Application of Ftir for the Characterisation of Sustainable Cosmetics and Ingredients With Antioxidant Potential

7/25/2019 Application of Ftir for the Characterisation of Sustainable Cosmetics and Ingredients With Antioxidant Potential

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Environmental Engineering and Management Journal January 2014, Vol.13, No. 1, 105-113http://omicron.ch.tuiasi.ro/EEMJ/

Gheorghe Asachi Technical University of Iasi, Romania

APPLICATION OF FOURIER TRANSFORM INFRARED

SPECTROSCOPY FOR THE CHARACTERIZATION OF SUSTAINABLE

COSMETICS AND INGREDIENTS WITH ANTIOXIDANT POTENTIAL

Anca Maria Juncan1, 2

, Florinela Fetea3, Carmen Socaciu3

1Babe-Bolyai University of Cluj-Napoca, Faculty of Chemistry and Chemical Engineering,Arany Janos Str. 11, 400028, Cluj-Napoca, Romania

2S.C FARMPREV SRL, Suceava Str. 24-26, 400219, Cluj-Napoca, Romania3University of Agricultural Sciences and Veterinary Medicine, Calea Mntur 3-5, 400372, Cluj-Napoca, Romania

Abstract

The aim of this study is to elaborate a survey on the efficiency of three anti-aging cosmetic formulations by applying Fourier

Transform Infrared Spectroscopy (FTIR) with Attenuated Total Reflection (ATR) in order to characterize and identify thespecific recognition markers of the active ingredients. FTIR (ATR) spectrometry in specific regions was applied also to the

ingredients used in these products, depending on their role in the specific cream. Comparing the different composition of thecreams, depending on the ratio of lipophylic to hydrophylic ingredients, of emollient-emulsifier type ingredients, antioxidant and

active ingredients, it has been noticed identification of differences between the natural (-tocopherol acetate) and the syntheticantioxidant (BHA) by characteristic markers.

The antioxidant potential of -tocopherol acetate and of BHA, usually used in cosmetic formulations or added in a controlledway, at known levels of concentration in a standard cream, were evaluated by the DPPH method. Their antioxidant effect couldnot be demonstrated in our experiments with controlled concentrations (below 1% and even higher), added to complex mixtures

with lipids. Higher sensibility methods, like electronic spin resonance (ESR) could probably deliver additional information aboutthe antioxidant potential of some complex mixtures, like anti-aging creams.

Key words:anti-aging products, antioxidants, cosmetic formulations, DPPH method, FTIR analysis

Received: April, 2011; Revised final: April, 2012; Accepted: April, 2012

Author to whom all correspondence should be addressed: E-mail: [email protected]; Phone: +40-264-434194; Fax: +40-264-484712.

1. Introduction

Determination and quantitation of activeingredients in cosmetic and hair care productsfrequently proves to be challenging for analyticalchemists. Often the active ingredients are present inlow concentrations and the formulations havecomplex composition. A typical oil in water (o/w)formulation might contain ingredients such as water,glycerin, stearic acid, mineral oil, triethanolamine,

cetyl alcohol, carbomers and preserved with parabensand antioxidants, which mostly occur in mixtures in

cosmetic fromulations (Juncan, 2011; Sabo et al.,

1984). The actual European legislation prohibits theuse of cosmetic ingredient concentrations higher than

the maximum authorized levels of ingredientsdepending to the toxicity of some components andthe part of the body where they are to be applied.Control of the composition of cosmetic finishedproducts must be monitored to avoid excessiveconcentrations that could cause consumersdermatological diseases (Salvador et al., 2001).

Several components of a cosmetic formulation

are able to interact with active ingredients (volatileoils, pigments, antioxidants, etc.), reducing their

stability and efficacy. It is important to determine the


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activity of antioxidants and their long term stabilityin the final formulations (Jung et al., 2007).

Firstly, for a developed cosmetic formula to

fulfill all the requirements, it is necessary to have asuitable vehicle (that encompasses emulsions,emollients, moisturizers, preservatives, perfumes,colorants) and to include in its formulation all the

active ingredients (UV filters, botanical orbiotechnological extracts), necessary to attain what isclaimed by its advertising (Salvador and Chisvert,2007). Ingredients, that make the object of a cosmetic

formulation can be generically classified in threecategories: substances with lipophilic character - oil,fats, tocopherols (Vitamin E), synthetic preservativeswith antioxidant effect, emulsifiers - siliconic oils,C16- C18 fatty alcohols and hydrophilic ingredients,mainly glycerin, emollient that is often used incosmetic formulations (Juncan, 2011).

Vitamins are used in the cosmetics industry inskin care, hair care and oral hygiene products.

Vitamins have been added to skin care products toboost the skins antioxidant or anti-inflammatoryresponse. They also function as immune systemstrengtheners, clarifiers or wrinkle reducers. VitaminE is also called the protecting vitamin and is usedin the cosmetic industry as antioxidant either for the

skin or protector of the formulation stability. It alsosoftens the skin and alleviates dry skin conditions.Esterified forms such as vitamin E acetate are usedbecause of their superior stability (Salvador andChisvert, 2007).

In cosmetics there are added reducing agentsand free radical scavengers, known generically as

antioxidants. Antioxidant preservatives are able toinhibit reactions promoted by oxygen, thus avoidingthe oxidation and rancidity of commonly used fats,oils, waxes, surfactants, perfumes, etc. (Juncan et al.,2011). Considering the importance of Vitamin E forskin protection against oxidative damage, and thenecessity of a proper evaluation of antioxidantpotential in cosmetic formulation, it is of great

interest to determine this property for tocopherols orfor topical formulations containing these ingredients,

by measuring the hydrogen donor capability (DiMambro et al., 2003). The DPPH method is based onthe quenching of stable DPPH radicals.

This is one of the few stable nitrous radicals,having a purple colour which fades when reduced byan antioxidant. The reaction is monitored by a

spectrometer at the wavelength of 515 nm. The IRspectrometric analysis, along its improved version,

Fourier Transform (FTIR) allows the registration ofspecific fingerprints based on functional groups, andalso some chemical changes taking place during theoxidation processes (Juncan, 2011). FTIR is one ofthe most widely used methods to identify thechemical constituents and elucidate the compoundsfunctional groups and has been used as a method to

identify medicines in Pharmacopoeia of manycountries. Owing to the fingerprint characters andextensive applicability to the samples, FTIR hasplayed an important role in pharmaceutical analysis

(Liu et al., 2006), being non-destructive, rapid, easyto apply for emulsions, powders, liquids, withoutpreliminary extactions.

Recent reports show two different applicationareas of this method. The first field covers biologicaland medical applications, and the second area dealswith chemical process analysis, involving, for

example, the identification of chemicals orapplications in the field of reaction monitoring(Kpper et al., 2001). Currently, FTIR spectroscopyhas gained a special attention as a reliable technique

for fat and oil analysis, due to its fingerprinttechnique (Pui et al., 2013; Foudjo et al., 2013; Liu etal., 2006; Strasburger and Breuer, 1985). The FTIRmethod allows qualitative and quantitative analysisof the chemical composition of emulsions, lotions,hair care products and other categories of cosmeticproducts (Masmoudi et al., 2005). Studies of thermal

degradation by FTIR have been performed on oils(Moya Moreno et al., 1999), and it was shown that

the method was used to follow the degradation of theraw materials, or to measure the hydration of thecream on the skin. FTIR can be successfully usedalso for peroxide value (PV) determination in edibleoils based on the reaction between hydroperoxidesand triphenylphoshine stoichiometrically resulting of

triphenylphosphine (Marigheto et al., 1998).Fourier transform infrared (FTIR)

spectroscopy with sample handling technique ofattenuated total reflectance (ATR) was successfullyused to analyze virgin coconut oil (VCO)quantitatively in cream cosmetic preparations. FTIRspectroscopy combined with chemometrics of PLS

regression can be used as an analytical technique forquantification of VCO content in cream cosmetics

formulation (Rohman et al., 2009).Masmoudi et al. (2005) showed how the

utilization of FTIR spectroscopy can be applied instudying the stability of cosmetic or pharmaceuticaloil in water (O/W) emulsions. In this studytemperature storage tests were performed to

accelerate the aging process and evaluate the stabilityof five emulsions. Emulsions were analyzed by FTIR

and classical methods (conductivity, viscosity, pH,texture analysis) in order to determine a method thatwould enable predicting the emulsions stability.

Epidermal surface characterization andconcentrations of vitamin E acetate (-tocopherolacetate) in the stratum corneum were measured after

topical skin application and were performed by mid-infrared attenuated total reflection spectroscopy. The

infrared methodology is rapid and can be applied tosmall areas of skin. It is also sufficiently sensitive foranalysis of a large variety of cosmetic formulations(Heise et al., 2001).

FTIR spectroscopic measurements have beenperformed also on human hair (Dubief, 1992;Strasburger and Breuer, 1985) and proved practical

use in the formulation and testing of milder, lessdamaging, cosmetic products for hair care (Pande,1994).


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Application of Fourier Transform Infrared Spectroscopy for the characterization of sustainable cosmetics

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The use of IR spectroscopy for qualitativeidentification of anionic surfactants has beenreported. Five raw materials, sodium lauryl sulphate,

ammonium lauryl sulfate, sodium lauryl ether sulfate,sodium lauryl di-ether sulfate, and sodium alphaolefin sulfonate (AOS), and four finished shampooshave been analyzed (Sabo and Rosenberg., 1984).

The aim of this study is represented by thesurvey of FTIR (ATR) specific fingerprints for thecharacterization of three anti-aging cosmeticformulations and the identification of specific

recognition markers of the active ingredients. Theantioxidant potential of alpha tocopherol acetate andof the preservative BHA, usually used in cosmeticformulations or added in a controlled way at knownlevels of concentration, in a standard cream wereevaluated by the DPPH method, in parallel to FTIRanalysis (Juncan, 2011).

2. Materials and methods

Three types of cosmetic formulations,obtained from a local supplier, were used; these weredenominated according to their intended purpose:Anti-Wrinkle Eye Contour Cream, IntensiveMoisturizing Day Lift Cream and Replenishing Night

Lift Cream.The raw materials used for the manufacturing

of the creams were analized by FTIR spectrometry:Glycine Soja Oil,Persea Gratissima Oil (Robot SRL,Cluj-Napoca, Romania), Theobroma Cacao (EltonImport - Export SRL), Octyldodecanol (CognisGmbH, Dsseldorf, Germany), Dimethicone

(Chematex S.A, Bucharest, Romania), CetearylAlcohol (Cognis GmbH, Dsseldorf, Germany),Stearic Acid (Biesterfeld Spezialchemie RomaniaSRL, Bucharest, Romania), Cetearyl Alcohol/Ceteareth 20 (Croda Europe Ltd, Cowick Hall, UK),Glyceryl Stearate (ISP, Kln, Germany),Acrylates/C10-C30 Alkyl Acrylate Crosspolymer(Lubrizol Corp., Ohio,USA, Glycerin (Robot SRL,

Cluj-Napoca, Romania), Cucumis SativusExtract&Propylene Glycol (Geniana SRL, Cluj-

Napoca, Romania).In performing the FTIR spectrometric method,

following reagents were used: ethanol (98%) (MerckKgaA, Darmstadt, Germany), tetrahydrofuran (THF)(Merck KgaA, Darmstadt, Germany), -tocopherolacetate (BASF SRL, Bucharest, Romania), BHA (Jan

Dekker, Langenfeld, Germany). For thedetermination of the antioxidant activity, following

reagents were used: 2,2-diphenyl-1-picrylhydrazyl(DPPH), 6 - hydroxy - 2,5,7,8 -tetramethylchroman -2-carboxylic acid (TROLOX), ethanol (98%) (MerckKgaA, Darmstadt, Germany), THF (Merck KgaA,Darmstadt, Germany), -tocopherol acetate (BASFSRL, Bucharest, Romania), BHA (Jan Dekker,Langenfeld, Germany).

2.1. FTIR spectrometric analysis

For the FTIR analysis, the three cream

samples were applied as is, on the ATR plate. Theraw materials used for the manufacturing of thecreams, Glycine Soja Oil, Persea Gratissima Oil,

Octyldodecanol, Dimethicone, Acrylates/C10-C30Alkyl Acrylate Crosspolymer, Tocopherol Acetate,Glycerin, Cucumis Sativus Extract&PropyleneGlycol, were also applied directly on the plate, 1 mL

each. The other studied raw materials, TheobromaCacao, Cetearyl Alcohol, Stearic Acid, CetearylAlcohol, Ceteareth 20, Glyceryl Stearate, BHA werefirst dissolved in THF:H2O, (4:1 v/v) and sonicated

for 5 minutes, then applied on the plate.

2.2. Application of the FTIR method

The recording of the infrared absorptionspectra was performed directly by utilizing aShimadzu IR Prestige-21 spectrophotometer with a

HATR (Horizontal Attenuated Total Reflectance)accessory. The spectra were recorded over the

wavelength range of 500 - 4000 cm -1 and absorptionbands were identified, corresponding to types ofbonds and functional groups (expressed as cm

-1).

The unsaturation, peroxidation and carbonylindices (Dubois et al., 1996; Guillen and Cabo, 2000;Masmoudi et al., 2005) of the three studied anti-

aging creams were calculated starting from the dataobtained by FTIR spectrometry, using absorbancevalues for certain frequencies and considering Eqs.(1, 2). Unsaturation index (related to the absorptionbandC=CHat 3006 cm

1):

285129213006

3006

AAA

A

(1)

Carbonyl index (related to the respective the

absorption band C=O at 1746 cm1):

i

1746

A

A

(2)

where Ai represents the sum of the area between1800 and 650 cm-1.

The peroxidation index (the widening of the3460-3480 cm-1band).

2.3. Determination of the antioxidant activity using

the DPPH method

The antioxidant activity of the creamingredients was evaluated using two types ofmeasurements: by the controlled dosing of knownconcentrations of alpha-tocopherol acetate (-TA)and of the preservative butylated hydroxyanisole(BHA) (Experiment A) and by direct measurement of

the respective antioxidant activity, at theconcentrations levels usualy mixed into the threestudied creams (Experiment B).

Experiment A.The antioxidant activity of thealpha-tocopherol acetate and of the preservativebutylated hydroxyanisole (BHA) was tested on a


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Intensive Moisturizing Day Lift Cream cream, by thecontrolled addition of various concentrations ofalpha-tocopherol acetate (-TA) and/or BHA. Table

1 shows the C0 - C6 concentrations of alpha-tocopherol acetate (-TA) and/or BHA that wereadded to the Intensive Moisturizing Day Lift Cream,in order to evaluate the antioxidant activity via the

DPPH method.Experiment B. The antioxidant activity was

determined for creams 1 - 3, which previously had aclaimed concentration of 0,5 % -TA and 0,05 %

BHA. For the determination of the antioxidantactivity of the active ingredients through the DPPHmethod, a BIOTEK Synergy HT Multi-Detectionspectrometer was employed. Using the analyticalbalance, 0.5 g of sample (cream) were weighed ontowhich 5mL of solvent THF: H2O (4:1 v/v) wereadded. The samples were sonicated for 15 minutes

and centrifuged for 10 minutes at 10000 rpm. Theobtained supernatant liquid was used for the

determinations of the antioxidant activity, utilizingsystems of 24-well plates.

Table 1.Concentrations of -TA and BHA added in acontrolled manner to the Intensive Moisturizing Day Lift

Cream in order to determine the antioxidant activity

Intensive Moisturizing Day Lift Cream

Concentration, (%) -Tocopherol acetate, %) BHA, (%)

C0 - -

C1 0.1 -

C2 0.2 -

C3 0.5 0.05

C4 0.5 -

C5 - 0.05C6 0.1 0.05

The working procedure consisted ofdissolving DPPH (80 M) in ethanol (98%). Thestock solution was freshly prepared every day; themixture was shaken and kept at room temperature, ina dark environment, for 10 minutes. For a volume of20 L cream sample with 1750 L solution were

added onto each plate and the modification of thesolutions absorbance was monitored at 515 nm for 30minutes, with respect to ethanol. The reference

sample contained 1750 l DPPH and 20 l ethanol.

The DPPH solution discolors from violet to yellow inthe presence of a hydrogen donor, and thus thedegree of free radical inhibition (I %) is established.

The same procedure was applied to -

tocopherol acetate and BHA for differentconcentrations in the sample: -tocopherol acetate:

0.25 %; 0.5 %; 1.5 %, BHA: 0.2 %; 0.1 %; 0.05 %;0.025 % (Table 1). BHA was dissolved in H2O andslightly heated to 37

0C, while -tocopherol acetate

was dissolved in THF:H2O (4:1 v/v).

3. Results and discussion

3.1. Reference data on the compositions of creamsand FTIR spectra specific of some oily products

Fig. 1 shows by comparison, the compositionof the three studied creams. The different ratiosbetween lipophilic and hydrophilic components are

noticed. While the Anti-Wrinkle Eye Contour Creamcontains Stearic Acid, Cetyl alcohol, Octyldodecanoland Glycerol, Cucumber extract and Potassium CetylPhosphate, all organic components, the Intensive

Moisturizing Day Lift Cream has a higher ratio ofnon-polar components (Glyceryl Stearate, Avocadooil, Soja oil, Ceteareth 20) balanced with Glyceroland Cucumber extract.

On the other hand, the Replenishing NightLift Cream contains less Soja oil and Cetyl Alcoholbut more Ceteareth 20 and Cocoa butter. To properlyinterpret the FTIR fingerprint specific to this creams,the generic FTIR spectra, specific to oily productswas chosen as guide, where the specific frequenciesof the functional groups and fingerprint areas were

marked (Fig. 2) (Shahidi, 1997; van de Voort., 2006).Based on this spectrum, the specific frequency

regions (I-IV) were identified, which can be assignedto some functional groups from ingredients andcreams (Table 2). The region IV (below 1000 cm

-1) is

marked by three frequencies characteristic to doublecis or trans bonds from unsaturated compounds(unsaturated fatty acids, carotenoids or tocopherols)

which have a antioxidant potential. Zone III (1000-1800 cm

-1) shows the presence of esters, saturated

fats or fatty acids (1718, 1743, 1379-14 cm-1

) andalcohols (1205-1165 cm-1) or esters (1043 cm-1).

Water absorbs in the areas higher than 3000cm-1and the oxidation products of lipids (peroxidesor epoxides) absorb above 3400 cm-1. Zone II (2270-

2400 cm-1) is specific to carbonilic compounds,generaly CO2 dissolved in creams generates suchsignals. Zone I (frequencies above > 2800 cm

-1) is

specific to C H and C = C bonds from lipidspolienic chains and natural fitosterols or cholesterol.

Based on this remarks, the specific spectra ofthe components of the studied creams and namely thenatural emollients (Fig. 3), synthetic emollients (Fig.

4), of emulsifiers (Fig. 5) and of antioxidants (Fig. 6)were characterized.

3.2. Characterization of the main classes ofingredients, emollients, emulsifier and antioxidant byFTIR spectrometry

Fig. 3 shows the specific fingerprint for

different types of natural emollients found in thecompostion of the studied creams. Overall, these oils

have similar FTIR fingerprints, with similar signalpositions. Nevertheless, specific marker frequencieswere identified at 518, 912, 1257, 1317, 1396, 1417cm-1, and 1654 cm-1for Soja oil, respectively at 669cm

-1for Avcado oil and at 1070 and 1363 cm

-1 for

Cocoa butter.Fig. 4 shows the specific fingerprints of

synthetic type emollients used in the studied creams.

Differences in the shape and intensity of the signalsare observed. Thus, the recognition markers forOctyldodecanol are at 721, 1035, 2852 and 3319 cm

-


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1, and for Dimethicone at 661-700, 1012, 1078 and1411 cm-1. Fig. 5 shows the characteristic fingerprintof the emulsifiers used in the studied creams.

Similarities in the spectra of Gglyceryl Stearate andof Stearic Acid are noticed, however frequenciescharacteristic of the Stearic Acid are observed at1710, 890 and 1031 cm-1. For Cetearyl Alcohol and

for Ceteareth 20, the lack of the 1710-1734 cm-1frequencies is noticed. In case of acrylates, thefingerprint is totally different and has much lesssignals. Fig. 6 shows the characteristic fingerprint for

different types of natural and synthetic antioxidantsfound in the creams.

Characteristic frequencies (recognitionmarkers) for tocopherol acetate, were identified at624, 678, 704, 736, 848, 898, 920, 1010, 1716, 2868,

2926 and at 2949 cm-1

, 800, 1541 and 1636 cm-1

forBHA. Thus it can be said that there are significantdifferences between BHA and tocopherol acetate,especially in the fingerprint area V-IV-III.

Tocopherol acetate shows many signals of highintensity whilst it has less specific signals, only thosefrom 1541 and 1635 cm-1. In area I, the intensity ofthe tocopherol signal is much higher and is

characteristic.

Fig. 1. The composition of the used creams in a graphical representation

Fig. 2.The generic FTIR spectrum characteristic to oily products, specific fingerprint area with the characteristic frequencies for

functional groups


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Table 2. Identification of specific frequency regions characteristic for some oils and suspensions (creams) and their designations

Frequency area

(cm -1)

Characteristic frequencies

(cm -1)Assignment

Zone IV< 1000

721

921954

995

- C = C trans

- C = C cis

Compounds with conjugated double bonds:polyunsaturated fatty acids, carotenoids, tocopherols

Zone III

1100 - 1800

1743

1718

1643

1465

13791111

1109

11651205

1043

COOH

C = O

|

OR

-CH2-CH3

- O-CH2

- C - O

C- OR

Esters

Free fatty acids

Aldehydes and ketones(flavours)

Saturated fats

Glycerin

Zone II

2270 - 2400

2358

2331

C = OCO2

Zone I> 2800

28502916

2954

C H

(C = C) cis

Natural fatty acidsCholesterol or fitosterols

Fig. 3.FTIR fingerprint of natural emollients

(oils and Cococa butter) used in the the studied creams

Fig. 4.Characteristic FTIR fingerprint of the synthetic

emollients

Fig. 5.Characteristic frequencies and signal strengths for differenttypes of emulsifiers

Fig. 6.Characteristic FTIR fingerprint of natural andsynthetic antioxidants


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3.3 Characterisation of the active hydrophiliccomponents

Fig. 7 shows the characteristic fingerprint of

Glycerol and of Cucumber extract used in the studiedcreams. Characteristic frequency (recognition

marker) for Glycerol was identified at 850 cm-1.The fingerprint of Cucumber extract is

characteristic and given by the signals at 1259-1288,1381, 1643 and 2978 cm-1. Especially the 1643 cm-1

frequency is a flavour marker (aldehydes andketones).

Fig. 7.The characteristic FTIR fingerprint of Glycerol and

of Cucumber extract

3.4. Cosmetic cream characterisation by genericFTIR spectra and fingerprint areas

Fig. 8 and Fig. 9 show the characteristic FTIR

(ATR) fingerprintareas of the studied creams. Fig. 8shows the general spectra with the four characteristicareas (I-IV) marked and Fig. 9, details aboutfingerprint zone IV. All three studied creams have asimilar FTIR spectrum and are hard to tell apart; thedifferences in composition shown in Fig. 1 are toolow to affect the IR absorptions.

Fig. 8.Represantation of the FTIR (ATR) spectrum of the

three creams, with the evidence of the specific I-IV areas

The fingerprint area IV (Fig. 9) however doesshow higher intensities for the region 1150-1200 cm-1

(esters and fats) for the Intensive Moisturizing DayLift Cream and 800-1000 cm-1for the Anti-Wrinkle

Eye Contour Cream (which contains more polarcompounds).

Fig. 9.Representation of the fingerprint area (area IV) of

the three studied creams

The zoom of the region 800-1300 cm-1

shows some differences only at 1200 cm

-1, where

the Replenishing Night Lift Cream has signalsattributed to C-O bands, found for Collagen,Ceteareth and Theobroma Cocoa.

Table 3 includes the values of characteristicfrequencies and signal strength for the three studied

creams. Besides quantitative similarities marked withbolded numbers, two types of characteristicfrequencies are also noticed, marked with ** and ***respectively, for the Intensive Moisturizing Day LiftCream and Replenishing Night Lift Cream creams.

These data can be considered minimal markers ofdiscrimination between the three studied creams.

3.5 Antioxidant activity of the investigated creams

The cream to which -TA and BHA(experiment A) were added in a cotrolled way did notexhibit antioxidant activity by the DPPH method.The obtained result is also confirmed by other studiesshowing that the synergic antioxidant tocopherol

acetate, although more stable than tocopherol, doesnot have any antioxidant activity (Di Mambro, 2003;

Fuchs, 1998; (Graf et al., 2008; Jung et al., 2007;).

Our complementary studies showed that evenwhen increasing the concentration of BHA or -TA,there is no proportional increase of the antioxidantactivity. Table 4 shows the degree of unsaturationvalues and of the carbonyl index, considering the

values of measured absorptions at diferent IRfrequencies (described in the Materials and methodssection).

6. Conclusions

The use of FTIR spectrometry has allowed the

evidence of the characteristic fingerprint of the three

types of creams studied, and also of the ingredientsused to formulate the products, depending on theirrole in the specific cream.


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Table 3.Characteristic frequencies and signal strength for the three studied creams

Frequency

area (cm-1)Anti-Wrinkle Eye Contour Cream

Intensive Moisturizing Day Lift

CreamReplenishing Night Lift Cream

Wave number Intensity Wave number Intensity Wave number Intensity

920 0.331 921 0.0218 921 0.021IV

993 0.0662 995 0.0623 995 0.063

1043 0.1674 1043 0.1815 1043 0.1699

1078 0.0968 1080 0.1043 1080 0.1025

1109 0.0824 1111 0.1027 1109 0.0955

1165 0.0327 1168 0.0826 1170 0.0464

1205 0.038 1201 0.0571 1203 0.0433

1247 0.0468 1257 0.068 1246 0.0508

1261 0.0544 1286 0.0389 1259 0.0569

1379 0,0299 1379 0.0353 1379 0.0351

**1419 0.03 ***1417 0.0297

1465 0.0648 1465 0.0725 1465 0.0771

III

1701 0.0234 1718 0.0147 1718 0.0137

**1743 0.0286 ***1743 0.0171

2331 0.0993 2331 0.1011 2331 0.0864II

2358 0.1521 2358 0.1586 2358 0.13492848 0.182 2850 0.1606 2850 0.1891

2916 0.2633 2916 0.2372 2916 0.2891I

2954 0.0712 2954 0.0732 2956 0.1086

Table 4.Degree of unsaturation (UI) and carbonyl indices (CI) for the studied creams

Sample UI CI

Anti-Wrinkle Eye Contour Cream 3761.02315.03707.03631.0

3631.0

1107.0

3627.11008.0

1621.0

Intensive Moisturizing Day Lift Cream 3581.02295.03801.03401.0

3401.0

1320.0

3875.10942.0

1956.0

Replenishing Night Lift Cream 3347.0

2553.04296.03447.0

3447.0

1272.0

3594.10972.0

1854.0

Comparing the diferent compositions of thecreams, depending on the ratio of lipophylic tohydrophylic ingredients, of emollient-emulsifier typeingredients, antioxidant and active ingredients(Cucumber extract, tocopherol acetate) there have

been noticed:- similarities regarding the shape of FTIR spectra

between different natural emollients with theevidence of some characteristic frequencies andrecognition markers, especially for Soja oil.

- similarities of the FTIR fingerprints between the

stearate type and cetearyl type emulsifiers.- clear differences between acrylates and

respectively Stearates and Ceteareth.

- significant differences between syntheticemollients, Dimethicone and Oktyldodecanol.

- identification of differences between naturalantioxidants (-tocopherol) and synthetic ones(BHA) and characteristic marker highlighting(frequencies and signals).

- evidence of the active principles (flavours) from

Cucumber extract and its fingerprint in propyleneglycol compared to Glycerine both ingredientsbeing hydrophil.

For the studied creams, the FTIR the spectrumis similar, but some differences in band intensitiescan be noted and identified in the areas 1150-1200

and 800-1000 cm-1. In conclusion, the data obtainedfrom the analysis of the ingredients is very useful anddoes replace a database for their individual or class ofcompounds identification. For creams with acomplex composition, especially when they differ by

reduced percentages between the polar and nonpolaringredients, it is hard to evidentiate the recognition

markers by the FTIR (ATR) method. Later studieswill be dedicated to proving the FTIR method forinvestigating oxidative processes.

The antioxidant effect of creams which

include molecules with antioxidant potential seems tobe a complex issue needing further studies. Even if

molecules like BHA or -tocoferol, consideredindividually, with antioxidant effect (by the DPPHmethod), in complex mixtures with lipides, especiallywhen their concentration is below 1%, theantioxidant action cannot be registred by usualmeasurements. Higher sensibility methods, likeelectronic spin resonance (ESR) could probably

deliver additional information about the antioxidantpotential of some complex mixtures, like anti-aging

creams.

AcknowledgementsThe Biochemistry Department of the University ofAgricultural Sciences and Veterinary Medicine from Cluj-


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Napoca is acknowledged for facilities provided andassistence in this study. Special thanks are extended to

Prof. Dr. Johann Wiechers (JW Solutions, The Netherlands)and Prof. Dr. Maria Lungu (President of the RSCC-

Romanian Society of Cosmetic Chemists) for theirenthusiastic support.

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Application of Ftir for the Characterisation of Sustainable Cosmetics and Ingredients With Antioxidant Potential