Use of volatile components to limit or eliminate perception of faeces malodor

Abstract

The present invention relates to the field of malodor cancellation. More specifically, it relates to the use of volatile compositions to limit, reduce or eliminate perception of malodor of faeces. Such compositions include a malodor antagonist system associated with a perfuming ingredient as a malodor counteracting agent, the combination of which significantly reduces the perception of faeces malodor. Such compositions, their use in combination with delivery systems and their use in consumer products are objects of the invention.

Description

[0001] This application is a divisional application of the patent application No. 201780071199.9, with the invention title of "Using Volatile Ingredients to Limit or Eliminate the Perception of Fecal Odor", filed on November 17, 2017.

[0002] Cross - reference to related applications

[0003] This application claims the priority of U.S. Provisional Patent Application Serial No. 62 / 424,072 filed on November 18, 2016, U.S. Provisional Patent Application Serial No. 62 / 485,060 filed on April 13, 2017, European Patent Application No. 17175114.2 filed on June 8, 2017, and U.S. Provisional Patent Application Serial No. 62 / 556,714 filed on September 11, 2017, the entire contents of which are hereby incorporated by reference in their entirety. Technical field

[0004] The present invention relates to the field of malodor antagonism. More specifically, it relates to the use of volatile compositions to limit, reduce or eliminate the perception of fecal odor. Such compositions include a malodor antagonist system associated with fragrance ingredients as malodor antagonists, the combination of which significantly reduces the perception of fecal odor. The use of such compositions in combination with delivery systems and their application in consumer products are the objects of the present invention. Background art

[0005] Malodorous smells exist in many environments and can be encountered in our daily life. The odors causing this negative association can consist, for example, of commercial and residential environmental odors, which can be generated by waste, garbage containers, toilets, cat litter, and food handling and processing. Toilet (especially feces), kitchen and body odors are just some of the several common environmental sources of malodor in daily life. The malodor is a complex mixture of more than one malodor compound, which generally can include various amines, thiols, sulfides, short - chain aliphatic unsaturated acids, such as fatty acids and their derivatives.

[0006] Residential or body - related malodors are usually caused by various compounds, such as indole, skatole and methanethiol found in fecal odor; piperidine and morpholine found in urine; pyridine and triethylamine found in kitchen and garbage odors; perhydro - 4α,8αβ - dimethyl - 4α - naphthol (geonol), 1 - octen - 3 - ol, dimethyl disulfide, dimethyl trisulfide, 3 - methyl - 1 - butanol found in laundry odors; short - chain fatty acids such as 3 - methyl - 3 - hydroxyhexanoic acid, 3 - methylhexanoic acid or 3 - 20 - methyl - 2 - hexenoic acid found in axillary odors.

[0007] This malodor is unpleasant to humans, so there has always been a need for malodor antagonism (MOC) technology that can reduce or inhibit the perception of malodor. However, the task is usually very difficult because the chemicals responsible for malodor produce extremely strong odors and may have much lower detection thresholds than the odors commonly used to mask them. Therefore, an excessive amount of MOC composition / compound must be used to achieve acceptable malodor antagonism.

[0008] A class of compounds has been identified and reported to be useful for reducing the perception of certain malodors. For example, US20100111889 describes a malodor control system suitable for disposable articles, such as disposable cleaning wipes, baby wipes, or skin care wipes, which contains aldehydes, esters, ionones, and macrocyclic musks. A malodor neutralizing composition containing acids and acyclic ketones has also been disclosed in US9774180. Other publications describe the use of compositions containing ionones, irone, and damascenone in a similar context. These classes of compounds have also been described as part of an odor masking matrix in personal care compositions - US2919440 - or as part of a method for freshening the air - US20040223871.

[0009] There is still a need to find compositions that are effective in reducing the sensation of malodor at lower concentrations. There is a particular need to provide effective products that will limit, reduce, or eliminate the perception of malodors generated in toilets, especially fecal malodors, to promote public acceptance and use of toilets and discourage open defecation. The present invention provides a solution to the above problems by significantly enhancing the efficiency of known malodor antagonist classes by adding a malodor antagonist system composed of compounds that block specific receptors of malodor targets. Summary of the Invention

[0010] The present invention relates to the use of a composition comprising a malodor antagonist system composed of components that have been found to block specific receptors of fecal malodor, including those disclosed in WO2014210585, and a functional perfume blend made from odor components having some malodor antagonistic properties. It has been found that the combination of the present invention provides unexpected results in limiting or eliminating the sensation of fecal malodor.

[0011] Therefore, in a first aspect, the present invention relates to the use of a composition comprising the following components for reducing, limiting, or eliminating the perception of fecal malodor:

[0012] (i) from about 2 wt% to about 85 wt% of a malodor receptor antagonist system, which comprises at least one component selected from the groups in Table 1;

[0013] (ii) From about 15 wt% to about 98 wt% of a functional perfume comprising at least two perfume ingredients, provided that any ingredient listed in Table 1 is excluded, and the blend has a fragrance note selected from floral, citrus, and jasmine.

[0014] (iii) Optionally, a non-functional perfume blend.

[0015] An odorant receptor antagonist system composed of at least two ingredients selected from the groups in Table 1 is also an object of the present invention.

[0016] Another object of the present invention is an odorant antagonistic composition comprising:

[0017] a) From about 2 to about 85 wt% of an active amount of an odorant receptor antagonist system comprising at least one, or at least three ingredients selected from Table 1;

[0018] b) From about 15 to about 98 wt% of a functional perfume blend comprising at least two ingredients selected from the group consisting of ionones, irone, damascenone, citral, methyl cinnamaldehyde, pelargodienal, orivone, their derivatives, and mixtures; and

[0019] c) Optionally, a non-functional perfume blend comprising at least two perfume ingredients.

[0020] A perfumed consumer product comprising an effective amount of the odorant antagonistic composition as defined above is another object of the present invention.

[0021] A non-therapeutic method for antagonizing fecal odors, comprising treating a surface with the composition as defined above or at least partially dispensing the composition as defined above in the air, is also part of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1a Shows the results of an antagonistic screening of a live neuron assay against an indole odorant target.

[0023] Figure 1b Shows the results of an antagonistic screening of a live neuron assay against a dimethyl trisulfide (also known as DMTS) odorant target.

[0024] Figure 1c Shows the results of an antagonistic screening of a live neuron assay against a p-cresol odorant target.

[0025] Figure 1d Shows the results of an antagonistic screening of a live neuron assay against a butyric acid odorant target.

[0026] Figure 2Reported are the results of the fecal scores remaining when combining a malodor antagonist system consisting of (2,5-dimethyl-2,3-dihydro-1H-inden-2-yl)methanol (also known as ) with a functional fragrance blend consisting of α-ionone (also known as Violet AT) and isoraldeine (composed of isomethyl-α-ionone and α-methyl-ionone).

[0027] Figure 3 Shows the performance of three single compounds and their mixture (floral blend) against fecal malodor restorers.

[0028] Figure 4 shows a graph of the scores for the fecal, freshness, and pleasantness attributes of a single fecal restorer ( at a single concentration in all tests ) and combinations of different compositions.

[0029] - Figure 4a (i)(ii)(iii): Compositions tested at 3.4 μg / l (C1) in air against fecal restorers (i) floral; (ii) citrus; (iii) jasmine;

[0030] - Figure 4b : Compositions tested at 1.1 μg / l (C2) in air against fecal restorers;

[0031] - Figure 4c : Compositions tested at 0.33 μg / l (C3) in air against fecal restorers.

[0032] Figures 5 - 10 Represents the average malodor intensity measured in the chamber.

[0033] Figure 11 Represents a model toilet. In the left side view of the model toilet, A: laminar flow filter; B: damper; C: odor generator, right front view of the odor generator placed behind the model toilet; D: injection pump; E: round-bottom glass mounted on a heating plate; (F) intake pipe, guiding the air carrying odor treatment inside the model toilet.

[0034] Figure 12 Represents the relationship between the predicted quantity and the measured quantity of the components of the toilet malodor in the model toilet. The odor mixing uniformity between one toilet and three toilets. Comparison of the mean ± standard deviation (SD) of the measured gas phase concentration with the expected value, N = 9.

[0035] Figure 13Represents sensory data, showing the effects of the fragrance composition according to the present invention on the perceived pleasure, desire to enter, fecal characteristics, and fecal intensity in a model toilet. Validation of the sensory protocol. Mean ± 95% confidence interval (CI) for pleasure, willingness to enter, fecal characteristics, and odor grade intensity. Mo: Malodor. Perf: 4.9 μg / l fragrance formulation floral D - see Table 14.

[0036] Figure 14 A) Evaluation of the intensity of sensory stimuli with constant Mukuru feces reconstitution and increasing fragrance concentration. Mean intensity ± 95% CI as a function of odor treatment, temperature, and relative humidity. Figure 14 B) Intensity evaluation at 22 °C and 35 °C; data at 30% and 80% humidity were combined. Figure 14 C) Intensity evaluation at 30% and 80% humidity; data at 22 °C and 35 °C were combined. Asterisks indicate the level of significant difference in the means, ***P < 0.0001, *P < 0.05.

[0037] Figure 15 Sensory evaluation of the effects of reference malodor or fragrance on the response variable, fecal characteristics. Mean ± 95% CI of fecal characteristics for odor treatment. Blue represents the odor group compared to malodor, while pink represents the group compared to fragrance. After pairwise testing based on ANOVA, means with different letters are significantly different.

[0038] Figure 16 Sensory evaluation of the effects of reference malodor or fragrance on the response variable, pleasure. Mean ± 95% CI of pleasure ratings as a function of odor treatment. Blue represents the odor group compared to malodor, while pink represents the group compared to fragrance. After pairwise testing based on ANOVA, means with different letters are significantly different.

[0039] Figure 17 Input rating as a function of pleasure rating. The line shows the linear model for predicting the rating from the pleasure rating.

[0040] Figure 18 Represents the mean ± 95% confidence interval (CI) of pleasure (black line) and fecal characteristics (gray line) ratings for testing toilets at 25 °C (upper three graphs) and 40 °C (lower three graphs) as a function of time for Mukuru feces reconstitution malodor (MO) + floral V, feces reconstitution malodor + jasmine E, and Mukuru feces reconstitution malodor alone.

[0041] Figure 19Shows the average gas-phase concentration of antagonist compounds shown in the Floral V formulation (triangles) and the Jasmine E formulation (circles) as a function of time, observed at 25 °C (dark line) and 40 °C (light line). The horizontal solid line is the ODT.

[0042] Figure 20 Shows the mean comfort level ± SEM of the test formulations Jasmine E (left vertical column), Floral V (middle vertical column), and citrus 259389B (right vertical column) in two countries (top row: Durban, South Africa; bottom row: Pune, India); the numbers 1, 2, 3 correspond to the three toilets tested. Asterisks indicate that the scores obtained without treatment and with treatment showed significant differences: ns P > 0.05; *P <= 0.05; **P < 0.01; ***P < 0.001. The black bars represent the pleasant ratings observed for the test formulations. The grey bars represent the pleasant ratings observed in the absence of the test formulations.

[0043] Figure 21 Shows the mean fecal characteristics level ± SEM of the test formulations Jasmine E (left vertical column), Floral V (middle vertical column), and citrus 259389B (right vertical column) in two countries (top row: Durban, South Africa; bottom row: Pune, India); the numbers 1, 2, 3 correspond to the three toilets tested. Asterisks indicate that the scores obtained without treatment and with treatment showed significant differences: ns P > 0.05; *P <= 0.05; **P < 0.01; ***P < 0.001. The black bars represent the fecal characteristics levels observed for the test formulations. The grey bars represent the fecal characteristics levels observed in the absence of the test formulations.

[0044] Figure 22 Shows the mean comfort, fecal characteristics, and intensity levels as a function of time ± SEM in two separate toilets in Durban. "WO": without test formulation (baseline). "W": with test formulation. The left vertical bars represent the values observed with or without treatment with Jasmine E in toilet 1. The right vertical bars represent the values observed with or without treatment with Floral V in toilet 2.

[0045] Figure 23 Shows the mean comfort, fecal characteristics, and intensity levels as a function of time ± SEM in two separate toilets in Durban. "WO": without test formulation (baseline). "W": with test formulation. The left vertical bars represent the values observed with or without treatment with the Floral V formulation in toilet 3. The right vertical bars represent the values observed with or without citrus treatment with the 259389B formulation in citrus toilet 2.

[0046] Figure 24 Mean ± SEM of pleasantness, fecal characteristics, and intensity ratings as a function of time in two separate toilets in Durban and Pune. "WO": No test formulation (baseline). "W": With test formulation. The left vertical bars represent values observed in toilet 2 in Durban with or without treatment with Floral V formulation. The right vertical bars represent values observed in toilet 2 in Pune with or without treatment with Floral V formulation.

[0047] Figure 25 Represents the observed gas-phase concentrations of compounds found in air samples collected at two different heights in each toilet. "Low": 0.15 - 0.3 m; "High": 1.5 - 1.7 m. "amy": Amyl cinnamic aldehyde; "benz": Benzyl acetate; "benzph": Benzyl phenylacetate; "dihyd": Dihydrolinalool; "io": α-Ionone; "iso": Isomethyl ionone; "jas": cis-Jasmone; "lily": Lyliflore; "lina": Linalyl acetate; "ros": Terpineol; "zest": Zestover. The upper left panel represents values observed in toilet 2 in Durban. The upper right panel represents values observed in toilet 3 in Durban. The lower left panel represents values observed in toilet 1 in Pune. The lower right panel represents values observed in toilet 2 in Pune.

[0048] Figure 26 Represents the gas-phase concentrations (log10 μg / L) of compounds found in air samples collected in the field (triangles) and model toilets (circles). "amy": Amyl cinnamic aldehyde; "benz": Benzyl acetate; "benzph": Benzyl phenylacetate; "dihyd": Dihydrolinalool; "io": α-Ionone; "iso": Isomethyl ionone; "jas": cis-Jasmone; "lily": Lyliflore; "lina": Linalyl acetate; "ros": Terpineol; "zest": Zestover.

[0049] Figure 27 Represents the average attribute scores of the test and three control formulations evaluated in combination with the odor of Mukuru fecal restitution.

[0050] Figure 28 Represents the average attribute scores of the test and three control formulations evaluated in combination with the odor of Mukuru fecal restitution.

[0051] Figure 29 Represents the average attribute scores of the test and four control formulations evaluated in combination with the odor of Mukuru fecal restitution. Detailed Description of the Invention

[0052] Definition

[0053] Unless otherwise indicated, percentages are by weight.

[0054] As used herein, the terms "comprising" or "including" are meant to be non-limiting.

[0055] As used herein, the terms "odorant receptor antagonist", "odor antagonist system", or "odor antagonist component" (also referred to as Group I) mean one or more compounds, each having the ability to inhibit at least one olfactory receptor in response to an odorant target. Identification is by measuring the activity of olfactory neurons or isolated receptors in a cultured cell line, the response of which is receptor-driven, as described in the Examples below.

[0056] As used herein, "odorant target" refers to the molecular components of fecal odor, as characterized by Lin et al., Environ. Sci. Technol., 2013, 47(14), pp 7876-7882, and includes indole, butyric acid, p-cresol, skatole, and dimethyl trisulfide.

[0057] As used herein, the term "functional fragrance blend" (referred to as Group II) means a mixture of at least two fragrance ingredients, which as functional fragrance ingredients are determined by, for example, sensory measurement of at least one element of fecal odor.

[0058] As used herein, the term "non-functional fragrance blend" (referred to as Group III) means a mixture of at least one, or at least two, fragrance ingredients, which as non-functional fragrance ingredients do not act as fecal odor counteragents, i.e., fragrance ingredients that do not belong to Group I or Group II.

[0059] As used herein, the terms "fragrance", "fragrance oil", or "fragrance blend" are used to denote a mixture of fragrance ingredients.

[0060] In addition, "fragrance ingredient" herein refers to a compound that can be used in a fragrance formulation or composition to impart at least one hedonic effect. In other words, an ingredient considered to be a fragrance ingredient must be recognized by those skilled in the art of fragrances as being able to impart or modify the odor of a composition in a positive or pleasant manner, and not merely to have an odor.

[0061] The nature and type of the perfume ingredients are not guaranteed to be described in more detail here, and they cannot be exhausted in any case. Those skilled in the art can select them based on their common sense and according to the intended use or application and the desired sensory effects. Generally speaking, these perfume ingredients belong to different chemical classifications, such as alcohols, lactones, aldehydes, ketones, esters, ethers, acetates, nitriles, terpenoids, nitrogen- or sulfur-containing heterocyclic compounds, and essential oils, and the perfume adjuvants can be of natural origin or synthetic origin.

[0062] In particular, the perfume ingredients commonly used in perfume formulations can be listed, for example:

[0063] - Aldehyde perfume ingredients: decanal, dodecanal, 2-methylundecanal, 10-undecenal, octanal, and / or nonenal;

[0064] - Aromatic herb ingredients: eucalyptus oil, camphor, eucalyptol, menthol, and / or α-pinene;

[0065] - Balsam ingredients: coumarin, ethyl vanillin, and / or vanillin;

[0066] - Citrus perfume ingredients: dihydromyrcenol, citral, orange oil, linalyl acetate, citronellonitrile, orange terpenes, limonene, 1-p-menthene-8-yl acetate, and / or 1,4(8)-p-menthadiene;

[0067] - Floral perfume ingredients: methyl dihydrojasmonate, linalool, citronellol, phenylethyl alcohol, 3-(4-tert-butylphenyl)-2-methylpropanal, hexyl cinnamaldehyde, benzyl acetate, benzyl salicylate, tetrahydro-2-isobutyl-4-methyl-4(2H)-pyranol, β-ionone, methyl (2-methylamino)benzoate, (E)-3-methyl-4-(2,6,6-trimethyl-2-cyclohexen-1-yl)-3-buten-2-one, hexyl salicylate, 3,7-dimethyl-1,6-nonadien-3-ol, 3-(4-isopropylphenyl)-2-methylpropanal, tricyclodecenyl acetate, geraniol, p-menth-1-en-8-ol, 4-(1,1-dimethylethyl)-1-cyclohexyl acetate, 1,1-dimethyl-2-phenylethyl acetate, 4-cyclohexyl-2-methyl-2-butanol, amyl salicylate, highly cis-methyl dihydrojasmonate, 3-methyl-5-phenyl-1-pentanol, tricyclodecenyl propionate, geranyl acetate, tetrahydrolinalool, cis-7-p-menthol, (S)-2-(1,1-dimethylpropoxy)propyl propionate, 2-methoxynaphthalene, 2,2,2-trichloro-1-phenylethyl acetate, 4 / 3-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1-carbaldehyde, amyl cinnamaldehyde, 4-phenyl-2-butanone, isononyl acetate, 4-(1,1-dimethylethyl)-1-cyclohexyl acetate, tricyclodecenyl isobutyrate, and / or a mixture of methyl ionone isomers;

[0068] - Fruity components: γ-undecalactone, 4-decalactone, ethyl 2-methylvalerate, hexyl acetate, ethyl 2-methylbutyrate, γ-nonalactone, allyl heptanoate, 2-phenoxyethyl isobutyrate, ethyl 2-methyl-1,3-dioxolane-2-acetate and / or diethyl 1,4-cyclohexanedicarboxylate;

[0069] - Green components: 2,4-dimethyl-3-cyclohexene-1-carbaldehyde, 2-tert-butyl-1-cyclohexyl acetate, styralyl acetate, allyl (2-methylbutoxy)acetate, 4-methyl-3-decen-5-ol, diphenyl ether, (Z)-3-octen-1-ol and / or 1-(5,5-dimethyl-1-cyclohexen-1-yl)-4-penten-1-one;

[0070] - Musk components: 1,4-dioxaspiro[5.17]docosane-5,17-dione, pentadecenolide, 3-methyl-5-cyclopentadecen-1-one, 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta[g]-2-benzopyran, (1S,1'R)-2-[1-(3',3'-dimethyl-1'-cyclohexyl)ethoxy]-2-methylpropyl propionate, pentadecanolide and / or (1S,1'R)-[1-(3',3'-dimethyl-1'-cyclohexyl)ethoxycarbonyl]methyl propionate;

[0071] - Woody components: 1-(octahydro-2,3,8,8-tetramethyl-2-naphthalenyl)ethan-1-one, patchouli oil, terpene fraction of patchouli oil, (1'R,E)-2-ethyl-4-(2',2',3'-trimethyl-3'-cyclopenten-1'-yl)-2-buten-1-ol, 2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol, methyl cedrylone, 5-(2,2,3-trimethyl-3-cyclopentenyl)-3-methylpentan-2-ol, 1-(2,3,8,8-tetramethyl-1,2,3,4,6,7,8,8a-octahydronaphthalen-2-yl)ethan-1-one and / or isobornyl acetate;

[0072] - Other components (such as amber, powder, spicy or watery): dodecahydro-3a,6,6,9a-tetramethylnaphtho[2,1-b]furan and any of its stereoisomers, piperonal, anisaldehyde, eugenol, cinnamaldehyde, clove oil, 3-(1,3-benzodioxol-5-yl)-2-methylpropanal and / or 3-(3-isopropyl-1-phenyl)butanal.

[0073] The citronitrile perfume ingredient can be not limited to the above ingredients, and many other ingredients among these are listed in the references, such as S. Arctander, Perfume and Flavor Chemicals, 1969, Montclair, New Jersey, USA or its updated versions, or other works of similar nature, as well as a large number of patent documents in the field of the perfume industry. It should also be understood that the auxiliary ingredients can also be compounds known to release various types of perfume compounds in a controlled manner.

[0074] It has now been unexpectedly determined that the combination of a malodor receptor antagonist system comprising at least one ingredient selected from the group in Table 1 and a functional perfume composition composed of perfume ingredients for combating fecal malodor improves the effect of the functional perfume composition on restricting, reducing or eliminating the perception of fecal malodor.

[0075] Therefore, a first object of the present invention is the use of a composition comprising the following ingredients for reducing, restricting or eliminating the perception of fecal malodor:

[0076] (i) About 2 wt% to about 85 wt% of a malodor receptor antagonist system, which comprises at least one ingredient selected from the group in Table 1;

[0077] (ii) About 15 wt% to 98 wt% of a functional perfume composition, comprising at least two perfume ingredients, provided that any ingredient listed in Table 1 is excluded, or selected from Table 2, and the composition has a fragrance note selected from floral, citrus and jasmine; and

[0078] (iii) Optionally, a non-functional perfume composition.

[0079] Table 1 : Malodor receptor antagonist - Group I

[0080]

[0081]

[0082]

[0083]

[0084] Table 2 : Functional perfume ingredient - Group II

[0085]

[0086]

[0087] Group I:

[0088] The components in Table 1 account for 2 - 85 wt% of the composition used according to the present invention. According to one embodiment, the composition used according to the present invention contains the malodor antagonist system as defined above, in an amount of 6 - 70 wt%. According to another embodiment, the composition used according to the present invention contains the malodor antagonist system as defined above, in an amount of 8 - 60 wt%. According to another embodiment, the composition used according to the present invention contains the malodor antagonist system as defined above, in an amount of 8 - 46 wt%.

[0089] According to a specific embodiment of the present invention, the malodor receptor antagonist system (Group I) from the composition used according to the present invention comprises at least three components selected from Table 1. According to another embodiment, at least four, or at least five, or at least six, or at least eight components selected from Table 1 are part of the malodor receptor antagonist system.

[0090] Group II:

[0091] Group II in the present invention is the functional perfume blend as defined above. Its content is 15 - 98 wt% of the composition used according to the present invention. According to one embodiment, its content is 30 - 94 wt%. According to another embodiment, its content is 40 - 92 wt% of the composition. According to another embodiment, its content is 29 - 92 wt% of the composition.

[0092] According to a specific embodiment, Group II consists of components selected from the group consisting of ionone, irone, damascenone, citral, citronellol BJ, citronellonitrile, citric acid, methyl citral, cinnamaldehyde, methyl cinnamaldehyde, hexyl cinnamaldehyde, geranial, C11 undecanal, aldehyde supra, dodecanal, aldehyde C8, aldehyde C9, aldehyde C12, p - tert - amylcyclohexanone (orivone) and mixtures thereof.

[0093] According to a specific embodiment, Group II consists of components from the group of Table 2.

[0094] According to a specific embodiment, Group II consists of the group consisting of ionone, irone, damascenone, citral, methyl cinnamaldehyde, geranial, p - tert - amylcyclohexanone, their derivatives and mixtures.

[0095] In some embodiments, ionone, irone, damascenone (including α - damascenone, β - damascenone, δ - damascenone), firascone, galione, γ - damascenone, α - irone, β - irone, isomethylionone 70P, β - methylionone, γ - methylionone Coeur IFF, ionone AI, ionone AT and ionone BC.

[0096] In some embodiments, methyl cinnamaldehyde includes alkyl derivatives, including cinnamaldehyde, methyl cinnamaldehyde, and ethyl cinnamaldehyde.

[0097] In some embodiments, methyl cinnamaldehyde includes alkyl derivatives, including cinnamaldehyde, methyl cinnamaldehyde, and ethyl cinnamaldehyde.

[0098] Group III:

[0099] According to a specific embodiment, the composition used according to the present invention comprises a non-functional perfume blend as defined above. The non-functional perfume blend consists of perfume ingredients as defined above, which are neither part of Group II nor part of Group I. If present in the composition according to the present invention, the non-functional perfume blend can generally be present in an amount of 0.5 to 70 wt%, or alternatively, 0.5 to 50 wt% of the composition as defined in any of the above embodiments.

[0100] Group IV: Delivery systems

[0101] According to a specific embodiment, the composition as defined above can be used in combination with a delivery system. Using a delivery system can achieve an optimal gas-phase concentration of the active ingredient in the composition. Suitable delivery systems for the purposes of the present invention include, but are not limited to:

[0102] · Amorphous coated carriers, including one or more porous or non-porous substrates in the form of loose powders or compacts, selected from the following non-limiting examples: cellulose (paper / cardboard), vermiculite, other industrial absorbents, perlite, calcium carbonate, pumice, other minerals, wood, sawdust, corn cobs, ground rice husks, rice husk ash, other agricultural by-products, biochar, starch, modified starch;

[0103] · Spray-dried moisture-activated encapsulation systems, wherein the composition according to the present invention is encapsulated in a matrix by a spray-drying method, and the matrix comprises one or more of the following, but is not limited to: maltodextrin, octenyl succinic anhydride starch (modified starch);

[0104] · Core-shell encapsulation systems, such as mechanically activated microcapsules, which have an impermeable shell (e.g., polyurea, polyurethane, etc.) and the composition according to the present invention in the core;

[0105] · Liquid mixtures containing surfactants;

[0106] · Polymer materials.

[0107] The use of the composition as defined in any of the above embodiments is also an object of the present invention, wherein the composition further comprises an encapsulating material such as a polymer to form microcapsules or microparticles, or comprises materials to form a liquid delivery system for the composition, such as an emulsion, microemulsion, nanoemulsion, gel, microgel, anhydrous gel or dispersion.

[0108] According to a specific embodiment, the composition as defined in any of the above embodiments is absorbed on a porous or non-porous substrate in loose powder or compacted form, the substrate being selected from cellulose (paper / cardboard), vermiculite, other industrial absorbents, perlite, calcium carbonate, pumice, wood, sawdust, ground corn cobs, ground rice husks, rice husk ash, biochar, starch, modified starch and mixtures thereof.

[0109] The second object of the present invention consists of a malodor receptor antagonist system, said malodor receptor antagonist system consisting of at least three, or at least four components selected from the group of Table 1.

[0110] Another object of the present invention is a malodor antagonistic composition, which comprises:

[0111] a) An active amount of a malodor receptor antagonist system of about 2 to about 85 wt%, which comprises at least one, or at least three components selected from Table 1;

[0112] b) A functional perfume blend of about 15 to about 98 wt%, which comprises at least two components selected from the group consisting of the components of Table 2; and

[0113] c) Optionally, a non-functional perfume blend, which comprises at least two perfuming ingredients.

[0114] According to a specific embodiment, the composition comprises about 6 to about 70 wt% of Group I. According to another embodiment, the composition comprises about 8 to about 60 wt% of Group I.

[0115] According to a specific embodiment, the malodor receptor antagonist system comprises (2,5-dimethyl-2,3-dihydro-1H-inden-2-yl)methanol in an amount of at least 2 wt%, or at least 3 wt% of the composition.

[0116] Without wishing to be bound by any particular theory, the combination of components within the malodor receptor antagonist system may exhibit a synergistic reduction or elimination of the perception of fecal malodor. Examples of such malodor antagonistic compositions are shown in Example 16 below. Thus, in some embodiments, the malodor receptor antagonist system comprises (2,5-dimethyl-2,3-dihydro-1H-inden-2-yl)methanol And the functional perfume composition comprises isomethyl ionone (α-methyl ionone and isomethyl-α-ionone) and α-ionone (also known as ionone AT). Alternatively, the functional perfume composition further comprises citral.

[0117] Alternatively, in some embodiments, the malodor receptor antagonist system comprises (2,5-dimethyl-2,3-dihydro-1H-inden-2-yl) methanol and (+-)-3,7-dimethyl-1-octen-3-ol (dihydrolinalool), and the functional perfume composition comprises isomethyl ionone (α-methyl ionone and isomethyl-α-ionone) and α-ionone (also known as ionone AT).

[0118] The compositions of the present invention can be used in any consumer product in which MOC activity is at least potentially useful. Accordingly, the compounds of the present invention can also be advantageously used in any consumer product in which MOC activity is at least potentially useful. Accordingly, another object of the present invention is represented by an MOC consumer product comprising at least one composition of the present invention as defined above as an active ingredient.

[0119] The composition can be added as such according to the embodiments presented herein or as part of an MOC composition (including delivery systems) of the present invention.

[0120] It should be understood that the MOC consumer product can itself also be a perfumed product by its nature.

[0121] For the sake of clarity, it must be mentioned that by "MOC (optionally perfumed) consumer product" or similar expressions, it is meant a consumer product that is intended to deliver at least an MOC effect to the surface to which it is applied (such as skin, hair, textiles, or household surfaces, and also air), and optionally also a pleasant perfuming effect. In other words, a consumer product according to the present invention is a perfumed consumer product that comprises a functional formulation and optionally additional beneficial agents corresponding to the desired consumer product such as a detergent or an air freshener, and an effective amount of at least one compound or composition from the present invention. For the sake of clarity, the consumer product is a non-edible product.

[0122] The nature and type of the components of the MOC consumer product are not guaranteed to be described in more detail herein, which in any case cannot be exhaustive, and those skilled in the art can select them based on their common general knowledge and according to the nature of the product and the desired effect.

[0123] Non-limiting examples of suitable perfumed consumer products can be:

[0124] - Fabric care products, such as liquid detergents, powder detergents, sheet detergents, bar detergents, paste detergents, liquid fabric softeners, sheet fabric softeners, fabric fragrance boosters, laundry pre-treatments, fabric fresheners, ironing water, laundry bleaches, carpet cleaning powders or carpet cleaners; the use of such products will be particularly beneficial in cases where the standard water available to the consumer may be associated with the described malodors (e.g., putrid water bodies);

[0125] - Toilet paper or sanitary napkins;

[0126] - Air freshening products, such as air freshener sprays, gel-type air fresheners, liquid-wick air fresheners, solid air fresheners comprising a porous substrate (e.g., paper or card absorbent paper, porous ceramics or porous plastics), liquid-type or gel-type air fresheners comprising a permeable membrane, electric air fresheners and dual-action air freshener / disinfectant sprays; and / or

[0127] - Surface care products, such as multi-purpose cleaners, furniture polishes, wood floor cleaners, toilet care products (e.g., toilet bowl cleaners, cistern-type toilet cleaners, hanging toilet cleaning blocks or hanging toilet cleaning liquids); pet litter.

[0128] Some of the above MOC consumer products can represent the aggressive media of the compounds of some embodiments of the present invention and may therefore need to be protected from premature decomposition, for example by encapsulation or by chemically binding them to another chemical substance that is adapted to release the ingredients of the present invention upon exposure to a suitable external stimulus, such as an enzyme, light, heat or pH change.

[0129] Those skilled in the art should understand that the disclosed concepts and specific embodiments can be readily used as a basis for modifying or formulating other formulations for the same purpose of the present invention. Those skilled in the art should also recognize that such equivalent formulations do not depart from the spirit and scope of the present invention as defined in the appended claims.

[0130] The proportions in which the compounds according to the invention can be incorporated into the various above products or compositions can vary within a wide numerical range. When the compounds according to the invention are mixed with other ingredients, solvents or additives commonly used in the art, these values depend on the nature of the MOC consumer product and the desired sensory effect as well as the nature of the co-ingredients in the given composition.

[0131] Generally, for example, in the case of a flavoring composition, the typical concentration of the compounds of the present invention is from 0.01 wt% to 60 wt%, or even higher, based on the weight of the composition incorporated. When these compounds are incorporated into MOC consumer products, lower concentrations can be used, for example from 0.01 wt% to 2 wt%, the percentages being relative to the weight of the consumer product.

[0132] In particular, the concentration of the MOC compound of the present invention used in the various above-mentioned consumer products varies within a very wide range according to the nature of the consumer product.

[0133] A non-therapeutic method for antagonizing fecal odor is also an object of the present invention, the method comprising treating a surface with a composition as defined in any of the above embodiments or at least partially dispensing in air a composition as defined in any of the above embodiments.

[0134] Example

[0135] The present invention will now be described in further detail by the following examples, where the abbreviations have their usual meanings in the art and the temperature is expressed in degrees Celsius (°C).

[0136] Example 1

[0137] Antagonist Identification - Identification of Odorant Receptor Antagonists by Ex Vivo Living Neuron Assays

[0138] In an in vitro live neuron assay, olfactory sensory neurons (OSNs) are extracted from the olfactory epithelium of mice and the response to sequentially delivered stimuli can be tested, where the response is detected by live cell calcium imaging microscopy. At least 1000 and approximately 5000 - 10000 OSNs are tested for each compound listed in Table 1. It has been determined by previous studies in the art that the vast majority of the extracted OSNs express 1 out of approximately 1200 odorant receptors (ORs) present in the mouse genome, such that in a sample of our extracted OSNs, most of the 1200 ORs should have been represented in at least one OSN. Since the response of OSNs to delivered stimuli is entirely driven by the expressed ORs, OSNs selectively detect and co-encode the identity and intensity of odors. By stimulating OSNs with MO molecules and measuring the response of each OSN, the subset of induced responses is the subset that detects and thus potentially encodes the MO. By subsequently delivering a mixture of MO and a candidate antagonist to the same cells, the degree of inhibition of the signal in each MO-responsive OSN ("inhibition level") can be determined. The degree of inhibition in each cell is divided into one of three groups: low inhibition (10 - 25%), medium inhibition (25 - 75%) and strong inhibition (75 - 100%). In addition, the proportions of MO-responsive OSNs showing low inhibition, medium inhibition and strong inhibition are calculated. Examples of such data are shown in Figures 1a - 1d . A compound for which the minimum intensity of inhibition is greater than the minimum proportion of OSNs is considered an antagonist "hit" and a putative malodor inhibition compound. The minimum levels are 10% of the population showing strong inhibition and / or 25% of the population showing medium inhibition and / or 40% of the population showing weak inhibition, respectively.

[0139] The genetic similarity between mouse and human receptors, due to their common evolutionary history and a natural odor environment that is likely similar on an evolutionary time scale, leads us to believe that overall observations of the MO-responsive population of mouse ORs should be relevant to those from human ORs, even though individual orthologous receptors (i.e., those thought to have a common ancestor and typically most similar in genetic sequence) may show different levels of functional similarity to those from mice.

[0140] Figures 1a - 1d Examples representing the results of a live neuron assay antagonism screen against a target fecal MO provide evidence of MO receptor antagonism. The level of inhibition of the neuron population is divided into high (75 - 100%, black), medium (25 - 75%, dashed), and low (10 - 25%, white). Compounds considered antagonists or "hits" need to pass the population amounts indicated by the vertical lines (A, B, C), where high inhibition must pass through A (10% of the MO-responsive OSN population), and / or medium inhibition must pass through B (25% of the MO-responsive OSN population) and / or low inhibition must pass through C (40% of the MO-responsive OSN population).

[0141] Example 2

[0142] Sensory Measurement of Residual Fecal Odor Scores for Individual Odorant Receptor Antagonist Systems, Individual Functional Perfuming Ingredients, and for Compositions According to the Invention Figure 2

[0143] The malodor receptor antagonist system and composition are carried out at a unique gas-phase concentration of 3.4 μg / l air.

[0144] The sensory method for evaluating the composition requires the use of an air dilution olfactometer designed by Firmenich to achieve good control and a stable gas-phase concentration of the composition as well as of the malodor for a group of test subjects.

[0145] Thirty subjects must first evaluate the fecal reconstitute* individually and then rate three attributes, "freshness", "pleasantness", and "fecal" (malodor nature), on a scale of 0 - 10. The next evaluation is carried out after 30 seconds to avoid odor adaptation; the fecal malodor reconstitute is injected into the olfactometer together with the test composition. The ratings of the same description are recorded.

[0146] *Model malodor is a fecal resynthesis product made from indole, methanethiol, p-cresol, and butyric acid. The gas-phase concentrations of the fecal malodor resynthesis product and its components correspond to the headspace analysis results from toilet gas-phase sampling (Charles JF Chappuis, Yvan Niclass, Christine Vuilleumier, and Christian Starkenmann, Quantitative Headspace Analysis of Selected Odourants from Latrines in Africa and India Environ. Sci. Technol. 2015, 49, 6134-6140).

[0147] Results are expressed as the average rates of three descriptors for the individual fecal resynthesis product and the fecal resynthesis product in combination with the test composition.

[0148] Example 3 Results are reported for the scoring when combining the malodor antagonist system consisting of (2,5-dimethyl-2,3-dihydro-1H-inden-2-yl)methanol with a functional fragrance blend consisting of α-ionone (also known as ionone AT) and isomethylionone.

[0149] It can be seen that when submitted at the same concentration, valuable inhibition of the fecal resynthesis product perception can be obtained (residual fecal odor < 50%):

[0150] - The independent malodor antagonist system, especially (2,5-dimethyl-2,3-dihydro-1H-inden-2-yl)methanol and the single components of the functional fragrance blend (ionone AT or isomethylionone), or

[0151] - Combining the malodor antagonist system consisting of (2,5-dimethyl-2,3-dihydro-1H-inden-2-yl)methanol with a functional fragrance blend (hereinafter referred to as "mixture"), or

[0152] - Adding a malodor antagonist system with an increasing amount of antagonist in Table 1 to a composition containing functional and non-functional fragrance blends.

[0153] Alias is a floral composition designed not to include the antagonists in Table 1 but to include fragrance components known to those skilled in the art; however, its effect on the fecal resynthesis product is limited. The fecal fraction remaining when combining this composition with the fecal resynthesis product is > 50%. This indicates that the malodor reduction effect is due to the antagonists being specific rather than due to a simple masking of the fragrance components.

[0154] Sensory Properties of Compositions According to the Invention

[0155] Description

[0156] The ability of the mixture of the inventive composition, which consists of the following components, to inhibit the malodor of the fecal model * is significantly increased (70%) compared to the ability of each component in the mixture when used alone (up to 58%):

[0157] - As a malodor antagonist system ((2,5-Dimethyl-2,3-dihydro-1H-inden-2-yl)methanol)

[0158] - Isomethyl ionone and ionone AT (α-ionone) as a functional fragrance blend.

[0159] Figure 3 : Figure 3 The performance of three single compounds and a schematic diagram of their mixture (floral fragrance blend) against fecal restitution are given.

[0160] Example 4 The ability of the composition according to the invention to inhibit the malodor of the fecal model is specifically described. Each component is tested alone at its dose in the mixture. The mixture is tested at 3.4 μg / l air.

[0161] A blind sensory evaluation was organized; the information on the randomly submitted odorous stimuli was not disclosed to the 31 participants. The tests were repeated and the observations were accumulated.

[0162] Compositions According to the Invention

[0163] Table 3 - Composition Floral E

[0164] The following table represents the composition according to the invention.

[0165] Table 4 - Composition Floral P

[0166]

[0167] Table 5 - Composition Floral RD

[0168]

[0169] Table 6 - Composition Citrus B

[0170]

[0171] Table 7 - Composition Citrus H

[0172]

[0173] Table 8 - Composition Citrus

[0174]

[0175] Table 9 - Composition Jasmine E 259389B

[0176]

[0177] Example 5

[0178]

[0179] Sensory Evaluation of Compositions According to the Invention

[0180] Description

[0181] The sensory method for evaluating the composition described in Example 4 requires the use of an air dilution olfactometer designed by Firmenich to achieve good control of the malodor of the composition and a stable gas-phase concentration for a group of test subjects.

[0182] Thirty subjects must first evaluate the fecal restitution separately and then evaluate the same descriptors previously expressed on a linear scale. The next evaluation is carried out after 30 seconds to avoid odor adaptation; the fecal malodor restitution is injected into the olfactometer together with the composition to be tested. The ratings of the same descriptors are recorded.

[0183] The results are expressed as the average rates of three descriptors for the fecal restitution alone and the fecal restitution combined with the test composition.

[0184] Figure 4a : The graph (Figure 4) represents the scores for the fecal, freshness, and pleasantness attributes for the fecal restitution and the combination of the following compositions with this fecal restitution (unique concentrations in the test):

[0185] - The composition without a determined antagonist (named Alias).

[0186] - Iterations of the floral compositions (called Floral E, P, and RD) gradually involving the antagonist system.

[0187] -

[0188] - Iterations of the citrus compositions (called Citrus B and H) gradually involving the antagonist system.

[0189] - Iterations of the jasmine composition (called Jasmine E) involving the antagonist system.

[0190] Shows the number and weight % of the components from Category I (antagonist system), II (functional fragrance blend), and III (non-functional fragrance blend).

[0191] All these compositions were tested at three decreasing concentrations C1, C2, and C3.

[0192] The lower the fecal score, the better the performance of the antagonist composition.

[0193] Figure 4b : The composition tested at 3.4 μg / cavity (lair) (C1) against fecal restitution

[0194] Figure 4c : The composition tested at 1.1 μg / cavity (lair) (C2) against fecal restitution

[0195] Example 6 : The composition tested at 0.33 μg / cavity (lair) (C3) against fecal restitution

[0196] When evaluating the individual Floral RD, Citrus H, or Jasmine E at the C1 concentration (not combined with fecal restitution), the dashed lines on the three graphs give the scores for the three attributes. These three graphs show the lowest possible fecal scores and the highest values for freshness and pleasantness.

[0197] There was no statistical difference between the fecal scores of Floral RD, Citrus H, or Jasmine E evaluated individually at the C1 concentration and the fecal scores of these compositions tested at the C1 concentration and combined with fecal restitution (confirmed by Student's test, 99% confidence).

[0198] - When adding the antagonist system, the performance of the floral and citrus compositions was improved. From Floral E to Floral RD, the perception of fecal odor was less and less. Similar observations can be made for the citrus compositions, which have improved performance of Citrus H over Citrus B.

[0199] - The iteration gradually included more components in the antagonist system.

[0200] - The jasmine composition also demonstrated an interest in the antagonist system.

[0201] - Floral RD, Citrus H, and Jasmine E eliminated the perception of fecal odor.

[0202] Table 10 - "Floral V" is a floral - type aromatic composition according to the invention, as follows:

[0203] Table 11 - "Citrus B2" is a citrus - type aromatic composition according to the invention, as follows:

[0204]

[0205] Table 12 - "Jasmine E" is a jasmine - type aromatic composition according to the invention, as follows

[0206]

[0207]

[0208] Example 7 :

[0209]

[0210] Toilet Malodor Reduction Efficacy Test of Cellulose - Based Air Fresheners Containing an Aromatic Composition According to the Invention

[0211] Evaluation Chamber Label Evaluation Chamber Content

[0212] The air freshener device used in this example is of the cellulose air freshener type. These air fresheners include absorbent materials infused with a specific amount of fragrance. The material is then placed in a container to control the delivery of the fragrance composition. For this example, a cellulose pad is used as the absorbent material placed in an aluminum can.

[0213] Test samples were prepared by applying 3 g of the fragrance composition to a cellulose pad (2.5 square inches) placed in a round aluminum can (3 inches in diameter). The fragrance compositions used for this test were "Floral V" (Example 6), two samples of "Citrus B2" (Example 6), and "Jasmine E" (Example 6).

[0214] The synthetic toilet malodor formulation was prepared as follows:

[0215]

[0216] 70 wt% of vermiculite containing toilet malodor was prepared by mixing 350 g of toilet malodor with 150 g of vermiculite (fine grade, Specialty Vermiculite Corp, Enoree, SC).

[0217] The efficacy of the cellulose-based air freshener containing the fragrance formulation according to the present invention was evaluated according to the practice described in ASTM E 1593-06 "Method for Assessing the Efficacy of Air Care Products in Reducing Sensorialy Perceived Indoor Air Malodour Intensity". Six 72-cubic-foot evaluation chambers had olfactory windows inside the doors for the sensory evaluation of the samples. Five of the evaluation chambers contained aluminum cans 3 inches in diameter and 9 g of vermiculite containing toilet malodor; one evaluation chamber contained an aluminum can 3 inches in diameter and 9 g of vermiculite (without malodor).

[0218] One evaluation chamber containing only malodor (without test products) was identified as the reference; the other five evaluation chambers were labeled with randomly generated three-digit codes. The evaluation chambers were set up as follows:

[0219] Reference Only toilet malodor Toilet malodor + Jasmine E Toilet malodor + Citrus B2 196 Only toilet malodor 274 Only Citrus B2 326 Toilet malodor + Floral V 487 Figure 5 571 Example 8

[0220] These evaluation chambers were evaluated by 21 untrained but experienced assessors. "Untrained but experienced assessors" refers to individuals who have not received formal olfactory training but have participated in aroma evaluations and have experience in rating odor attributes.

[0221] During the evaluation, the environmental conditions in the evaluation chambers were 72°F, 35% RH, with 5 air changes per hour. A low portable table fan was placed on the floor of the evaluation chamber to allow air circulation. All assessors were first asked to smell the odor in the reference evaluation chamber to familiarize themselves with the malodor. Then they were instructed to smell the odor in the evaluation chambers and rate the intensity of the malodor using a 1 to 7 category scale, where 1 indicates no perceivable malodor and 7 indicates a very strong malodor. The introduction of the evaluation chambers was a blind, balanced, random, and single-product test. The assessors were instructed to open the olfactory window to evaluate each sample and wait 60 seconds before moving on to the next sample.

[0222] The data was analyzed using one-way analysis of variance (ANOVA), and then multiple comparisons were made using the Fisher's least significant difference (LSD) method (α = 0.05). The number of assessors (N) and LSD were as follows: N = 21, LSD = 0.60. The average malodor intensity of the evaluation chambers was as Toilet Malodor Reduction Efficacy Test of Candles Containing an Aromatic Composition According to the Invention shown.

[0223] The perceived malodor intensity of the evaluation chamber with only Citrus B2 (without malodor) was significantly lower than that of all other evaluation chambers. The perceived malodor intensity of the evaluation chamber containing the malodor and aromatic composition according to the present invention was significantly lower than the malodor intensity of the evaluation chamber with only malodor; therefore, the cellulose air freshener containing the aromatic composition according to the present invention is useful for reducing the perception of toilet malodor.

[0224] Figure 6

[0225] Example 9

[0226] The air freshener device used in this example was a candle; this device provided fragrance in two ways. First, the fragrance added to the candle slowly evaporated as it migrated through the wax to the surface of the candle. The second way was more through the "melt pool". When the candle was lit, a melt pool was formed, and the flame melted a part of the candle, forming a pool at the top. The warm mixture released the fragrance at a higher rate.

[0227] The aromatic compositions used for this test were "Floral Scent RD" (Example 4), two samples of "Citrus H" (Example 4), and "Jasmine E" (Example 6). The aromatized candles were prepared by mixing the above aromatic compositions with the candle formulations shown in the table below. Then, 100 grams of the wax mixture was placed in a 3-inch-high, round glass container with a 3-inch diameter and a wax-coated felt wick (CD#6, clamped at 0.5 inches high). For the test samples with only malodor, candles without an aromatic agent were prepared (candle wax 4625A IGI, 88%).

[0228]

[0229] Candle Formulations

[0230]

[0231] Control Formulations

[0232] The malodor preparation and testing procedures were the same as those described in Example 6. The evaluation room was evaluated by 15 untrained but experienced assessors. The data was analyzed using one-way analysis of variance (ANOVA), and then multiple comparisons were made using the Fisher's least significant difference (LSD) method (α = 0.05). The number of assessors (N) and LSD were as follows: N = 15, LSD = 0.70. The average malodor intensity of the evaluation room was as Toilet Malodor Reduction Efficacy Test of Aerosol Air Fresheners Containing an Aromatic Composition According to the Invention shown.

[0233] The perceived malodor intensity of the evaluation room with only Jasmine E (no malodor) was significantly lower than that of all other evaluation rooms. The perceived malodor intensity of the evaluation rooms containing malodor and the aromatic composition according to the present invention was significantly lower than the malodor intensity of the evaluation rooms with only malodor; therefore, the candles containing the aromatic composition according to the present invention are useful for reducing the perception of toilet malodor.

[0234] Figure 7

[0235] Example 10

[0236] The air freshener device used for this example was an aerosol; this device delivers the aromatic agent into the environment by means of a pressurized aqueous aromatized solution.

[0237] The aromatic compositions used for this test were "Floral Scent V" (Example 6), two samples of "Citrus B2" (Example 6), and "Jasmine E" (Example 6). The aromatized aerosol was prepared by mixing the aromatic compositions with the aerosol formulations shown in the table below.

[0238]

[0239] Aerosol Formulations

[0240] The malodor preparation and testing procedures were the same as those described in Example 6. The evaluation chambers were evaluated by 19 untrained but experienced assessors. The data were analyzed using one-way analysis of variance (ANOVA), and then multiple comparisons were performed using the Fisher's least significant difference (LSD) method (α = 0.05). The number of assessors (N) and LSD were as follows: N = 19, LSD = 0.70. The average malodor intensity of the evaluation chambers was as Toilet Malodor Reduction Efficacy Test of Sachet - Type Air Fresheners Containing an Aromatic Composition According to the Invention shown.

[0241] The perceived malodor intensity of the evaluation chamber with only Jasmine E (no malodor) was significantly lower than that of all other evaluation chambers. The perceived malodor intensity of the evaluation chambers containing malodor and the aromatic composition according to the present invention was significantly lower than the malodor intensity of the evaluation chambers with only malodor; therefore, the aerosol air freshener containing the aromatic composition according to the present invention is useful for reducing the perception of toilet malodor.

[0242] Figure 8

[0243] Example 11

[0244] The air freshener device used in this example was a sachet-type air freshener; this device utilizes a granular matrix and injects an aromatic agent contained in a permeable bag formed of paper, fabric, or non-woven fabric material.

[0245] The aromatic compositions used for this test were "Floral V" (Example 6), two "Citrus B2" samples (Example 6), and "Citrus E" (Example 6). The aromatized sachets were prepared by mixing the aromatic compositions with ground corn cob particles ( -100, source: Aproa) at a 20 wt% loading. Then, 12 g of the resulting mixture was placed in a 2.5-inch × 2.5-inch paper bag. Samples containing non-aromatized corn cob were prepared for the evaluation chambers with only malodor.

[0246] The malodor preparation and testing procedures were the same as those described in Example 8. The evaluation chambers were evaluated by 21 untrained but experienced assessors. The data were analyzed using one-way analysis of variance (ANOVA), and then multiple comparisons were performed using the Fisher's least significant difference (LSD) method (α = 0.05). The number of assessors (N) and LSD were as follows: N = 21, LSD = 0.62. The average malodor intensity of the evaluation chambers was as Toilet Malodor Reduction Efficacy Test of Liquid Electric Air Fresheners Containing an Aromatic Composition According to the Invention shown.

[0247] The perceived malodor intensity of the evaluation chamber with only jasmine E (without malodor) was significantly lower than that of the evaluation chamber with only malodor and the malodor intensity of the floral scent V + malodor evaluation chamber. The malodor perception levels of the jasmine E + malodor evaluation chamber and the citrus B2 + malodor evaluation chamber were not significantly stronger than those of the evaluation chamber without malodor, demonstrating the effect of these two compositions in reducing the perception of toilet malodor. The perceived malodor intensity of the evaluation chamber containing malodor and the aromatic composition according to the present invention was significantly lower than that of the evaluation chamber with only malodor; therefore, the pouch-type air freshener containing the aromatic composition according to the present invention is useful for reducing the perception of toilet malodor.

[0248] Figure 9

[0249] Example 12

[0250] The air freshener device used in this example was a wick-type freshener; this device uses a heating element to drive the aromatic composition from a wick inserted into a reservoir with an aromatic agent.

[0251] The aromatic compositions used for this test were "floral scent RD" (Example 4), two "citrus H" samples (Example 4), and "jasmine E" (Example 6). The aromatic compositions were mixed with an equal weight portion of Augeo Clean Multi (Solvay). Then, 20 g of the resulting mixture was placed in a reservoir with a wick (sintered plastic). The heater unit used was designed to heat the wick to 70 °C.

[0252] The malodor preparation and testing procedures were similar to those described in Example 8. However, in this example, the test evaluation chambers had a volume of 812 cubic feet, and the assessors evaluated the odors by entering each evaluation chamber. Other details were as described previously. The evaluation chambers were evaluated by 23 untrained but experienced assessors. The data was analyzed using one-way analysis of variance (ANOVA), and then multiple comparisons were performed using the Fisher's least significant difference (LSD) method (α = 0.05). The number of assessors (N) and LSD were as follows: N = 23, LSD = 0.56. The average malodor intensity of the evaluation chambers was as Figure 10 shown.

[0253] The perceived malodor intensity of the evaluation chamber with only jasmine E (without malodor) was significantly lower than that of the evaluation chamber with only malodor and the floral scent RD + malodor evaluation chamber. The malodor intensity of the jasmine E + malodor evaluation chamber and the citrus H + malodor evaluation chamber was not significantly stronger than that of the evaluation chamber without malodor, demonstrating that these two compositions effectively reduced the perception of toilet malodor. The perceived malodor intensity of the malodor evaluation chamber containing malodor and the aromatic composition according to the present invention was significantly lower than that of the evaluation chamber with only malodor; therefore, the liquid electric air freshener containing the aromatic composition according to the present invention is useful for reducing the perception of toilet malodor.

[0254] Example 13

[0255] The reduction of malodor of the aromatic composition described by the present invention was measured in a bleaching cleaning powder.

[0256] The bleaching cleaning powder is a bleaching powder combined with a spray-dried fragrance. The standard use of this product is to apply the powder to the area to be treated, dissolve it in water, then scrub to loosen all particles, and then rinse.

[0257] An aromatized bleaching sample was prepared by adding 0.15 g of spray-dried powder (containing 50% w / w fragrance and 50% w / w octenyl succinic anhydride modified starch) to 9.85 g of stabilized bleaching powder (Grade I, Gujarat Alkalies and Chemicals Limited, Gujarat, India).

[0258] The malodor composition detailed in Table 1 was applied to fine vermiculite (Specialty Vermiculite Corp, Enoree, SC) with a 70 wt% loading. Then, 9 g of the composition was provided to the evaluator in a round aluminum can. The aluminum can had a diameter of 3 inches and a height of 1 inch. For the test samples containing only the fragrance, cans with untreated vermiculite were used.

[0259] Table 13

[0260]

[0261] A 70 wt% vermiculite containing toilet malodor was prepared by mixing 350 g of toilet malodor with 150 g of vermiculite (fine grade, Specialty Vermiculite Corp, Enoree, SC). The efficacy of a cellulose-based air freshener containing a fragrance formulation according to the present invention was evaluated according to the practice described in ASTM E 1593-06 "Method for Assessing the Efficacy of Air Care Products in Reducing Sensorialy Perceived Indoor Air Malodour Intensity". The booth labeled "reference" contained only one malodor can. First, the evaluators were shown whether they were familiar with the malodor. Then, the evaluators used a scale of 1-7 (1 indicating no odor, 4 indicating moderate odor, and 7 indicating extremely strong malodor) to evaluate each sample in the designated order and evaluate the malodor intensity and total odor intensity.

[0262] The samples were evaluated by 19 untrained assessors. "Untrained assessors" refers to users of air fresheners who have not received formal olfactory training but have experience in participating in fragrance evaluations and rating odor attributes.

[0263] A 60-cubic-foot evaluation chamber was used. The floor of the evaluation chamber was wetted with water, and the sample was scrubbed onto the floor until it dissolved. Then, malodor was added. The environmental conditions during the test were 72°F, 40% RH, and 5 air changes per hour. A low-profile portable table fan was placed on the floor of the evaluation chamber to circulate the air inside the evaluation chamber. The booths were labeled with randomly generated 3-digit codes. The presentation of the samples was blind, balanced, random, and single-product testing. Five minutes after activation, the assessors were instructed to open the olfactory window to evaluate each sample and wait for 60 seconds, and then answer a series of questions related to the odor they perceived in the room. The assessors were asked to evaluate the malodor intensity and the total odor intensity.

[0264] The data were analyzed using one-way analysis of variance (ANOVA), and the least significant difference (α = 0.05) was used to determine the difference between two means. The average malodor intensity of the evaluation chamber is shown below; the minimum difference between the means is 0.61.

[0265] The results are shown in Toilet Malodor Reduction Efficacy Test of an Aromatic Composition According to the Invention in a Model Toilet in

[0266] The perceived malodor intensity of the floral RD + bleach evaluation chamber (without malodor) was significantly lower than that of the evaluation chamber with only malodor. The malodor intensity of the floral RD + bleach + malodor evaluation chamber was not significantly stronger than that of the evaluation chamber without malodor, demonstrating the effectiveness of this composition in reducing the perception of toilet malodor. The perceived malodor intensity of the evaluation chamber containing malodor and the floral RD composition according to the present invention was significantly lower than the malodor intensity of the evaluation chamber with only malodor; therefore, the bleaching cleaning powder containing the aromatic composition according to the present invention is useful for reducing the perception of toilet malodor.

[0267] Table 14: Floral D Perfume Formula

[0268] Figure 11

[0269] In this example, to evaluate the performance of the composition according to the present invention, a model toilet was constructed. The model toilet was equipped with an odor generator that injected hydrogen sulfide, methanethiol, butyric acid, p-cresol, and indole, and could accurately and reliably reproduce the toilet malodor headspace. The malodor concentration in the model toilet matched the quantitative headspace analysis of toilets in Africa and India. The toilet malodor headspace performance was verified by chemical and sensory analysis. Olfactory stimuli were presented to participants in different climates to evaluate the impact of climate on odor perception. The sensory data showed that an increase in temperature and humidity reduced the intensity level of the malodor but not its quality. The fragrance formulations could be delivered in these model toilets by forced evaporation to control the headspace concentration, or by delivery systems such as cellulose pads, liquids, and powders. Our experimental setup provided dose-response curves to evaluate the performance of the fragrance formulations in reducing toilet malodor and increasing pleasantness.

[0270] Materials and Methods

[0271] Chemicals

[0272] The compounds triethylamine, N-ethylmaleimide (NEM), and methyl octanoate were purchased from Sigma-Aldrich (Buchs, Switzerland), while butyric acid, p-cresol, indole, and L-cysteine were in-house products. The solvents diethyl ether, methanol, ethyl acetate, and acetone were purchased from Carlo Erba (Val de Reuil, France). For methanethiol and hydrogen sulfide, a 15 ppm (v / v) nitrogen mixture was used in pressurized cylinders purchased from Carbagas (Carouge, Switzerland). Oasis HLB 1-g columns were purchased from Waters (Montreux-Chailly, Switzerland). The fragrance formulations used in this example are described below.

[0273] Figure 11

[0274]

[0275] Model Toilet

[0276] Three 1.7 m model toilets (1.95 m × 0.985 m × 0.89 m) made of 8 mm transparent polyethylene terephthalate were placed in a climate chamber, and each toilet was equipped with a 29 cm × 39 cm revolving door to evaluate the odor ( 3 ). Air from the climate chamber entered each toilet through an odor generator located at a height of 45 cm on the rear wall (the odor generator is described in detail below). Air was drawn in from the roof of each toilet through a double-sided 82 cm × 91 cm layered filter (thick cotton fabric) and through a 100 mm aluminum exhaust pipe ( Figure 11 ). Figure 11)。Three exhaust pipes are connected to an adjustable fan through a main 100 mm stainless steel pipe. The air flow of each toilet can be adjusted individually using dampers (SPI 160, Systemair, Skinnskatteberg, Sweden) placed in the exhaust pipes ( Figure 11 )。A hot wire anemometer is placed in the main exhaust pipe to control the main exhaust air flow. If necessary, the air flow can be adjusted by changing the suction generated by the fan. The air velocity inside the main exhaust pipe of each toilet is maintained at an air flow of 17 cubic meters per hour. This air flow and the air changes generated per hour (about 10) are within the measurement range of the improved ventilated pit latrine.

[0277] Odor generator

[0278] To force liquid evaporation, we modified the lower chamber of an openly available olfactometer. A 500 ml round bottom flask was flushed with a nitrogen gas flow of 150 L / h, into which the liquid was introduced through a polytetrafluoroethylene (PTFE) capillary connected to a 1 ml polypropylene syringe ( Figure 11 )。The liquid flow rate was delivered by an injection pump, and its range could be from 0.04 ml / h to 10 ml / h. The flask was covered with a glass cap and heated to 160 °C using a stainless steel heating block mounted on a hot plate ( Figure 11 )。The flask outlet (inner diameter 2 mm) was placed in a 15 cm long stainless steel pipe with a diameter of 109 mm, which passed through the rear wall of the toilet. This pipe was connected to a 127 mm diameter aluminum exhaust pipe (80 cm long) located on the rear wall ( Sensory protocol ) to avoid inhaling the hot air inside the toilet. The nitrogen rich in odor molecules was mixed with the air entering the toilet. In addition to the forced evaporation release system, two stainless steel pipes were welded inside the pipe to fix a 6 mm PTFE pipe, and methanethiol and hydrogen sulfide were released from a pressurized gas cylinder. The PTFE pipe was sealed with Parafilm, and two 0.8 mm openings were punctured in each pipe ( Figure 11 )。

[0279] The nitrogen gas flow rate for each toilet was controlled using three rotameters (25 L / h to 250 L / h; Krohne, Duisburg, Germany). The flow rates of methanethiol and hydrogen sulfide were independently controlled using six mass flow meters (three toilets, two gases) (Red-y, AG, Aesch, Switzerland).

[0280] Climate chamber

[0281] The climate chamber has an area of 3.42 m × 2.95 m × 2.5 m and a volume of 25 m 3 。The temperature and humidity of the climate chamber are controlled at 540 m 3in a closed cycle of / h. Fresh air enters the chamber at a rate of 51 m 3 / h, and air leaves the chamber at the same rate. The working ranges of temperature and relative humidity (RH) are 12 °C to 45 °C and 30% RH to 90% RH, respectively. The climatic chamber is equipped with temperature and RH probes placed at the inlet and outlet of the temperature and humidity control cycle. Data from the inlet probe are recorded every 5 minutes, allowing the temperature and RH of the air inside the climatic chamber to be measured during the experiment. In addition, a probe ( hygrometer, VWR International, Radnor, PA, USA) was placed in the toilet to measure RH and temperature in a timely manner to ensure that the differences in temperature and RH between the air inside the climatic chamber and the air inside the toilet were minimized. The temperature difference was kept below 1.5 °C while the RH difference was kept below 5%.

[0282] Participants

[0283] The participants were employees from the research center of Firmenich SA (Geneva, Switzerland). Ten meetings were organized, and the number of participants in each meeting was as follows: 26, 24, 26, 27, 26, 30, 25, 27, 25, 23. The participants signed a consent form before participating in the study. The consent form and the experimental protocol were approved by the Firmenich Internal Review Board, in accordance with the Declaration of Helsinki, regarding medical research involving human subjects.

[0284] Stimulation

[0285] The participants were exposed to six odor mixtures released in the toilet under four different climates. The odor mixtures were the individual Mukuru (Nairobi) UDT stench, the individual fragrance (Floral D), and mixtures of stench and fragrance released at four different concentrations (0.18, 0.54, 1.62, 4.9 μg / l).

[0286] The malodor was recovered from the Mukuru washroom as it contained all the important molecules and it was from a well-maintained toilet. The Mukuru malodor source consisted of hydrogen sulfide, methanethiol, butyric acid, p-cresol, and indole, with their gas-phase concentrations being 0.26, 0.018, 0.004, 0.0027, and 0.00018 μg / l respectively. Hydrogen sulfide and methanethiol were released from pressurized cylinders at 20.8 l / h and 9.8 l / h respectively. The remaining malodor products were released in the toilet by forcing the evaporation of propylene glycol solutions containing 0.775, 0.526, and 0.035 mg / ml of butyric acid, p-cresol, and indole respectively. The fragrance formulation was released in pure form in the forced evaporation chamber, resulting in a gas-phase concentration of 4.9 μg / l. Lower gas-phase concentrations of the fragrance were achieved by dilution in propylene glycol. Gas-phase concentrations of 0.18, 0.54, and 1.62 μg / l were obtained using 3.62%, 11.13%, and 33.31% (w / w) propylene glycol solutions respectively. To release the malodor and fragrance in the same toilet, two syringes were connected to the same forced evaporation chamber through two PTFE capillaries. One syringe contained the malodor solution while the other syringe contained the fragrance formulation, which could be in pure form or diluted in propylene glycol. Both syringes were mounted on the same syringe pump and their pistons were pushed at a rate of 0.088 mm / h, with a release rate of 0.088 ml / h. When either the malodor or the fragrance was present alone, pure propylene glycol was injected into the forced evaporation chamber using a second syringe. Each odor was presented in four climates: 22°C, 30% RH, 22°C, 80% RH, 35°C, 30% RH, and 35°C, 80% RH.

[0287] Figure 12

[0288] Participants were randomly exposed to odor stimuli in different climates. Since there were only three toilets, the six odors were divided into two groups, each group containing either the malodor alone or the fragrance alone, the malodor plus a low dose of the fragrance, and the malodor and a high dose of the fragrance. The first and the last were used as controls to evaluate the reliability of the groups and consisted of the malodor alone, the fragrance alone, and a mixture of both. Participants entered the climate chamber and directly evaluated the odors of the three toilets by answering a paper questionnaire made by the software FIZZ (Biosystems, Courtenon, France). After adapting to the climate for 3 minutes, they re-evaluated the odor of each toilet. They were asked to rate on a 0 - 10 linear scale the pleasantness from "I don't like" to "I like", the familiarity from "not familiar" to "very familiar", the intensity from "no odor" to "very strong", the fecal / toilet character from "no feces / toilet" to "very fecal / toilet", and whether they wanted to enter the toilet from "not at all willing" to "very willing".

[0289] Headspace analysis

[0290] As described above, Mukuru malodor was released in the model toilet. The climate was set at 25 °C and 50% RH. Compounds released into the air were collected with an Oasis column, which was conditioned with 20 ml deionized water, 20 ml methanol, 20 ml acetone, and 20 ml diethyl ether and dried in an oven at 50 °C for 1 h. Hydrogen sulfide and methanethiol were derivatized with NEM in an Oasis column containing 2 ml of diethyl ether with 25 mg NEM and 100 μl triethylamine and dried at 50 °C for 1 h. Air was pumped through the column at a rate of 1 l / min by using a GilAir Plus pump connected with a silica tube. The volume of the sample was 100 l. Three columns were used to sample the air of one toilet. One column was placed at the center of the model toilet, the second column was located 23 cm from the evaluation door, and the third column was located at the upper right of the toilet (171 cm from the ground). The columns were desorbed with 10 ml of diethyl ether, which was added to 100 μl of an ethyl acetate solution of 10 ng / μl methyl octanoate (internal standard [IS]). To remove the excess NEM, the eluate was washed with 3 ml of a 10 mg / ml aqueous solution of L-cysteine buffered with 0.1 M potassium phosphate at pH 8. The aqueous phase was removed, and the organic phase was dried with sodium sulfate. The aqueous phase was acidified with 100 μl of 37% aqueous HCl; butyric acid was extracted with 4 ml of diethyl ether added with 100 μl of IS. Before injection into the GC-MS, the two organic phases were gently concentrated to 1 ml under an argon stream. Analysis was carried out by injecting 1 μl of the eluate into the GC-MS as described below.

[0291] Headspace analysis calibration was performed using an olfactometer

[0292] Using an olfactometer, headspaces were prepared with butyric acid, indole, p-cresol, methanethiol, and hydrogen sulfide at known concentrations to calibrate the analytical method. Briefly, air with a known amount of compounds was sampled at the outlet of the olfactometer with an Oasis column containing the derivatization reagent NEM (as described above). Methanethiol and hydrogen sulfide were released from a pressurized gas cylinder containing a mixture of 15 ppm of the two sulfur compounds in nitrogen into the olfactometer. With a rotameter ( TV 100) Controls the flow of two sulfur compounds. Butyric acid, indole, and p-cresol are released by forcing the evaporation of a propylene glycol solution from a 1-ml polypropylene syringe mounted on an injection pump at a rate of 0.101 ml / h. The solution is introduced into the lower chamber and heated to 150 °C using an oil bath. Nitrogen is introduced into the lower chamber at a rate of 60 l / h to collect the evaporated products and mix with the air stream in the upper chamber. The air stream is set at 540 l / h and humidified by bubbling through a water-jacketed wash bottle filled with distilled water. The upper chamber of the olfactometer is water-jacketed and the temperature is maintained at 29 °C using a water bath. At the outlet of the olfactometer, the temperature is 30 °C and the RH is 40%. The concentrations of methanethiol and hydrogen sulfide compounds obtained in the olfactometer are 0.1, 0.05, 0.0250, and 0.0125 μg / l, respectively. The concentrations of butyric acid, p-cresol, and indole obtained are 0.0001, 0.001, 0.01, and 0.1 μg / l.

[0293] Gas chromatography - mass spectrometry (GC-MS)

[0294] Compounds were identified using a GC 6890N (Agilent, Palo Alto, CA, USA). A fused silica SPB-1 capillary column (30 m × 0.25 mm i.d., 0.25-μm film thickness, Supelco, Bellefonte, PA, USA) was installed in the GC. The carrier gas was He (52 kPa) and the injector temperature was set at 250 °C. Injection was performed using a Combi-Pal autosampler (Zwingen, Switzerland). For the analysis of the NEM derivatives of butyric acid, p-cresol, indole, and methanethiol and hydrogen sulfide, the initial oven temperature was maintained at 50 °C for 5 minutes and then increased to 250 °C at a rate of 5 °C / min in split mode 1 / 5. The GC was coupled to an MS 5975B Inert XL MS from Agilent. Mass spectra in electron impact mode were measured in SIM mode at 70 eV. The ions monitored were butyric acid (60), p-cresol (107), indole (117), NEM-S-CH3 (127), and NEM-S-NEM (127).

[0295] Data analysis

[0296] The questionnaires were scanned and the data were stored in FIZZ and analyzed using R (https: / / cran.r-project.org). The response variables - pleasantness, entering the toilet, intensity, familiarity, and fecal characteristics were analyzed by using one-way analysis of variance (ANOVA), and any significant effects were confirmed using the non-parametric Kruskal-Wallis test. Pairwise comparison tests were performed using the Tukey honest significant difference test (Tukey HSD function in R). The relationship between the pleasantness of different odor treatments and the willingness to enter the toilet was studied using linear models. In addition, linear models were used to analyze the pleasant ratings from the odor treatments and the pleasant ratings from the climate. The significance level was set at P < 0.05. To determine the concentration of malodorous compounds in the headspace of the model toilet, calibration curves were established using linear models, where the ratio of the volatile peak area to the IS was used as a function of the gas-phase concentration in the olfactometer. Using these calibration curves and the inverse prediction function in R (chemCal package), the gas-phase concentration inside the model toilet was predicted based on the ratio of the volatile peak area to the IS.

[0297] Results

[0298] Three 1.7 m 3 toilet models were constructed in a climatic chamber of 25 m 3 . Each toilet was ventilated 10 times per hour. Inside the toilet, a scale was installed to monitor weight gain or loss and a hard surface to receive liquids or powders. When the subjects entered the climatic chamber, they were exposed to the temperature and humidity set for the experiment; thus, for this study, they were asked to evaluate the odor directly after entering the chamber and to perform a second evaluation after a few minutes of climate adaptation. Adaptation had no significant effect on the criteria used to evaluate the odor. Then the averages were taken for the data with and without adaptation.

[0299] Typical Mukuru pit latrine malodors were generated by controlled release of methanethiol, hydrogen sulfide, butyric acid, p-cresol, and indole by jetting gases and evaporating liquids in a hot chamber flushed with nitrogen( Figure 13 ). The headspace was analyzed at three different locations in the toilet bowl and in the three toilets. The quantitative results are shown as Figure 14 . The target concentrations of methanethiol, hydrogen sulfide, butyric acid, p-cresol, and indole reached 101%, 66%, 130%, 93%, and 138% of the expected values, respectively. The standard deviations showed relatively small intervals, indicating that the headspace inside the chamber was uniform in addition to being reproducible between chambers.

[0300] Four descriptors were presented to the subjects: pleasantness, entering the toilet, fecal characteristics, and intensity. The panel was reliable as there were no significant differences in the results obtained by the panel when we repeated the first and last sessions( Figure 14)。

[0301] Climate significantly affected intensity, but had no significant effect on other criteria such as pleasantness, familiarity, fecal characteristics, and willingness to enter the toilet. An increase in temperature significantly decreased overall intensity (ANOVA, P < 0.0001; Kruskal-Wallis, P < 0.001), independent of odor ( Figure 14 ). Similarly, but to a lesser extent, an increase in humidity significantly decreased intensity (ANOVA, P < 0.05; Kruskal-Wallis, P < 0.05), as Figure 15 shown. However, increases in humidity and temperature did not significantly combine to further decrease overall intensity. The significant effect of temperature was mainly due to differences in the methods obtained for pure malodor, mixtures of malodor and the highest spice concentration, and pure spice alone. The significant effect of humidity was mainly due to mixtures of malodor and the highest spice concentration and pure spice alone. Odor had no significant effect on intensity because paired comparisons (Tukey's honest differences) showed no significant differences ( Figure 15 )。

[0302] Next, appropriate controls were evaluated. The choices were: malodor (blue bars, Figure 15 and 16 ) or spice (pink bars, Figure 15 and 16 ). As the spice concentration increased, fecal characteristics significantly decreased, as Figure 15 shown. The reduction of this characteristic as a percentage of the fecal characteristics of malodor is also shown in Figure 15 . However, the efficiency of the spice decreased when only the spice was present in the mixture of malodor and spice (blue bars, Figure 16 ). In contrast, the efficiency of the spice was higher when only the malodor was present in the mixture (pink bars, Figure 16 ).

[0303] In the opposite direction to the fecal characteristics rating, as the spice concentration increased, the pleasantness rating significantly increased ( Figure 17 ). The treatment group also had an effect on pleasantness, but only at lower spice concentrations ( Table 15 Measurement of Temperature and Relative Humidity in the Climate Chamber and Toilet ).

[0304] Compared with the pleasantness rating, similar results were obtained for the willingness to enter the toilet rating. As the spice concentration increased, the willingness rating significantly increased. The willingness to enter the toilet was closely related to the willingness to experience pleasantness ( Example 14 , linear model, slope = 0.97, P < 0.0001; intercept = 0.27, P < 0.001, adjusted R 2= 0.7986). This linear model explained approximately 80% of the variance of the ratings entering the ratings with the pleasantness on the abscissa. The effect of the treatment group on the willingness ratings to enter the toilet was much lower than the effect on the pleasantness ratings.

[0305] Temperature measurement

[0306] The climatic chamber was set to four climatic conditions: 22 °C, 30% RH, 22 °C, 80% RH, 35 °C, 30% RH, and 35 °C, 80% RH. The temperature and RH conditions were achieved by using a temperature control system (Table 15). The temperature and RH inside the climatic chamber and inside the model toilet were less than 1.5 °C and 5%, respectively (Table 15).

[0307] Toilet Malodor Reduction Efficacy Test of an Aromatic Composition According to the Invention in a Toilet Using a Passive Delivery System

[0308]

[0309] Figure 18

[0310] Figure 19

[0311] Without wishing to be bound by any particular theory, the performance of the composition may be affected by many factors, e.g., the volatility of the compounds in the formulation, temperature, air flow, depth of the boundary layer, interactions between the compounds of the substrate having a passive delivery system, the concentration of each compound in the delivery system, climate, etc. These factors can affect the duration and / or magnitude of the perceived reduction in fecal malodor, and / or the duration and / or magnitude of changes in other sensory effects, such as an increase in perceived pleasantness.

[0312] To further explore this, in this example, the performance of the compositions according to some embodiments of the invention in a toilet was evaluated, wherein the compositions were incorporated into a passive delivery system. In a first series of experiments using a model system, the following two formulations were tested: Floral V (as described in Table 10) and Jasmine E (as described in Table 9). Nineteen to thirty-two participants were trained on-site to evaluate the performance of the test compositions over 10 days. The headspace of the model toilet was also sampled and analyzed to determine the gas-phase concentration of the fragrance components in the toilet.

[0313] Expose the panelists to the odors of three model toilets. Except for the malodorous Mukuru restorative released by the forced evaporation system as described in the previous examples, the odors of two toilets consist of the perfume Jasmine E and the floral scent V released from the cellulose pads. The odor of the third model toilet consists only of the malodor alone except for the blank cellulose pad. The cellulose pads are 10.8 cm × 7.3 cm × 0.15 cm and carry a mixture of 2.2 g of 60% perfume oil and 40% isopropyl myristate (IPM). Place the pads on the scales equipped in each toilet. Connect the scales to a computer and monitor the mass loss of each pad every 5 min. The implementation time of the pads is time 0. Conduct sensory analysis and headspace analysis according to the method described in the previous example.

[0314] Reference Figure 19 (Report the perceived intensity of fecal malodor and the reported pleasantness score), both the floral scent V and Jasmine E formulations reduced the fecal characteristics of toilet malodor and increased the pleasantness. The highest performance of both formulations was obtained at the start of the experiment (day 0), where the pleasantness was the highest and the fecal nature was the lowest.

[0315] At 25 °C, the performance of the formulations tended to decrease over time and decreased significantly at 40 °C. For the floral scent V, after 10 days at 25 °C and after 4 days at 40 °C, the pleasantness at the neutral limit (5) dropped to negative valence (I don't like it). In fact, an inversion between the pleasantness and the fecal characteristics was observed. The Jasmine E formulation showed better performance under both climatic conditions, as during the investigation, the pleasantness remained at positive valence (I like it), while the fecal characteristic ratings were lower than those observed with the floral scent V formulation. Different from the floral scent V formulation, no inversion was observed for the Jasmine E formulation. Since the relevant ratings were very stable over time, the fluctuations were not related to the malodor.

[0316] Analysis of the headspace of the test toilets revealed changes in the gas-phase concentrations of all compounds of the floral scent V formulation and the selected compounds of the Jasmine E formulation. Table 16 Specific MOC Concentrations Reduce the Perceived Intensities of Indole, DMTS, p - Cresol, and Butyric Acid Shows the changes (i.e., headspace concentrations) of the antagonist molecules common to the two test formulations.

[0317] Refer to Figure 18 , the concentration of dihydrolinalool decreased rapidly on the 4th day at 40 °C and on the 5th day at 25 °C to reach the olfactory detection threshold (ODT). Dihydrolinalool is an antagonist of the butyric acid receptor. These data indicate that when the gas-phase concentration of dihydrolinalool is below its ODT, the inhibition of the perception of butyric acid should be minimal or ineffective.

[0318] Violet AT and isomethyl ionone (isomethyl ionone) 70P showed similar decreases in headspace concentration. Here, their gas-phase concentrations were stable at 25 °C, while at 40 °C, they began to increase and decreased faster.

[0319] It remained stable during the experiment, but the concentration at 40 °C was higher than that at 25 °C. At this time, these data indicate that the increase in temperature helps to release During the experiment, all antagonist compounds except dihydrolinalool were present in perceptible amounts in the air.

[0320] Figure 18

[0321]

[0322] Using the performance of the Floral V formulation at 40 °C as an example, referring to Table 17 below, on Day 0, when the performance of the formulation was at its maximum (for fecal odor reduction and increased pleasantness), the headspace concentrations of most components were at or above the effective antagonist concentration for at least one odor target. On Day 2, the headspace concentrations of the components decreased, and only one component was at or above the effective antagonist concentration for at least one odor target. Four components were close to the effective antagonist concentration for at least one odor target, while seven components were below the effective antagonist concentration for at least one odor target. A corresponding decrease in formulation performance was observed ( Table 17. Headspace Concentrations of MOC ). An inversion between pleasantness and fecal characteristics was observed ( Figure 20 ), and the headspace concentrations of all components were below the effective MOC concentration for at least one odor target.

[0323] Figure 20

[0324]

[0325] In another study of toilet use in Durban (South Africa) and Pune (India), the performance of the following two formulations was tested: Floral V Jasmine E and Citrus 259389B (as described in Table 8). The formulations were incorporated into cellulose pads. A group of participants was trained on-site to evaluate the characteristics of the test compositions over a 3-day period. The headspace of the toilet was also sampled and analyzed to determine the gas-phase concentration of the fragrance components in the toilet.

[0326] Odor evaluations were conducted by 11 subjects. The test formulations were diluted in isopropyl myristate (IPM; 60% oil, 40% IPM) and loaded onto plain cellulose pads (10.8 cm × 7.3 cm × 0.15 cm) of 42% w / w dry substrate. Depending on the fragrance intensity generated during implementation, one or two pads were used per toilet. In both countries, we used three toilets (three replicates) for each formulation. In Durban, Jasmine E and Floral V were implemented in six private and independently ventilated pit latrines, while Citrus 259389B (as described in Table 7) was implemented in three ventilated improved pit latrines in the community bathing area. In Pune, each test formulation was implemented in three toilets in a dedicated bathing area.

[0327] Subjects evaluated the olfactory stimuli using a web questionnaire that we developed in-house and accessed on the Internet via the following link: http: / / www.pacchiani.ch / firmenich / . They were asked to rate on a linear scale (from 0 - 100) the pleasantness from "I don't like" to "I like", the intensity from "no odor" to "very strong", and the fecal character from "no feces" to "very fecal". They were able to add comments at the end of the questionnaire.

[0328] The odor of the toilets was evaluated before and after the implementation of the pads. The first evaluation was conducted in the afternoon to determine the baseline. Then the pads were implemented, and the second evaluation was conducted 10 - 30 minutes after implementation. The third and fourth evaluations were conducted the next morning after implementation. For the evaluation, participants were asked to enter the toilet one by one. The toilets were used as usual.

[0329] Headspace analysis: On the day after the implementation of the test formulation, air from two toilets treated with the test formulation was sampled. The air was pumped at a rate of 1 L / min through an OASIS HLB 1 g column suspended on the toilet wall. One column was placed near the ground, at a height of 0.15 - 0.3 m, and the second column was placed at a height of 1.5 - 1.7 m. The total pumped volume was 87 L - 100 L. Analysis and quantification were carried out according to the standard protocol. To determine whether the test formulation significantly changed the pleasantness and fecal character ratings, the Wilcox signed-rank test was used for the data of each toilet, comparing the ratings before and after the implementation of the test formulation. Data obtained from the evaluations conducted after implementation were aggregated. Evaluation data when the pads from the toilets were stolen, displaced, or removed were not considered.

[0330] Reference Figure 20 and 21 , the comfort levels of most of the tested toilets were significantly improved by incorporating Floral V, Jasmine E, or Citrus 259389B into the cellulose pads ( Figure 21)。In addition, in most cases, even in toilets with an unpleasant baseline odor, both formulations increased the pleasantness towards the positive valence ( Figure 21 )。The increase in pleasantness was associated with a significant reduction in fecal characteristics ( Figure 22 ), showing the malodor suppression effect of the formulation containing the antagonist of fecal malodor molecules.

[0331] The fecal malodor observed in all tested toilets was not constant. For example, compared to the fecal malodor observed in the toilets tested in Durban, the fecal malodor level tested in Pune was very low and more similar in the toilet pools ( Figure 23 )。

[0332] In Pune, the test formulations were implemented in three public bathing areas consisting of approximately 10 flush toilets. They were well maintained and cleaned several times a day. Each toilet was ventilated through open windows. In contrast, the toilets in Durban were dirty individual pit toilets and poorly maintained. For some toilets, the pits were full and the vents were missing. This could explain the variation in malodor levels in different toilets. Examples are Toilet 2 treated with Jasmine E and Toilet 1 treated with Floral Scent V, and this formulation hardly increased the average comfort that was unstable over time ( Figure 24 )。In addition, fecal malodor was not the only cause of the unpleasant odor in the two toilets: malodor was also urine and chicken manure. When the malodor in the toilets equipped with an appropriate ventilation system was strong, the test formulations reduced the malodor, and this effect was stable over time ( Figure 23 )。 Figure 25 Results of clean and well-maintained toilets in Africa and India were reported. Interestingly, when the malodor was very strong in terms of fecal characteristics and intensity, the test formulations reduced the fecal characteristics but also the total intensity ( Figure 25 ), indicating that the effect of malodor suppression was independent of the spices overwhelming the malodor.

[0333] Analysis of the toilet headspace showed that a large number of MOC molecules, α-ionone, isomethyl ionone, dihydrolinalool, were found in the air sampled in Pune and Durban. The detected gas-phase concentrations exceeded their respective individually determined olfactory detection thresholds (ODTs), i.e.: 5.08×10 -4 , 1.92×10 -4 , 1.28×10 -4 , 1.37×10 -3 μg / L ( Figure 26 ). Surprisingly, similar concentrations were observed at both low and high heights in each toilet except Toilet 3 in Durban ( ​ )。

[0334] Despite the lack of airflow control, headspace analysis showed a certain degree of uniformity. The exception for Toilet 3 can be explained by the fact that during sampling, the column at a high height was too close to the mat. Additionally, the gas-phase concentrations in both countries were similar. However, two mats were used per toilet in Pune, indicating a higher ventilation rate in Pune than in Durban.

[0335] The analysis also showed that the distribution of compound concentrations obtained in the field was similar to that found in model toilets at similar temperatures ( ​ ). The temperatures in Durban, Pune, and the model toilet were 28 °C, 25 °C, and 25 °C, respectively. The gas-phase concentration in the model toilet was approximately twice as high as that observed in the toilets in Durban and India, indicating a higher ventilation rate in actual toilets than in the model toilet.

[0336] In summary, these data demonstrated the correlation between model toilets and field toilets, further confirming the use of model toilets for experiments under controlled conditions. Additionally, the Jasmine E formulation seemed to perform longer than the Floral V formulation in suppressing toilet malodor recovery at 25 °C and 40 °C. Headspace analysis showed that the gas-phase concentrations of MOC compounds were similar compared to the two fragrances, and the topnote compounds did not participate in suppressing malodor, thus challenging their presence in these formulations.

[0337] Formulations containing antagonists of fecal odor (Jasmine E, Floral V, Citrus 259389B) increased the pleasantness of toilet odor by reducing fecal characteristics in different and challenging environments. However, the performance limit was reached in dirty toilets without ventilation and with a full pit, which was not the target of this study. Additionally, even in challenging environments, MOC was significant, and the inhibitory effect on fecal characteristics was not due to overpowering fragrances.

[0338] Example 15

[0339] Synergistic effects of certain malodorant receptor antagonists according to some embodiments of the present invention

[0340] The performance of a test formulation containing Violet AT and isomethylionone was tested to counteract the perceived fecal odor of fecal odor reconstitution. The amount of each single ingredient in the test formulation was the same as the corresponding concentration of the ingredient incorporated in the floral composition. Separate control formulations were also included, which contained Violet AT and isomethylionone, respectively, at the same concentration as each single ingredient in the test formulation. The sensory evaluation was blind and was conducted using an olfactometer and a group of over 30 participant evaluators in a blind test. At the same time, the headspace concentrations of the ingredients from the test and three control formulations were determined. The results are shown in Tables 18 and Figure 27 .

[0341] Table 18 Gas-phase concentrations and attribute scores of test and control formulations evaluated in combination with fecal resuspensions.

[0342]

[0343] In summary, these data indicate that, compared with the control formulations of the single components tested at the same concentration in the mixture, the test formulation containing the mixture of ionone AT and isomethyl ionone can better reduce the fecal score, thus better perceiving fecal malodor, and also improve the pleasantness and freshness scores..

[0344] The performance of another test formulation containing ionone AT and dihydrolinalool to counteract the fecal malodor perceived by the fecal malodor reductant was tested. Separate control formulations were also included, which contained ionone AT and dihydrolinalool, respectively, at the same concentration as each single component in the test formulation. The sensory evaluation was blind and was conducted using a olfactometer and a blinded test with a panel of more than 30 assessors. At the same time, the headspace concentrations of the components from the test and the three control formulations were determined. The results are shown in Table 19 below and Figure 28 in

[0345] Table 19 Gas-phase concentrations and attribute scores of test and control formulations evaluated in combination with fecal resuspensions.

[0346]

[0347] In summary, these data indicate that, compared with the single-component control formulations tested at the same concentration in the mixture, the test formulation containing the mixture of ionone AT and dihydrolinalool is better at reducing the fecal score, thus better perceiving fecal malodor, and also improves the pleasantness and freshness scores.

[0348] The performance of another test formulation containing isomethyl ionone (isomethyl ionone), ionone AT and dihydrolinalool was tested to counteract the fecal malodor perceived by the fecal malodor reductant. Separate control formulations were also included, which contained ionone AT, isomethyl ionone and dihydrolinalool, respectively, at the same concentration as each single component in the test formulation. The sensory evaluation was blind and was conducted using a olfactometer and a blinded test with a panel of more than 30 assessors. At the same time, the headspace concentrations of the components from the test and the three control formulations were determined. The results are shown in Table 20 below and Figure 29 in

[0349] Table 20 Gas-phase concentrations and attribute scores of test and control formulations evaluated in combination with fecal resuspensions.

[0350]

[0351] In summary, these data indicate that the test formulation containing a mixture of Violet AT, isomethylionone, and dihydromyrcenol is better at reducing fecal scores compared to single-component control formulations tested at the same concentrations in the mixture, resulting in a better perception of fecal odor, and also improving the pleasantness and freshness scores.

[0352] Publications cited throughout this application are hereby incorporated by reference in their entirety. Although the various aspects of the invention have been illustrated above by reference to examples and preferred embodiments, it is to be understood that the scope of the invention is not limited by the foregoing description, but rather by the claims as properly construed under the principles of patent law.

Claims

1. Use of a composition comprising the following components for reducing, limiting or eliminating the perception of fecal malodor: (i) A malodor receptor antagonist system of 2 wt% to 85 wt%, comprising at least three components selected from the group consisting of: (2,5-dimethyl-2,3-dihydro-1H-inden-2-yl)methanol; phenethyl acetate; (±)-2,2,2-trichloro-1-phenylethyl acetate; (±)-2-pentylcyclopentanone; allyl (3-methylbutoxy)acetate + (±)-allyl (2-methylbutoxy)acetate; (3aRS,5aSR,9aSR,9bSR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan; (±)-3,7-dimethyl-1-octen-3-ol; (+)-(R)-3,7-dimethyl-6-octenal; (±)-3-(4-isopropylphenyl)-2-methylpropanal; (±)-1-phenylethyl acetate; and benzyl acetate; (ii) A functional perfume blend of 15 wt% to 98 wt%, comprising at least two components selected from the group consisting of: isomethyl-α-ionone + α-methylionone; α-ionone; (E)-3,7-dimethyl-2,6-octadienal + (Z)-3,7-dimethyl-2,6-octadienal; (±)-3,7-dimethyl-6-octen-1-ol; (-)-(R)-3,7-dimethyl-6-octenenitrile; (2E)-1-[(1RS,2SR)-2,6,6-trimethyl-3-cyclohexen-1-yl]-2-buten-1-one; (1RS,2RS)-2,4-dimethyl-3-cyclohexene-1-carbaldehyde + (1RS,2SR)-2,4-dimethyl-3-cyclohexene-1-carbaldehyde; 1-methyl-4-(2-propylidene)cyclohexene; decanal; octanal; and nonanal, the blend having a fragrance note selected from floral, citrus and jasmine; (iii) Optionally, a non-functional perfume blend.

2. The use according to claim 1, characterized in that The malodor receptor antagonist system comprises at least four components selected from the group consisting of: (2,5-dimethyl-2,3-dihydro-1H-inden-2-yl)methanol; phenethyl acetate; (±)-2,2,2-trichloro-1-phenylethyl acetate; (±)-2-pentylcyclopentanone; allyl (3-methylbutoxy)acetate + (±)-allyl (2-methylbutoxy)acetate; (3aRS,5aSR,9aSR,9bSR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan; (±)-3,7-dimethyl-1-octen-3-ol; (+)-(R)-3,7-dimethyl-6-octenal; (±)-3-(4-isopropylphenyl)-2-methylpropanal; (±)-1-phenylethyl acetate; and benzyl acetate.

3. The use according to claim 1 or 2, characterized in that The composition further comprises an encapsulating material to form microcapsules or microparticles, or a material to form a liquid delivery system for the composition.

4. The use according to any one of claims 1 to 3, characterized in that The composition is absorbed on a porous or non-porous substrate in loose powder or compacted form, said substrate being selected from cellulose (paper / cardboard), vermiculite, other industrial absorbents, perlite, calcium carbonate, pumice, wood, sawdust, ground corn cobs, ground rice husks, rice husk ash, biochar, starch, modified starch and mixtures thereof.

5. A malodor counteracting composition for reducing, limiting or eliminating the perception of fecal malodor, comprising: a) 2 to 85 wt% of an active amount of a malodor receptor antagonist system, which comprises at least three components selected from the group consisting of: (2,5-dimethyl-2,3-dihydro-1H-inden-2-yl)methanol; phenethyl acetate; (±)-2,2,2-trichloro-1-phenylethyl acetate; (±)-2-pentylcyclopentanone; allyl (3-methylbutoxy)acetate + allyl (±)-(2-methylbutoxy)acetate; (3aRS,5aSR,9aSR,9bSR)-3a,6,6,9a-tetramethyldodecahydronaphtho[2,1-b]furan; (±)-3,7-dimethyl-1-octen-3-ol; (+)-(R)-3,7-dimethyl-6-octenal; (±)-3-(4-isopropylphenyl)-2-methylpropanal; (±)-1-phenylethyl acetate; and benzyl acetate; b) 15 to 98 wt% of a functional perfume blend, which comprises at least two components selected from the group consisting of: isomethyl-α-ionone + α-methylionone; α-ionone; (E)-3,7-dimethyl-2,6-octadienal + (Z)-3,7-dimethyl-2,6-octadienal; (±)-3,7-dimethyl-6-octen-1-ol; (-)-(R)-3,7-dimethyl-6-octenenitrile; (2E)-1-[(1RS,2SR)-2,6,6-trimethyl-3-cyclohexen-1-yl]-2-buten-1-one; (1RS,2RS)-2,4-dimethyl-3-cyclohexene-1-carbaldehyde + (1RS,2SR)-2,4-dimethyl-3-cyclohexene-1-carbaldehyde; 1-methyl-4-(2-propylidene)cyclohexene; decanal; octanal; and nonanal; c) Optionally, a non-functional perfume blend, which comprises at least two perfuming ingredients.

6. The composition according to claim 5, characterized in that The malodor receptor antagonist system comprises (2,5-dimethyl-2,3-dihydro-1H-inden-2-yl)methanol, and the functional perfume blend comprises isomethyl-α-ionone + α-methylionone and α-ionone.

7. The composition according to claim 6, wherein (2,5-dimethyl-2,3-dihydro-1H-inden-2-yl)methanol is present in the composition at at least 2%.

8. The malodor counteracting composition according to any one of claims 5 to 7, characterized in that It further comprises an encapsulating material or other material to form an emulsion, dispersion, microemulsion, fine emulsion, gel, microgel, microcapsule or microparticle.

9. A perfumed consumer product, which comprises an effective amount of the malodor counteracting composition as defined in any one of claims 5 to 7.

10. The perfumed consumer product according to claim 9, which is selected from air care products, household care products and laundry care products.

11. The perfumed consumer product according to claim 9 or 10, characterized in that It is in the form of: aerosol and / or water-based air freshener sprays, core / pad air fresheners, liquid electric (plug-in) air fresheners, solid supported air fresheners, gel-based air fresheners, film-containing air fresheners, bleaching, cleaning, detergent powders, liquid all-purpose cleaners, specialty cleaners and liquid detergents.

12. A non-therapeutic method for counteracting fecal malodor, the method comprising treating a surface with the composition of claim 5 or at least partially dispensing the composition of claim 5 in air.

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