p ofile simila o ha o digoxin, leading o mul iple case epo s o he use o hese aph odisiacs esul ing in dea h. Howe e , whe eas digoxin is no dialyzable due o i s size, bu adienolides lack one o he side chains ound on digoxin, po en ially allowing hem o be dialyzed Fig. 5. fla an-3-ol, ca echol, oxindole and alpha-py one. Table 1 Assignmen s o he ATR-FTIR bands o he ‘Jamaican s one’ aph odisiac. Wa enumbe (cm 1 ) Assignmen 3428 n OH phenolic g oup alipha ic and a oma ic CH, phenolic and alcoholic OH s e ching 2921 n CH and CH 2 /OH in ol ed in H bonding 2851 n CH and CH 2 1734 n C ¼ O Py 1700 n C ¼ O 1684 n C ¼ O Py 1652 n C ¼ C Py 1576 1558 n C ¼ C (1566 cm 1 in Py) 1539 n C ¼ C skele al, a oma ic ing 1521 n C ¼ C 1507 n C ¼ C 1456 n CC (CH 2 g oups) 1436 d CH in he CH 2 C ¼ C a omic g ouping 1419 n CC 1156 d CHPh 1086 n CC/ d (CH), n (NC) in indole/ n CO-C in cyclic e he s (Py) 1023 n CO-C Py/CO in cyclic e he s 929 g CH Py 851 g CH 759 g CHPh 668 g Py 577 g OH 525 d Ph 448 g Ph y : s e ching; d : in-plane de o ma ion; g : ou -o -plane de o ma ion; Py = py one ing; Ph = phenyl ing. 32 P. Ma ín-Ramos e al. / Phy ochemis y Le e s 19 (2017) 30–33 (B essman e al., 2016). Consequen ly, he use o hemodialysis could be a iable ea men o ‘Jamaican s one’ o e dose. 4. Conclusions The ATR-FTIR cha ac e iza ion o he ‘Jamaican s one’ aph odi- siac e ealed he p esence o di e en unc ional g oups belonging o bu o oxin and bu alin (bu no o bu o enine) bu odienolides. A compa a i e s udy o he spec um wi h hose o he phy ochemi- cal componen s o gambi and ca ’s claw, wo Unca ia species also p econized as aph odisiacs and sugges ed in he li e a u e as p obable ing edien s o he ‘s one’, showed ha hey we e no amongs he cons i uen s o he sample unde s udy. Since bu adienolides can be dialyzed, he use o hemodialysis is en a i ely p oposed as a iable ea men o ‘Jamaican s one’ poisoning. Re e ences Ba oso-Bogea , A., Alexand e-F anco, M., Fe nández-González, C., Gómez-Se ano, V., 2014. FT-IR analysis o py one and ch omene s uc u es in ac i a ed ca bon. Ene gy Fuels 28, 4096–4103. B essman, M., Repplinge , D., Sla e , W., Pa , M., 2016. Elec ophysiologic simila i ies o o e dose be ween digoxin and bu adienolides ound in a Chinese aph odisiac. J. 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Cons i uen s om he s ems o malaysian Unca ia omen osa. Open Con . P oc. J. 4, 88–92. 4000 3000 2000 1500 1000 500 Abso bance (a.u.) Wa enu mbe (cm -1 ) Fig. 6. ATR-FTIR spec um o a sample o ‘Jamaican s one’ aph odisiac. P. Ma ín-Ramos e al. / Phy ochemis y Le e s 19 (2017) 30–33 33