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J. Braz. Chem. Soc., Vol. 21, No. 10, 2000-2004, 2010. Printed in Brazil - ©2010 Sociedade Brasileira de Química 0103 - 5 05 3 $ 6 .00+ 0.00

* e-mail: lh meller@ uf p a.b r

Fatty Acid Proiles and Tocopherol Contents of Buriti (Mauritia lexuosa), Patawa

(Oenocarpus bataua), Tucuma (Astrocaryum vulgare), Mari (Poraqueiba paraensis)

and Inaj a (Maximiliana maripa) Fruits

Antonio M. da Cruz R odrigues,a S ylvain D arnetb and L uiza H . Meller da S ilva*,a

aInstituto de Tecnologia and bInstituto de Ciências Biológicas, Universidade Federal do P ará,

6 6 .0 7 5 - 9 0 0 Belém- P A , Brazil

O b uriti, tucumã, inaj á, mari e p atauá são p almeiras endêmicas da reg ião A mazônica. A s p olp as destes f rutos são tradicionalmente consumidas p ela p op ulação local, mas ainda não g anh aram os mercados nacionais e internacionais. A comp osição nutricional em ácidos g rax os f oi determinada p or cromatog raia g asosa ( C G ) e a de tocof erol determinada p or cromatog raia liq uida de alta eiciência ( C L A E ) . A s p olp as se mostraram b astante energ éticas, com um alto teor de óleo q ue v ariou entre 31,0 a 41,8 % . O s ácidos g rax os q ue ap resentaram maiores concentrações f oram o

oleico ( C 18 : 1) e o p almítico ( C 16 : 0) , p ara todas as p olp as estudadas. A p olp a de b uriti f oi a q ue ap resentou maior teor de v itamina E sendo considerada uma ótima f onte de tocof erol. O α-tocof erol

f oi o tocof erol p redominante, com ex ceção da p olp a de b uriti. O s dados indicaram q ue as f rutas estudadas são b oas f ontes de ácidos g rax os insaturados e tocof eróis.

A mazonian f ruits are rich in f at b ut h av e a f atty acid p roile th at may b e b eneicial in relation to risk of coronary h eart disease. A mazonian f ruits also contain oth er p otentially cardiop rotectiv e constituents including tocop h erols. T ocop h erol p roiles w ere determined b y h ig h p erf ormance

liq uid ch romatog rap h y ( H PL C ) , and f atty acid p roiles w ere determined b y g as ch romatog rap h y ( G C ) . I n th e p resent study , th e total oil content, f atty acid comp osition and tocop h erol content of

th e p ulp s of iv e A mazonian f ruits ( b uriti, p ataw a, tucuma, mari and inaj a) w ere measured. T h e total oil content of th e f ruits rang ed f rom 31.0 to 41.8 % . T h e maj or f atty acid in all of th e f ruits w as oleic acid ( C 18 : 1) , th oug h sub stantial lev els of p almitic acid ( C 16 : 0) w ere p resent. L inoleic acid ( C 18 : 2) w as th e main p oly unsatured f atty acid ob serv ed. α-T ocop h erol w as th e most p rev alent

tocop h erol ex cep t in b uriti p ulp . Buriti and mari p ulp h av e a h ig h content in α-tocop h erols w ith 29 7 and 15 5 µg g-1 of dry matter. O ur data indicate th at all iv e of th ese A mazonian f ruits are g ood

sources of unsaturated f atty acids and tocop h erols.

K eywords: A mazonian f ruits, f atty acids, v itamin E , A recaceae, I cacinaceae

Introduction

T h e A mazonian reg ion h ouses a larg e v ariety of

f ruit crop s, some of w h ich h av e p otentially p romising

h ealth and nutritional p rop erties. I n p articular, buriti

(M auritia lex uosa) , p ataw a (O enocarp us bataua) , tucuma

(A strocary um vulgare) and inaj a (M ax imiliana marip a)

h av e sig nif icant nutritional v alue and are ap p reciated

b y th e p op ulation of th is reg ion.1 T h ese f ruits b elong to

th e f amily A recaceae, and are distrib uted th roug h out th e

A mazon and north ern South A merica. T h e mesocarp is

comestib le and nutritious, containing h ig h q uality oil.2

M ari (P oraq ueiba p araensis) , b elong s to th e f amily

Icacinaceae, and is a nativ e sp ecies, ex clusiv e to Pará State,

common th roug h out th e estuary of th e low A mazon. T h e mesocarp and ep icarp sh ell are edib le, and are also used

to p roduce oil and w ine.3

A mazonian f ruits are rich in f at, b ut more th an 6 1% of th ese f ats are unsaturated and could b e considered h ealth y f ats w ith cardiop rotectiv e p otential. A mazonian f ruits also h av e h ig h lev els of tocop h erols, w h ich are p resent in th e

unsap oniiab le lip id f raction of f oods.4 T ocop h erols are

sy nth esized in p h otosy nth etic microorg anisms and p lants

and are most concentrated in p lant seeds.5

Vitamin E is an imp ortant natural antiox idant in f oods,

esp ecially th ose rich in p oly unsaturated f atty acids. D ue to its

role as a scav eng er of f ree radicals, v itamin E is also b eliev ed

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R odrig ues et al. 2001 Vol. 21, No. 10, 2010

p articularly cancer and cardiov ascular diseases.5 Natural

v itamin E is comp osed of eig h t ch emical comp ounds: α-, β-,

γ- and δ-tocop h erols and th eir corresp onding tocotrienols.6

α-T ocop h erol is th e most activ e f orm of v itamin E . Th e δ and

γ f orms of th e v itamin are ab sorb ed ef iciently b y the h uman

b ody , b ut af ter 24 h th e α f orm is p ref erentially enrich ed in

th e p lasma.5α-T ocop h erol h as th e h ig h est b iolog ical activ ity

b ased on f etal resorp tion assay s and is less susceptib le to

deg radation th an th e oth er f orms.7

M onounsaturated f atty acids ( M U F A s) are th e

p redominant f atty acids in f ruits and contrib ute, on av erag e,

ap p rox imately 6 2% of th e total f at. I t is w idely recog nized

th at dietary f at ty p e inluences p lasma ch olesterol lev els to a

g reater ex tent th an does total f at intak e. T h eref ore, rep lacing

saturated f at w ith unsaturated f at may b e more ef f ectiv e in low ering th e risk of coronary h eart disease ( C H D ) th an

reducing f at intak e p er se.4

Sev eral dif f erent meth ods f or th e analy sis of v itamin E

b y g as ch romatog rap h y ( G C ) as w ell as b y h ig h -p erf ormance

liq uid ch romatog rap h y ( H PL C ) h av e b een describ ed in th e

literature.8 T raditionally , analy sis of f at solub le v itamins

h as b een p erf ormed w ith sev eral meth ods, including solv ent sy stem ex traction and/ or sap oniication f ollow ed b y liq uid ex traction w ith org anic solv ents lik e p etroleum

eth er or h ex ane. W h en sap oniication f ollow ed b y liq uid

ex traction w ith org anic solv ents is used, th e ex traction

ratio of toch ocromanols ( tocop h erols and tocotrienols)

f rom th e sap onif ication medium can b e af f ected b y

th e matrix , th e ex traction solv ents, th e sap onif ication

temp erature and th e p resence of an antiox idant; th eref ore, th e ex traction conditions must b e caref ully controlled. T h e sap oniication p rocedure h as th e adv antag e of sep arating

th e tococh romanols f rom acy l lip ids and transf orming esters

into th eir corresp onding alcoh ols. T h is f acilitates sep aration

as w ell q uantiication v ia H PL C , b ecause th ese analytes are

easily deined as f ree comp ounds.9

E x perimental

A mazonian f ruit samp les

F iv e ty p es of A mazonian f ruits w ere analy zed in th is

study : b uriti (M auritia lex uosa) , p ataw a (O enocarp us

bataua) , tucuma (A strocary um vulgare) , mari (P oraq ueiba

p araensis) and inaj a (M ax imiliana marip a) . T h e f ruits w ere collected in th e State of Pará in Brazil.

R eagents

Solv ents ( H PL C g rade and G C g rade) w ere p urch ased

f rom M erck ( G ermany ) . T h e α, β, γ and δ-tocop h erol

standards w ere p urch ased f rom M atrey a I nc. ( U SA ) , and th e f atty acids standard ref erence 7 4X w as p urch ased f rom Nuch eck ( U SA ) .

L ip id ex traction

T h e Blig h and D y er meth od10 w as used to ex tract

f rom dried p ulp . T h is meth od is comp atib le w ith th e determination of f at content in all ty p es of liq uid,

semi-liq uid and solid f oodstuf f s. A dditionally , th e ex tracted

lip ids may b e f urth er esteriied and conv erted to meth y l esters f or g as ch romatog rap h ic determination of f atty acid

p roiles. T h e total lip id f raction w as ex tracted b y ex h austiv e

maceration w ith ch lorof orm and meth anol. F ollow ing iltration of solids and sep aration of th e solv ent/ f at lay er, th e f at ex tract w as collected and th en used to calculate f at p ercentag e or to measure f atty acid meth y l ester content.

G enerally , dried samp les ( 10% moisture) w ere used to

f acilitate th e ex traction w ith org anic solv ents.

Tocop herols q uantiication

Vitamin E content w as q uantiied according Brub ach er

et al.11 f or p ulp f ruits. A 1 g samp le of dry f ruit p ulp

w as sap oniied under nitrog en w ith eth anolic p otassium

h y drox ide ( 5 mL 5 0% K O H m/ v : 30 mL 9 6 % eth anol;

2 mL 12% Na2S m/ v ; 100 mg h y droq uinone) at 8 0 oC f or

30 min. F at-solub le v itamins w ere th en ex tracted f rom

th e sap oniied samp le tw ice w ith 15 0 mL of stab ilized

dieth y l eth er ( 7 mg L-1 b uty lated h y drox y toluene) . T h e

org anic p h ases w ere p ooled and w ash ed w ith 5 0 g L-1 NaC l

( 100 mL ) and w ater p uriied w ith a M illiQ p uriication

sy stem ( M illip ore, U SA ) ( 100 mL , sev eral times) until

a neutral p H w as ob tained. T h is material w as th en

iltered and dried w ith a rotary ev ap orator at 35 oC . T h e

residue w as dissolv ed in 10 mL of meth anol. Vitamin E analy sis w as p erf ormed on a Sh imadzu H PL C model

L C 10A TVP ch romatog rap h w ith a p ump ( L C -10 A D ) ,

ov en, Sh imadzu SPD 10A VVP U V-Visib le detector, and

Sh imadzu R F 10AX L luorescence detector and eq uip p ed

w ith a G emini C 18 Ph enomenex ( 25 0 mm × 4.6 0 mm, 5 µ p articles) rev erse p h ase column. T h e mob ile p h ase w as a mix ture of meth anol and w ater ( 9 5 : 5 v / v ) . Solution of tocop h ery l acetate w as used as standard ref erence and w as

sub j ected to ex traction and H PL C under th e same op erating

conditions as th e unk now n samp les, b ut th e q uantities of ch emicals used f or sap oniication w ere ( 10 mL K O H ,

100 mg h y droq uinone, 25 mL 9 6 % eth anol) and ex traction

( tw ice w ith 100 mL of dieth y l eth er) w ere slig h tly dif f erent. A s an internal standard, 200 µL of tocop h ery l

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F atty A cid Proiles and T ocop h erol C ontents of iv e A mazonian f ruits J. Braz. Chem. Soc.

2002

U V ab sorp tion at 28 4 nm. D etermination of tocop h erol

v itamers content w as p erf ormed b y luorescence detection ( ex citation 29 0 nm, emission 330 nm) . C oncerning tocop h erol analy sis, rev erse p h ase ch romatog rap h y does

not disting uish b etw een β and γ-isomers of tocop h erol,

th us th e sum of th ese isomers is sh ow n th roug h out as

β+γ-tocop h erol. T h e conv ersion to α-tocop h erol eq uiv alent

units (α-T E ) w as ob tained b y multip ly ing w ith a coef icient

of 1 f or α-tocop h erol, 0.3 f or γ- and β-tocop h erol f raction and

0.1 f or γ-tocop h erol.6

Fatty acid p roile

T h e f atty acid p roile w as ob tained b y G C of th e f atty acid meth y l esters ( F A M E s) . T h e oils w ere conv erted to th eir corresp onding meth y l ester. T h e meth y l esters w ere

p rep ared v ia sap oniication and esteriication w ith potassium

h y drox ide in meth anol ( 0.1 mol L-1) and h y droch loric acid

in meth anol ( 0.12 mol L-1) . T h e f atty acid meth y l esters

w ere ex tracted w ith h ex ane and run on a G C C P 338 0 Varian

g as ch romatog rap h . T h e ch romatog rap h w as eq uip p ed with

a C P-Sil 8 8 ( 6 0 m × 0.25 mm) cap illary column ( Varian I nc., U SA ) and a lame ionization detector. H elium w as used as th e carrier g as. T h e temp erature p rog ram used w as as f ollow s: 3 min at 130 ºC ; g radual h eating to 220 ºC f or 9 min; 35 min at 220 ºC . T h e detector temp erature w as 28 0 ºC , and th e inj ector temp erature w as 245 ºC . T h e f atty acid p eak s w ere identiied b y comp aring retention times: a

calib ration curv e w as p erf ormed w ith a mix ture of standard

F A M E s ( Nuch eck 7 4X ) . E ach F A M E samp le w as analy zed in trip licate.

R esults and D iscussion

T h e total oil content of th e iv e selected A mazonian

f ruits rang ed f rom 31.0 to 41.8 % : th e p ataw a f ruit h ad

th e h ig h est oil p ercentag e, and th e mari f ruit h ad th e least

( T ab le 1) . I n comp arison, p alm f ruit p ulp (E . guineensis)

h as an oil content of ab out 7 3% and is th e most f req uently

used oil p roducing p lant in th e A mazon reg ion.12

T h e f atty acid p roile of iv e A mazonian f ruits, as determined b y cap illary -column G C , is p resented in

T ab le 2. T h e maj or M U F A in all iv e A mazonian f ruits w as oleic acid ( C 18 : 1) , w h ile lesser lev els of p almitoleic acid ( C 16 : 1) w ere also p resent ( T ab le 2) . L inoleic acid ( C 18 : 2) w as th e maj or p oly unsaturated f atty acid ( PU F A ) p resent, f ollow ed b y linolenic acid ( C 18 : 3) . Buriti and p ataw a h ad p articularly h ig h oleic acid contents ( 7 5 .5 and 7 6 .7 % of

total f at, resp ectiv ely ) comp ared w ith th e oth er A mazonian

f ruits, w h ich h ad oleic acid contents of ab out 45 %

( T ab le 2) .12-18 Palmitic acid ( C 16 : 0) and stearic acid ( C 18 : 0)

w ere th e maj or saturated f atty acids p resent in all samp les

( T ab le 2) . T h e total lev els of U F A in th e iv e A mazonian

f ruits rang ed f rom 6 1.6 to 8 1.5 % . A naly sis of th e fatty acid

p roile of th e f ruits indicates a h ig h unsaturated/ saturated ratio. T h e maj or contrib uting saturated f atty acids f or all

f ruits included p almitic acid ( C 16 : 0) and in inaj a p ulp w ith

traces of my ristic ( C 14: 0) and eicosanoic acid ( C 20: 0) .

T h e h ig h est lev els of saturated f atty acid w ere f ound in th e

inaj a and mari. T h e p rop ortion of unsaturated f atty acids in

p ataw a and b uriti p ulp s is similar to th at of oliv e oil, and th ese oils sh ould b e considered to h av e g ood nutritional

v alue.18 H ow ev er, th ere w ere larg er v ariations in th e PU F A

and M U F A contents of th e iv e f ruits. F or ex amp le, MU F A

and PU F A contents of th e b uriti p ulp w ere 7 5 .7 g 100 g-1

and 2.2 g 100 g-1, resp ectiv ely . T h is is in contrast to

inaj a p ulp w h ich contained th e low est lev els of M U F A s

( 5 2.5 g 100 g-1) , and 9 .1 g 100 g-1 PU F A f or a PU F A / M U F A

ratio of 1.7 : 10. T h is oil could also b e considered as h ealth y

and could act as a cardio p rotectiv e f ood.18

T h e tocop h erol contents of th e iv e A mazonian f ruits

w ere also measured ( T ab le 3) . T h e lev els of total tocop h erol

activ ity rang ed f rom 22.0 to 441.0α-T E ( b uriti > mari >

p ataw a > tucuma > I naj a) .

α-T ocop h erol w as th e most p rev alent tocop h erol

( 7 5 .2% to 9 5 % ) , ex cep t in b uriti w ith a p redominant

β+γ tocop h erol f raction ( 5 8 .3% ) . T ocop h erol p roile of

b uriti p ulp is similar to seed and any nut oil, as Brazil

nut, w alnut, mustard, p ump k in, w ith h ig h content of

β tocop h erol.19 -21

M ost p lant-deriv ed f oods contain low to moderate lev els

of v itamin E activ ity . H ow ev er, ow ing to th e ab undance of p lant-deriv ed f oods in our diets, th ey p rov ide a sig niicant and consistent source of v itamin E . Ph otosy nth etic tissues h av e th e g reatest content of tocop h erols and f ruit,

seed and nuts h av e low er concentration.22 F or ex amp le,

determination of α-tocop h erol in trop ical p lants sh ow ed

th at in leav es th e concentration could reach 8 00 µg g-1

of α-tocop h erol and th e h ig h est content in f ruit is ab out

15 0-300 µg g-1 in p ep p er p lants and in any nuts, as h azelnuts

Tab le 1 . T otal oil contents of iv e A mazonian p ulp f ruits ( f resh w eig h t

b asis)

O il Samp le T otal O il ( g p er 100 g )

Buriti 38 .42 ± 1.45

T ucuma 38 .5 0 ± 0.46

Pataw a 41.7 8 ± 0.39

I naj a 35 .5 2 ± 0.5 2

M ari 31.04 ± 0.41

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R odrig ues et al. 2003 Vol. 21, No. 10, 2010

Tab le 2 . F atty acid comp osition ( total % ) of oils ex tracted f rom th e p ulp s of iv e A mazonian f ruits

Buriti T ucuma Pataw a I naj a M ari

12: 0 0.10 ND ND 3.7 0 ND

14: 0 0.10 0.10 0.10 7 .6 0 ND

15 : 0 ND ND 0.30 ND ND

16 : 0 18 .7 5 24.6 0 13.30 20.10 20.8 0

16 : 1 0.25 0.10 0.7 0 0.10 0.30

17 : 0 0.05 0.10 0.10 ND 0.10

18 : 0 1.35 3.00 4.10 3.5 0 6 .40

18 : 1 7 5 .5 0 6 5 .10 7 6 .7 0 5 2.40 6 7 .6 0

18 : 2 2.15 2.6 0 3.9 0 8 .9 0 3.40

18 : 3 0.10 0.20 0.10 0.20 0.10

20: 0 1.6 5 4.10 0.6 0 3.20 1.10

22: 0 ND 0.10 ND ND ND

R esults g iv en are th e mean ± standard error of th e mean f rom th ree indep endent analy ses. ND means not detected.

Tab le 3 . T ocop h erol content of oil ( µg g-1 dry matter)

α-tocop h erol β+γ-tocop h erol δ-tocop h erol

Sum (α-T E U nit) *

Buriti 441.0 19 6 .8 ± 28 .8 47 6 .4 ± 28 .6 44.1 ± 2.4

T ucuma 5 2.9 5 2.0 ± 2.6 2.8 ± 0.2 Not detected

Pataw a 5 9 .1 5 6 .5 ± 2.9 7 .8 ± 1.1 7 .7 ± 0.3

I naj a 22.0 20.0 ± 2.0 6 .6 ± 0.4 Not detected

M ari 15 7 .9 15 5 .1 ± 14.3 9 .3 ± 1.2 1.0 ± 0.1

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F atty A cid Proiles and T ocop h erol C ontents of iv e A mazonian f ruits J. Braz. Chem. Soc.

2004

and almond, 310 µg g-1 and 439 µg g-1 resp ectiv ely .19 ,20,23

α-T ocop h erol content of b uriti and mari is 29 6 µg g-1 and

15 5 µg g-1 and th is f ruits could b e considered as v ery rich in

v itamin E . A ll oth er th ree f ruits are g ood source of v itamin

E , w ith concentration sup erior of many cereals and leg umes

and eq uiv alent of many nuts ( p eanut, w alnut) .

I n g eneral, tocop h erol lev els w ere in accordance w ith

p rev iously p ub lish ed v alues.15 ,23 H ow ev er, inaj a h ad a

h ig h er tocop h erol content ( 20.0 µg g-1) th an w as p rev iously

rep orted b y Bereau et al.,13 w h o rep orted lev els of 9 .2 µg g-1.

H ow ev er, it h as b een rep orted th at th e f atty acid proile and

p h y toch emical content of f ruits v aries b etw een cultiv ars.24

T h is could ex p lain th e discrep ancy b etw een th e tw o studies,

as th e inaj a ex amined b y Bereau et al.13 w ere f rom F rench

G uiana and th e inaj a used in th e p resent study w as ob tained

in Brazilian A mazon reg ion.

Conclusions

I n conclusion, th is study illustrates some dif f erences in total oil, f atty acid comp osition and tocop h erol contents b etw een dif f erent ty p es of A mazonian f ruits. I n g eneral, h ow ev er, all f ruits studied h av e a f av orab le unsaturated/ saturated f atty acid ratio. Vitamin E activ ity lev els w ere

h ig h est in th e b uriti, and th e α-tocop h erol, ex cep t in b uriti,

w as th e maj or comp onent in all of th e f ruits studied.

S upplementary Information

Sup p lementary inf ormation data are av ailab le f ree of ch arg e at h ttp : / / j b cs.sb q .org .b r, as PD F ile.

Ack nowledg ments

W e ack now ledg e C A PE S, C NPq ( p rocess 6 20209 / 2008 -9 ) and F A PE SPA ( F undação de A mp aro a Pesq uisa

do E stado do Para) ( p rocess 05 8 / 2008 ) f or inancial sup p ort

and f ellow sh ip s.

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15 . L ub rano, C .; R ob in, J . R .; K h aiat, A .; O léagineux 1 9 9 4, 4 9, 5 9 . 16 . Sh uk la, V. K . S.; J ensen, O . H .; J. Food L ip ids 1 9 9 6, 3, 149 .

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Int. J. Food Sci. N utr. 2 0 0 3, 5 4, 49 .

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( USA ) 1 9 9 2, 1 1 7, 5 18 .

Submitted: O ctober 2 1 , 2 0 0 9

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J. Braz. Chem. Soc., Vol. 21, No. 10, S1-S6, 2010. Printed in Brazil - ©2010 Sociedade Brasileira de Química 0103 - 5053 $6.00+0.00

*e-mail: lhmeller@ufpa.br

Fatty Acid Proiles and Tocopherol Contents of Buriti (Mauritia lexuosa), Patawa

(Oenocarpus bataua), Tucuma (Astrocaryum vulgare), Mari (Poraqueiba paraensis)

and Inaj a (Maximiliana maripa) Fruits

Antonio M. da Cruz R odrigues,a S ylvain D arnetb and L uiza H . Meller da S ilva*,a

aInstituto de Tecnologia and bInstituto de Ciências Biológicas, Universidade Federal do P ará,

6 6 .0 7 5 - 9 0 0 Belém- P A , Brazil

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Fatty Acid Proiles and Tocopherol Contents J. Braz. Chem. Soc.

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Figure S2. RP-HPLC-FLD chromatogram of tocopherols in inaja pulp.

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Rodrigues et al. S3 Vol. 21, No. 10, 2010

Figure S4. RP-HPLC-FLD chromatogram of tocopherols in tucuma pulp.

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Fatty Acid Proiles and Tocopherol Contents J. Braz. Chem. Soc.

S4

Figure S6. GC-FID chromatogram of fatty acids in buriti pulp.

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Rodrigues et al. S5 Vol. 21, No. 10, 2010

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Imagem

Figure S1. RP-HPLC-FLD chromatogram of tocopherols in buriti pulp.
Figure S2. RP-HPLC-FLD chromatogram of tocopherols in inaja pulp.
Figure S4. RP-HPLC-FLD chromatogram of tocopherols in tucuma pulp.
Figure S7. GC-FID chromatogram of fatty acids in inaja pulp.
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