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Prediction Model for the Odor Intensity of Fragrance Mixtures: A


Valuable Tool for Perfumed Product Design
Miguel A. Teixeira, Oscar Rodríguez, and Alírio E. Rodrigues*
LSRE−Laboratory of Separation and Reaction Engineering, Associate Laboratory LSRE/LCM, Department of Chemical Engineering,
Faculty of Engineering, University of Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal

Rebecca L. Selway, Michelle Riveroll, and André Chieffi


Procter & Gamble Tecnical Centre Limited, Whitley Road, Longbenton, Newcastle upon Tyne, NE12 9TS, United Kingdom

ABSTRACT: In this work a previous model developed to account for the odor intensity of liquid perfumes was validated using
sensory evaluations performed by two different panels, one of professional perfumers and another of nontrained individuals
(consumers). For that purpose, several fragrance mixtures containing three perfumery raw materials (having different
physicochemical properties) and a solvent were formulated attending to the expertise of experienced perfumers. These mixtures
were then placed on textiles, allowed to evaporate, and then were subjected to experimental olfactory evaluations, being their
perceived intensity rated by perfumers and nontrained panelists. The perceived odor intensity of these samples was also predicted
using our model that considers fragrance release and intensity perception. The results obtained show a good correlation with the
ratings from both perfumers and nontrained panelists. In this way, it was shown that odor intensity can be predicted using a
structured model which accounts for the evaporation and olfactory perception of fragrances.

■ INTRODUCTION
Product development has been evolving rapidly since the 1990s
base notes.9 A note, for itself, defines the olfactory impression
of a single smell, or more specifically the perceived scent of a
where globalization pressures have triggered the need for better single or mixture of fragrance ingredients and/or essential
product designs, faster time to market, and lower cost of oils.7,10,11 Psychophysically it is the perceived odor sensation
production.1,2 The flavor and fragrance business is no exception induced by a stimulus magnitude.12 In this way, top and base
on this matter, with new trends and consumer products being notes are the most and least volatile ones, respectively, while
launched every year. However, the creation of perfumed middle notes are in between. According to Carles, we would
products, especially fine fragrances, is still an artistic, highly perceive top notes more strongly in the first moments after
individualistic, and creative job developed by well-trained application of the perfume and as these start to fade, the odor
perfumers. Consequently, the application of Product Engineer- would evolve into the middle notes and, finally, would reach
ing to fragrance design emerges as a valuable tool for that of the base notes (some of which are often used as fixatives
introducing scientific knowledge into a so far empiric and because they can change the tendency of evaporation of the
experimental area. Product design for fragrances will differ from remaining fragrances, thus allowing the perfume to last longer).
other formulated products as well as within its final application However, in terms of olfactory perception this is an
(eau de toilette, shampoos, or soaps). However, recent works oversimplification because all fragrant species evaporate
suggest that it is possible to reduce the number and quantity of continuously, though at different rates (which depend on
chemicals used in perfume formulation through the use of volatility, composition, molecular structure, and molecular
scientific principles, without any measurable reduction in interactions). These and other effects make it extremely
perceptual complexity.3−6 complex to formulate a perfume which will later have the
Fragrances are intrinsic to many consumer products globally desired smell whereby predicting that behavior becomes even
and are known to be a predominant reason for consumer harder. Due to these issues, perfumers play an important role in
delight, thus motivating purchase and repurchase. The main the formulation of such products. They have a deeper and more
function of a fragrance is, probably, to instill a pleasant and detailed perspective of the structure of a perfume, dividing it
harmonious odor to the product in which it has been into three important aspects: (i) the perfumery accord
incorporated and, thus, translate pleasant sensations when (aesthetical pleasantness of a mixture of fragrances); (ii) the
one perceives it.7 In short, fragrances have the role of enhancing relationship between top, middle, and base notes (composi-
products′ performance and attractiveness to consumers.8 tion); (iii) the balance between simplicity and complexity
However, perfumes are complex mixtures comprising different
fragrance ingredients mixed in a solvent matrix along with other Received: September 18, 2012
stabilizing compounds. In simple terms, the famous perfumer J. Revised: December 11, 2012
Carles compared the structure of a perfume to a pyramid Accepted: December 18, 2012
composed by three types of fragrant notes: top, middle, and Published: December 18, 2012

© 2012 American Chemical Society 963 dx.doi.org/10.1021/ie302538c | Ind. Eng. Chem. Res. 2013, 52, 963−971
Industrial & Engineering Chemistry Research Article

Figure 1. Molecular structures of the perfumery raw materials (PRMs) used in the formulation of the studied mixtures.

Table 1. Properties of the Chemical Components Used in This Work


mol. weight ODT P&Gc vapor pressure log
compound name CAS mol. form. (g/mol) (mg/m3) (Pa)a Pa n odor family
mineral oil (considered as hexadecane for 8042-47-5 odorless odorless
calculations) 544-76-3 C16H34 226.4 odorless 6.66 × 10−1 8.86 odorless
geraniol 106-24-1 C10H18O 154.2 0.077c 2.67 × 10−0 4.95 0.36b,c floral
habanolide 111879-80-2 C15H26O2 238.4 13.717c 7.05 × 10−3 4.95 0.80c amber-musk
iso-e-super 54464-57-2 C16H26O 234.4 0.107c 7.17 × 10−2 5.29 0.35c fresh-woody
a
From the Chemspider−RSC Database.35 bFrom the work of Devos et al.23 cCalculated from P&G data.

Table 2. PRM Mixtures with Corresponding Concentrations and Compositions in the Liquid Phase, Predicted Odor Intensities
(ψi), Together with Their Olfactory Evaluations Performed by Perfumers and Panelists
concentration (mg/fabric) mole fraction ψi intensity grade
iso-e- mineral iso-e- iso-e- perfumer panelist
N geraniol habanolide super oil geraniol habanolide super geraniol habanolide super average average
1 0.8 1.0 4.0 0.929 0.014 0.011 0.046 6.21 3.70 × 10−3 1.74 108.8 6.2
2 0.8 1.0 0.973 0.015 0.012 6.52 4.00 × 10−3 105.0 6.1
3 0.8 4.0 0.939 0.014 0.047 6.27 1.75 107.5 6.0
4 0.8 0.985 0.015 6.61 107.5 4.8
5 1.0 4.0 0.941 0.012 0.047 3.80 × 10−3 1.76 65.0 5.0
6 1.0 0.988 0.012 4.10 × 10−3 32.5 1.9
7 4.0 0.953 0.047 1.78 81.3 1.9
8 1 26.3 0.5
9 0.1 0.2 0.1 0.995 0.002 0.002 0.001 3.23 1.10 × 10−3 0.50 63.8 3.6
10 0.1 0.2 0.996 0.002 0.002 3.23 1.10 × 10−3 47.5 2.4
11 0.1 0.2 4.0 0.949 0.002 0.002 0.047 3.05 1.10 × 10−3 1.77 71.3 5.4
12 0.1 0.0 0.1 0.997 0.002 0.001 3.23 0.50 43.8 4.3
13 0.1 1.0 0.1 0.985 0.002 0.012 0.001 3.20 4.10 × 10−3 0.50 82.5 2.6
14 0.0 0.2 0.1 0.997 0.002 0.001 1.10 × 10−3 0.50 45.0 1.5
15 0.8 0.2 0.1 0.982 0.015 0.002 0.001 6.59 1.10 × 10−3 0.49 126.3 5.0
16 0.7 0.2 0.1 0.984 0.013 0.002 0.001 6.30 1.10 × 10−3 0.50 97.5 6.6
17 0.3 0.4 0.3 0.985 0.006 0.005 0.004 4.71 2.00 × 10−3 0.74 86.3 5.3

(number of ingredients) which also influences the price.7 sensation with concentration increase); (iii) perceived character
Altogether, these facts are reasons enough to consider human or quality (classification into olfactive families like floral or
sensory perception when designing new chemical products, citrus); (iv) hedonic tone (the degree of pleasantness or
despite the difficulties that may arise.4,13 annoyance of an odor).16−18 For all these reasons, the
For that purpose, the process of evaporation of a fragrance evaluation of the desired perceived odor is extremely difficult
from a specific substrate presents itself as an important step for to predict and so it is often experimentally determined by
the design and evaluation of novel fragrance materials or olfactory evaluations performed by trained or nontrained
products containing fragrance ingredients. Other authors have panelists.19 The use of nontrained panelists relies on the fact
reported that fragrance evaporation from different substrates that although perfumers play a key role in the formulation and
like the skin, clothes, or a paper blotter (often used in perfume evaluation of fragrances, the final product will ultimately be
try-outs) may be completely different, thus changing the evaluated by consumers who buy them. Thus, the design of
perceived odor (intensity, character, or both).14,15 This is so perfumed products must take into account both quantitative
because the process depends not only on the fragrances’ and qualitative parameters for odor perception. Although the
properties (physicochemical properties, molecular interactions latter is without a doubt very important from the consumer
within fragrance molecules, temperature, or pH, just to mention point of view, the former is easier to be evaluated.
a few) but also on fragrance interactions with the substrate in In this work, the odor intensity of several fragrance mixtures
which they are applied.15 When measuring odors there are (binary, ternary, and quaternary, including the solvent) placed
some parameters to be considered: (i) detectability (detection on textiles (substrate) were evaluated with two different panels
or recognition thresholds); (ii) intensity scale (the perceived and also predicted with a theoretical model. This model
964 dx.doi.org/10.1021/ie302538c | Ind. Eng. Chem. Res. 2013, 52, 963−971
Industrial & Engineering Chemistry Research Article

accounts for fragrance evaporation and human perception, ether, and an alcohol of low olfactive intensity) for the
predicting the odor intensity from the liquid composition of dissolution of the PRMs, but these performed poorer than the
perfumery raw materials (PRMs) using physicochemical and mineral oil because they either left residues or significantly
psychophysical properties that can be estimated from hampered the perceived odor.
correlations or obtained from the literature. The different Olfactory Evaluations. The headspace of the fragrance
intensity ratings were correlated in order to demonstrate that mixtures applied on the textiles was evaluated for all samples,
human evaluations and predicted odor intensities are after equilibration and near the point of application. It should
comparable and simply recall different scales of the same be highlighted that the solvent matrix (mineral oil) is odorless
property. Three PRMs selected by perfumers from Procter & and so is not perceived. For the case of the binary mixtures,
Gamble were used. The PRMs partly follow the definitions of they consist of a single PRM dissolved in the odorless mineral
Carles:9 geraniol is a middle note, habanolide is a typical base oil (matrix), hence what is expected to be perceived is the PRM
note and also a fixative, and iso-e-super represents a low middle alone. Samples were evaluated through olfactory analysis made
to base note. by perfumers from P&G and nontrained panelists. This panel

■ MATERIALS AND METHODS


The experimental work was carried out at Procter & Gamble
was composed by 30 nontrained people, 13 men and 17
women aged between 17 and 57 years. The panelists presented
averages of 31.6 and 35.9 years for male and female panelists,
(P&G) while all the modeling was performed at LSRE. respectively. For the olfactory evaluations, panelists were able
Materials. Two of the fragrance ingredients used in this to smell the pure fragrance components prior to the analysis of
work were supplied by IFF as geraniol (3,7-dimethyl-2,6- the samples. These were presented to panelists and perfumers
octadien-1-ol, CAS no. 106-24-1) and iso-e-super (1- enclosed in tin foil and were analyzed independently in blind
(1,2,3,4,5,6,7,8-octahydro-2,3,8,8-tetramethyl-2-naphthalenyl)- tests (without knowing the concentrations). These evaluations
ethan-1-one, CAS no. 54464-57-2) while habanolide (12E- were performed at controlled room temperature, were not
oxacyclohexadec-12-en-2-one, CAS no. 423773-57-3) was intensive, and were carried out at the same time of the day per
obtained from Firmenich. The mineral oil was supplied by mixture stimulus and subject. Throughout the testing protocol
Sigma-Aldrich (CAS no. 8042-47-5). Textiles used in this work each nontrained panelist evaluated five samples randomly
were woven cotton towels with 100 cm2 (10 cm × 10 cm, dry (which could be repeated, although every sample was new and
textile). The molecular structures of fragrant molecules studied not reused). This corresponds to an incomplete block design,
in this work are presented in Figure 1, and their corresponding as panelists only judge a subset of the samples (more details on
psycho-physicochemical properties are shown in Table 1. this type of design of experiments are given by Lawless and
Perfume Mixture Formulation and Application on Heymann,20 and examples of this design applied for fragrance
Textile. Fragrance mixtures were formulated by P&G mixtures and olfactory evaluations are presented in the
perfumers, who defined the required concentrations of each extensive compilation of design of experiments from Cochran
PRM for each sample in order to obtain a pleasant odor as and Cox21). Panelists rated the perceived intensity on a 10 cm
presented in Table 2. This is based on the olfactory expertise of line scale as described in the literature.22 This linear or line
P&G perfumers (both in terms of quality and intensity) for the scale method uses marks or anchors at both ends of the scale,
formulation of different fragranced consumer products with starting from “none” or zero perceived stimulus (at the left end
specific concentrations that correspond to pleasant odors in the of the scale) to “strong” or high intensity stimulus (at the right
olfactive intensity scale shown in Figure 2. Consequently, these end of the scale). Panelists rated the perceived odor intensity of
each sample by placing a mark on the horizontal line scale. Such
marks were then converted to numbers by measuring the
position of each mark on the scale using a ruler.22 Moreover,
fresh coffee beans were used to clear the nose receptors in
Figure 2. Olfactive intensity scale used from perfumers at Procter & between every evaluation.
Gamble. Four perfumers also rated samples randomly in nonintensive
tests using an olfactive scale as presented in Figure 2. This
mixtures have a combination of a blooming floral note intensity scale ranges from 0 to 200 units where values close to
(geraniol) with a heavier fresh-woody scent (iso-e-super) zero mean no detection, values near 20−30 represent
together with a fixative compound (habanolide) to increase recognition thresholds, values above 120 may provoke nuisance
its long lastingness. For that purpose, different fragrance and at the top end of the scale (200 units) they are considered
mixtures were formulated comprising seven quaternary, six as painful.
ternary, and three binary mixtures plus a blank and two Odor Detection Thresholds and Intensity−Concen-
validation samples. In all mixture formulations, the PRMs tration Plots. Odor detection thresholds (ODT) and power-
(Table 2) were made into respective one, two, or three stock law exponents (n) were calculated by P&G. The ODT data
solutions (the PRMs added gravimetrically into 10 mL of were calculated by P&G using a QSAR (quantitative structure−
mineral oil) of varying ratios with aliquots of 100 μL taken and activity relationship) model that is proprietary from P&G. The
added to the fabric as per the design of experiments (DoEs). power-law exponents were calculated from line scale experi-
Each 100 μL fragrance solution was dispensed onto a 10 cm × ments carried out by P&G perfumers, as presented for geraniol,
10 cm square of cotton textile (dry textile), which was habanolide, and iso-e-super in Figure 3. Throughout these
immediately enclosed by hand in a flat tin foil and left to experiments, samples with increasing concentrations were rated
equilibrate (at controlled room temperature) for 2 h prior to by perfumers using a line scale. The same intensity scale
the olfactory analysis of their headspace (by panelists who previously used for the samples was applied here (see Figure 2),
opened the foil and smelled the fabric immediately after). It is while concentrations are indicated as headspace chromato-
to be noted that other matrices were tested (e.g., pentane, ethyl graphic areas (arbitrary units). This allows avoiding a complex
965 dx.doi.org/10.1021/ie302538c | Ind. Eng. Chem. Res. 2013, 52, 963−971
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contained only three odorant species the PTD methodology is


perfectly suitable to predict and graphically represent the
perceived odor intensity and character of any ternary fragrant
mixture.10,26 For that purpose, the odor intensity above a liquid
mixture of any volatile PRM (ψi) can be calculated using
Stevens’ Power Law for olfaction as presented in eq 1.12,27
⎛ C g ⎞ni
ψi = ⎜ i ⎟
⎝ ODTi ⎠ (1)

where Cgi is the concentration of an odorant i in the gas phase


(g/m3), ODTi is its corresponding odor detection threshold
(g/m3), and ni is the power law exponent for intensity
perception. As previously mentioned, the ODT and n
parameters were calculated by P&G, and a summary of these
results is presented in Table 1. Moreover, once we did not
know the concentrations in the gas phase for each fragrance
compound, we have used the PTD predictive methodology to
calculate it, which is based on the (liquid) mass composition of
each PRM (plus the solvent) applied in the fabric as
experimentally performed by P&G. From that, mole fractions
for those mixtures can be calculated and then the perceived
odor intensity (ψi) of each PRM can be predicted using the
PTD methodology.10,26 For that objective, in a mixture of N
fragrant components it is necessary to account for the
molecular interactions in the liquid phase and so the
composition of the different fragrant components in the gas
phase above the liquid can be calculated from the modified
Raoult’s law for vapor−liquid equilibria (VLE) as previously
reported elsewhere.10,26,28 That includes the determination of
activity coefficients in the liquid phase (γi) due to nonidealities,
reflecting the affinity and interactions of each molecule with the
other compounds. While for an ideal solution γi is unity, for a
nonideal solution γi ≠ 1, evidencing deviations from Raoult’s
Law.28 Therefore, in a perfume mixture, the activity coefficient
can be seen as a measure of the tendency of a fragrance
molecule to stay in the liquid phase or to be “pushed out” into
the headspace. In this way, if γi > 1, the concentration of the
fragrant component i in the headspace will be higher than in an
ideal solution, which means that molecules will be more pushed
out from the solution into the gas phase. When γi < 1, the
Figure 3. Curves of odor intensity versus headspace peak areas for
geraniol, habanolide, and iso-e-super. opposite effect happens and so lower concentrations of the
odorant species i will be found in the headspace due to a higher
affinity to the surrounding medium.10,26 Like this, eq 1 can be
experimental setup for the measurement of fragrance rewritten as:
concentrations in air. It is important to note that the power- ⎡ ⎛ P satM ⎞⎛ 1 ⎞⎤ni
law exponent calculated for geraniol is the same as that ψi = ⎢γixi⎜ i i ⎟⎜ ⎟⎥
recommended by Devos et al.23 Iso-e-super is a mixture of ⎢⎣ ⎝ ODTi ⎠⎝ RT ⎠⎥⎦ (2)
isomers so its intensity scale depends on their relative
composition, which is critical once they have very different As a result, the odor intensity of each perfumery raw material
ODTs.24 The power-law exponent for habanolide is not (ψi) can be predicted from pure component data as the
available in the literature. Moreover, the character classification composition in the liquid phase (xi), molecular weight (Mi),
of each PRM was defined by the perfumers through olfactory saturated vapor pressure (Psati ), and odor detection threshold
evaluations (see Table 1). (ODTi), plus the psychophysical power law exponent (ni). R
Modeling of Perceived Odor. In order to establish a and T are the universal gas constant and absolute temperature,
simple model that could replicate the physical experiments respectively. The molecular weight appears in the numerator
performed in this work, it is necessary to account for fragrance due to unity consistency with the ODT. Additionally, in eq 2
evaporation and odor perception. A previously developed appears the activity coefficient (γi), which is a function of the
methodology at LSRE, called Perfumery Ternary Diagram composition and can be calculated from experimental vapor−
(PTD) seems to be suitable for modeling these phenomena as liquid equilibrium (VLE) data or predicted using suitable
will be presented ahead.10,25 For that purpose, it was assumed a methods. In this work the UNIFAC28,29 group contribution
dry fabric substrate where the fragrance ingredients placed on it method was used for the prediction of the VLE and the activity
were evaporating into the air. Since the perfumery mixtures coefficients of the chemical components. The solvent used in
966 dx.doi.org/10.1021/ie302538c | Ind. Eng. Chem. Res. 2013, 52, 963−971
Industrial & Engineering Chemistry Research Article

Table 3. UNIFAC Groups Used for the Perfumery Raw Materials (PRMs) with the Corresponding Volume and Surface
Parameters
molecule (i) subgroup (j) group number subgroup number νj(i) Rj(i) Qj(i)
geraniol CH3 1 1 3 0.9011 0.848
CH2 1 2 3 0.6744 0.540
CHC 2 8 2 0.8886 0.676
OH 5 15 1 1.0000 1.200
habanolide CH2 1 2 11 0.6744 0.540
CHCH 2 6 1 1.1167 0.867
CH2COO 9 19 1 1.6764 1.420
iso-e-super CH3 1 1 4 0.9011 0.848
CH2 1 2 5 0.6744 0.540
CH 1 3 2 0.4469 0.228
C 1 4 1 0.2195 0.000
CC 2 70 1 0.6605 0.485
CH3CO 9 18 1 1.6724 1.488
hexadecane CH3 1 1 2 0.9011 0.848
CH2 1 2 14 0.6744 0.540

the experiments (mineral oil) is a mixture of hydrocarbons. Carles. It allows mapping the perceived dominant odor for any
Thus, in order to estimate the solvent activity coefficients, it possible ternary/quaternary mixture of fragrance ingredients. In
was considered as hexadecane, since their physical and chemical the case of a ternary mixture, the three components A, B, and
properties are similar (see Table 1). C, represent three types of fragrant notes used in the
For the intensity of a mixture of PRMs with N fragrant formulation where each one will be placed in the vertex of
components, there will be N different odor intensities, one for the triangle. Within this diagram it is then possible to express
each component, to be calculated in the headspace. In order to any composition of three components by a set of ternary
account for the odor intensity of such mixtures, the stronger fractions (e.g., molar, volume, weight). It is possible, though, to
component (SC) model was used. It states that within a incorporate another component in the system (for example a
mixture of perceived scents in the air the odorant with the solvent, S) in order to differentiate it from the concentrated
highest odor intensity will be more strongly perceived and perfume mixtures and also to get closer to a real perfume
recognized by the human nose.30,31 This model is expressed by formulation, as was done in this work. In a four component
eq 3: mixture, it is necessary to define pseudoternary compositions
using a solvent-free basis composition, which is performed by
ψmix = max{ψi }, i = 1, ..., N (3) recalculating the ternary molar fractions of the three other
Like this, if we consider a quaternary fragrance mixture, eq 3 components as follows:
reduces to xA xB
xA′ = , x B′ = ,
ψmix = max{ψA , ψB , ψC , ψS} xA + x B + xC xA + x B + xC
(4)
xC
where the subscripts are defined in this case as follows: A xC′ =
xA + x B + xC (5)
geraniol, B habanolide, C iso-e-super, and S mineral oil.
This SC model is an approximation to the odor intensity of where xi′ is a pseudoternary composition for the corresponding
mixtures of odorants and presents several advantages when fragrant component (A, B, C) in the quaternary system (A, B,
compared with others like the vectorial model, U model, UPL2 C, S).
model, additivity model, the equiratio mixture model, or the So, for any composition of a mixture of PRMs, it is possible
euclidean additivity model.27,30,31 Most of them use binary to predict the perceived odor intensity and, thus, map in the
parameters that need to be obtained from experimental data PTD the different odor zones where one PRM presents the
(e.g., for a quaternary mixture, there are six different binary highest odor intensity, dominating the scent over the others.
pairs for which these parameters have to be determined). The Finally, it is noteworthy that in this odor perception model
SC and euclidean models are simpler since they do not need no interactions between the textiles and the PRMs were
such parameters, but even so, they perform as well as the considered (e.g., adsorption of PRMs to the fibers and their
others.25,26 Note that the SC model (as well as others) does not partitioning between air and fibers). To support this premise, it
reflect quite common observations in olfaction (like weaker was assumed that a thin film of a liquid mixture of PRMs highly
odors being able to increase or decrease the intensity of a dissolved in the mineral oil was placed over a textile (dry fabric)
strong odorodor enhancementor effects of hypoadditivity and from that point the evaporation of PRMs occurred at
or hyperadditivity). It is a simple method for the prediction of different rates.
odor intensities of mixtures and gives some assurance that the All calculations were computed in MATLAB software.
intensity of a mixture will not be grossly larger than the odor Molecule group assignments for the UNIFAC method are
intensity of its strongest odorant. shown in Table 3. For each fragrant molecule it is presented the
PTD Methodology. The concept of PTD10,32 is a division into groups and subgroups, the number of groups of
combination between engineering ternary diagrams (commonly type j in molecule I (v(i)
j ); the parameters of molecular van der
used in thermodynamics or phase separation processes) and the Waals volumes (R(i) (i)
j ), and surface area (Qj ). As the solvent
tripartite, pyramidal structure of a perfume suggested by J. (mineral oil) is a mixture of paraffins, hexadecane was
967 dx.doi.org/10.1021/ie302538c | Ind. Eng. Chem. Res. 2013, 52, 963−971
Industrial & Engineering Chemistry Research Article

considered for calculation purposes and it is included in Tables in the reported evaluations than with perfumery experts.
1 and 3 with its properties and UNIFAC groups. Further details Nevertheless, a good correlation was obtained between the
on the UNIFAC method can be obtained from the literature.28 predicted odor intensities and the evaluations from nontrained

■ RESULTS AND DISCUSSION


Comparison between Olfactive Evaluations and the
panelists (r2 = 0.70, F = 35.6, p-value < 0.0001). Again, the
correlation is statistically significant, and the existence of a
linear relationship (r2 = 0.70) indicates that both odor intensity
Model. One of the targets of this work was to evaluate the scales are equivalent. Thus, it seems reasonable to assume that
relationship between olfactive evaluations carried out by to the light of the model applied here for odor intensity, the
perfumers and the predicted odor intensity for each mixture evaluations performed by panelists are not so different from
(ψi) using the proposed model. For that purpose, the those of the perfumers. This shows that, in terms of quantifying
evaluations from perfumers were arithmetically averaged (four odors, the olfactory mechanism presents little discrepancies
perfumers) as presented in Table 2. It should be noted that 13 (especially for higher concentrations) between perfumers and
out of the 17 experiments are mixtures, while the remaining nontrained panelists, although it is known that, in terms of
refer to pure raw materials (PRMs) dissolved in mineral oil and qualitative classification, the latter have much more difficulty to
a blank. A correlation between the perfumers’ average assign fragrances to words.33,34
evaluations and the predicted maximum odor intensity values Finally, in order to avoid getting results affected by the
was obtained. This correlation is presented in Figure 4 together properties of the original sample we have performed a
validation test using the jackknife procedure for the experi-
ments with perfumers and nontrained panelists. The jackknife
estimate of standard error for the reference set is determined by
successively leaving one sample out. This means that applied to
a sample with size N, it performs the computation of each
sample statistics on N separate samples of size N − 1 (where
each sample contains the original data with a single observation
omitted). From the jackknife statistical analysis applied to our
samples for the correlation coefficient, it was seen that the bias
for this statistic is equal to −0.0044 and −0.0081 for perfumers
and panelists, respectively. This means that the sample
correlation is probably underestimating the true correlation
by these amounts. Moreover, it was obtained a low value for the
estimate of the standard error which was equal to 5.1% and
8.1% for perfumers and panelists, respectively. Consequently, it
is concluded that the jackknife estimates are very consistent,
indicating that our results are not biased by the influence of any
sample. Therefore from the jackknife analysis alone, it is
Figure 4. Correlation between the predicted mixture odor intensity possible to say that our results are consistent and valid.
(ψ) and the arithmetic average grade from perfumers. Finally, from the obtained correlations with perfumers and
nontrained panelists, we have also calculated the estimated
with the statistics obtained (r2 = 0.81, F = 62.4, p-value < error for the two validation samples (N = 16 and 17). It was
0.0001). It is seen that the correlation is statistically significant observed an average error in the prediction of 14.5% (average
and that the coefficient of correlation between the two variables of 19.8% and 9.3%) and 4.9% (average of 2.7% and 7.2%) for
is very good, showing a strong linear relationship between perfumers and panelists, respectively.
perfumers’ evaluations and the maximum odor intensity (ψmix) Application of the PTD Methodology. The previous
predicted from the odor perception model. The existence of a section shows the proof of concept for our model and its
linear relationship (r2 = 0.81) indicates that predicted odor predictive ability for the perceived odor intensity of simple
intensities and perfumers’ olfactive evaluations are equivalent fragrance mixtures. It is possible at this point to extend its
odor intensity scales. It is also seen that the two validation applicability to all the composition range of three PRM
samples (N = 16 and 17) are well-predicted by the correlation mixtures or even to other ternary/quaternary mixtures using
represented in Figure 4 (squares). the PTD methodology. Such a model would be extremely
Furthermore, an olfactory intensity analysis was also helpful for designing new fragranced products. This perfumery
performed by nontrained panelists at P&G. In this way, it tool combined with the psychological power law and the
was intended to correlate the maximum predicted odor stronger component model was used to predict the perceived
intensity (ψi) with the olfactory evaluations performed by odor of any possible mixture with the selected three PRMs and
panelists. Each sample was rated by nontrained panelists at least a constant amount of solvent. The obtained PTDs are
8 times (see Table 4). From these evaluations the arithmetic presented in Figure 6 showing the map of the perceived
averages were calculated and then correlated with the predicted dominant odors for any mixture of three fragrant components
intensities from the odor perception model. The obtained (the perfume concentrate, left) and for the quaternary mixtures
correlation using the evaluations from nontrained panelists is (right) with an average molar composition of mineral oil (xS =
shown in Figure 5. It is seen that the correlation performed 0.975). This composition (xS) is an average value obtained
with nontrained panelists is not as good as that obtained with from all mixtures used in the experiments (see Table 2) which
perfumers. However, it should be emphasized that the use of a have a very narrow range (from 0.928 to 1.000). It is seen that
nontrained panel together with the incomplete block design the middle note (geraniol) and the middle-to-base note (iso-e-
used for their evaluations is likely to introduce more variability super) divide the left diagram into two parts, while the fixative
968 dx.doi.org/10.1021/ie302538c | Ind. Eng. Chem. Res. 2013, 52, 963−971
Industrial & Engineering Chemistry Research Article

Table 4. Evaluations of the PRM Mixtures Carried out by the Panel of ConsumersReference Number (ref) and Intensity
Grade (IG)
sample panelist average standard deviation
1 ref 4 12 20 24 25 25 26 26 30
IG 7.5 4.9 5.6 4.2 7.6 3.9 7.5 9.1 5.1 6.2 1.8
2 ref 2 9 13 13 16 23 26 28
IG 8.7 9.6 7 3.9 4 6.2 5.4 3.8 6.1 2.2
3 ref 1 9 9 10 11 12 21 23
IG 2.1 4.3 9 6.4 8.9 6.2 5.4 5.6 6.0 2.3
4 ref 8 16 20 20 21 22 25 27
IG 8.9 3.3 2.2 3.1 4.9 8.5 3 4.6 4.8 2.6
5 ref 3 3 7 11 17 18 23 27
IG 4.3 5.8 6.9 3.3 1.6 5 6.5 6.2 5.0 1.8
6 ref 1 3 6 9 11 16 18 21
IG 0.6 0.4 3.7 1.9 5.1 0.3 2.8 0.4 1.9 1.8
7 ref 2 5 6 9 13 15 18 22 29
IG 4.9 0.2 5.4 0.4 0 0.8 5.5 4.4 0.3 2.4 2.5
8 ref 2 5 14 19 23 26 27 29
IG 0.3 0.1 0.7 0 2.1 0.2 0.8 0.1 0.5 0.7
9 ref 1 2 4 7 10 14 17 23 28
IG 0.5 2.5 0.4 1.6 4.8 8.2 3.6 8.4 1.8
ref 1 4 5 8 10 15 17 28
IG 0.9 2 1.4 5.9 1.8 10 2.9 4.3 3.6 2.9
10 ref 2 12 13 14 14 18 19 21 24
IG 1.2 2.5 0 5.8 5 1.7 1 1.3 3.1 2.4 1.9
11 ref 4 6 6 8 8 12 24 24
IG 5.3 6.4 5.1 6.1 8.2 6.8 1.4 3.8 5.4 2.1
12 ref 6 7 10 15 15 17 20 22 27
IG 3.3 4.4 5.3 4.1 5.1 3.8 1.1 6.7 4.9 4.3 1.6
13 ref 4 5 7 13 16 16 19 21
IG 6.7 1.5 4.5 2.7 1.2 1.5 2.1 0.3 2.6 2.1
14 ref 1 7 8 11 11 12 19 25 30
IG 0.3 1.1 2.6 3.2 1.8 0.3 0.3 4 0.3 1.5 1.4
15 ref 3 5 18 19 20 22 25 29
IG 8.1 3.6 5.5 2.6 3.6 9.8 2.5 4.4 5.0 2.7
16 ref 10 22 24 27 28 28 30 30
IG 6.9 9.4 2.4 8.2 5.9 7.9 5.7 6.3 6.6 2.1
17 ref 3 14 15 17 26 29 29 30
IG 7.3 4.9 6.1 5.2 7.1 3.3 3.6 4.6 5.3 1.5

since habanolide is a fixative. The odor zone for geraniol is also


larger than for iso-e-super as expected for a middle and a
middle-to-base note, respectively. On the other hand, a
significant difference in the odor zones of the PTDs is
observed when the mineral oil is introduced. It appears that
when the PRMs are dissolved in mineral oil, iso-e-super tends
to be more retained in the solution, and so, it is only strongly
perceived at low geraniol concentrations. This prediction was in
fact reported by P&G perfumers throughout their olfactory
evaluations.
Consequently, the PTD can be used as a tool to map the
odor character as shown in Figure 6, and it can also represent
the odor intensity of each PRM as a function of its
concentration in the mixture. Thus, the predicted odor
intensities for each PRM are shown separately in Figure 7 for
the perfume concentrate as a function of the composition. It is
seen that the odor intensity scales plotted on the right of the
Figure 5. Correlation between the predicted mixture odor intensity PTDs have different ranges (so that the gradient colors for odor
(ψ) and the arithmetic average grade from panelists. intensity can be discriminated), especially for habanolide whose
odor intensity range is very low as expected for a fixative note.
(habanolide) is only strongly perceived when pure. This It is known from perfumery that this component is not strongly
phenomenon was expected from the perfumery point of view perceived but has an important role when in a mixture by
969 dx.doi.org/10.1021/ie302538c | Ind. Eng. Chem. Res. 2013, 52, 963−971
Industrial & Engineering Chemistry Research Article

Figure 6. PTDs for the ternary mixture (left) of geraniol (A, green squares) + habanolide (B, pink triangle) + iso-e-super (C, yellow circles) and
quaternary mixture (right) including a fixed composition of mineral oil (xS).

Figure 7. Predicted odor intensities for each fragrance ingredient as a function of its composition in the ternary mixture: (A) geraniol, (B)
habanolide, (C) iso-e-super.

retaining longer in the solution the other PRMs. Finally, it is


also observed that geraniol has higher odor intensities than iso-
■ ACKNOWLEDGMENTS
This work is partially supported by project PEst-C/EQB/
e-super for low concentrations of it (lower part of the diagram)
LA0020/2011, financed by FEDER through COMPETE−
because it is typically more volatile than the latter.


Programa Operacional Factores de Competitividade and by
FCT−Fundaçaõ para a Ciência e a Tecnologia. O.R. acknowl-
CONCLUSIONS edges financial support of Programme Ciência 2007 (FCT).
Two correlations were obtained between both the perfumer M.A.T. acknowledges his Postdoc. grant from FCT (SFRH/
average and panelist average olfactory evaluations with a BPD/76645/2011).


predictive model for the odor intensity of fragrance mixtures.
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