Академический Документы
Профессиональный Документы
Культура Документы
pubs.acs.org/IECR
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 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
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
CHC 2 8 2 0.8886 0.676
OH 5 15 1 1.0000 1.200
habanolide CH2 1 2 11 0.6744 0.540
CHCH 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
CC 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 odorodor enhancementor 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
Table 4. Evaluations of the PRM Mixtures Carried out by the Panel of ConsumersReference 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
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.
■
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.
Although these use different metric scales and comparisons are REFERENCES
not straightforward, the obtained results have shown a good
agreement between our predictive model and the experimental (1) Wesselingh, J. A.; Kiil, S.; Vigild, M. E. Design & development of
evaluations, which are very difficult to model at this level so far. biological, chemical, food and pharmaceutical products; Wiley: Chi-
chester, U.K., 2007.
It should be noted, however, that although the applied model
(2) Costa, R.; Moggridge, G. D.; Saraiva, P. M. Chemical product
neglects specific fragrance−textile interactions, it is able to
engineering: an emerging paradigm within chemical engineering.
describe a large part of the variance from olfactory evaluations AIChE J. 2006, 52 (6), 1976−1986.
using humans. And very important from a product engineering (3) Teixeira, M. A.; Rodríguez, O.; Rodrigues, S.; Martins, I.;
perspective, it is a purely predictive model. In this way, it is Rodrigues, A. E. A case study of Product Engineering: Performance of
possible to use the proposed odor perception model, which has microencapsulated perfumes on textile applications. AIChE J. 2011, 58
its own metric scale for odor intensity, for comparison with the (6), 1939−1950.
intensity rating scales obtained from perfumers or panelists. (4) Cussler, E. L.; Wagner, A.; Marchal-Heussler, L. Designing
The achievements found in this work are of great relevance Chemical Products Requires More Knowledge of Perception. AIChE J.
once the developed odor perception model can be applied for 2010, 56 (2), 283−288.
the prediction of the odor intensity of fragrance mixtures and, (5) Bagajewicz, M.; Hill, S.; Robben, A.; Lopez, H.; Sanders, M.;
thus, be useful in the preformulation stages of fragrance design. Sposato, E.; Baade, C.; Manora, S.; Coradin, J. H. Product Design in
■
Price-Competitive Markets: A Case Study of a Skin Moisturizing
Lotion. AIChE J. 2011, 57 (1), 160−177.
AUTHOR INFORMATION (6) Ulrich, K. T.; Eppinger, S. D. Product Design and Development, 5th
Corresponding Author ed.; McGraw-Hill: New York, 2011.
*Phone: +351 22 508 1671. Fax: +351 22 508 1674. E-mail: (7) Calkin, R.; Jellinek, S. Perfumery: Practice and Principles; John
arodrig@fe.up.pt. Wiley: New York, 1994.
(8) Bagajewicz, M. On the Role of Microeconomics, Multi-scale
Notes Planning and Finances in Product Design. AIChE J. 2007, 53 (12),
The authors declare no competing financial interest. 3155−3170.