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.
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