PROCEEDING ICPAPS UGM 2013 hal 78 84

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STUDY li'lTERACTION OF ACE"TAMINOPHEN AND o-(3·OilOAOBENlOYL)-ACETAMINOPfj(N WITH CVClooXIGENASE·1 (3L/l1l8ASE ON IN SlUCO APPflOADl Tri Wi,fjGnd<>ni. IYifGoon. SiIWGndono

TKE DEVELOPMENT OF THEOPHYLLINE - ｏｩｲｲｾ MlCl<OPAATICLE FOR MOOIFIEO RELEASE OOSAGE fORMMitra TriGs PrGdana. Mun. Agus 5y<>msuc Rijat

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ANTIBACTERIAL AND fRH RADICAL SCAVENGINGACTlVITYOFAcanthusjfidfoJiu> l.-(ACANTHACfAE) FROMQiACAI'INOONESiA

Blntr Asriniog Dhiani, DinialiE lJ;,,;arik, Siti ""'mf"""fj

ACVH TOXICITY HST OF ETHANOl ExTRACT Of KEMANGI HERB(Dcimum ((Inum Sims)ONMALEWHITE MICE<1mPurti, Nurm.nis,Aj<ngAyu FeMeni

THE EMPlOYMENTOf fTlR SPECTROSCOPY COUPLWWITH OlEMOMETRlC5 FOR ANAlYSISOfLAl\D INCREAMCOSMETICS

Zilhadi<), Nurmojfi.

INFlUENCE OF SODIUM O<LORIDE CONCENTRATION ON THE AMOUNT OF METAaOlITE THAT PROOLJCED fROM KIMO<I FERMENTATION

Mira Andam0...;,NunljanahA2j""c,Mati"", Wijayo

ANTIINFLAMMATORY POWER Of ｏｬｒｙｾｅｍｕｍ H[RBS METHANOllC EXTRACTONMAliWHIT< RATSINDlJCf.D BY CARAGENIN

Sri Haryantl,{lisaRillillepsari. Wiele FeI>)"'ntiJa,irsa

THE OPTIMIZATION OF AViCEl PH 101 AND MANNrTOlINNigdlasati"" l. EXTllACT TROCHES BY SiMPlEX LATTICE DESIGN

fndongOw;Wulansati. fnoong DiJl<1h Ikasan. Sis,", Prima

MACRONUTRIENT ANAlVSiS, GlVCEMIC INDEX AND ANTI-CHOlESTEROl ACTIVITY OfARROWROOT(MO(ont"""'ndino,eal-1

Fedlila'uuanman, Rumiyati. Iko Pusplta Sari, tnda"fl Lukitoni"flsih

PROCH, VAUDATION Of OIClOfENAC SOQIUM PATCH MEMBRANE TYPE WITH MENTHOL A, ENI-lANCFR

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FORMULATION AND Hf£CTS Of THE ADDITION Of THE HI-lANOliC EXTRACT Of MANGOSl[(N RIND TOWARDS THE CM£MICAl PROPERTI£S Of T1i£ TRANSPARENT 5Ol10 BATM SOAP

NPeS. Bh"""", "PAC'. Wijayan'i, IGNAD. Purre

AtnVliY or ｍａｎｾｬ｛ｅｎ (""coni<) mango"o"o LI PERICAAP EXTRACT AS RNA HWCASE INHIBITOR OF HEPATITIS C VIRuS

Lino {!fite,A.Zoonal Musropc, PI'"," 5yajarwa:

fORMUl/ITION PROCESS VAliDATION Of OIClOfENAC SODIUM TRANSOERMAl. PATCHMATRIXT'/P(

cymhi<> Man«o Mum", [sli Hondrodi,RioyaPrlmahorirlasriti

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56-59

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-Abstract

The objective of this rese<lrd! was to ellaluate the possibility of FnR spectroscopy in combil\iltion with <:hemometries for "n"lysis of lard in binary

mixture with corn oil in cream cosmetics formulation. Lard, com oil and their binary

mixture were extracted from cream using liquid-liquid extraction with hexane as "><lracting solvents. These fats and oils were subsequently subjected to FnR

spectral measurem<!nt at mid intr"red region. Quantitative analysis of lard w","

performed withtheaid of multivariate e<>libration ofpartial least square, meanwhile,

the classification of cream containing lard, corn oil, and its mixture was e<>rried out using principal component analysis. Alter the extensive optimization, PlS at

the

combined frequency regions of 3024 - 2981

on"

and 1107- 1006

on-'

was prefereed to be exploited for such quantification. Furthermore, PCA /It frequency region of 10S9 - 1199an" can be used for c1/1ssification among creams containing

100 % lard, 100 % com oil and the mixture of lard and com oil stXcessfully. FTlR

spectroscopy offers ",pid (3 minute/sample), ease in sample preparation, and not involving the excessive use of solvents and reagents.

Keywords: FTIRspectroscopy, chemometrics, lard, com oil, cream.

ｚｩｬｨｾ＼ｬｩ .. '· "nd ｎｵｲｭｾｩｬｩＮﾷ

Ｇｄ･ｰｾｲｴｭ｣ｮｴ 01 ｐｨｾｲｭ［ｋｹＮ F"rultyofMMid"" and ｈｾ ..lthｓ､｣ｮ＼ｾＮＬ St"te Isl"m;c Unl.et"Sityall

Sv"nl Hidayatullah, Jak.rta 15417 100"".,1" ·Cor... ponding Author:

Email;."lh60iiyaho9.com

The employment of FTIR spectroscopy coupled with chemometrics

for analysis of lard in cream cosmetics

Introduction

PhaJ1l1aceutical Creams are semisolid preparations et:mt·aining one Or more medical agents dissolved

or

dispersd in either a W/O (water in oil) emulsion or an

O/W (oii in w,lter) emulsion) or in another type of water-washable base. The so-called vanishing ｾ｡ｭｳ are oil-in-water emulsions containing large percentages of wate, and stearic add or other oleaginous components. Alter application of the cream, the water evaporates, le/lving behind a thin residue film of the stearic acid or other oleaginous component ([I. The use of cream in modem society has increased

dramatically in recent yea",. There are three main goal of using cream as one of types cosmetics, namely (1) to enhance personal appeal through decoration of body and (21 to CilmOll!1age flaws in the integument and (3) to alter or improve upon nature ')

In cream preparation, oil is used as viscosity-inCrc3Sing agent. Compared with other fats and oil, in some countries like China and Europe, lard is commonly available because it is the cheapest oil. Lard is the fat rendered from fresh, dean, sound fatty tissues from swine (Sus sctJfa) in good health, at the time of slaughter and fit from consumption lJI. Food and drug administration (FDA) has stated that

lard is generally recognized as safe substances(GRAS) to be used in food, phaJ1l1aceutical, and cosmetics products. However, in some ｲ･ｬｩｾｩｯｮｳ like Istam, Judaism and Hinduism, the uS!! of lard in any products is forbidden 41.

Some of analytical methods for lard detection in food and drug have been developed. Identification of lard in some vegetable oils has been done by Gas-liquid chromatography (GlC) c,!mbined with chemometrics of multivariate data I'). ITIIl Spectroscopy combined with chemometries for analysis of lard in the mixtures with body fats of lamb, cow and chicken has been published 1'1.

Oii in cosmetics product has been analyzed using ITIR spectroscopy. IR spectroscopy is based on the interaction between infrared electromagnetic radiation and samples (lard). fTlR spectroscopy has rn"ny advantages. It is non-destnJctive

(4)

tedlolque, faster, dl9pe1", setISltive and simple in sample p"'l)aration 17), In

eosmeties products,

,,;rg;n

c:oo;onut

oil

used lIS

on

emulsifying llgent in

O"fam

formulation has bftn all.1!y2ed using mR spectrosc:opy Illl, mRspedroscopy has

itlso been used to slmulUlneous lII\itlysis of virgin cocoout

oil

itnll lard \91. Reoent

publlc:atlon has reported that tIM! mil<ture

ot

lard itnd palm oil in CO!imetic: lotion

could be an.alyzed using FTlR ｳｾ and partibl least s.q,-",re Citr.bnItion Uti,

Therefore, this stucly was to employ FTlRｾ O:OUPIed with d>emomet.riai

for aNllysis of lard in the binary mil<ture with com oil lIS oil ph;,se in cream

cosmetics.

Materials and Methods

lArdｾｲ｡ｄｏｴｬ

Lard

was

prep.'lred aOCl.lrding to Rohman and CIle Manltl, The part of pig body (Sus

suoflt) used is adipose tissue that obtained from lIarious slaugnter houses around

Ｎｬｯｧｊ｡ｾｲｴ｡Ｌ Indonesia. Lard was extraet.ed by heating Or adipose tissue at 90-100 'C

for

2

nour in a ollen. The melted fat was strained tnrougn trIple-folded muslin cloth,

drled wltn a"hydrou, Na,SO. and the" centrifuged at 300 rpm for 20 minutl!$. The

tat layer was decanted, SNlken v;gOnlusly and centrifuged agai"9 before belrog

ｍ･ｮｾ､ ...si"ll Whatman "Iter paper. The f,ltered fats were stored in thigUy dosfId

｣ｯｮｴ｡ｬｾｲｳ in the refligerator until being used for preparation of <:r1'am cosmetics.

Com 011 and other matern.1sused were bought inJogjakarta.

ｾｦＳｴｊｯｴｬ ofUl!am

Nine fOlTTlula aIcreamwith ､ｾｮｴ lewis oflardand

com

oilwe... prepared. using

the compositionoflard and

com

oil

itSfollows:

Faf5/oilsutraction

Before extnK:ting the

miJ«ure

of oil, ｾｭ should be hydrotyzed with h;drod\lorid

acid. 5 g of<:noiIm cosmetics was added 5 ml aI hidrochlorid.xid and 10 mI

ot

water, and

then

he<lted at atlOut 60

"'C

for 1 hour. cream cosmetics hydrolyzed

-.e

tnnsfeIoed to separMory funnel and itdded 20 ml hexane and shaken

vigOl'OUSty for 5 minutes, allo-..ed until Ilel<ane phase and water phase sepoa"'ted.

Hexane phase witS tnnsterred to round-bottom fla.slc itnd evaporated using a

vacuum rotary "",aporator at 40

'C

until hexane cornplety removed.

The...sult

Of

extnlCtion obtained were fufther determined using an FlUt spectmmetel".

FnRI>pet;tral measuremefIC

To each SO 9 ofcream cosmetics, it(IlI'lsisted aIstearic lldcI 2.5 g; the mixture of

lard and corn oil 12.5 51, with

the

ｦｍＧＺｉＧｃＢｮｴ｡ｾ ",tio as itbolle; cetyl "Iwho! 2.2 g;

propyl PlI13ben 0.1 g; butyle<l hidroxytolueoe 0.1 g; distilled water 30 g; dinatrium

etilendlamlne tetnoacetate 0.5 g; gly<:l!rin 0.75 g; titandioxide 0.1 g;

triethanolamine 0.9 0; (!"tocoPherol0.1 g and green tea

oil

0.25g.

Ingred;ent on Ol!:am cosmetics composition WitS wel¢ted usirog an llllalytical

balance with sensitillity of0.1 mg. Oil phases, consisted of stearic add, the ｭｩｸ｜ｵｾ

of oil, cetyl alcohol, propyl pa",ben and butyled hidnlxytoluene. were mixtured and

heated at about 70

"C.

The water phase consisting of distilled water, dinatrium

etllendlamlne tetfaacetate, glycerln, titllndioxide and lriethanolamin" was mixed and

is also heated at about 60

'C.

Oil pnase was taken and stand loc 60

"C,

and

subseQuently poured into tile water phase with

the

same:

temper"ture. The mi:o:ture

of

011

phase and waterphase WitS stirred with a magnetoe Stirrer until forming cream

CO$ITIetics and thnl o-toeophe:roI and green tea oil witS itdded. The fat/oil in

aum

cosmetics was furtherextracted using liquid-liquid e>ctraetiorl,

"

"'"

t l

12.5

1.5 0

"

•

'.5

..

'.5

5

"

,

'.5

,.

'.5

,

"

,

'.5

Form""'"

Fl F2

Fat/oilUrd (g) 0 1.5

(5)

mR spectra

01

the

ｭｩｬ＼ｴ｜ｬｾ 01 oil ｾｾ

us;ng

;II

mR soearometer A88

MB300 FnR

Spectrophotometer

(Cll6ret.

5Oemil\c,

Northilmptorl,UIC) at

m.c

infr"llred region

(4000-650

em-') with

the

resolution of 4 em-' and number nt scanning

Or

32. The

samples ｷ･ｾ place in contact with horizontal attenual tota, reflectance (HATR) element (ZnSe cryStal) at a control ambient ｴ･ｭｰ･ｲｬｬｴｵｾＮ All

spectra were

rationed

against a

bIICkgrQund

of air

spectrum.

After

every

scan, a new

,eference

ai' bacl<.ground

spectrum wn

taken.

These

spectra _ .. recorded as

absorbance value at eam data poin intriplicate.

O>emometncs

PlS and PCA

were

iIoCCOffllllished using Horizon MB FTlR soIl;ware version 3.0.13.1

(AB8, CaMd").

The

ｶ｡ｬｾ offOOt mean standard en'Ol' 01 alibBtIon (RMSEC)

¥Ill

coeff\dent of ck!termination {R'l wef1l! used as va&d"oty aiteriol for

the

alibratiGn. Theｾｾ ability01 PlSaSbration model was use<!toalaJlate

the

validation or

pUdietionSlImples.

Fogure 1.

FTlR speetr"ll

of

lard and com oil from cream ｦｯｲｭｵｾｴｩｯｮ in finge",rint '""9ion .

• 1

,

\:1*

I

k

ＯｾＬＭ

J

I

--

,

I

,

\J,

,

•

!'

! ..

"

,

..

.

_.",

(6)

-81

•

i

I :.

ｾＮａ

•

1

•

•. The re5lclual iII\lIlysis descrlbing ｾ differeoc:e

between

actual value and

VlI.lue of lardin comｯｾ •

•

--.---=-.

ｾﾷｉ

•

...ｾ 3. Theｲ･ｾｳｨｉｰ betweenacl\lal value1Ir.:1 fTIR predictedvalue inlard at

frequerw;y region 1006-1107

ｦＹＡｾＲＮ

rnR spectr;l of ｉｾｲ､ e><:trKI.ed hom prepared "",,am formulation with different

(7)

C·H Yiftyti( (5tmelWtgl

rnetl'lyI(Old ,""""(1ItMd'Iing)

Asymn_iuInd

syrnrnetrk..-..,-(<1'12,)g""",(sttetd'llng)

c.rt>onyI(-c_O)rrom

m. ...

ter1inQ<;i. of ｬｲＡｋｹｬｧｾｲｮＱ

m.u.ylen. (-cH2-)grouo(bending) m.t!1yl ('CH,-) g,cwO (!Jt!Mln,)

-Ol

-.:lin9

and -04cldonnalDloffatty

-

ｾｲｲＢＬＢＮｾＢＬ (-otT).-od<ing .oMloi,andoutofplane _ 011

＼［ｩｈｾ oIelIns 1465 1377 1269 1238 lIill

1117and 1098 1743

,

0

•

,

"._ ..-r.1ot ••

'-"

,

•

••

-

'U

1 1. . . . _

.,

of_" _ _

-IT

•

..

-,

[.

•

• •

•

., .,

....'e

••

•

, ,

•

Ｎｾ

82

I

Till>le I. Funnional9"O"PS andn'><>Clf$0 1 1 _inｉ｡＼ｾＢＧＢ a>moilＨｾｮＮ 2010).

Au9...

ol.

fftcll>eftC'l'

(em ') _ _ 011 ftlncI:k>nIoIgroup

Resultand dis<:.US5lon

Srx.-etra BniJ!ysis

Spe<:ua for F1 (com oil ｬＰＰｾＩ ilnd spec;:lr1I for F9

(lard

oil ｬＰＰｾＩ that

extractedfrom

oum

cosmetics

could

be shownit

"",,ute

1

that

Is in4000-650

em'

(IingerJ)rint regiott). SpectrII of Iud and com 01 Iool< very similar and typlc:ar

chill3CtCristicofabsorption band for

common

."fble

oils.

E..m peak in

mR

spectr3

ｾｰｯｮ､･ｮｳ to tunctional groups

responsible for

IR aMorptlontul. The peak

assignment ｾ with fundional groups te$p(II'ls.ible for peak absorption In Figure 1is shown In U1ble 1.

All:hough both spectra look similar. they revealed slight dilTererKe5 In terms of band intensities and exilct ｾｱｵ･ｾ ilt wh\c;h the maximum abso<'ban ｷ･ｾ

generated for each fat and oil. lard l'Iave overlapoing

two

peaks of Frequencies

1117 and 1097

em"

that

can

be used to extract a difference with

<:om

oil. These

ｾｱｵ･ｮｯ［ｩ･ｳ show C-H bending vibration aJlCl C-H deformation vibrations of fatty

acid. It means that

Lam

has unsaturated fatty add. especially oleic and linoleic acid F'9ure S.

The

PCA

smre

plot fordasslfK.lltionof

cream

COnt.!lining

com

eli

or lam

in their

formulations.

ｓＨｬＬＬｾｬＧｴｯｯ＼｡ｦｉｄＺＵＶＮＹＱｾ ....ＱＱＹＹｾ

f"

'"

(3) and(il)

(5) _ (6)

'"

(0'

,OJ

(10) (It)

(12) aM (13)

(8)

, , _ .

-ｔｾ｢ｬｾ 2. PLS model C11libration ｏｰｾＢＢＧｬｬｯｮ

F",quor>d.. Multi.a""t" Spectral region. Calibration T,..,,,tm.nl

29111-30H&. ｾ No"",,1 0.304 1006-1107

IOQ6-1107 ｾ First､ＮｲｩＢＮｾＢＮ 0.69

ｾ SC<;ondOo,i"."""O.71

ｾ Normal 0.076

ｾ First derivative ｏＮｏＶｾ

K'

S«ond deri"atiueQ.18

R,MSEC

2.18

1.29

1.73

10.4

Quantification ofLardincream cosmetics.

IR methods can be used to quantifi<:<ltion and v.lid"tion analysis however,

sOme modifications halle to be made to account for differences between spect...

intensities. The critena suggested for validating" lR trall5mission method indude;

linierit••, root mean square error of cross validation (RM$ECV) and Residual

"""lysI5 that appear aCC1JrlI!ion "aluem • Three of these criteria could be accounted

using PLS calibriltion model. PLS C3libration model was developed based on the

calibration standard that ,ndude<! the different weighted amount of lard and com oil. Data of PLS model calibratation optimatlon could ｢ｾ shown at table 2.

Unearity (R') or response <IS the first aiteria was study for m<lklng the relationship between ＮｸｴｾＱｶ｡ｬｵｾ of lard ＨｾＭ｡ｾｩｳＩ and FnR predi<:ted value of lard

ＨｹＭ｡ｾｬｳＩ In mixture011 in cream cosmetics. Based on the highest values ofR' and the

lowest values of RMSEC <IS shown in ｴ｡｢ｾ 2, frequency ｾｩｯｮ or 1006-1107 0'11-1

was selected for quantif,cation of lard In the mixture oil in cream cosmetics. The

rel<ltionship between actual value and FTIR pre<:lleted has R' value of 0.89 with linear regression eql.lation ｹｾＱＮＰＴｓＮｾＭＱＮＱｬＸＴＴ (Figure 3). This valtre is could still be <lccepted. R' v<llue is lower becau!ie of getting lard from Cream cosmetics ｾ､

extraction

process.

The second criteria, the root mean standard error of cross validMjon (RMSECV) is relative low (1.29%). Third aitelia, the residual analysis, revealed that the errors occu,.,-ing duling analysis is random error and there is no systematic error ob!ierved (l'"lgur3).

All of these cliteria indic;>ted that FnR spectroscopy was reliable enough for the analysis01mixture lard and com oil in cream cosmetics.

C1assifiCiJtion ofcreamcosmeticsCCfltaininglard

Classification of cream cosmetics with and without lard in their formulatkln was performed using plincipal component analysis accomplished using

mR

spectra absorbances of cream containing lard and com oil <It freqtrency regionof 1200-1000

em-I.

Base on figure 5, score plot of PeA of lard and corn oil in Cream cosmetics can divided in three area as follow: cream containing 100% lard, cream containing 100% com oil and cream containing ｭｩｾｴｵｲ･ of lard and com oil. Unknown cream samples suspected of containing one of both lard and com oil or ｭｩｾｴｵｲ･ of lard and com oil can be classified. The closer the distance, the higher the possibilities of unknown ｳ｡ｭｰｾｳ falling into one of the three groups.

(9)

Condusions

it OlIn be

conduded

thoot mR spedroscopy coupled with ｾ Qn

be used toanalyle ｾ oflardIt$

oil

phaseincream CO$JTIeti($.

ａ｣ｫｮｯｷｬｾｧ･ｭ･ｮｴ

This research was fully supported by project ;rant from Research Institute State ls1amit Vnlve....ity Syarif Hldayatullah Jakll<U. The aulho.... thanks to AbdUl

RohrnllnfCM' oiticlIlreading of

the

manuscript.

Referen<:e$

(1) Allen, LV., PopOvich, N.G. and Ansel, H.C. 2011. An..el's Pharmaceutlclll

ｾ Forms and Drvg Delivery Si$tems. 9'" Edn. LOndon: Lippincott

ｗｾｭｳ and Wlllcin:s.

(2) Milstein,S. 11.., Bailey, J. E. and Halper, A. II.. 2001. Del'initionof cosmetic. In Paye.M.. &rel, A. D., and Maib3dl. H.I. (Ells). Handbook of oosmetlC science and technology, p. 5-18. New York.

(3) Codex Allimentartus Commision, 1991. ｃｯ､･ｾ standard for ""med animal fats, ｃｯ､･ｾ stan 211-1999, Food and Agriwltu'" Drg<Inization of

the

Unlt.ed

Nations,

Rome.

(4) Regermeln, J.M., OwIudry, M. M. lIt>d Rege<lst:ein, C.E. 2006. The Kosher

and Halal Food LAlws. Comprehensive RevieWS in Food Sc:ierocc: and Food

safety.

2(3): 111-127.

(5) Marikkllr, '.M.N., ｇｨ｡ｾ｡ｬｩＬ H.M., Che Man, V.B., Pelris, T.S.C. and Lai.D.H. Distinguishlng lan:l from otJ'>e,.animal fats in admixWres of some vegetable

oils

uslno;I

liquid dlromlItogl'ilPhic

data

coupled with multiVariate dlltoJ

al\lllysis. FoodChern. 91:5-14.

(6) Rohman, A. and Che Man, V.B. 2010.

mit

spe<:troscopy combined with chemometries for analysis of lard in the mixture with bodyfats of lamb, cow and chicken. ｉｮｴ･ｭ｡ｾＱ Food Research Joumal. 17:519-526

(7) Pilolen'no, PJ. 2001. Solid Dosage-fom! Analysis. In Ahuja, S. lind Scypircsla,

S. liandboolc

01

Hodtm Phannaa:utical Analysis. p.235-268. san DIego:

Ac.lIdemlc: Press

(8) Rohman, A. lind Che Man, V.B. 2009. A....1ysis of mel-liver oil adulteration using Fourier trllnsform infrared (mR) spectroscopy. Joumal of the AmeriaJn oilchemists'society. 86:1149-1153

(9) Rohman,A. and Ole Man, V.B. 2011. Analysis of lard in Cteam

Cosmetics

FormulatIOnS Vsio; mR Spectroscopy and ｾＬ Mlddle'East

Journal

01

StiEntlic

Research. 7(5);726-732.

(10) Lukitaningsih,E., &ladah, M., Purwanto., and Rohmlln, A. 2012.

Quantitative analysis of lard in cosmetic lotion formulation using mR spectroscopy and Partial ｌｾ｡ｳｴ Square Calibration. klurnal of the American

Oil Chemists Society.89:1537-1543.

(11)

8endlnl,

A., ｾｴ｡ｮｩＬ L, DiV">lilio., BeIlonI, P., 8onoli<aroognin, M. and

Lerd<er, G. 2007. Prdiminary evaluation

d

the

application of mR

spectroscopy to control the lleogrllphic origin Bod qua.nty d vil'\lin Olive oilS. Joumal of Food Quality. 30:424-437.