Note: Descriptions are shown in the official language in which they were submitted.
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IMPROVING THE VALUE OF VOLATILE MATERIALS
FIELD OF THE INVENTION
The present invention relates to the use of volatile, normally complex,
materials,
especially complex materials having a distinct physiological effect, to
influence consumer
attitudes, e.g., acceptance and/or preference, toward products and/or
services. The invention
comprises improvements in: novel complex materials including those useful in
influencing
consumer attitudes and the definition of such complex materials; improvements
in research and
production processes relating to such complex materials, especially complex
materials having a
volatile component and physiological activity; and/or to the use of such
definitions of such
materials for purposes of obtaining patents, trademarks, copyrights, etc. to
improve the value of
such materials.
BACKGROUND OF THE INVENTION
A traditional and very subjective approach for determining a perfume's odor
character is
the use of odor descriptors. This method is not very reliable because the
result can vary from
judge to judge. One effort to simulate the human olfactory system was the
development of
different "electronic noses" which are arrays of multiple sensors where each
sensor yields a
different response to a specific type of chemical in a "headspace". The
signals recorded by the
sensors give a spectral signature or characteristic pattern that can be
associated with a given odor.
The current electronic noses are not yet adequate to describe a perfume's
character. The
electronic nose provides a "finger print" of the whole headspace without the
capability of
isolating the effect of the extraneous and non-contributing ingredients, such
as highly volatile
solvents. These solvents normally exist as major components in the headspace,
do not contribute
noticeably to the character of the fragrance, but can interact strongly with
the sensors and are
reflected prominently in the measurements.
Volatile materials such as perfumes are often used to help create a favorable
impression
for consumer products such as detergents, fabric softeners, etc, and to
improve the impression of
the fabrics treated with such products. Perfumes are also sold to create
favorable impressions for
consumers themselves, either directly, or by addition to consumer products
that are used, e.g., in
the mouth such as mouthwashes, tooth pastes, etc., or on the body, such as
skin soaps, shampoos,
etc. However, many products such as designer clothing and other expensive
items are not
normally associated with perfumes. Often, the consumer learns to associate
these volatile
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materials with particular suppliers, whereupon many unscrupulous competitors
of those suppliers
try to appropriate the resulting good will by copying the volatile materials
as closely as they are
able. Protection of the good will and defining the volatile materials for the
purpose of providing
such protection has been very difficult. Thus, there has been a long-standing
need for a better
way to define such complex materials, especially those that are volatile, and
especially those with
a physiological effect such as perfumes and/or flavors. For example,
International Application
WO 02/48700 A2 for METHOD FOR CLASSIFYING CHEMICAL SUBSTANCES
ACCORDING TO OLFACTORY CHARACTERISTICS filed in Germany on Dec. 14, 2000,
discloses a method of checking detergent finished products using an electronic
nose with a
preferred sensor system having 12 sensors.
It has been reported that applications were filed in Europe for a method of
defining
perfumes in trademark applications using the artificial nose. There is still a
need to develop an
improved method for digitally mapping and objective classification of perfume
odor character
and/or flavor character, for use in, e.g., prevention of imitation via
trademark and/or patent.
SUMMARY OF THE INVENTION
The present invention relates to: A. the definition of either a single complex
material
comprising a mixture of compounds, especially those having a physiological
action, and/or a
definition of all of the complex materials that share one or more
characteristics, especially by an
improved method for digitally mapping and objective classification of complex
materials having
one or more similar characteristics such as perfume odor character and/or
flavor character and/or
physiological effects, using the results from an analytical procedure that
provides more multiple
results (multivariate results) than an artificial nose, and desirably provides
results for most of the
volatile components, such as headspace mass spectrometry, and/or optionally by
combining such
results with, the results of other analytical methods that provide multiple
results, such as nuclear
magnetic resonance spectroscopy, etc., and even more especially where the
definition is based on
the comparison of the analytical results for the single complex material with
the analytical results
for more than one complex reference material; B. the use of complex materials
such as perfumes
to identify the source of products, services, etc. that originate from a
specific supplier, and
especially the use of the improved definitions of A. to provide intellectual
property protection for
such use; C. the methods of influencing consumers to purchase a product of
service in which one
or more complex materials, typically and desirably a volatile material having
an odor, are used to
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influence a consumer to purchase a product or service not normally sold in
association with an
odor, or in association with a separate odor; D. the evaluation of two or more
complex materials
having one or more similar characteristics to define a range of mixtures
sharing one or more
common characteristics and/or to determine which, if any, specific members of
the mixture are
responsible for a specific characteristic; andlor E. novel complex materials
or individual novel
materials identified with the assistance of the methods of A. and/or D.
BRIEF DESCRIPTION OF THE FIGURES OF THE DRAWINGS
FIGURE I is a dendrogram of the Hierarchical Cluster Analysis of 12 reference
perfume
compositions (Perfume Set A).
FIGURE II is a pictorial representation of a Principal Components Analysis of
the spatial
relationship between 11 reference perfume compositions (Perfume Set A).
FIGURE III are spider diagrams providing a pictorial representation of several
perfumes
as compared to 11 reference perfume compositions (Perfume Set A).
FIGURE IV is a dendrogram of the Hierarchical Cluster Analysis of 12 reference
perfume compositions (Perfume Set B).
FIGURE V is a pictorial representation of a Principal Components Analysis of
the spatial
relationship between 11 reference perfume compositions (Perfume Set B).
FIGURE VI are spider diagrams providing a pictorial representation of several
perfumes
as compared to 11 reference perfume compositions (Perfume Set B).
FIGURE VII is a dendrogram of the Hierarchical Cluster Analysis of 5 reference
coffee
compositions.
FIGURE VIII is a pictorial representation of a Principal Components Analysis
of the
spatial relationship between 5 reference coffee blends.
FIGURE IX are spider diagrams providing a pictorial representation of several
coffees as
compared to 5 reference coffee compositions.
DETAILED DESCRIPTION OF THE INVENTION
A. DEFINITION OF COMPLEX MATERIALS
The definition of complex materials, especially those having a physiological
action, is
complicated. The number of ingredients can be very large and, for naturally
occurring materials,
can involve subtle differences in the mixture and/or the compounds of the
mixture. In order to
describe all of the complex materials that share one or more characteristics,
the present invention
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makes use of an improved method for digitally mapping and objective
classification. The
methods described herein can define complex materials having one or more
similar
characteristics such as perfume odor character and/or flavor character and/or
other physiological
effects including medicinal effects, using an analytical procedure giving
multiple results such as
headspace mass spectrometry, and optionally using such results, or combining
such results with,
the results from other analytical methods that provide multiple results, such
as nuclear magnetic
resonance spectrometry, etc. The methods can also evaluate complex materials
to discover
problems with the said complex materials that need to be corrected.
It is highly desirable to have a definition of a composition that uses only
the essential
information needed to ensure that the composition has the desired
characteristics. The
"electronic nose" does not provide sufficient and adequate information and can
provide
information that is misleading since the "electronic nose" does not
discriminate between
compounds that share similar response characteristics to the sensor array used
in the electronic
nose, and is severely affected by the presence of nonessential components in
the composition,
thus a definition provided by the "electronic nose" will include compounds
that do not provide
the desired characteristics of the composition. On the other hand, elaborate
and thorough
chemical analysis methods typically can provide too much information and
unnecessarily define
all aspects of chemical compounds including those that are not relevant to the
desired
characteristics, nor wanted in the definition. Such a definition based upon a
complete analysis
can also exclude desirable compounds by providing a definition that is limited
to just those
compounds found by the analysis and thus excluding optional, but desirable
compounds. It is
desirable for many reasons, including quality control, intellectual property
protection, etc., to
provide a definition that prescribes limits on the structure and amounts of
compounds that are
relevant to the desired characteristics of the compositions containing them.
The present method
achieves this difficult compromise by utilizing complex reference materials.
The present invention desirably utilizes one or more analytical methods that
provide
analytical results for many different constituent materials of a mixture
(multivariate results). The
results of the analysis of any given complex mixture are then defined by
relating said results to
the results obtained by a similar analysis of one or more complex materials
that are defined as
"reference materials". This technique allows one to define and/or create a
range of complex
mixtures that are related, especially with respect to one or more
physiological effects. The
definitions herein are desirably based on more than one complex reference
material.
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Thus, the method herein can comprise defining the character of at least one
specific
complex material in digital form wherein the said complex material is analyzed
using at least one
multivariate analytical method, the results of the analysis are normalized
with respect to at least
two different complex reference materials, said reference materials
representing a range of
5 complex materials that is of interest and sharing at least one or more
traits of the character of the
specific complex material, and the results are given as a number, a range of
numbers, and/or a
geometric figure on a graph that defines the said complex material by
comparison with the said
reference materials. Said number and/or said geometric figure is desirably
expressed as a range
defining an area comprising similar specific complex materials, especially
when the complex
material is volatile and the analysis is obtained from vapor phase mass
spectrometry. The
materials can also be analyzed by other analytical methods including nuclear
magnetic resonance
spectroscopy, and/or Fourier transform infrared spectroscopy, and/or Raman
spectroscopy. The
results of the resulting analysis or analyses by such analytical methods can
be analyzed using a
computer and a pattern recognition program to determine the degree of
similarity/difference to
the reference material or materials and the results are desirably stored in
digital form.
The use of multiple complex reference materials enables one to identify a
range of
materials with greater accuracy and with more variation in characteristics
than the use of a single
complex reference material. The use of two reference materials enables one to
identify a range
of mixtures of materials with more precision and the use of at least three
reference materials
enables one to define an area in which the materials share one or more
characteristics.
Vapor phase mass spectrometry, for example, can be accomplished with
commercially
available equipment in a matter of minutes, yet can successfully predict the
behavior of complex
materials having physiological effects like perfumes, especially when multiple
complex reference
materials having similar physiological effects are used. The definition can be
made more precise
by using reference materials with similar compositions, or can be used to
define the "perfume
character" more broadly by utilizing reference materials with more diverse
compositions. The
results show that vapor phase mass spectrometry is a better predictor of
perfume character than
the "electronic nose", which was specifically developed for the purpose of
analyzing perfumes
and other environmental volatile materials.
During the work which demonstrated the effectiveness of using vapor phase mass
spectrometry for characterizing perfumes, it was found that an even better
and/or broader
definition could be achieved if the analyzed perfume was compared to more than
one other
"reference" perfume, even perfumes which had different characters than the
analyzed perfume.
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The selection of the other reference perfumes increases the range of the
method to allow one to
determine "areas" of perfume products that share the same character, even
though the formulas
for the perfumes are quite different. If multiple reference perfumes with
highly different
compositions and/or characters are used, the definition can predict, with a
good degree of
confidence, composition areas where new character traits can be found. With
reference perfumes
that are very different in character, it is possible to map out areas of
different perfume character,
even character that has been previously unknown.
It was also discovered that by using available pattern recognition software,
one can
compare various perfumes and establish the components responsible for the
differences in
character. Thus, one can create a family of perfumes with similar character
while minimizing the
number of ingredients, the amount of research involved, and/or the cost of the
perfume, e.g., by
using synthetic ingredients for non-essential components of the perfume.
It was also discovered that one can determine what compound structure(s) are
responsible
for a given character, thus allowing one to predict new perfume ingredients
with desired
character to simplify research in developing such new ingredients.
A highly desirable method uses a rapid headspace analyzer that combines mass
spectrometry and chemometrics for discrimination and classification of
fragrance samples by
their volatile compositions. This chemical sensor relies on a scan of mass
fragments over a m/z
range of 35-200 of the total headspace, which essentially provides 165 nearly
independent
channels of information. Chemometric software is desirably then used to
organize that
information and build models for discrimination and classification.
As discussed before, the only previous attempt to define complex mixtures such
as
perfumes involved the "electronic nose", which was not acceptable. The
electronic nose is
composed of a solid-state sensor array. The electronic nose provides a "finger
print" of the
whole headspace without the capability of isolating the effect of the
extraneous and non-
contributing ingredients, such as highly volatile solvents that do not
contribute to the character of
the fragrance, but exist as major components in the headspace and are present
prominently in the
measurements.
The use of vapor phase mass spectrometry for determining whether a product
meets
certain specifications has been disclosed. However, it has only now been
discovered that vapor
phase mass spectrometry can be used to establish whether a material is a
functional equivalent of
another material, even when the overall analysis of the materials differs
substantially.
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In vapor phase mass spectrometry, the effect of highly volatile solvents,
e.g., those that do
not contribute to the character of a fragrance, can be isolated and removed
from the data
analyses. Surprisingly, it has been determined that a mass spectrometer using
vapor phase mass
spectrometry is capable of determining the physiological effect of an unknown
volatile complex
material by relating to known reference complex materials with known
physiological effects.
Even when the volatile portion of a complex material is only a small part of
the total complex
material, the results of the analysis can predict the physiological effect
with a relatively high
degree of accuracy. With respect to perfumes, the results are much better than
from the
electronic nose that uses multiple sensors and takes much longer. The
resulting digital display
from the vapor phase mass spectrometer can be used for purposes of defining a
range of mixtures
sharing one or more characteristics.
A headspace analyzer that is especially useful in the present invention is a
"chemical
sensor" which combines a mass spectrometer that is adapted to sample the
headspace with
software that provides a pattern recognition capability to provide data
analysis and classification.
An instrument that is well suitable for use in the present invention is the
Gerstel ChemSensor
4440 Chemical Sensor system. The Gerstel ChemSensor 4440 Chemical sensor
system has four
components: an HP 7694 headspace automatic sampler for introduction of
headspace samples, a
mass spectrometer with a sensor array using quadrapole technology, an
integrated
chemometric/pattern recognition software package from Infometrix, Inc., for
instrument control,
data analysis, and reporting, that is loaded in a high-performance personal
computer. The whole
mixture of headspace volatiles from a perfumed sample is transferred directly
to the mass
spectrometer where all of the volatiles are fragmented and ionized. The mass
spectrometer is
designed to register the signals of the resulting charged ions over a user-
selectable range from 2
to 800 atomic mass units. This results in a pattern that is unique to the
particular sample. Pattern
recognition and clustering software are capable of differentiating and
grouping samples
according to their unique mass spectral pattern or "fingerprint". Samples that
are more similar to
one another in volatile chemical composition, and hence odor character, are
grouped more
closely together, while samples that differ widely will be far apart.
A suitable method for objective classification of odor characters of the
present invention
comprises the following steps:
I. Select two or more reference materials of known composition, desirably
about 5,
more desirably about 10, even more desirably 15 or more, reference materials.
This is the
reference set or the training set. Reference samples should be chosen that are
representative of
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and span the range of compositions and odor characters that are likely to be
encountered in the
application. This is true whether the application be fragrances, perfumes,
foods, beverages, etc.
Desirably, reference samples can be characterized by using sensor descriptors
recognized by
those skilled in the art; however, this is not a prerequisite to successful
application of this
method.
2. Make multiple (n) measurements on each reference sample. Measurements are
done by headspace-mass spectrometry. Data obtained are the mass spectral
channel signals (m/z)
after electron-ionization of the volatiles in the headspace over the sample.
More generally, data
can consist of signals from any multivariate analysis system or be a
collection of univariate data
obtained from several independent measurement techniques. Replications of the
(n)
measurements, desirably at least about 4 times, more desirably at least about
6 times, should be
made on each reference sample. Each set of replicates for a given sample is
hereinafter referred
to as a reference "class".
3. Pre-process the data. The data in this example are desirably pre-processed
by
vector normalization, however there are several options for pre-processing
depending on the type
of data obtained.
4. Verify class distinctions for the reference set. Verify that differences
within a
reference class (intra-class variance) are smaller than differences between
reference classes
(inter-class variance). This may be done using any of a variety of clustering
methods, such as
Hierarchical Cluster Analysis (HCA), factor analysis techniques such as
Principal Components
Analysis (PCA), or any other statistical or discriminant analysis tests. Those
skilled in the art
will recognize that significant difference can be defined by any of several
statistical criteria.
5. Build a classification model for the reference set. Those skilled in the
art would
recognize that there are a variety of classification methods available. In the
present method,
apply SIMCA classification (Pirouette 0.0, Infometrix, Inc.) to the reference
set to determine the
inter-class distances between the reference set samples.
6. With the reference samples established, one can make one or multiple (n)
measurements on test, or unknown, samples. Test samples can be unknown samples
or any
samples for which objective classification relative to the reference set of
samples is desired.
Replications of the (n) measurements can be desirable for averaging or for
comparison to other
test, or unknown, samples. Measurements should be made on each test sample in
an identical
manner as for the reference samples.
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7. Determine the "distance" from each test sample to each of the reference
classes.
(In the art, typically, test samples are given to trained sensory experts who
assign scores using
sensory descriptors recognizable by those skilled in the art.) In the present
method, test samples
are compared to a set of reference materials for which the composition is
known and well-
defined. Ideally, the reference samples can also be characterized by unique
sensory descriptors.
In typical use, the SIMCA classification model constructed from a training set
would be used to
"predict" the class assignment of test samples. This determination is based on
how well the test
sample can be modeled by any one of reference class models, relative to the
others. A good or
poor "fit" into a class depends on the magnitude of a test "residual",
"distance" or error of fit. In
this example, an average "distance" is calculated from each test sample to
each of the reference
classes. A smaller distance implies similarity to the reference class, while a
larger distance
implies difference.
8. Optionally, but desirably, one can display result(s) which visually depict
the
similarity or difference of the test sample relative to reference samples.
This can be done using a
radial plot (also called "spider diagram" or "star plot") in which each of the
reference classes is a
terminal point. The "distance" of the test sample to each of the reference
classes is plotted
graphically. In situations where the reference samples are readily
characterized by sensory
descriptors and the measurements can be shown to correlate with these sensory
descriptors, then
the similarity or difference of the test sample relative to the reference can
be used to predict the
sensory characteristics of the test sample. In situations where these criteria
are not met, this tool
nonetheless offers a means by which to objectively classify test samples
relative to a set of
reference samples of known and well-defined composition.
By using suitable reference fragrances with known chemical composition and
character, it
is possible to classify new perfumes by their distance from these references,
i.e., as coordinates in
a multidimensional perfume space. The selection of preferred reference
standards and their
formulation are part of the invention and are exemplified herein.
It was also found, surprisingly, that complex materials having a physiological
effect could
be defined in terms of other different complex materials, even those having
different characters
and/or physiological effects. However, desirably, the other complex materials
are of similar
character or effect. The method involves analyzing such a material using a
mass spectrometer,
optionally normalizing the data, and using pattern recognition software to
determine the degree
of similarity of said material to the same data derived from known reference
materials having the
same or different characters, but which are generally representative of the
desired character, the
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character of the reference materials being determined by their effect on at
least one person.
Surprisingly, the comparison results in the definition and/or determination of
the character of the
"unknown" material.
Suitable software for practicing the methods herein include:
5 Pirouette (Infometrix, Inc., 10634 E. Riverside Dr., Suite 250, Bothell, WA
98011) ; Simca-P
(Umetrics, Inc., 17 Kiel Avenue, Kinnelon, NJ 07405) ;
The Unscrambler (CAMO Software Inc., Aspen Corporate Park, 1480 Route 9 North,
Suite 209, Woodbridge, NJ 07095); MatLAB-Statistics Toolbox (The MathWorks,
Inc., 3 Apple
Hill Drive, Natick, MA 01760-2098); and SAS/STAT software (SAS Institute Inc.,
100 SAS
10 Campus Drive, Cary, NC 27513-2414).
It is possible, by using a spider graph, to define an area that represents
complex materials
sharing the same physiological effects. This definition is based upon a
comparison with
reference materials of known physiological effects. The process desirably
includes the provision
of a collection of data from reference materials comprising one or more
volatile compounds and
representing a variation in at least one character element based on a
physiological effect as
experienced by at least one individual. Such an area can be used for
definitions used in obtaining
intellectual property including trademarks, copyrights, and patents, as
discussed hereinafter,
where claims can contain definitions utilizing such an area.
For example, one can define the limits of one or more odor or flavor
characters,
optionally as specified by at least one flavor or odor expert, in terms of the
said analytical results.
For purposes of creating new materials, defining complex materials, and/or
comparing
complex materials, it is desirable to have a computer program to combine and
compare the
results of mass spectrometry and/or nuclear magnetic resonance spectrometry
analytical
procedures on different complex materials. Therefore, it is desirable to have
a computer-readable
medium containing instructions for comparing an analysis of a target complex
material, said
analysis being derived from a mass spectrometer, nmr, or combinations thereof,
to one or more
similar analyses of other reference complex materials and defining the target
complex material in
terms of the differences between the target complex material and the reference
complex
material(s).
The method herein can also be described as the method of defining a specific
complex
material comprising the steps of analyzing said complex material using at
least one multivariate
analytical method, normalizing the results with respect to at least one
complex reference
material, said reference material, or materials, representing the range of
complex materials that is
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of interest, and giving the results as at least one number or geometric figure
that defines the said
complex material by its relationship to the said reference material or
materials, said number
and/or said geometric figure optionally defining an area comprising similar
specific complex
materials.
When the complex material is volatile the analysis is desirably obtained from
a vapor
phase mass spectrometer but the complex material can be analyzed using
headspace mass
spectrometry, and/or nuclear magnetic resonance spectroscopy, and/or Fourier
transform infrared
spectroscopy, and/or Raman spectroscopy. As described above, the results are
desirably
analyzed using a pattern recognition program to determine the degree of
similarity to the
reference material or materials and the results are desirably given in digital
form.
When the complex material is volatile and has at least one physiological
effect that is
odor and/or taste, it is preferred that there are at least two complex
reference materials that
represent a range of complex materials having similar physiological effects.
A desirable method comprises the following steps: (a) select a reference set
comprising a
number, n, of reference complex material samples which span the breadth of
odor and/or taste
characters of interest, and which are used as n distinct references; (b) using
headspace mass
spectrometry, determine the mass spectral channel signal pattern of the
headspace of each of said
n reference samples, and use them to define an "n-dimension space" with each
reference sample
defining one dimension; (c) determine the mass spectral channel signal pattern
of the headspace
of one or more test samples; (d) define the location of said test sample or
test samples, in said n-
dimension space, by determining the differences between said test sample or
samples and each of
the reference samples, by defining the distances from said test sample or test
samples to the
reference samples; and, optionally, (d) defining an area around the test
sample or test samples
that contains complex materials having similar physiological properties.
In another preferred highly desirable method, reference materials are chosen
that are
representative of, and span the range of, compositions and characters that are
likely to be of
interest for the specific complex material to comprise a reference set;
multiple measurements are
made on each reference material; the data for the reference set are optionally
pre-processed by
vector normalization; optionally, verify that differences within a reference
set are smaller than
differences between the reference set and a different set having different
characteristics;
optionally, build a classification model for the reference set; optionally,
make multiple
measurements on the said specific complex material; determine the "distance"
from each test
sample of the specific complex material to the reference sets; and optionally
display the result to
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visually depict the similarity or difference of the said specific complex
material relative to the
reference sets. The above method can also be used to predict characteristics
of a mixture of
complex materials by using the method on each component of the mixture and
combining the
results mathematically and comparing the combined results to the said
reference material or
materials.
Desirably the methods herein utilize a computer-readable medium containing
instructions
for comparing an analysis of a target specific complex material said analysis
being derived from
mass spectrometry, nuclear magnetic resonance spectroscopy, gas
chromatography, infrared
spectrometry, and/or Raman spectrometry, electronic nose, image analysis, or
combinations
thereof, to more than one similar analysis of other reference complex
materials and defining the
target complex material in terms of the differences between the target complex
material and the
reference complex materials.
The method herein desirably can use as the reference material or materials
ingredients
that have been determined in previous iterations to provide the most influence
on the
determination of the characteristic of interest.
B. Intellectual Property Protection
The methods described herein can be used to define a complex material, or a
range of
complex materials, for the purpose of obtaining trademark, copyright, or
patent protection. The
application for a trademark or a trade name on a material, including complex
materials or
commercial products, uses at least a portion of either its mass spectrometry,
its nuclear magnetic
resonance spectroscopy, or both, to cover both the material and other
materials having the same
essential characteristics if the definition allows for variability of the
relative frequency for at least
some of the individual points in the resulting spectrograph or spectrographs.
Thus, the discovery, in one preferred embodiment, involves the use of vapor
phase mass
spectrometry to define a material such as a perfume by digital means. The
digitized results can
then be used, for example, for the purpose of filing trademark applications,
patent applications,
etc. The digital expression can also be copyrighted. For a trademark, the
issue, as always, is
whether there is an association of the perfume with the source of the product
in the mind of the
consumer and whether another perfume being used by a competitor will result in
confusion.
Although one can simply file a trademark application on the digital version of
the vapor
phase mass spectrometry analysis of a specific complex material, it is
normally desirable to use a
broader definition. For example one can use a relative similarity index as
exemplified
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hereinafter. For definitions that are more usable to cover functional
equivalents, it is desirable to
use a"pattern recognition" software program to compare the analyzed material
to one or more
similar reference materials and allow for a reasonable degree of variation,
or, more desirably, the
complex material is defined by comparison to more than one reference material.
The use of
multiple complex reference materials allows one to define complex materials
as, e.g., an "area"
of materials on a spider diagram when plotted against the multiple reference
materials where said
complex materials share at least one common characteristic.
The use of results from a different, or additional, analytical process such as
nuclear
magnetic resonance spectrometry can be helpful in providing a definition for
purposes of
applying for trademarks, copyrights, patents, etc., since nuclear magnetic
resonance spectrometry
can be used for non-volatile materials. Thus, the invention comprises the
method, or process, of
filing an application for a trademark, copyright, patent, or a trade name on a
material, including
commercial products, in which the material is characterized by at least a
portion of its mass
spectrometry, of its nuclear magnetic resonance spectrometry, or of both, the
application
covering both the material and other materials having the same essential
characteristics by
utilizing a definition allowing for variability of the relative frequency
(which correlates with the
amounts of materials of components of materials indicative of the amounts of
individual
compounds) for at least some of the individual points in the resulting
spectrograph or
spectrographs from the analyses.
It has long been desired to protect complex materials such as perfumes from
piracy.
However, it has not been possible heretofore to reliably and easily identify
either a perfume or
perfumes that share the same odor characteristics. The current methods allow
one to effectively
use them to identify individual perfumes and even equivalent perfumes, for
products, services,
etc. that originate from a specific supplier. The improved definitions herein,
which are desirably
in digital form, can be used to define areas that can be used in claims for
intellectual property
protection for such uses.
When a complex material is effective in creating good will on the part of the
consumer,
competitors try to copy the material to take advantage of the reputation and
good will built up by
the material. This invention provides protection, especially intellectual
property protection, of
complex, normally volatile, materials so they can used to provide favorable
impressions for
consumer products and services. The use of normal analytical methods,
especially vapor phase
mass spectrometry, to define complex materials, especially complex materials
containing one or
more volatile components, and especially complex materials useful in providing
favorable
CA 02684181 2009-10-30
14
impressions to consumers, and more especially such complex materials having a
physiological
action such as perfumes and/or flavors, allows one to provide effective
intellectual property
protection. The use of such analytical methods allows one to define a complex
material in
digital form, which is also very convenient when computers are used to control
quality,
production, etc. The digital definition of such complex materials can be
copyrighted to prevent
"pirates" from using the digital definition; can be used as the basis for a
trademark application;
and can be used to define inventions for patent purposes.
As described above, one can also use definitions of perfumes using less than a
complete
spectrum analysis by limiting the definition to the content of the most
important components,
especially those listed herein, so as to minimize the size of the definition
and to eliminate less
relevant components such as solvents which can be present in much less and/or
much greater
amounts without making a major change in the perfume character. Thus, one can
define a
perfume by that portion that remains after the first few minutes, after the
most volatile
compounds have evaporated.
In order to ensure that the perfume as perceived by the consumer is correct,
the perfume
can be checked by using individual compounds as reference points when
analyzing the headspace
over, e.g., a substrate treated with the perfume or a composition containing
the perfume.
Trademark Protection
The use of vapor phase mass spectrometry to provide a definition of a complex
material,
especially a perfume, for purposes of obtaining trademark protection is highly
desirable. Vapor
phase mass spectrometry has proven more accurate than the "electronic nose"
for defining such
materials. It is also much easier to use. The trademark can be coupled with a
copyright on the
digital expression of the mass spectrometry results to prevent would-be
pirates from stealing the
essence of a perfume for their purposes.
The trademark can be on the name of the perfume itself, or on the perfume as
it provides
an identity for a product or service with which it is associated.
The identity of the perfume can be defined based on a specific analytical
result obtained
by using specific analytical equipment, or, more desirably, to such a result
with a certain
percentage variation in the results. The identity of the perfume can also be
conveniently defined
to allow for variation by making a graph of the results of a vapor phase mass
spectrometry
analysis and then providing upper and lower limits by using lines both above
and below the
graph. The definition can also be made by comparison to one or more complex
reference
materials and by utilizing only the fragments that make the major contribution
to the character.
CA 02684181 2009-10-30
Thus, the trademark can comprise only the more substantive ingredients.
However, one can use
both the complete perfume and one or more distinctive fractions of the perfume
as trademarks.
Copyright Protection
It is highly desirable to copyright the digital expression of the results of
any of the
5 described mass spectrometry analyses. One can also copyright the digital
expression of the
results of the digital analysis by means of the "electronic nose" although
such a copyright is
much less useful. The copyright of the broader protection is not as useful,
but can be included
using a series of graphs with gradually increasing limits. Each of the limits
can be more, or less,
than the analytical results or definition by, e.g., 1, 2, 3, 4, 5, 10, or 20%
in decreasing order of
10 specificity and increasing order of scope of coverage.
Patent Protection
The use of analytical results for filing patent applications is well known.
However, it has
not been suggested that the analysis of a perfume, flavor, etc. using vapor
phase mass
spectrometry could adequately define the range of compositions that would be
operable in
15 providing a desired physiological effect. As in the copyright applications,
each of the limits can
be more, or less, than the analytical results or definition by e.g., 1, 2, 3,
4, 5, 10, or 20% in
decreasing order of specificity and increasing order of scope of coverage.
C. METHODS OF IMPROVING ACCEPTANCE OF PRODUCTS AND/OR
SERVICES (Association of a Complex Material with a Product or Service)
The invention comprises methods of improving commercial acceptance of
products, e.g.,
goods, and/or services comprising at least one step of associating a volatile
material having a
physiological effect of a particular character with a commercial product used
by a consumer or a
service performed for a consumer where said commercial product or service has
a primary
benefit unrelated to the said physiological effect, and where either the: (1)
said association takes
place at one or more times after the initial exposure of the said commercial
product to the said
consumer, or, (2) where said commercial product is designer clothing or other
branded articles,
the association can take place starting at the point where the consumer is
initially exposed to the
said designer clothing or other branded articles, or before, or, (3) where the
said commercial
product is a food, or drink, the said volatile material is collected at some
time during the
preparation of said food or drink and is exposed to the consumer independent
of the product, but,
optionally, where the product is either present, or is being advertised or
sold.
Typically, the association is created by advertising that can be either on the
product
container, on other product packaging, in print advertising, or in electronic
media advertising,
CA 02684181 2009-10-30
16
and the association clearly states the connection of the volatile material's
character with the
product or service.
Typically, the products can be: (a) a personal care product which is: either a
skin care
product; an antiperspirant or underarm deodorant; air care product; or tanning
product and the
volatile material has the same, or complementary, character as the perfume of
the said personal
care product, the volatile material being exposed to the consumer after the
initial use so as to
reinforce the association of the volatile material and the product; (b) a
laundry product and the
volatile material has the same, or complementary, character as the perfume of
the said laundry
product, the volatile material being exposed to the consumer after the initial
use so as to reinforce
the association of the volatile material and the product; (c) clothing,
especially designer clothing,
optionally bearing a specific designer label and the volatile material,
optionally, but desirably, a
perfume, has a character that either identifies the said clothing as being
from a specific supplier,
or, in another aspect, is used to create a desire in the consumer to purchase
the clothing, e.g., by
eliciting an emotional response associated with the end use of the clothing;
(d) branded articles of
manufacture such as hand bags, ski equipments, automobiles, and the like where
the volatile
material is used as an identifier and/or to elicit an emotional response that
promotes sale, (e)
brewed coffee, especially where the volatile material is obtained during the
roasting of one, or
more of the coffee beans used to brew the said coffee; (f) cooked, especially
baked or fried
goods, where the volatile material is collected when the goods are baked or
fried and then
exposed to the consumer nearer the point of sale; and/or (g) perfume products
where the volatile
material is part of the perfume product and is exposed to the consumer at a
time before sale, e.g.,
to demonstrate the character without using the total perfume and/or after the
consumer has used
the perfume to augment the perfume portions that are lost first.
The use of volatile materials to create a favorable consumer impression
requires that the
character of the physiological effect of the volatile materials be desirable
and consistent with the
consumers' expectations for the product and/or service that is being offered
to the consumer.
This is a complex interaction and a successful selection of such volatile
materials normally
requires considerable effort by experts who have both scientific and artistic
abilities. The
creation of such volatile materials typically results in complex formulations
in which the effect of
each ingredient is extremely difficult to quantify.
The protection of such formulations has typically been by use of a "trade
secret" in which
the formulation has been protected from becoming public knowledge. This has
allowed "pirates"
to create similar formulations, often without regard to the quality, safety,
and aesthetic issues
CA 02684181 2009-10-30
17
faced by the originator of the original formulation. Consumers are therefore
put at risk when
they select the product or service with the mistaken belief that it originated
from the first
supplier.
Heretofore it was difficult to protect the good will created by the use of a
complex
material such as a perfume in association with a product or service. The
ability to define and
protect such a complex material and the good will that it can create is a
major advantage of the
invention. The choice of a perfume for association with a particular product,
or service, can be
very difficult, involving the creation of many different perfumes and the
consumer research to
determine which of the many possible perfumes best complements the product or
service
objective. The character of a perfume that best influences the perception of
the consumer that the
product or service is acceptable for the consumer's need is primarily
determined by relatively
few of the components in the perfume, but it is very difficult to determine
which components are
responsible for the good effect.
As discussed hereinbefore, it is possible to use the methods herein to create
intellectual
property to protect the complex materials and/or their association with
products and/or services.
II. Tvpes of Products and Services
Branded Personal Care Products
It is highly desirable to associate a perfume with a branded commercial
product that is a
personal care product. Non-limiting examples of personal care products
include: (a) a skin care
product; (b) an antiperspirant or underarm deodorant; (c) hair care product;
(d) tanning product,
and the like. It is preferable that the volatile material has the same, or
complementary, character
as the perfume of the said personal care product. Thus, it is possible to
create an association of
the perfume of the product with the product itself so that the consumer
recognizes that the
perfume indicates the source of the product and it is also possible to create
an association of a
portion of the perfume of the product with the product, i.e., the volatile
portion of the perfume of
the product can be used independently of the product to create a feeling of
comfort for the
consumer in selecting the product.
An example of the above would be the presentation of the volatile portion of
the perfume of
a product at the point of selection to confirm that the consumer has located
the desired product.
This presentation can be accomplished by a spray that is either activated by
the consumer, or
automatically by some means, or by a "scratch and sniff" strip on the product
package. This is
especially important where the product comes in a variety of perfume
variations and the
CA 02684181 2009-10-30
18
consumer prefers one of the variations or wants to check the perfume before
the purchase. This
approach is particularly desirable for perfumes and colognes and would
supplement the "sample"
approach that can often cause distress for others in the area. The scratch and
sniff approach
typically provides a bare minimum of the volatile portion of the fragrance. If
desired, the
residual perfume can be placed in a separate strip so the consumer can
appreciate what it will
smell like.
The volatile portion can be sold separately to supplement the perfume and/or
to create the
desired feeling.
Thus, the perfume and/or its volatile portion can be used as trademarks for
the product,
assuring the consumer that the product is, in fact, the one that is desired.
It is also possible to use a perfume (volatile material) that has a
complementary character
to the perfume of the said personal care product for more than associative
purposes. For
example, a more business oriented addition for the workplace and a more casual
addition for after
work. When the perfumes are compatible, the mood can be changed without
changing the base
impression. Similarly, one could add perfume to keep one alert during slow
times and an
addition to calm during stress times. Progressive modification of a perfume's
physiological
effect could become its own trademark.
Branded Laundry Products
The present invention relates to a method of imparting odor character of a
branded
laundry product to fabric comprising the step of applying said fabric with a
perfume composition,
desirably an aqueous perfume composition, having an odor, wherein said odor of
said perfume
composition comprises an odor character substantially similar to the odor
character of a branded
laundry product. Non-limiting examples of branded laundry product include
laundry detergent
products, fabric softening products, fabric wrinkle releaser products, and
combinations thereof.
A "substantially similar" odor character is defined herein below.
The use of a perfume in laundry products is highly desirable. Many consumers
associate
the laundry experience with a particular perfume, or at least the volatile
portion of said perfume.
Again, many laundry products come in a variety of perfumes and the consumer
needs to know
that the product is in fact the proper one. The association of the perfume
which has the same
character as, or a character that is complementary to, the character of the
perfume of the said
laundry product with the product, especially at the point of purchase helps
the consumer make
the appropriate selection. The association can be by vapor creation near the
product shelf, or by
using a typical "scratch and sniff' strip on the product package. If
complementary products are
CA 02684181 2009-10-30
19
desired, the association of the perfume assures the consumer that the perfumes
are compatible
and/or that the source of the product can be trusted.
It is also preferable to create an association of the perfume of the product
with the product
itself so that the consumer recognizes that the perfume indicates the source
of the product and it
is also possible to create an association of a portion of the perfume of the
product with the
product, i.e., the volatile portion of the perfume of the product can be used
independently of the
product to create a feeling of comfort for the consumer in selecting the
product. It is optional but
preferable to provide a fabric perfume that is associated with a laundry
product, such as a fabric
softener, to apply on the clothing to replenish or enhance the favorite scent.
The normal habit of
the most consumers is to launder the laundry at some intervals, then store the
washed fabrics for
later use. In storage, the clothes may loose a substantial amount of product
perfume, and by the
time the clothes are used, the scent can be very faint. The fabric perfume can
then be used to
replenish the scent, and give the clothes in storage or already worn a "just
washed feeling"
impression. Furthermore, such fabric perfume provides the consumer the
opportunity to apply
the preferred scents on clothing that she cannot use the laundry product on,
such as garments that
require dry cleaning, or large items that do not fit in her washer, such as
bed comforters and
sleeping bags. Desirably, these perfumes that are designed specifically for a
direct application on
clothing and other fabrics are essentially free of any ingredient that stains
fabric or damages the
colors and designs of color fabrics.
As with the personal products, the approach to sampling is useful for the
consumer and
can be accomplished with minimum distress to others in the area.
Branded Articles of Manufacture
The present invention relates to a method of identifying a branded article
(wherein a
branded article is an article with insignia, logo, trade name, trademark,
etc.) comprising the steps
of (a) providing said branded article to a consumer; (b) providing a branded
perfume
composition to the consumer; and (c) instructing said consumer to apply said
branded perfume
composition to said branded article; desirably wherein the brand of said
branded perfume
composition is the same as the brand of said branded article.
In a preferred embodiment, the present invention relates to a method of
identifying a
branded line of clothing, e.g., a line of clothing designed by a fashion
designer, comprising the
steps of: (a) providing an article of clothing of said branded line of
clothing to a consumer; (b)
providing a branded perfume composition, desirably a branded fine fragrance
composition, to the
consumer; and (c) instructing said consumer to apply said branded perfume
composition to said
CA 02684181 2009-10-30
branded clothing article; wherein the brand of said branded perfume
composition is the same as
the brand of said branded clothing article.
Thus, the present invention also relates to a method of improving product
recognition
and/or acceptance wherein a particular fragrance is associated with a
particular source, especially
5 a particular fashion designer. Such a perfume serves as the olfactory
signature of a line of
fashion, so that people can subtly recognize the line of designer clothes that
one is wearing,
without having to read, or in addition to reading, the labels. Thus, when one
smells the particular
fragrance, one knows that the designer is the source and that the clothing is
not a "knock-off' by
some cheap copier. Desirably, these perfumes that are designed specifically
for a direct
10 application on clothing and other fabrics are essentially free of any
ingredient that stains fabric or
damages the colors and designs of color fabrics.
The present invention also relates to a method of improving product
recognition and/or
acceptance wherein an up-scale branded product, such as fine fragrances for
body, fine
fragrances for fabrics, luxury automobile brand, upholstery furniture brand,
leather goods such as
15 designer hand bags, ski equipments, and the like, is associated with a
distinctive perfume,
desirably a fabric perfume, for use as the signature for the brand.
The use of perfume with clothing is not conventional. Perfume is a personal
preference
ordinarily. However, perfume can evoke feelings without being so obvious as to
intrude upon
ones personal preference. It is possible to create a perfume that evokes the
sea for nautical wear
20 or the outdoors for outdoor wear, etc. It is also possible to create
personalized fragrances that are
based on personal preference and/or personality, and thus provide and/or
establish a "scent
signature" for each consumer and/or for their family. The present invention
relates to a method
of protecting this scent signature, and a method for others to identify the
consumer and/or their
family by this distinctive fragrance.
The present invention relates to a method of targeted perfume delivery on
fabrics for the
branded laundry perfumes and/or branded fine fragrances of the present
invention, by applying
the perfume in only a part of the garment, e.g., a small area of a upper part
of the outside of a vest
or a blouse, or an area underneath the tab of a collar, to provide the
olfactory benefit, instead of
the need for applying the whole inside and/or outside of a garment with
perfume, as in the case of
a laundry product. It is also possible to apply the fabric perfume to a patch
that can be placed in
inconspicuous area of clothing, e.g., under the tab of a collar, etc. This
method of the present
invention provides many advantages as compared to the conventional method of
applying
perfume to fabrics via a laundry process, such as, (a) reduction of skin
irritation and sensitization
CA 02684181 2009-10-30
21
due to an application of a smaller amount of perfume to the outside of a
garment, thus, not having
a direct contact with the skin, as compared to a total application of perfume
to the inside and
outside of the garment via a laundry product, and (b) improvement of the
environment
conservation benefit, due to the much smaller amount of perfume that is needed
to treat a
garment, and still obtain the olfactory benefit of the fragrance.
Brewed Coffee
The popularity of coffee houses has created a host of competitors. In order to
know that
the coffee being sold is in fact the desired coffee, one can associate the
smell of the brewed
coffee with the coffee house, thus assuring the consumer of the source and
quality of the coffee.
For example, one can extract the desired volatiles from the roasting of the
beans and present
them from time to time in the coffee house to assure potential consumers of
the quality and
source of the brewed coffee being served. The use of the odor in this way will
be a trademark
that assures the consumer that the product is one that is from a trusted
source. A discontinuous,
e.g., pulsed, presentation of the odor after a time sufficient for the nose to
recover can minimize
olfactory fatigue.
Baked Goods
In order to inform the consumer that baked goods are in fresh condition, it is
desirable to
collect a portion of the volatiles released during the baking and either
present them in the
atmosphere near the display point or in a scratch and sniff on the product.
Since the flavor is due
in great part to the odor, the consumer will be able to more accurately assess
whether the baked
good encased in a package that protects it will meet the consumer's need. The
use of the odor in
this way will be a trademark that assures the consumer that the product is one
that is from a
trusted source.
D. ImprovingLComplex Mixtures.
As previously mentioned, it is possible to use the methods herein to improve
existing
complex mixtures and or to identify new useful materials.
One can predict the odor or flavor character of new mixtures of one, or more,
of
compounds or old mixtures of compounds that have been analyzed separately, by
combining the
results mathematically. Accordingly, one can use the process to help create
new odors or flavors.
Thus, the invention can comprise a step in the creation of a new odor or
flavor comprising
creating a collection of data as discussed above by analyzing existing odors
or flavors by vapor
phase mass spectrometry, optionally normalizing the results, plotting the
results, and selecting
CA 02684181 2009-10-30
22
individual components that, when combined, will create an odor of flavor that
is outside the area
defined by the existing odors or flavors.
The above process can also be useful in selecting and/or identifying new
materials,
especially those that have complex formulae, that have novel effects, by
selecting materials that
are statistically different from known complex materials of similar effect
based upon their mass
spectrometry and/or nuclear magnetic resonance spectrometry digital analyses.
One can define
such novel complex materials by the differences from the said reference
material or materials.
The methods can be used in a process of creating new complex materials having
similar
characteristics to an existing complex material by using the method to
determine which
components of the existing complex material are primarily responsible for its
position with
respect to a reference set and using those components with new additional
components to create a
new complex material. The method can also be used to create a new odor or
flavor by creating a
collection of data for existing odors or flavors, plotting the results, and
selecting individual
components that will create an odor of flavor that is outside the area defined
by the existing odors
or flavors. The perfumes or other complex materials created by this process
can be patented as
new and novel compositions. These new complex materials can be patented as
complete
compositions or by defining only that portion of the mixture of compounds,
e.g., that is present
after the volatile materials have evaporated and/or the mixture of compounds
that is most
important to the perceived odor or effect.
The process can also be used to help determine what structure of a volatile
compound will
provide a specific character by analyzing a set of complex mixtures having the
desired character
and using a pattern recognition method of statistical analysis to determine
combinations of
specific compound structures that make the maximum contribution to the desired
character. The
use of comparative software also allows one to determine the compound
structure that results in a
physiological effect, thus assisting research into compounds that possess, or
in the case of
undesirable effects, do not possess, a given physiological effect.
The above process is especially useful in creating a branded perfume having a
specific
name that is different from existing branded perfumes or a food flavor that is
different from
existing flavors. The process is also useful for optimizing the formulation of
an odor or flavor in
which each component of the odor of flavor is analyzed and at least one of the
potential binary
mixtures is analyzed to provide a weighted value for the contribution of each
material to the odor
or flavor character.
CA 02684181 2009-10-30
23
One can create a branded perfume or flavor that has a new character by
comparing the
perfume or flavor to existing perfumes or flavors, especially those that have
been previously
branded, i.e., those that have been previously sold under a brand name.
The method can be used in research to define new useful materials by analyzing
a known
complex material using mass spectrometry, nuclear magnetic resonance
spectroscopy, or both,
and comparing the known complex material to at least one different complex
material analyzed
by the same method or methods, and then using pattern recognition software to
determine the
components of the two materials that are responsible for the difference in
analytical results and
relating said difference to an observed difference in the effects of the two
complex materials.
For example, the evaluation of complex materials having one or more similar
characteristics to define mixtures sharing one or more common characteristics
and/or to
determine which, if any, specific members of the mixture are responsible for
the characteristics
allows one to determine the components within an odor or flavor that are
responsible for the
contribution of a particular odor or flavor character, by comparing the
analytical results having a
particular character or odor to the analytical results from other complex
materials having
different characters or odors. The knowledge of the different components in
the different
perfumes enables the perfumer, or flavor expert, to create improved variations
more efficiently.
Odors and/or flavors created by this method have the advantage of using
materials that are
primarily responsible for the difference in character. Therefore, the
differences can be made
more pronounced, or, the number of trials to create the odor or flavor can be
reduced.
The method of doing research to define new materials, including the complex
materials
that can be used in the method of improving product recognition and/or
acceptance described
hereinbefore, can include analyzing one or more known complex materials having
specific
physiological effects using mass spectrometry, nuclear magnetic resonance
spectrometry, or
both, and comparing these known complex materials to themselves or a different
complex
material analyzed by the same method or methods, and then using pattern
recognition software to
determine the components of the materials that are responsible for the
difference in analytical
results and, by association, relating said differences to any observed
differences in the effects of
the complex materials.
E. Novel Complex Materials or Individual Novel Materials
The invention also comprises the novel complex material mixtures and
individual
materials that are found by the methods described above. The ability to define
mixtures and
CA 02684181 2009-10-30
24
materials that have novel properties allows one to find such novel materials.
Without the
method, there would be no way to determine these materials.
Following are non-limiting examples of the practice of the methods of the
present
invention.
Example 1. Method for Defining the Uniqueness andJor Similarity of the
Character of a Neat
Perfume Composition. This example illustrates the method of the present
invention for digitally
defining the character of neat perfume compositions, and their relative
similarity and/or
difference with character of other perfumes.
1. Reference Perfume Compositions A. Eleven perfume accords of known
composition that are
representative of and span the range of compositions and odor characters
likely to be
encountered are prepared as the reference set or training set. Sensor
descriptors recognized
by those skilled in the art characterize each of the reference samples. These
descriptors
desirably match with characters assigned to these reference compositions by
those skilled in
the art, but are used herein for the classification purpose only, and not
necessarily claimed to
broadly represent each assigned character. The 11 reference compositions are
as follows:
Reference 1 A - Rose (Floral)
Ingredients Wt. %
Phenyl Ethyl Alcohol 50
Citronellol 15
Geraniol 15
Citronellyl Acetate 10
Geranyl Acetate 10
Total 100
Reference 2A - Minty
Ing_redients Wt. %
Peppermint Rp 50
Spearmint, Natural 15
Laevo Carvone 15
CA 02684181 2009-10-30
Menthyl Acetate 10
Methyl Salicylate Usp 10
Total 100
5
Reference 3A - Muguet (Floral)
Ingredients Wt. %
Hydroxycitronellal 50
10 Cymal 15
Lyral 15
P. T. Bucinal 10
Phenyl Ethyl Acetate 10
Total 100
Reference 4A - Jasmin (Floral)
Ingredients Wt. %
Methyl Dihydro Jasmonate 50
Hexyl Cinnamic Aldehyde 15
Benzyl Acetate 15
Iso Jasmone 10
Ylang Ylang 10
Total 100
Reference 5A - Citrus (Floral)
Ingredients Wt. %
Orange Terpenes 50
Citral 15
Citronellal Nitrile 15
CA 02684181 2009-10-30
26
Citrathal (conf.-frag) 10
Iso Bergamate 10
Total 100
Reference 6A - Fruity (Apple)
Ingredients Wt. %
Fructone 50
Fructene 15
Flor Acetate 20
Allyl Cyclohexane Propionate 10
Alpha Damascone 5
Total 100
Reference 7A - Woody
Ingredients Wt. %
Gamma Methyl lonone 50
Sandalwood 15
Iso E Super 15
4-Tertiary-Butyl Cyclohexyl Acetatel0
Cedarwood Terpenes 10
Total 100
Reference 8A - Musk
Ingredients Wt. %
Ethylene Brassylate 50
Musk Plus 15
Ambrox DI 10% in DPG 15
CA 02684181 2009-10-30
27
Exaltolite 10
Musk 771 Nmf (conf.-tak) 10
Total 100
Reference 9A - Green Floral
Ingredients Wt. %
Cis-3-Hexenyl Salicylate 50
Agrumen Aldehyde Light-4 15
Iso Cyclo Citral 15
Cis-3-Hexenyl Acetate 10
Leaf Acetal 10
Total 100
Reference 10A - Spice
Ingredients Wt. %
Eugenol 50
Iso Eugenol 15
Cinnamic Alcohol 15
Elemi Oil 10
Anisic Aldehyde 10
Total 100
Reference 11A - Lavender
Ingredients Wt. %
Lavender 50
Eucalyptol 15
Rosemary 15
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Linalyl Acetate 10
Terpinyl Acetate 10
Total 100
2. Reference Perfume Compositions B. Eleven perfume accords of known
composition that
are representative of and span the range of compositions and odor characters
likely to be
encountered are prepared as the reference set or training set. Sensor
descriptors recognized by
those skilled in the art characterize each of the reference samples. These
descriptors desirably
match with characters assigned to these reference compositions by those
skilled in the art, but are
used herein for the classification purpose only, and not necessarily claimed
to broadly represent
each assigned character. The 11 reference compositions are as follows:
Reference 1B - Rose Floral
Perfume Ingredients Wt. %
alpha-Damascone 0.5
Benzophenone 1.0
Citronellol 19.0
Citronellyl acetate 5.0
beta-Damascone 1.0
Dimethyl benzyl carbinyl acetate 3.0
Dimethyl octanol 3.0
Geraniol 16.0
Geranyl acetate 7.0
Hydroxycitronellal 5.0
Methyl lonone 3.0
para Hydroxy phenyl butanone 0.5
Phenyl ethyl acetate 7.0
Phenyl ethyl alcohol 21.0
Phenyl hexanol 5.0
Rosalva(a) 3.0
Total 100.0
(a) 9-Decen-l-ol.
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Reference 2B - Jasmin Floral
Perfume Ingredients Wt. %
Amyl cinnamic aldehyde 8.0
Amyl salicylate 5.0
Anisic aldehyde 3.0
Benzyl acetate 16.7
Benzyl salicylate 5.0
cis Jasmone 2.0
Flor acetate 5.0
gamma Decalactone 2.0
Hexyl cinnamic aldehyde 20.0
Indol 0.3
Jasmal 2.0
Jasmolactone 3.0
Methyl benzoate 3.0
Methyl dihydro jasmonate 20.0
Phenyl ethyl iso butyrate 5_0
Total 100.0
Reference 3B - Muguet Floral
Perfume Ingredients Wt. %
Bourgeonal(b) 5.0
Cymal( ) 5.0
Floralozone(d) 5.0
Florhydral(e) 5.0
Helional(f) 7.0
Hydroxycitronellal 20.0
Lyral(g) 5.0
Mayol(h) 5.0
P. T. Bucinal(') 10.0
Phenyl acetaldehyde dimethyl acetal 5.0
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Phenyl ethyl alcohol 5.0
Phenyl ethyl phenyl acetate 7.0
Rhodinol 700) 3.0
Terpineol 3.0
Tetra hydro linalool 5.0
Tetra hydro muguol 5^0
Total 100.0
3-(4-( 1,1-Dimethylethyl)phenyl)propanal.
2-Methyl-3-(para iso propyl phenyl)propionaldehyde.
(d) para-Ethyl-alpha, alpha-dimethyl hydrocinnamaldehyde.
(e) 3-(3-Isoropylphenyl)butanal.
5 alpha-Methyl-3,4, (methylenedioxy) hydrocinnamaldehyde.
4-(4-hHdroxy-4-methyl-pentyl) 3-cylcohexene-l-carboxaldehyde.
(h) cis-4-(10-Methylethyl)-cyclohexanemethanol.
Lilial, or para-tertiary-butyl-alpha-methyl hydrocinnamic aldehyde.
laevo-Citronellol.
Reference 4B - Citrus Lemon
Perfume Ingredients Wt. %
Citral 15.0
Citral dimethyl acetal 7.0
Citronellyl nitrile 5.0
Decyl aldehyde 2.0
Dihydro myrcenol 6.0
Geranyl nitrile 10.0
Lime oxide 5.0
Linalool 9.0
Methyl beta-naphthyl ketone 3.0
Methyl nonyl acetaldehyde 1.0
Nonyl aldehyde 1.0
Octyl aldehyde 1.00
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31
Orange terpenes 35.0
Total 100.0
Reference 5B - Fruity
Perfume Ingredients Wt. %
Allyl amyl glycolate 5.0
Allyl cyclohexane propionate 7.0
alpha Damascone 1.0
Amyl acetate 1.0
Benzyl propionate 3.5
Ethyl methyl phenyl glycidate 3.0
Ethyl-2-methyl butyrate 2.0
Fructone 18.0
Frutene 5.0
Galaxolide 50 25.0
Hexyl acetate 2.5
Methyl anthranilate 3.0
Prenyl acetate 2.0
Triplal(k) 1.0
Undecalactone 3.0
Verdox(') 18.0
Total 100.0
(k) 2, 4-Dimethyl-3-cyclohexene-l-carboxaldehyde.
(') 4-(4-Hydroxy-4-methyl-pentyl) 3-cylcohexene-l-carboxaldehyde.
Reference 6B - Green
Perfume Ingredients Wt. %
Allyl caproate 3.0
beta gamma Hexenol 2.0
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cis 3 Hexenyl acetate 3.0
cis-3-Hexenyl salicylate 25.5
Cyclal C 2.0
Cyclo galbanate 5.0
Hexyl salicylate 10.0
iso Cyclo citral 5.0
Leaf Acetal 2.0
Liffarome(m) 1.0
Methyl heptine carbonate 1.5
Neobutanone( ) 0.5
Phenyl ethyl dimethyl carbinyl 5.0
acetate
Phenyl ethyl phenyl acetate 12.0
Tridecene 2 nitrile 0.5
Trifone( ) 2.0
Undecavertol 20.0
Total 100.0
(m) cis-3-Hexenyl methyl carbonate.
(n) 1 -(5, 5-Dimethyl-l-cyclohexen-l-yl)-4-penten-l-one.
Schiff base of methyl anthranilate and 3-phenylbutanal.
Reference 7B - Woody Balsamic
Perfume In gLeLlients Wt. %
4-Tertiary butyl cyclohexyl acetate 7.0
Bacdanol 4.0
Cedac(P) 2.0
Cedrol 2.0
Cedroxide 5.0
Coumarin 3.0
Guaiacwood acetate 3.0
lonone alpha 5.0
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lonone Beta 3.0
gamma Methyl ionone 15.0
Iso E Super(9) 10.0
Koavone 5.0
Methyl cedrylone 10.0
Ockumal(`) 5.0
Patchouli 5.0
Trimofix O(S) 4.0
Vetivert 5.
Vetivert Acetate 3.0
Lrg 201 (`) 4.0
Total 100.0
(P) Cedryl acetate.
(q) 7-Acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethyl naphthalene.
(<)2,4,-Dimethyl-2-(1,1,4,4-tetramethyltetralin-6-yl)-1,3-dioxoiane (trans &
cis isomers).
2, 5,10-Trimethyl-2,5,9-cyclododecatrien-l-yl methyl ketone and isomers.
2,4-Dihydroxy-3,6-dimethyl benzoic acid methyl ester.
Reference 8B - Musk Sweet
Perfume Ingr~edients Wt. %
Ambrettolide 1.0
Ambroxan 0.5
Bisabolene 3.0
Cashmeran(Q) 5.0
Cetalox( ) 1.0
Cyclohexadecenone 10.0
Ebanol 3.0
Ethyl Vanillin 0.9
Ethylene Brassylate 27.6
Exaltolide 2.0
Habanolide 100% 15.0
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Heliotropin 3.0
Musk Indanone 5.0
Musk Plus 10.0
Sanjinol("") 3.0
Musk RI(X' 7.0
Vanillin 3.0
Total 100.0
(u) 2-Ethyl-4-(2,2,3-trimethyl-3-cyclopentenyl)-2-buten-l-ol.
Dodecahydro-3A,6,6,9A-tetramethylnaphtho[2,1B]-furan.
6,7-Dihydro-1,1,2,3,3-pentamethyl-4(5th)-indanone.
(x) 1,7-Dioxacycloheptadecan-8-one.
Reference 9B - Lavender
Perfume Ingredients Wt. %
beta Pinene 5.0
Camphor Gum 4.0
Caryophyllene Extra 5.0
Ethyl amyl ketone 1.0
Eucalyptol 32.0
Linalool 24.0
Linalyl acetate 20.0
Methyl amyl ketone 1.0
Myrcenyl acetate crude 3.0
Terpinyl acetate 5_0
Total 100.0
Reference l OB - Spice
Perfume Ingredients Wt. %
Amyl cinnamic aldehyde diethyl 8.0
acetal
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Cinnamic alcohol 27.0
Cinnamic aldehyde 4.0
Cuminic aldehyde 2.0
Ethyl cinnamate 5.0
Eugenol 15.0
beta lonone 5.0
iso Eugenol 10.0
Jasmolactone 3.0
Methyl benzoate 2.0
Methyl cinnamate 7.0
Methyl eugenol 5.0
Myrcenyl acetate crude 5.0
Methyl chavicol 2_0
Total 100.0
Reference 11B - Pine, Orange Flower
Perfume Ingredients Wt. %
alpha Pinene 5.0
alpha Terpineol 10.0
Aurantiol 3.0
Beta naphthol methyl ether 3.0
beta Pinene 5.0
Camphene 3.0
Dimetol(l) 5.0
Diphenyl oxide 3.0
Fenchyl acetate 3.0
iso Borneol 2.0
iso Bornyl Acetate 20.0
Lauric aldehyde 2.0
Methyl anthranilate 5.0
Myrcene 3.0
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para Cymene 5.0
Koavone(Z) 6.0
Terpineolene 4.0
Verdantiol 10.0
Ligantraal(aa) 3.0
Total 100.0
('") Terpineolene.
(z) 3,4,5,6,6-Pentamethyl-3-hepten-2-one.
(-) Methyl2-((7-hydroxy-3,7-dimethyloctylidene)amino)-1-benzenecarboxylate.
2. Data Collection. Measurements are made by headspace-mass spectrometry and
require an
equilibration of about 100 0 L of the perfume in a 10 mL headspace vial at
about 50 C, followed
by an injection of about 3 mL of headspace into an HP 5973 benchtop single
quadrapole mass
spectrometer. Data obtained are the mass spectral channel signals m/z=46 to
200 after electron-
ionization of the volatiles in the headspace. Six replications are made on
each reference sample.
Each set of replicates for a given sample comprises a reference "class".
3. Data Processing for the Reference Perfume Compositions. The data in this
example are pre-
processed by vector normalization using an integrated chemometric/pattem
recognition software
package (Pirouette v.4.0, Infometrix, Inc.) loaded on a high-performance
personal computer.
4. Data Analysis for the Reference Perfume Compositions. Hierarchical Cluster
Analysis
(HCA) of the normalized data clusters the reference samples into 11 classes by
calculation of
Euclidean distance. The resulting dendrograms for Reference Perfume
Compositions A
presented herein as FIGURE 1, and for Reference Perfume Compositions B
presented herein as
FIGURE IV, illustrate that intra-class distances (m=6 replications) are
smaller that the inter-class
distances.
This concept is further illustrated by the results of a Principal Components
Analysis (PCA)
which shows a 3-dimensional spatial relationship among the reference classes.
These results are
presented herein as FIGURE II for Reference Perfume Compositions A and as
FIGURE V for
Reference Perfume Compositions B.
The eleven reference classes are subjected to SIMCA classification analysis
(Soft-
Independent Modeling of Class Analogy) in order to verify class distinctions.
An examination of
interclass and intraclass residuals verifies that differences within a
reference class are smaller
CA 02684181 2009-10-30
37
than differences between reference classes. A matrix of interclass distances
was constructed,
where
FS2~.
Interclass distance, D i 1- D
12 21
The terms
s12 and s21 are interclass residuals and si I and s22 are intraclass residuals
for classes
I and 2, respectively. In this sense, D is essentially a ratio of standard
deviations so a value
greater that 3 is deemed significant at the 95% confidence level. Those
skilled in the art will
realize that the calculation of residuals, and hence interclass distances,
will depend on the number
of factors retained for each class within the SIMCA model. As a general rule,
the number of
factors retained should describe the majority of variance within a class,
desirably greater than
90% but less than 100%. The number of factors chosen defines the reference set
model and
should be consistent for all subsequent calculations. The resulting interclass
distances are
presented herein as Tables 1 and 2.
TABLE 1 Perfume Set A - Interclass Distances
Rose Mint Muguet Jasmin Citrus Fruity
Rose 0.0 38.6 33.9 28.9 40.4 56.8
Mint 0.0 72.0 125.5 193.8 370.6
Muguet 0.0 72.2 79.0 73.2
Jasmin 0.0 133.8 159.3
Citrus 0.0 383.9
Fruity 0.0
Woody Musk Green Spice Lavender
Rose 24.9 17.3 40.4 34.7 37.4
Mint 33.5 25.1 184.1 114.1 131.7
Muguet 41.0 25.1 77.2 78.5 80.2
Jasmin 55.9 30.5 132.8 111.3 124.6
Citrus 45.5 22.7 60.0 86.7 213.0
Fruity 67.9 37.7 345.3 297.1 402.3
Woody 0.0 16.5 44.5 35.3 36.6
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38
Musk 0.0 23.1 21.0 25.0
Green 0.0 99.2 208.8
Spice 0.0 66.6
Lavender 0.0
TABLE 2 Perfume Set B - Interclass Distances
Rose Jasmin Muguet Citrus
Floral Floral Floral Lemon Fruity Green
Rose Floral 0.00 48.85 49.97 60.57 87.98 73.65
Jasmin Floral 0.00 78.62 146.87 173.29 146.05
Muguet Floral 0.00 86.33 75.85 71.22
Citrus Lemon 0.00 310.04 176.02
Fruity 0.00 178.06
Green 0.00
Pine,
Woody Musk Orange
Balsamic Sweet Lavender Spice Flower
Rose Floral 60.33 7.16 71.84 40.15 66.82
Jasmin Floral 101.71 9.17 145.04 31.36 132.89
Muguet Floral 56.40 6.43 65.05 52.12 83.71
Citrus Lemon 113.09 8.50 255.59 71.70 321.88
Fruity 68.03 9.55 257.48 81.50 343.96
Green 89.72 8.16 175.20 63.66 237.57
Woody Balsamic 0.00 7.08 96.79 61.37 118.08
Musk Sweet 0.00 7.84 8.25 9.57
Lavender 0.00 74.18 249.93
Spice 0.00 74.82
Pine, Orange
Flower 0.00
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6. Test Perfume Samples. One or more replicate headspace-mass spectrometry
measurements
are made on each of the test samples. The test samples consist of commercial
perfumes and
colognes and/or experimental perfume compositions. Measurements are made and
data are
normalized in an identical manner as the reference samples.
7. Test Perfume Samples in the "Eleven-Dimension Perfume Space". All of the
samples, test
and reference samples, are projected into the SIMCA model created with the
reference samples.
A "distance" matrix is output that contains the sample residuals that result
when attempting to
project the test sample data into each the reference classes. This residual or
"distance" is a
measure of how well or poorly the sample is modeled by the principal features
of each of the
reference classes, and as such is a useful measure of similarity or
dissimilarity. Shown in Table 3
(Perfume Set A) and Table 4 (Perfume Set B) is a matrix for each perfume set
of the mean
"distance" values for the test samples relative to each of the reference
samples
TABLE 3 Perfume Set A - Residuals or "Distances"
Rose Mint Muguet Jasmin Citrus Fruity
Test Perfume 7.36 5.59 8.44 8.54 0.92 10.05
Comp Perf 1 6.91 6.42 7.76 8.15 4.85 9.81
Comp Perf 2 6.94 5.14 8.00 8.26 1.60 9.74
Comp Perf 3 7.47 6.97 7.74 8.61 6.36 9.63
Comp Perf 4 6.89 5.12 7.94 8.21 1.68 9.73
Comp Perf 5 7.33 6.75 7.54 8.62 5.73 9.43
Comp Perf 6 8.58 7.91 8.93 9.42 6.84 10.39
Woody Musk Green Spice Lavender
Test Perfume 5.18 4.78 1.59 2.73 5.07
Comp Perf 1 5.68 4.66 5.02 5.06 6.27
Comp Perf 2 4.38 4.36 1.91 2.61 4.63
Comp Perf 3 6.15 5.47 6.43 6.41 7.06
Comp Perf 4 4.30 4.30 2.01 2.59 4.58
Comp Perf 5 5.73 4.99 5.79 5.92 6.76
Comp Perf 6 7.71 6.93 6.98 7.14 7.97
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TABLE 4 Perfume Set B - Residuals or "Distances"
Rose Jasmin Muguet Citrus
Floral Floral Floral Lemon Fruity Green
Test Perfume 6.00 7.59 8.36 0.79 9.70 6.88
Comp Perf 1 6.55 8.04 8.41 1.16 9.89 7.25
Comp Perf 2 6.65 8.21 8.31 0.67 9.73 6.76
Comp Perf 3 5.05 6.50 7.00 3.43 8.03 5.97
Comp Perf 4 6.38 7.84 8.54 0.54 9.92 7.19
Comp Perf 5 5.52 7.12 7.84 1.41 9.31 6.72
Comp Perf 6 5.99 6.57 8.06 2.66 10.16 8.03
Woody Musk Pine, Orange
Balsamic Sweet Lavender Spice Flower
Test
Perfume 8.10 7.27 6.00 7.99 5.59
Comp Perf
1 8.52 7.64 6.25 8.40 5.51
Comp Perf
2 8.28 7.52 5.93 8.29 5.70
Comp Perf
3 5.50 5.80 5.14 6.69 5.65
Comp Perf
4 8.43 7.61 6.07 8.33 5.27
Comp Perf
5 7.33 6.83 5.48 7.67 5.22
Comp Perf
6 8.24 7.47 5.33 8.25 3.16
5 Because each of the reference classes here is assigned a sensory descriptor,
the "distance" of
a test sample to a reference class can be a measure of the sensory
characteristic of the test
sample. This is particularly probable when the test sample contains
substantially the same
chemical raw materials as the reference samples. A large distance implies that
the test sample
CA 02684181 2009-10-30
41
shares very little of the characteristics of the reference class, while a
small distance would imply
closeness in character.
8.Test Perfume Samples in the Eleven-Dimension Similarity Perfume Space. The
display
of results to visually depict the similarity or difference of the test sample
relative to reference
samples is conveniently accomplished with a radial plot (also called "spider
diagram" or "star
plot") in which each of the reference classes is a terminal point. The axes
are scaled by the
"similarity index" S, a number calculated from the "distance" as follows,
where d is the residual
or "distance" value for any individual test sample to a reference (i) and dMAx
is the maximum
distance value for the entire reference set:
S; = 1- (di / dMAx)
wherein each Si has values from 0 (very different) to 1(very similar). This
way, the uniqueness
of each test perfume or each commercial perfume can be defined digitally by
the similarity
indices Si relative to the 11 reference samples (i) for which composition is
well defined and
sensory character is known. For each test perfume, its 11 similarity indices
Si are compiled in the
form of a "similarity matrix" using the class distances generated from SIMCA,
as given in
TABLEs 5 and 6.
TABLE 5 Perfume Set A - Similarity Indices
Rose Mint Muguet Jasmin Citrus Fruity
Test Perfume 0.307 0.474 0.206 0.196 0.913 0.054
Comp Perf 1 0.350 0.396 0.270 0.233 0.544 0.077
Comp Perf 2 0.347 0.517 0.247 0.223 0.849 0.083
Comp Perf 3 0.297 0.344 0.272 0.190 0.402 0.094
Comp Perf 4 0.351 0.519 0.253 0.227 0.842 0.085
Comp Perf 5 0.310 0.365 0.290 0.189 0.461 0.113
Comp Perf 6 0.193 0.256 0.160 0.114 0.356 0.023
Woody Musk Green Spice Lavender
Test Perfume 0.513 0.551 0.851 0.743 0.523
Comp Perf 1 0.466 0.561 0.528 0.524 0.410
Comp Perf 2 0.588 0.590 0.820 0.754 0.565
Comp Perf 3 0.421 0.486 0.395 0.397 0.336
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42
Comp Perf 4 0.595 0.596 0.811 0.756 0.569
Comp Perf 5 0.461 0.531 0.455 0.443 0.363
Comp Perf 6 0.275 0.348 0.343 0.329 0.250
TABLE 6 Perfume Set B - Similarity Indices
Rose Jasmin Muguet Citrus
Floral Floral Floral Lemon Fruity Green
Test Perfume 0.437 0.288 0.216 0.926 0.091 0.355
Comp Perf 1 0.386 0.246 0.212 0.891 0.073 0.321
Comp Perf 2 0.377 0.230 0.221 0.937 0.087 0.366
Comp Perf 3 0.526 0.391 0.344 0.678 0.247 0.440
Comp Perf 4 0.402 0.265 0.199 0.949 0.070 0.326
Comp Perf 5 0.482 0.332 0.265 0.868 0.127 0.370
Comp Perf 6 0.438 0.384 0.244 0.750 0.047 0.248
Woody Musk Pine, Orange
Balsamic Sweet Lavender Spice Flower
Test Perfume 0.241 0.318 0.438 0.250 0.476
Comp Perf 1 0.201 0.284 0.414 0.212 0.483
Comp Perf 2 0.223 0.295 0.444 0.223 0.466
Comp Perf 3 0.485 0.456 0.518 0.373 0.470
Comp Perf 4 0.210 0.287 0.431 0.219 0.506
Comp Perf 5 0.312 0.360 0.486 0.281 0.511
Comp Perf 6 0.227 0.300 0.500 0.227 0.704
This similarity matrix can be visually depicted as a spider diagram to show
the similarity
and/or the difference of these perfumes from the 11 reference samples, and
from each other, as
follows. The similarity or dissimilarity of the character of two or more test
perfumes can be
readily estimated visually by the size and shape of their spider diagram.
Spider diagrams for the
above data are shown herein as FIGURE III for Perfume Set A and as FIGURE VI
for Perfume
Set B.
CA 02684181 2009-10-30
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9.Digital Definition of the Uniqueness and/or Similarity of Test Perfumes.
As given hereinabove, each perfume is defined by a set of 11 similarity
indices Si. The
difference or similarity between two or more test perfumes,, and/or how said
test perfume can be
distinguished from comparative perfumes for, e.g., protection purpose, can be
defined by the
differences between the similarity indices of said test perfume and the
similarity indices of each
of the comparative perfumes.
Thus, according to the method of the present invention, the difference or
similarity between a
pair of perfumes, e.g., between the test perfume (designated as t: test
perfume) and a comparative
perfume (designated as c: comparative perfume), is defined by a "relative
similarity index" (RSI)
as the average difference of the similarity indices Si of perfume (t) and
perfume (c), expressed as
a percent and calculated as:
o S~
RSI ( /o) = x 100
m
Where m(=11) is the number of reference points and Sit and Si, are the
similarity indices S of
perfume (t) and comparative perfume (c), respectively, relative to each
reference (i).
The sum of squares can be derived from the similarity matrix by adding each
individually
squared difference between the comparative and the test perfume for all 11
similarity indices.
The difference matrix, the sum of squares, and the relative similarity indices
are summarized for
the examples herein as TABLE 7 and TABLE 8.
The Tables show that the relative similarity indices for the comparative
perfumes vs. the test
perfume range from about 5% (slightly different) to 12% (different) to more
than 20% (quite
different).
TABLE 7 Perfume Set A - Relative Similarity Indices
Rose Mint Muguet Jasmin Citrus Fruity
Test 0.000 0.000 0.000 0.000 0.000 0.000
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44
Perfume
Comp Perf
1 0.019 0.027 0.097 0.036 0.163 0.179
Comp Perf
2 0.017 0.008 0.040 0.018 0.005 0.282
Comp Perf
3 0.001 0.075 0.102 0.001 0.313 0.519
Comp Perf
4 0.020 0.009 0.051 0.025 0.006 0.311
Comp Perf
0.000 0.053 0.166 0.001 0.245 1.157
Comp Perf
6 0.138 0.213 0.050 0.178 0.372 0.338
Woody Musk Green Spice Lavender RSI%
Test
Perfume 0.000 0.000 0.000 0.000 0.000 0.000 0.0
Comp Perf
1 0.008 0.000 0.144 0.087 0.046 0.807 8.2
Comp Perf
2 0.022 0.005 0.001 0.000 0.007 0.404 5.8
Comp Perf
3 0.032 0.014 0.287 0.217 0.128 1.688 11.8
Comp Perf
4 0.026 0.007 0.002 0.000 0.008 0.465 6.2
Comp Perf
5 0.010 0.001 0.217 0.163 0.093 2.107 13.2
Comp Perf
6 0.216 0.135 0.355 0.311 0.272 2.578 14.6
5
CA 02684181 2009-10-30
TABLE 8 Perfume Set B - Relative Similarity Indices
Rose Jasmin Muguet Citrus
Floral Floral Floral Lemon Fruity Green
Test
Perfume 0.000 0.000 0.000 0.000 0.000 0.000
Comp Perf
1 0.014 0.021 0.000 0.001 0.038 0.009
Comp Perf
2 0.019 0.041 0.000 0.000 0.001 0.001
Comp Perf
3 0.041 0.126 0.347 0.072 2.955 0.058
Comp Perf
4 0.006 0.007 0.006 0.001 0.052 0.007
Comp Perf
5 0.011 0.023 0.050 0.004 0.161 0.002
Comp Perf
6 0.000 0.111 0.016 0.036 0.229 0.091
Pine,
Woody Musk Orange
Balsamic Sweet Lavender Spice Flower RSI%
Test
Perfume 0.000 0.000 0.000 0.000 0.000 0.000 0.0
Comp Perf
1 0.027 0.011 0.003 0.024 0.000 0.149 3.5
Comp Perf
2 0.005 0.005 0.000 0.012 0.001 0.086 2.7
Comp Perf
3 1.029 0.189 0.034 0.240 0.000 5.090 20.5
Comp Perf
4 0.017 0.010 0.000 0.016 0.004 0.125 3.2
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Comp Perf
0.089 0.018 0.012 0.015 0.005 0.389 5.7
Comp Perf
6 0.003 0.003 0.020 0.009 0.228 0.747 7.9
Novel perfumes can be defined as having a RSI greater than a set value, which
is a measure
of overall difference as defined by the similarity matrix. For example, for a
meaningful
difference, we have found that the RSI would be typically greater than about
10%, desirably
5 greater than about 15%, more desirably greater than about 20%, and even more
desirably greater
than about 25%. For perfumes that are similar, the RSI would be expected to be
smaller than
10%. In fact, in Table 7 the Test Perfume and the Comparative Perfume 1 are
very similar, as the
RSI between these two is only 5.8% (we know one is derived from the other, and
they are very
similar).
Example 2. Method for Defining the Uniqueness and/or Similarity of the
Character of
Roasted Coffee. This example illustrates the method of the present invention
for digitally
definingthe character of roasted coffees and their relative similarity and/or
difference with the
character of other coffees.
1. Reference Coffee Compositions. Five coffee blends of known composition that
are
representative of, and span the range of, compositions and flavor and aroma
characters likely to
be encountered are prepared as the reference set or training set. Sensory
descriptors recognized
by those skilled in the art characterize each of the reference samples. These
descriptors desirably
match with characters assigned to these reference compositions by those
skilled in the art, but are
used herein for the classification purpose only, and not necessarily claimed
to broadly represent
each assigned character. The 5 reference compositions are as follows:
Reference 1- High Acid Blend
Ingredients Wt.%
Nicaragua arabica 40
Guatemala arabica 20
Colombia arabica 20
Mexico arabica 20
Total 100
Roasted to Hunter L = 18.6
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Reference 2 - Dirty/Earthy Blend
Ingredients Wt.%
Vietnam robusta 50
Thailand robusta 25
Indonesia robusta 25
Total 100
Roasted to Hunter L = 22.9
Reference 3 - High Prime/High Body Blend
Ingredients Wt.%
Guatemalan arabica 50
Mexican arabica 50
Total 100
Roasted to Hunter L = 18.1
Reference 4 - Medium Blend
Ingredients Wt.%
Honduras arabica 55
Mexico arabica 18
Brazil arabica 15
Guatemala arabica 12
Total 100
Roasted to Hunter L = 17.4
Reference 5 - Low Prime/Low Acid Blend
Ingredients Wt.%
Brazil arabica 100
Total 100
Roasted to Hunter L = 17.9
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2. Data Collection. Measurements are made by headspace-mass spectrometry and
require
equilibration of about 2 g of ground, roast coffee in a 10 mL headspace vial
at about 50 C,
followed by an injection of about 3 mL of headspace into an HP 5973 benchtop
single
quadrupole mass spectrometer. Data obtained are the mass spectral channel
signals m/z = 50 to
165 after electron-ionization of the volatiles in the headspace. Seven
replicates are made on each
reference sample. Each set of replicates for a given sample comprises a
reference "class".
3. Data Processing for the Reference Coffee Blends. The data in this example
are pre-processed
by vector normalization using an integrated chemometric/pattem recognition
software package
(Pirouette v.4.0, Infometrix, Inc.) loaded on a high-performance personal
computer.
4. Data Analysis for the Reference Coffee Blends. Hierarchical Cluster
Analysis (HCA) of the
normalized data clusters the reference samples into 5 classes by calculation
of Euclidean
distance. The resulting dendrogram shown herein as FIGURE VII, illustrates
that intra-class
distance (m=7 replications) is smaller that the inter-class distance.
This concept is further illustrated by the results of Principal Components
Analysis (PCA)
which shows a 3-dimensional spatial relationship among the reference classes
as shown in
FIGURE VIII.
The five reference classes are subjected to SIMCA classification analysis
(Soft-Independent
Modeling of Class Analogy) in order to verify class distinctions. Those
skilled in the art will
realize that the calculation of residuals, and hence interclass distances,
will depend on the number
of factors retained for each class within the SIMCA model. As a general rule,
the number of
factors retained should describe the majority of variance within a class,
desirably greater than
90% but less than 100%. The number of factors chosen defines the reference set
model and
should be consistent for all subsequent calculations. An examination of
interclass and intraclass
residuals verifies that differences within a reference class are smaller than
differences between
reference classes. A matrix of interclass distances was constructed and is
illustrated in TABLE
9.
TABLE 9 Coffee Set - Interclass Distances
dirtylearthy high acid low prime high prime medium prime
dirty/earthy 0.00 19.83 17.31 13.63 12.90
high acid 0.00 5.16 9.43 12.33
low prime 0.00 5.31 7.97
high prime 0.00 4.22
medium prime 0.00
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5. Commercial Coffee Samples. Three replicate headspace-mass spectrometry
measurements are made on each of 4 test samples. The test samples consist of 2
commercial
coffees and two test coffees blended to approximate the character of one of
the commercial
coffees. Data are normalized in an identical manner as the reference samples.
6. Test Coffee Samples in the "Five-Dimension Coffee Space". All of the
samples, test and
reference samples, are projected into the SIMCA model created with the
reference samples. A
"distance" matrix is output that contains the sample residuals that result
when attempting to
project the test sample data into each the reference classes. This residual or
"distance" is a
measure of how well or poorly the sample is modeled by the principal features
of each of the
reference classes, and as such is a useful measure of similarity or
dissimilarity. Shown in
TABLE 10 is a matrix of the mean "distance" values for the test coffee samples
and comparative
coffee samples relative to each of the reference samples.
TABLE 10 Coffee Set - Residuals or "Distances"
Dirty Earthy High Acid High Prime Low Prime Medium Prime
TestCoffee 2.01 0.62 0.60 0.84 1.16
CC 1 1.43 1.33 0.94 0.46 0.45
Comp Coffee 1 1.87 0.73 0.53 0.74 0.95
Comp Coffee 2 1.92 0.74 0.60 0.86 1.12
Because each of the reference classes here is assigned a sensory descriptor,
the "distance" of a
test sample to a reference class can be a measure of the sensory
characteristic of the test sample.
A large distance implies that the test sample shares very little of the
characteristics of the
reference class, while a small distance would imply closeness in character.
7. Test Coffee Samples in the Five-Dimension Similarity Coffee Space. The
display of
results to visually depict the similarity or difference of the test sample
relative to reference
samples is conveniently accomplished with a radial plot (also called "spider
diagram" or "star
plot") in which each of the reference classes is a terminal point. The axes
are scaled by the
"similarity index" S, a number calculated from the "distance" as follows,
where d is the
augmented residual or "distance" value for any individual test sample to a
reference (i) and dmAx
is the maximum distance value for the entire test set:
Si = 1- (di / dM.e,x)
wherein each S; has values from 0 (very different) to 1(very similar). This
way, the uniqueness
of each test coffee or each commercial coffee can be defined digitally by the
similarity indices Si
relative to the 5 reference samples (i) for which composition is well defined
and sensory
CA 02684181 2009-10-30
character is known. For each test coffee, its 5 similarity indices Si are
compiled in the form of a
"similarity matrix" using the class distances generated from SIMCA, as given
in TABLE 11.
TABLE 11 Coffee Set B - Similarities
Dirty Earthy High Acid High Prime Low Prime Medium Prime
Test Coffee 0.148 0.737 0.743 0.644 0.507
CC 1 0.392 0.435 0.603 0.806 0.808
Comp Coffee 1 0.204 0.689 0.774 0.684 0.594
5 Comp Coffee 2 0.184 0.685 0.745 0.636 0.525
This similarity matrix can be visually depicted as a spider diagram to show
the similarity
and/or the difference of these coffees from the 5 reference coffees, and from
each other, as
follows. The similarity or dissimilarity of the character of two or more test
coffees can be readily
10 estimated visually by the size and shape of their spider diagram. The
spider diagram for the
above data is shown herein as FIGURE IX.
8. Digital Definition of the Uniqueness and/or Similarity of Test Coffees. As
given
hereinabove, each coffee is defined by a set of 5 similarity indices Si. The
difference between a
test coffee and commercial coffees, and/or how the said test coffee can be
distinguished from
15 other test coffees or comparative coffees for, e.g., protection purpose,
can be defined by the
differences between the similarity indices of said test coffee and the
similarity indices of each of
the commercial coffees. The absolute difference matrix can be calculated using
the similarity
indices in TABLE12. Individual differences are calculated by taking difference
between the test
coffee and each of the commercial coffees on each of the 5 similarity indices.
20 9. Thus, according to the method of the present invention, the difference
or similarity
between a pair of coffees, e.g., between the test coffee (designated as t:
test coffee) and a
comparative or commercial coffee (designated as c: comparative coffee), is
defined by a "relative
similarity index" (RSI) as the average difference of the similarity indices S;
of coffee (t) and
coffee (c), expressed as a percent and calculated as:
s
~ s ;t
m
RSI (0/0) - x 100
m
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51
Where m(=5) is the number of reference points and Sit and Sic are the
similarity indices S
of coffee (t) and comparative coffee (c), respectively, relative to each
reference (i).
The sum of squares can be derived from the similarity matrix by adding each
individually
squared difference between the comparative and the test coffee for all 5
similarity indices. The
difference matrix, the sum of squares, and the relative similarity indices are
summarized for the
example herein as TABLE 12.
TABLE 12 Coffee Set A - Relative Similarity Indices
Dirty High High Low Medium
Earthy Acid Prime Prime Prime RSI%
Test Coffee 0.000 0.000 0.000 0.000 0.000 0.000 0.0
CC 1 2.729 0.167 0.036 0.063 0.350 3.346 36.6
Comp Coffee 1 0.146 0.004 0.002 0.004 0.029 0.185 8.6
Comp Coffee 2 0.061 0.005 0.000 0.000 0.001 0.067 5.2
TABLE 12 shows that the relative similarity indices for 2 comparative coffees
(Cl and C2)
vs. the test coffee (TC) and a commercial coffee (CC) vs. the test coffee (TC)
range from about
5.2% (slightly different) to 8.6% (slightly more different) to more than 36%
(quite different).
Novel coffees or coffee blends can be defined as having a RSI greater than a
set value,
which is a measure of overall difference as defined by the similarity matrix.
For example, for a
meaningful difference, we have found that the RSI would be typically greater
than about 10%,
desirably greater than about 15%, more desirably greater than about 20%, and
even more
desirably greater than about 25%. For coffees that are similar, the RSI would
be expected to be
smaller than about 10%. In fact the Test Coffee (TC) and the Comparative
Coffees (CCI and
CC2) above are very similar, and the RSI between these two are only 8.6% and
5.2%,
respectively (we know that they are blended from the same coffees and are
indeed very similar).
Example 3.
A novel perfume is created by analyzing existing perfumes according to the
method of
Example I and then modifying an existing perfume so that it is statistically
different from the
existing perfumes, i.e. exhibits a Relative Similarity Index that is greater
than a set value,
typically greater than about 10%, desirably greater than about 15%, more
desirably greater than
about 20%, and even more desirably greater than about 25%. .
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52
Example 4.
A novel perfume is created in accordance with Example 3. The digital
expression of the
results of the perfume's analysis and an area around the perfume that is
determined to be
substantially the same as the novel perfume are used to file: a patent
application with a claim to
the perfume and perfumes having a similar character that are substantially the
same as
determined by a Relative Similarity Index; a copyright application on the
digital expression; and
a trademark application for the use of the novel perfume and those perfumes
having a similar
character and that are substantially the same as determined by a Relative
Similarity Index to
identify one or more products or services as being provided by a given
manufacturer.
Example 5.
The perfume of Example 3 is used in association with one or more expensive
articles of
commerce like a designer line of clothing to identify the articles as being
from a specific designer
and to create a distinct impression for the purchasers of said articles.
The dimensions and values disclosed herein are not to be understood as being
strictly limited to
the exact numerical values recited. Instead, unless otherwise specified, each
such dimension is
intended to mean both the recited value and a functionally equivalent range
surrounding that
value. For example, a dimension disclosed as "40 mm" is intended to mean
"about 40 mm."
Every document cited herein, including any cross referenced or related patent
or application, is
hereby incorporated herein by reference in its entirety unless expressly
excluded or otherwise
limited. The citation of any document is not an admission that it is prior art
with respect to any
invention disclosed or claimed herein or that it alone, or in any combination
with any other
reference or references, teaches, suggests or discloses any such invention.
Further, to the extent
that any meaning or definition of a term in this document conflicts with any
meaning or
definition of the same term in a document incorporated by reference, the
meaning or definition
assigned to that term in this document shall govern.
While particular embodiments of the present invention have been illustrated
and described, it
would be obvious to those skilled in the art that various other changes and
modifications can be
made without departing from the spirit and scope of the invention. It is
therefore intended to
cover in the appended claims all such changes and modifications that are
within the scope of this
invention.
