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THE EMPlOYMENT Of fTlR SPECTROSCOPY COUPLW WITH OlEMOMETRlC5 FOR

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AbstractThe objective of this rese<lrd! was to ellaluate the possibility of FnR

spectroscopy in combil\iltion with <:hemometries for "n"lysis of lard in binarymixture with corn oil in cream cosmetics formulation. Lard, com oil and their binarymixture were extracted from cream using liquid-liquid extraction with hexane as"><lracting solvents. These fats and oils were subsequently subjected to FnRspectral measurem<!nt at mid intr"red region. Quantitative analysis of lard w","performed with the aid of multivariate e<>libration of partial least square, meanwhile,the classification of cream containing lard, corn oil, and its mixture was e<>rried outusing principal component analysis. Alter the extensive optimization, PlS at thecombined frequency regions of 3024 - 2981 on" and 1107- 1006 on-' wasprefereed to be exploited for such quantification. Furthermore, PCA /It frequencyregion of 10S9 - 1199 an" can be used for c1/1ssification among creams containing100 % lard, 100 % com oil and the mixture of lard and com oil stXcessfully. FTlRspectroscopy offers ",pid (3 minute/sample), ease in sample preparation, and notinvolving the excessive use of solvents and reagents.Keywords: FTIR spectroscopy, chemometrics, lard, com oil, cream.

Zilh~<li.. '· "nd Nurm~ili.·

'Dep~rtmcnt01 Ph~rm;Ky. F"rulty of MMid"" and H~..lth Sdcn<~., St"te Isl"m;c Unl.et"Sity allSv"nl Hidayatullah, Jak.rta 15417 100"".,1"

·Cor.....ponding Author:Email;."lh60iiyaho9.com

The employment of FTIR spectroscopy coupled with chemometricsfor analysis of lard in cream cosmetics

IntroductionPhaJ1l1aceutical 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 anO/W (oii in w,lter) emulsion) or in another type of water-washable base. The so­called vanishing ~ams are oil-in-water emulsions containing large percentages ofwate, and stearic add or other oleaginous components. Alter application of thecream, the water evaporates, le/lving behind a thin residue film of the stearic acid orother oleaginous component ([I. The use of cream in modem society has increaseddramatically in recent yea",. There are three main goal of using cream as one oftypes cosmetics, namely (1) to enhance personal appeal through decoration of bodyand (21 to CilmOll!1age flaws in the integument and (3) to alter or improve uponnature ')

In cream preparation, oil is used as viscosity-inCrc3Sing agent. Comparedwith other fats and oil, in some countries like China and Europe, lard is commonlyavailable 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 slaughterand fit from consumption lJI. Food and drug administration (FDA) has stated thatlard is generally recognized as safe substances(GRAS) to be used in food,phaJ1l1aceutical, and cosmetics products. However, in some reli~ions 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 beendeveloped. Identification of lard in some vegetable oils has been done by Gas-liquidchromatography (GlC) c,!mbined with chemometrics of multivariate data I'). ITIIlSpectroscopy combined with chemometries for analysis of lard in the mixtures withbody fats of lamb, cow and chicken has been published 1'1.

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

/

tedlolque, faster, dl9pe1", setISltive and simple in sample p"'l)aration 17), Ineosmeties products, ,,;rg;n c:oo;onut oil used lIS on emulsifying llgent in O"famformulation has bftn all.1!y2ed using mR spectrosc:opy Illl, mR spedroscopy hasitlso been used to slmulUlneous lII\itlysis of virgin cocoout oil itnll lard \91. Reoentpubllc:atlon has reported that tIM! mil<ture ot lard itnd palm oil in CO!imetic: lotioncould be an.alyzed using FTlRs~ and partibl least s.q,-",re Citr.bnItion Uti,Therefore, this stucly was to employ FTlR~ O:OUPIed with d>emomet.riaifor aNllysis of lard in the binary mil<ture with com oil lIS oil ph;,se in creamcosmetics.Materials and MethodslArd ~raDOtlLard was prep.'lred aOCl.lrding to Rohman and CIle Manltl, The part of pig body (Sussuoflt) used is adipose tissue that obtained from lIarious slaugnter houses around.logJa~rta, Indonesia. Lard was extraet.ed by heating Or adipose tissue at 90-100 'Cfor 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!$. Thetat layer was decanted, SNlken v;gOnlusly and centrifuged agai"9 before belrogMen~d ...si"ll Whatman "Iter paper. The f,ltered fats were stored in thigUy dosfIdcontal~rs in the refligerator until being used for preparation of <:r1'am cosmetics.Com 011 and other matern.1s used were bought in Jogjakarta.~f3tJotlofUl!amNine fOlTTlula aI cream with d~nt lewis of lard and com oil we... prepared. usingthe composition of lard and com oil itS follows:

Faf5/oils utractionBefore extnK:ting the miJ«ure of oil, ~m should be hydrotyzed with h;drod\loridacid. 5 g of <:noiIm cosmetics was added 5 ml aI hidrochlorid.xid and 10 mI otwater, 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 shakenvigOl'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 avacuum rotary "",aporator at 40 'C until hexane cornplety removed. The...sult OfextnlCtion obtained were fufther determined using an FlUt spectmmetel".

FnR I>pet;tral measuremefIC

To each SO 9 of cream cosmetics, it (IlI'lsisted aI stearic lldcI 2.5 g; the mixture oflard and corn oil 12.5 51, with the fM':I'C"nta~ ",tio as itbolle; cetyl "Iwho! 2.2 g;propyl PlI13ben 0.1 g; butyle<l hidroxytolueoe 0.1 g; distilled water 30 g; dinatriumetilendlamlne tetnoacetate 0.5 g; gly<:l!rin 0.75 g; titandioxide 0.1 g;triethanolamine 0.9 0; (!"tocoPherol 0.1 g and green tea oil 0.25g.Ingred;ent on Ol!:am cosmetics composition WitS wel¢ted usirog an llllalyticalbalance with sensitillity of 0.1 mg. Oil phases, consisted of stearic add, the mix\u~

of oil, cetyl alcohol, propyl pa",ben and butyled hidnlxytoluene. were mixtured andheated at about 70 "C. The water phase consisting of distilled water, dinatriumetllendlamlne tetfaacetate, glycerln, titllndioxide and lriethanolamin" was mixed andis also heated at about 60 'C. Oil pnase was taken and stand loc 60 "C, andsubseQuently poured into tile water phase with the same: temper"ture. The mi:o:tureof 011 phase and water phase WitS stirred with a magnetoe Stirrer until forming creamCO$ITIetics and thnl o-toeophe:roI and green tea oil witS itdded. The fat/oil in aumcosmetics was further extracted using liquid-liquid e>ctraetiorl,

"

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Form""'" Fl F2Fat/oilUrd (g) 0 1.5Com 01 (g) 12.5 11

mR spectra 01 the mil<t\l~ 01 oil~~ us;ng ;II mR soearometer A88MB300 FnR Spectrophotometer (Cll6ret. 5Oemil\c, Northilmptorl,UIC) at m.cinfr"llred region (4000-650 em-') with the resolution of 4 em-' and number ntscanning Or 32. The samples we~ place in contact with horizontal attenual tota,reflectance (HATR) element (ZnSe cryStal) at a control ambient temperlltu~. Allspectra were rationed against a bIICkgrQund of air spectrum. After every scan, a new,eference ai' bacl<.ground spectrum wn taken. These spectra _ .. recorded asabsorbance value at eam data poin in triplicate.

O>emometncsPlS and PCA were iIoCCOffllllished using Horizon MB FTlR soIl;ware version 3.0.13.1(AB8, CaMd"). The val~ of fOOt mean standard en'Ol' 01 alibBtIon (RMSEC) ¥Illcoeff\dent of ck!termination {R'l wef1l! used as va&d"oty aiteriol for the alibratiGn.The~~ ability 01 PlS aSbration model was use<! to alaJlate the validation orpUdietion SlImples.Fogure 1.FTlR speetr"ll of lard and com oil from cream formu~tion in finge",rint '""9ion.

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•. The re5lclual iII\lIlysis descrlbing ~ differeoc:e between actual value andVlI.lue of lard in com o~•

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...~ 3. The re~shIp between acl\lal value 1Ir.:1 fTIR predicted value in lard atfrequerw;y region 1006-1107

f9!~2.rnR spectr;l of I~rd e><:trKI.ed hom prepared "",,am formulation with different..-.centrlltion for preparing PLS calibl1ltion model.

C·H Yiftyti( (5tmelWtglrnetl'lyI (Old ,"""" (1ItMd'Iing)Asymn_iuInd syrnrnetrk..-..,­(<1'12,) g""", (sttetd'llng)c.rt>onyI (-c_O) rrom m. ...ter 1inQ<;i.of lr!Kylg~rn1

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

-Ol -.:lin9 and -04 cldonnalDl of fatty-~rr",".~", (-otT).-od<ing.oMloi, and out of plane _ 011<;iH~ oIelIns

1465137712691238lIill1117 and 1098

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82

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Till>le I. Funnional9"O"PS and n'><>Clf$ 011_ in Ia<~"'" a>m oil (~n. 2010).Au9..... ol. fftcll>eftC'l' (em ')__ 011 ftlncI:k>nIoI group

Result and dis<:.US5lonSrx.-etra BniJ!ysis

Spe<:ua for F1 (com oil l00~) ilnd spec;:lr1I for F9 (lard oil l00~) thatextracted from oum cosmetics could be shown it "",,ute 1 that Is in 4000-650 em'(IingerJ)rint regiott). SpectrII of Iud and com 01 Iool< very similar and typlc:archill3CtCristic of absorption band for common ."fble oils. E..m peak in mR spectr3~pondens to tunctional groups responsible for IR aMorptlontul. The peakassignment~ with fundional groups te$p(II'ls.ible for peak absorption InFigure 1 is shown In U1ble 1.

All:hough both spectra look similar. they revealed slight dilTererKe5 In termsof band intensities and exilct ~que~ ilt wh\c;h the maximum abso<'ban we~

generated for each fat and oil. lard l'Iave overlapoing two peaks of Frequencies1117 and 1097 em" that can be used to extract a difference with <:om oil. These~queno;ies show C-H bending vibration aJlCl C-H deformation vibrations of fattyacid. It means that Lam has unsaturated fatty add. especially oleic and linoleic acid

F'9ure S. The PCA smre plot for dasslfK.lltion of cream COnt.!lining com eli or lam intheir formulations.

S(l,,~l'too<afID:56.91~ ....1199~

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(5) _ (6)

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T~bl~ 2. PLS model C11libration Op~""'llon

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

29111-30H &. ~ No"",,1 0.3041006-1107IOQ6-1107 ~ First d.ri".~". 0.69

~ SC<;ond Oo,i"."""O.71

~ Normal 0.076

~ First derivative O.O6~

K' S«ond deri"atiueQ.18

R,MSEC

2.18

1.29

1.73

10.4

Quantification of Lard in cream 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 accountedusing PLS calibriltion model. PLS C3libration model was developed based on thecalibration standard that ,ndude<! the different weighted amount of lard and com oil.Data of PLS model calibratation optimatlon could b~ shown at table 2.

Unearity (R') or response <IS the first aiteria was study for m<lklng therelationship between .xt~1 valu~ of lard (~-a~is) and FnR predi<:ted value of lard(y-a~ls) In mixture 011 in cream cosmetics. Based on the highest values of R' and thelowest values of RMSEC <IS shown in tab~ 2, frequency ~ion or 1006-1107 0'11-1was selected for quantif,cation of lard In the mixture oil in cream cosmetics. Therel<ltionship between actual value and FTIR pre<:lleted has R' value of 0.89 withlinear regression eql.lation y~ 1.04S.~-1.1l844 (Figure 3). This valtre is could still be<lccepted. R' v<llue is lower becau!ie of getting lard from Cream cosmetics ~dextraction process. The second criteria, the root mean standard error of crossvalidMjon (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 nosystematic error ob!ierved (l'"lgur3).All of these cliteria indic;>ted that FnR spectroscopy was reliable enough for theanalysis 01 mixture lard and com oil in cream cosmetics.C1assifiCiJtion of cream cosmetics CCfltaining lardClassification of cream cosmetics with and without lard in their formulatkln wasperformed using plincipal component analysis accomplished using mR spectraabsorbances of cream containing lard and com oil <It freqtrency region of 1200-1000em-I.Base on figure 5, score plot of PeA of lard and corn oil in Cream cosmetics candivided in three area as follow: cream containing 100% lard, cream containing100% com oil and cream containing mi~ture of lard and com oil. Unknown creamsamples suspected of containing one of both lard and com oil or mi~ture of lard andcom oil can be classified. The closer the distance, the higher the possibilities ofunknown samp~s falling into one of the three groups.

83

Condusionsit OlIn be conduded thoot mR spedroscopy coupled with~ Qn

be used to analyle~ of lard It$ oil phase in cream CO$JTIeti($.

Acknowl~gement

This research was fully supported by project ;rant from Research InstituteState ls1amit Vnlve....ity Syarif Hldayatullah Jakll<U. The aulho.... thanks to AbdUlRohrnlln fCM' oiticlIl reading of the manuscript.

Referen<:e$(1) Allen, LV., PopOvich, N.G. and Ansel, H.C. 2011. An..el's Pharmaceutlclll~ Forms and Drvg Delivery Si$tems. 9'" Edn. LOndon: LippincottW~msand Wlllcin:s.

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

(3) Codex Allimentartus Commision, 1991. Code~ standard for ""med animalfats, Code~ stan 211-1999, Food and Agriwltu'" Drg<Inization of the Unlt.edNations, Rome.

(4) Regermeln, J.M., OwIudry, M. M. lIt>d Rege<lst:ein, C.E. 2006. The Kosherand Halal Food LAlws. Comprehensive RevieWS in Food Sc:ierocc: and Foodsafety. 2(3): 111-127.

(5) Marikkllr, '.M.N., Gha~ali, 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 vegetableoils uslno;I liquid dlromlItogl'ilPhic data coupled with multiVariate dlltoJal\lllysis. Food Chern. 91:5-14.

(6) Rohman, A. and Che Man, V.B. 2010. mit spe<:troscopy combined withchemometries for analysis of lard in the mixture with body fats of lamb, cowand chicken. Intema~1 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 adulterationusing Fourier trllnsform infrared (mR) spectroscopy. Joumal of theAmeriaJn oil chemists' society. 86:1149-1153

(9) Rohman,A. and Ole Man, V.B. 2011. Analysis of lard in Cteam CosmeticsFormulatIOnS Vsio; mR Spectroscopy and~, Mlddle'EastJournal 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 mRspectroscopy and Partial L~ast Square Calibration. klurnal of the AmericanOil Chemists Society. 89:1537-1543.

(11) 8endlnl, A., ~tani, L, Di V">lilio., BeIlonI, P., 8onoli<aroognin, M. andLerd<er, G. 2007. Prdiminary evaluation d the application of mRspectroscopy to control the lleogrllphic origin Bod qua.nty d vil'\lin OliveoilS. Joumal of Food Quality. 30:424-437.

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