Environmental Engineering and Management Journal

January 2014, Vol.13, No. 1, 105-113

http://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
1

Babe-Bolyai University of Cluj-Napoca, Faculty of Chemistry and Chemical Engineering,

Arany Janos Str. 11, 400028, Cluj-Napoca, Romania
2
S.C FARMPREV SRL, Suceava Str. 24-26, 400219, Cluj-Napoca, Romania
3
University 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 the
specific 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 the
creams, 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 synthetic
antioxidant (BHA) by characteristic markers.
The antioxidant potential of -tocopherol acetate and of BHA, usually used in cosmetic formulations or added in a controlled
way, at known levels of concentration in a standard cream, were evaluated by the DPPH method. Their antioxidant effect could
not 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 about
the 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

1. Introduction
Determination and quantitation of active
ingredients in cosmetic and hair care products
frequently proves to be challenging for analytical
chemists. Often the active ingredients are present in
low concentrations and the formulations have
complex 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 parabens
and antioxidants, which mostly occur in mixtures in
cosmetic fromulations (Juncan, 2011; Sabo et al.,

1984). The actual European legislation prohibits the

use of cosmetic ingredient concentrations higher than
the maximum authorized levels of ingredients
depending to the toxicity of some components and
the part of the body where they are to be applied.
Control of the composition of cosmetic finished
products must be monitored to avoid excessive
concentrations that could cause consumers
dermatological diseases (Salvador et al., 2001).
Several components of a cosmetic formulation
are able to interact with active ingredients (volatile
oils, pigments, antioxidants, etc.), reducing their
stability and efficacy. It is important to determine the

Author to whom all correspondence should be addressed: E-mail: anca_juncan@yahoo.com; Phone: +40-264-434194; Fax: +40-264-484712.

Juncan et al./Environmental Engineering and Management Journal 13 (2014), 1, 105-113

activity of antioxidants and their long term stability

in the final formulations (Jung et al., 2007).
Firstly, for a developed cosmetic formula to
fulfill all the requirements, it is necessary to have a
suitable vehicle (that encompasses emulsions,
emollients, moisturizers, preservatives, perfumes,
colorants) and to include in its formulation all the
active ingredients (UV filters, botanical or
biotechnological extracts), necessary to attain what is
claimed by its advertising (Salvador and Chisvert,
2007). Ingredients, that make the object of a cosmetic
formulation can be generically classified in three
categories: substances with lipophilic character - oil,
fats, tocopherols (Vitamin E), synthetic preservatives
with antioxidant effect, emulsifiers - siliconic oils,
C16- C18 fatty alcohols and hydrophilic ingredients,
mainly glycerin, emollient that is often used in
cosmetic formulations (Juncan, 2011).
Vitamins are used in the cosmetics industry in
skin care, hair care and oral hygiene products.
Vitamins have been added to skin care products to
boost the skins antioxidant or anti-inflammatory
response. They also function as immune system
strengtheners, clarifiers or wrinkle reducers. Vitamin
E is also called the protecting vitamin and is used
in the cosmetic industry as antioxidant either for the
skin or protector of the formulation stability. It also
softens the skin and alleviates dry skin conditions.
Esterified forms such as vitamin E acetate are used
because of their superior stability (Salvador and
Chisvert, 2007).
In cosmetics there are added reducing agents
and free radical scavengers, known generically as
antioxidants. Antioxidant preservatives are able to
inhibit reactions promoted by oxygen, thus avoiding
the oxidation and rancidity of commonly used fats,
oils, waxes, surfactants, perfumes, etc. (Juncan et al.,
2011). Considering the importance of Vitamin E for
skin protection against oxidative damage, and the
necessity of a proper evaluation of antioxidant
potential in cosmetic formulation, it is of great
interest to determine this property for tocopherols or
for topical formulations containing these ingredients,
by measuring the hydrogen donor capability (Di
Mambro et al., 2003). The DPPH method is based on
the quenching of stable DPPH radicals.
This is one of the few stable nitrous radicals,
having a purple colour which fades when reduced by
an antioxidant. The reaction is monitored by a
spectrometer at the wavelength of 515 nm. The IR
spectrometric analysis, along its improved version,
Fourier Transform (FTIR) allows the registration of
specific fingerprints based on functional groups, and
also some chemical changes taking place during the
oxidation processes (Juncan, 2011). FTIR is one of
the most widely used methods to identify the
chemical constituents and elucidate the compounds
functional groups and has been used as a method to
identify medicines in Pharmacopoeia of many
countries. Owing to the fingerprint characters and
extensive applicability to the samples, FTIR has
played an important role in pharmaceutical analysis

106

(Liu et al., 2006), being non-destructive, rapid, easy

to apply for emulsions, powders, liquids, without
preliminary extactions.
Recent reports show two different application
areas of this method. The first field covers biological
and medical applications, and the second area deals
with chemical process analysis, involving, for
example, the identification of chemicals or
applications in the field of reaction monitoring
(Kpper et al., 2001). Currently, FTIR spectroscopy
has gained a special attention as a reliable technique
for fat and oil analysis, due to its fingerprint
technique (Pui et al., 2013; Foudjo et al., 2013; Liu et
al., 2006; Strasburger and Breuer, 1985). The FTIR
method allows qualitative and quantitative analysis
of the chemical composition of emulsions, lotions,
hair care products and other categories of cosmetic
products (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 the
raw materials, or to measure the hydration of the
cream on the skin. FTIR can be successfully used
also for peroxide value (PV) determination in edible
oils based on the reaction between hydroperoxides
and triphenylphoshine stoichiometrically resulting of
triphenylphosphine (Marigheto et al., 1998).
Fourier
transform
infrared
(FTIR)
spectroscopy with sample handling technique of
attenuated total reflectance (ATR) was successfully
used to analyze virgin coconut oil (VCO)
quantitatively in cream cosmetic preparations. FTIR
spectroscopy combined with chemometrics of PLS
regression can be used as an analytical technique for
quantification 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 in
studying the stability of cosmetic or pharmaceutical
oil in water (O/W) emulsions. In this study
temperature storage tests were performed to
accelerate the aging process and evaluate the stability
of five emulsions. Emulsions were analyzed by FTIR
and classical methods (conductivity, viscosity, pH,
texture analysis) in order to determine a method that
would enable predicting the emulsions stability.
Epidermal surface characterization and
concentrations of vitamin E acetate (-tocopherol
acetate) in the stratum corneum were measured after
topical skin application and were performed by midinfrared attenuated total reflection spectroscopy. The
infrared methodology is rapid and can be applied to
small areas of skin. It is also sufficiently sensitive for
analysis of a large variety of cosmetic formulations
(Heise et al., 2001).
FTIR spectroscopic measurements have been
performed also on human hair (Dubief, 1992;
Strasburger and Breuer, 1985) and proved practical
use in the formulation and testing of milder, less
damaging, cosmetic products for hair care (Pande,
1994).

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

The use of IR spectroscopy for qualitative

identification of anionic surfactants has been
reported. Five raw materials, sodium lauryl sulphate,
ammonium lauryl sulfate, sodium lauryl ether sulfate,
sodium lauryl di-ether sulfate, and sodium alpha
olefin sulfonate (AOS), and four finished shampoos
have been analyzed (Sabo and Rosenberg., 1984).
The aim of this study is represented by the
survey of FTIR (ATR) specific fingerprints for the
characterization of three anti-aging cosmetic
formulations and the identification of specific
recognition markers of the active ingredients. The
antioxidant potential of alpha tocopherol acetate and
of the preservative BHA, usually used in cosmetic
formulations or added in a controlled way at known
levels of concentration, in a standard cream were
evaluated by the DPPH method, in parallel to FTIR
analysis (Juncan, 2011).
2. Materials and methods
Three types of cosmetic formulations,
obtained from a local supplier, were used; these were
denominated according to their intended purpose:
Anti-Wrinkle Eye Contour Cream, Intensive
Moisturizing 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 (Elton
Import - Export SRL), Octyldodecanol (Cognis
GmbH, Dsseldorf, Germany), Dimethicone
(Chematex S.A, Bucharest, Romania), Cetearyl
Alcohol (Cognis GmbH, Dsseldorf, Germany),
Stearic Acid (Biesterfeld Spezialchemie Romania
SRL, 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
Sativus
Extract&Propylene Glycol (Geniana SRL, ClujNapoca, Romania).
In performing the FTIR spectrometric method,
following reagents were used: ethanol (98%) (Merck
KgaA, Darmstadt, Germany), tetrahydrofuran (THF)
(Merck KgaA, Darmstadt, Germany), -tocopherol
acetate (BASF SRL, Bucharest, Romania), BHA (Jan
Dekker,
Langenfeld,
Germany).
For
the
determination 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%) (Merck
KgaA, Darmstadt, Germany), THF (Merck KgaA,
Darmstadt, Germany), -tocopherol acetate (BASF
SRL, 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. The

raw materials used for the manufacturing of the
creams, Glycine Soja Oil, Persea Gratissima Oil,
Octyldodecanol, Dimethicone, Acrylates/C10-C30
Alkyl Acrylate Crosspolymer, Tocopherol Acetate,
Glycerin, Cucumis Sativus Extract&Propylene
Glycol, were also applied directly on the plate, 1 mL
each. The other studied raw materials, Theobroma
Cacao, Cetearyl Alcohol, Stearic Acid, Cetearyl
Alcohol, Ceteareth 20, Glyceryl Stearate, BHA were
first 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 absorption
spectra was performed directly by utilizing a
Shimadzu 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 absorption
bands were identified, corresponding to types of
bonds and functional groups (expressed as cm -1).
The unsaturation, peroxidation and carbonyl
indices (Dubois et al., 1996; Guillen and Cabo, 2000;
Masmoudi et al., 2005) of the three studied antiaging creams were calculated starting from the data
obtained by FTIR spectrometry, using absorbance
values for certain frequencies and considering Eqs.
(1, 2). Unsaturation index (related to the absorption
band C=CH at 3006 cm1):
A3006
A3006 A2921 A2851

(1)

Carbonyl index (related to the respective the

absorption band C=O at 1746 cm1):
A1746
Ai

(2)

where Ai represents the sum of the area between

1800 and 650 cm-1.
The peroxidation index (the widening of the
3460-3480 cm-1 band).
2.3. Determination of the antioxidant activity using
the DPPH method
The antioxidant activity of the cream
ingredients was evaluated using two types of
measurements: by the controlled dosing of known
concentrations of alpha-tocopherol acetate (-TA)
and of the preservative butylated hydroxyanisole
(BHA) (Experiment A) and by direct measurement of
the respective antioxidant activity, at the
concentrations levels usualy mixed into the three
studied creams (Experiment B).
Experiment A. The antioxidant activity of the
alpha-tocopherol acetate and of the preservative
butylated hydroxyanisole (BHA) was tested on a

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Juncan et al./Environmental Engineering and Management Journal 13 (2014), 1, 105-113

Intensive Moisturizing Day Lift Cream cream, by the

controlled addition of various concentrations of
alpha-tocopherol acetate (-TA) and/or BHA. Table
1 shows the C0 - C6 concentrations of alphatocopherol acetate (-TA) and/or BHA that were
added 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 a
claimed concentration of 0,5 % -TA and 0,05 %
BHA. For the determination of the antioxidant
activity of the active ingredients through the DPPH
method, a BIOTEK Synergy HT Multi-Detection
spectrometer was employed. Using the analytical
balance, 0.5 g of sample (cream) were weighed onto
which 5mL of solvent THF: H2O (4:1 v/v) were
added. The samples were sonicated for 15 minutes
and centrifuged for 10 minutes at 10000 rpm. The
obtained supernatant liquid was used for the
determinations of the antioxidant activity, utilizing
systems of 24-well plates.
Table 1. Concentrations of -TA and BHA added in a
controlled 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
0.05
C6
0.1
0.05

The working procedure consisted of

dissolving DPPH (80 M) in ethanol (98%). The
stock solution was freshly prepared every day; the
mixture was shaken and kept at room temperature, in
a dark environment, for 10 minutes. For a volume of
20 L cream sample with 1750 L solution were
added onto each plate and the modification of the
solutions absorbance was monitored at 515 nm for 30
minutes, with respect to ethanol. The reference
sample contained 1750 l DPPH and 20 l ethanol.
The DPPH solution discolors from violet to yellow in
the presence of a hydrogen donor, and thus the
degree of free radical inhibition (I %) is established.
The same procedure was applied to tocopherol acetate and BHA for different
concentrations 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 and
slightly 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 creams
and FTIR spectra specific of some oily products

108

Fig. 1 shows by comparison, the composition

of the three studied creams. The different ratios
between lipophilic and hydrophilic components are
noticed. While the Anti-Wrinkle Eye Contour Cream
contains Stearic Acid, Cetyl alcohol, Octyldodecanol
and Glycerol, Cucumber extract and Potassium Cetyl
Phosphate, all organic components, the Intensive
Moisturizing Day Lift Cream has a higher ratio of
non-polar components (Glyceryl Stearate, Avocado
oil, Soja oil, Ceteareth 20) balanced with Glycerol
and Cucumber extract.
On the other hand, the Replenishing Night
Lift Cream contains less Soja oil and Cetyl Alcohol
but more Ceteareth 20 and Cocoa butter. To properly
interpret the FTIR fingerprint specific to this creams,
the generic FTIR spectra, specific to oily products
was chosen as guide, where the specific frequencies
of 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 assigned
to some functional groups from ingredients and
creams (Table 2). The region IV (below 1000 cm-1) is
marked by three frequencies characteristic to double
cis or trans bonds from unsaturated compounds
(unsaturated fatty acids, carotenoids or tocopherols)
which have a antioxidant potential. Zone III (10001800 cm-1) shows the presence of esters, saturated
fats or fatty acids (1718, 1743, 1379-14 cm-1) and
alcohols (1205-1165 cm-1) or esters (1043 cm-1).
Water absorbs in the areas higher than 3000
cm-1 and the oxidation products of lipids (peroxides
or epoxides) absorb above 3400 cm-1. Zone II (22702400 cm-1) is specific to carbonilic compounds,
generaly CO2 dissolved in creams generates such
signals. Zone I (frequencies above > 2800 cm-1) is
specific to C H and C = C bonds from lipids
polienic chains and natural fitosterols or cholesterol.
Based on this remarks, the specific spectra of
the components of the studied creams and namely the
natural 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 of
ingredients, emollients, emulsifier and antioxidant by
FTIR spectrometry
Fig. 3 shows the specific fingerprint for
different types of natural emollients found in the
compostion of the studied creams. Overall, these oils
have similar FTIR fingerprints, with similar signal
positions. Nevertheless, specific marker frequencies
were identified at 518, 912, 1257, 1317, 1396, 1417
cm-1, and 1654 cm-1 for Soja oil, respectively at 669
cm-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 signals
are observed. Thus, the recognition markers for
Octyldodecanol are at 721, 1035, 2852 and 3319 cm-

Application of Fourier Transform Infrared Spectroscopy for the characterization of sustainable cosmetics
1

, and for Dimethicone at 661-700, 1012, 1078 and

1411 cm-1. Fig. 5 shows the characteristic fingerprint
of the emulsifiers used in the studied creams.
Similarities in the spectra of Gglyceryl Stearate and
of Stearic Acid are noticed, however frequencies
characteristic of the Stearic Acid are observed at
1710, 890 and 1031 cm-1. For Cetearyl Alcohol and
for Ceteareth 20, the lack of the 1710-1734 cm-1
frequencies is noticed. In case of acrylates, the
fingerprint is totally different and has much less
signals. Fig. 6 shows the characteristic fingerprint for
different types of natural and synthetic antioxidants
found in the creams.

Characteristic
frequencies
(recognition
markers) for tocopherol acetate, were identified at
624, 678, 704, 736, 848, 898, 920, 1010, 1716, 2868,
2926 and at 2949 cm-1, 800, 1541 and 1636 cm-1 for
BHA. Thus it can be said that there are significant
differences between BHA and tocopherol acetate,
especially in the fingerprint area V-IV-III.
Tocopherol acetate shows many signals of high
intensity whilst it has less specific signals, only those
from 1541 and 1635 cm-1. In area I, the intensity of
the 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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Juncan et al./Environmental Engineering and Management Journal 13 (2014), 1, 105-113

Table 2. Identification of specific frequency regions characteristic for some oils and suspensions (creams) and their designations
Characteristic frequencies
(cm -1)

Frequency area
(cm -1)
Zone IV
< 1000

721
921
954
995
1743
1718

Zone III
1100 - 1800

Zone II
2270 - 2400
Zone I
> 2800

1643
1465
1379
1111
1109
1165
1205
1043
2358
2331
2850
2916
2954

- C = C trans
- C = C cis
COOH

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

C=O
|
OR

Free fatty acids

-CH2-CH3

Saturated fats

Aldehydes and ketones

(flavours)

- O-CH2
-C-O
C- OR
C=O
CH
(C = C) cis

Glycerin
CO2
Natural fatty acids
Cholesterol 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 different

types of emulsifiers

Fig. 6. Characteristic FTIR fingerprint of natural and

synthetic antioxidants

110

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

3.3 Characterisation of the active hydrophilic

components
Fig. 7 shows the characteristic fingerprint of
Glycerol and of Cucumber extract used in the studied
creams. 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 and
ketones).

(esters and fats) for the Intensive Moisturizing Day

Lift Cream and 800-1000 cm-1 for the Anti-Wrinkle
Eye Contour Cream (which contains more polar
compounds).

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

the three studied creams

Fig. 7. The characteristic FTIR fingerprint of Glycerol and

of Cucumber extract

3.4. Cosmetic cream characterisation by generic

FTIR spectra and fingerprint areas
Fig. 8 and Fig. 9 show the characteristic FTIR
(ATR) fingerprint areas of the studied creams. Fig. 8
shows the general spectra with the four characteristic
areas (I-IV) marked and Fig. 9, details about
fingerprint zone IV. All three studied creams have a
similar FTIR spectrum and are hard to tell apart; the
differences in composition shown in Fig. 1 are too
low to affect the IR absorptions.

The zoom of the region 800-1300 cm-1

shows some differences only at 1200 cm-1, where
the Replenishing Night Lift Cream has signals
attributed to C-O bands, found for Collagen,
Ceteareth and Theobroma Cocoa.
Table 3 includes the values of characteristic
frequencies and signal strength for the three studied
creams. Besides quantitative similarities marked with
bolded numbers, two types of characteristic
frequencies are also noticed, marked with ** and ***
respectively, for the Intensive Moisturizing Day Lift
Cream and Replenishing Night Lift Cream creams.
These data can be considered minimal markers of
discrimination 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 not
exhibit antioxidant activity by the DPPH method.
The obtained result is also confirmed by other studies
showing that the synergic antioxidant tocopherol
acetate, although more stable than tocopherol, does
not have any antioxidant activity (Di Mambro, 2003;
Fuchs, 1998; (Graf et al., 2008; Jung et al., 2007;).
Our complementary studies showed that even
when increasing the concentration of BHA or -TA,
there is no proportional increase of the antioxidant
activity. Table 4 shows the degree of unsaturation
values and of the carbonyl index, considering the
values of measured absorptions at diferent IR
frequencies (described in the Materials and methods
section).
6. Conclusions

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 does

show higher intensities for the region 1150-1200 cm-1

The use of FTIR spectrometry has allowed the

evidence of the characteristic fingerprint of the three
types of creams studied, and also of the ingredients
used to formulate the products, depending on their
role in the specific cream.

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Juncan et al./Environmental Engineering and Management Journal 13 (2014), 1, 105-113

Table 3. Characteristic frequencies and signal strength for the three studied creams
Frequency
area (cm-1)
IV

III

II

Anti-Wrinkle Eye Contour Cream

Wave number
920
993
1043
1078
1109
1165
1205
1247
1261
1379

Intensity
0.331
0.0662
0.1674
0.0968
0.0824
0.0327
0.038
0.0468
0.0544
0,0299

1465
1701

0.0648
0.0234

2331
2358
2848
2916
2954

0.0993
0.1521
0.182
0.2633
0.0712

Intensive Moisturizing Day Lift

Cream
Wave number
Intensity
921
0.0218
995
0.0623
1043
0.1815
1080
0.1043
1111
0.1027
1168
0.0826
1201
0.0571
1257
0.068
1286
0.0389
1379
0.0353
**1419
0.03
1465
0.0725
1718
0.0147
**1743
0.0286
2331
0.1011
2358
0.1586
2850
0.1606
2916
0.2372
2954
0.0732

Replenishing Night Lift Cream

Wave number
921
995
1043
1080
1109
1170
1203
1246
1259
1379
***1417
1465
1718
***1743
2331
2358
2850
2916
2956

Intensity
0.021
0.063
0.1699
0.1025
0.0955
0.0464
0.0433
0.0508
0.0569
0.0351
0.0297
0.0771
0.0137
0.0171
0.0864
0.1349
0.1891
0.2891
0.1086

Table 4. Degree of unsaturation (UI) and carbonyl indices (CI) for the studied creams
Sample
Anti-Wrinkle Eye Contour Cream
Intensive Moisturizing Day Lift Cream
Replenishing Night Lift Cream

UI
0.3631
0.3761
0.3631 0.3707 0.2315
0.3401
0.3581
0.3401 0.3801 0.2295
0.3447
0.3347
0.3447 0.4296 0.2553

Comparing the diferent compositions of the

creams, depending on the ratio of lipophylic to
hydrophylic ingredients, of emollient-emulsifier type
ingredients, antioxidant and active ingredients
(Cucumber extract, tocopherol acetate) there have
been noticed:
- similarities regarding the shape of FTIR spectra
between different natural emollients with the
evidence of some characteristic frequencies and
recognition 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
synthetic
emollients, Dimethicone and Oktyldodecanol.
- identification of differences between natural
antioxidants (-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 propylene
glycol compared to Glycerine both ingredients
being hydrophil.
For the studied creams, the FTIR the spectrum
is similar, but some differences in band intensities
can be noted and identified in the areas 1150-1200

112

CI
0.1621
0.1107
0.1008 1.3627
0.1956
0.1320
0.0942 1.3875
0.1854
0.1272
0.0972 1.3594

and 800-1000 cm-1. In conclusion, the data obtained

from the analysis of the ingredients is very useful and
does replace a database for their individual or class of
compounds identification. For creams with a
complex composition, especially when they differ by
reduced percentages between the polar and nonpolar
ingredients, it is hard to evidentiate the recognition
markers by the FTIR (ATR) method. Later studies
will be dedicated to proving the FTIR method for
investigating oxidative processes.
The antioxidant effect of creams which
include molecules with antioxidant potential seems to
be a complex issue needing further studies. Even if
molecules like BHA or -tocoferol, considered
individually, with antioxidant effect (by the DPPH
method), in complex mixtures with lipides, especially
when their concentration is below 1%, the
antioxidant action cannot be registred by usual
measurements. Higher sensibility methods, like
electronic spin resonance (ESR) could probably
deliver additional information about the antioxidant
potential of some complex mixtures, like anti-aging
creams.
Acknowledgements
The Biochemistry Department of the University of
Agricultural Sciences and Veterinary Medicine from Cluj-

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

Napoca is acknowledged for facilities provided and

assistence in this study. Special thanks are extended to
Prof. Dr. Johann Wiechers (JW Solutions, The Netherlands)
and Prof. Dr. Maria Lungu (President of the RSCCRomanian Society of Cosmetic Chemists) for their
enthusiastic support.

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