Molecularly imprinted polymer of sol-gel type for selectively trapping odorous molecules

Abstract

The invention relates to the use of molecularly imprinted polymer(s) or MIPs, of odorous molecule(s), as deodorant agent in particular for selectively trapping molecules that are the cause of human body odour. More particularly by using MIPs which may be obtained via polymerization of “sol-gel” type; it being understood that the polymerization is performed in the presence v) of one or more “templates” of target molecule(s) responsible for human body odour. Another subject of the invention concerns a NI process for preparing MIPs as defined previously, MIPs obtained via this process, and a cosmetic composition comprising at least one MIP as defined previously. Unexpectedly, it appears that the MIPs make it possible to specifically trap precursors of odorous molecules and odorous molecules that may be used in cosmetic formulations, especially those that are the cause of the unpleasant odour of sweat.

Claims

1. A cosmetic composition for reducing body odor, the composition comprising: a physiologically acceptable medium chosen from water, organic solvents, or mixtures thereof, at least one molecularly imprinted polymer configured to trap at least one molecule at the surface of keratin materials in order to reduce body odor, and at least one additional agent for reducing body odor chosen from at least one antiperspirant active agent or at least one deodorant active agent other than the at least one molecularly imprinted polymer, wherein the at least one molecularly imprinted polymer is obtained by: A) sol-gel polymerization of a mixture comprising: i) at least one functional silane monomer; ii) at least one crosslinking agent; iii) at least one porogenic solvent; iv) at least one template molecule chosen from: linear or branched, saturated or unsaturated, and/or optionally substituted C2-C13 aliphatic acids chosen from acetic acid, 2-propenoic acid, propanoic acid, 2-methylpropanoic acid, 2-methylpropenoic acid, 2-butenoic acid, 2-methyl-2-butenoic acid, 3-methyl-2-butenoic acid, butanoic acid, 2-methylbutanoic acid, 3-methylbutanoic acid, 3-hydroxybutanoic acid, 3-hydroxy-3-methylbutanoic acid, 2-pentenoic acid, 2-methyl-2-pentenoic acid, 3-methyl-2-pentenoic acid, pentanoic acid, 2-methylpentanoic acid, 3-methylpentanoic acid, 3-hydroxypentanoic acid, 3-hydroxy-3-methylpentanoic acid, 3-methyl-2-hexenoic acid, 3-hydroxy-3-methylhexanoic acid, 3-hydroxy-4-methyloctanoic acid, 3-hydroxyhexanoic acid, 2-heptenoic acid, 2-methyl-2-heptenoic acid, 3-methyl-2-heptenoic acid, heptanoic acid, 2-methylheptanoic acid, 3-methylheptanoic acid, 3-hydroxyheptanoic acid, 3-hydroxy-3-methylheptanoic acid, 2-octenoic acid, 2-methyl-2-octenoic acid, 3-methyl-2-octenoic acid, octanoic acid, 2-methyloctanoic acid, 3-methyloctanoic acid, 3-hydroxyoctanoic acid, 3-hydroxy-3-methyloctanoic acid, 2-nonenoic acid, 2-methyl-2-nonenoic acid, 3-methyl-2-nonenoic acid, nonanoic acid, 2-methylnonanoic acid, 3-methylnonanoic acid, 3-hydroxynonanoic acid, 3-hydroxy-3-methylnonanoic acid, 2-decenoic acid, 2-methyl-2-decenoic acid, 3-methyl-2-decenoic acid, decanoic acid, 2-methyldecanoic acid, 3-methyldecanoic acid, 3-hydroxydecanoic acid, 3-hydroxy-3-methyldecanoic acid, 10-hydroxydecanoic acid, 2-undecenoic acid, 2-methyl-2-undecenoic acid, 3-methyl-2-undecenoic acid, undecanoic acid, 2-methylundecanoic acid, 3-methylundecanoic acid, 3-hydroxyundecanoic acid, 3-hydroxy-3-methylundecanoic acid, dodecanoic acid, 2-hydroxydodecanoic acid, tridecanoic acid, or mixtures thereof; sulfanylalkanols or mercaptoalkanols; conjugated products of 3-methyl-3-sulfanylhexan-1-ol; sulfo-conjugated steroids; or mixtures thereof; and v) optionally at least one basifying agent and/or at least one acid; and B) subsequently removing the at least one template molecule to form vacant cavities that are complementary to the at least one template molecule.

2. The cosmetic composition according to claim 1, wherein the total amount of the at least one antiperspirant active agent, if present, ranges from 0.001% to 30% by weight, relative to the total weight of the composition, or the total amount of the at least one additional deodorant active agent other than the at least one molecularly imprinted polymer, if present, ranges from 0.01% to 10% by weight, relative to the total weight of the composition.

3. The composition according to claim 1, wherein the composition is: a) in pressurized form in an aerosol device or in a pump-dispenser bottle; b) in a device equipped with a perforated wall or a grate; c) in a device equipped with a ball applicator; d) in the form of a wand; or e) in the form of a loose or compacted powder; wherein the composition further comprises a physiologically acceptable medium.

4. The cosmetic composition according to claim 1, wherein the at least one template molecule further comprises a steroid.

5. The cosmetic composition according to claim 1, wherein the at least one template molecule further comprises a branched, saturated, and/or unsaturated aliphatic volatile fatty acid.

6. The cosmetic composition according to claim 1, wherein the at least one template molecule is a linear or branched, saturated or unsaturated, and/or optionally substituted C2-C13 aliphatic acid chosen from acetic acid, 2-propenoic acid, propanoic acid, 2-methylpropanoic acid, 2-methylpropenoic acid, 2-butenoic acid, 2-methyl-2-butenoic acid, 3-methyl-2-butenoic acid, butanoic acid, 2-methylbutanoic acid, 3-methylbutanoic acid, 3-hydroxybutanoic acid, 3-hydroxy-3-methylbutanoic acid, 2-pentenoic acid, 2-methyl-2-pentenoic acid, 3-methyl-2-pentenoic acid, pentanoic acid, 2-methylpentanoic acid, 3-methylpentanoic acid, 3-hydroxypentanoic acid, 3-hydroxy-3-methylpentanoic acid, 3-methyl-2-hexenoic acid, 3-hydroxy-3-methylhexanoic acid, 3-hydroxy-4-methyloctanoic acid, 3-hydroxyhexanoic acid, 2-heptenoic acid, 2-methyl-2-heptenoic acid, 3-methyl-2-heptenoic acid, heptanoic acid, 2-methylheptanoic acid, 3-methylheptanoic acid, 3-hydroxyheptanoic acid, 3-hydroxy-3-methylheptanoic acid, 2-octenoic acid, 2-methyl-2-octenoic acid, 3-methyl-2-octenoic acid, octanoic acid, 2-methyloctanoic acid, 3-methyloctanoic acid, 3-hydroxyoctanoic acid, 3-hydroxy-3-methyloctanoic acid, 2-nonenoic acid, 2-methyl-2-nonenoic acid, 3-methyl-2-nonenoic acid, nonanoic acid, 2-methylnonanoic acid, 3-methylnonanoic acid, 3-hydroxynonanoic acid, 3-hydroxy-3-methylnonanoic acid, 2-decenoic acid, 2-methyl-2-decenoic acid, 3-methyl-2-decenoic acid, decanoic acid, 2-methyldecanoic acid, 3-methyldecanoic acid, 3-hydroxydecanoic acid, 3-hydroxy-3-methyldecanoic acid, 10-hydroxydecanoic acid, 2-undecenoic acid, 2-methyl-2-undecenoic acid, 3-methyl-2-undecenoic acid, undecanoic acid, 2-methylundecanoic acid, 3-methylundecanoic acid, 3-hydroxyundecanoic acid, 3-hydroxy-3-methylundecanoic acid, dodecanoic acid, 2-hydroxydodecanoic acid, tridecanoic acid, or mixtures thereof.

7. The cosmetic composition according to claim 1, wherein the at least one template molecule is a sulfanylalkanol or mercaptoalkanol.

8. The cosmetic composition according to claim 1, wherein the at least one template molecule further comprises an amino acid.

9. The cosmetic composition according to claim 1, wherein the at least one template molecule further comprises an acid ester.

10. The cosmetic composition according to claim 1, wherein the at least one template molecule is a conjugated product of 3-methyl-3-sulfanylhexan-1-ol.

11. The cosmetic composition according to claim 1, wherein the at least one template molecule is a sulfo-conjugated steroid.

12. The cosmetic composition according to claim 1, wherein the composition further comprises a bacteriostatic agent or bactericidal agent.

13. The cosmetic composition according to claim 1, wherein the composition further comprises a zinc salt.

14. The cosmetic composition according to claim 1, wherein the composition comprises an odor absorber selected form the group consisting of zeolites, cyclodextrins, metal oxide silicates, metal oxide particles modified with a transition metal, aluminosilicates, and chitosan-based particles.

15. The cosmetic composition according to claim 1, wherein the composition comprises at least one substance which blocks enzymatic reactions responsible for the formation of odorous compounds selected from the group consisting of arylsulfatase, 5-lipoxygenase, am inocylase, and 13-glucuronidase inhibitors.

16. The cosmetic composition according to claim 1, having a pH ranging from 3 to 9.

17. The cosmetic composition according to claim 1, further comprising at least one excipient chosen from emulsifiers, oils, structuring agents, waxes, pasty compounds, gelling agents, thickeners, suspension agents, or propellants.

18. A composition for reducing body odor, the composition comprising: a physiologically acceptable medium chosen from water, organic solvents, or mixtures thereof, at least one excipient chosen from emulsifiers, oils, structuring agents, waxes, pasty compounds, gelling agents, thickeners, suspension agents, or propellants, at least one molecularly imprinted polymer configured to trap at least one molecule at the surface of keratin materials in order to reduce body odor, and at least one additional agent for reducing body odor chosen from antiperspirant active agents or deodorant active agents other than the at least one molecularly imprinted polymer, wherein the pH of the composition ranges from 3 to 9, and wherein the at least one molecularly imprinted polymer is obtained by: A) sol-gel polymerization of a mixture comprising: i) at least one functional silane monomer chosen from those of formulae (I) or
R.sub.1Si(OR.sub.2).sub.z(R.sub.3).sub.x  (I) in which:  R.sub.1 is a linear or branched, saturated or unsaturated, cyclic or acyclic C1-C6 hydrocarbon-based chain, optionally substituted with a group chosen from:  amine NH.sub.2 or NHR with R representing a C.sub.1-C.sub.4 alkyl group,  an aryl or aryloxy group, which is optionally substituted with an amino group or with a C.sub.1-C.sub.4 aminoalkyl group,  with the provisos that: Ri is optionally interrupted in its chain with a heteroatom, a carbonyl group —C(O)— or a combination thereof; and R.sub.1 is linked to the silicon atom directly via a carbon atom,  R2 and R3, which are identical or different, are a linear or branched alkyl group comprising from 1 to 6 carbon atoms,  z denotes an integer ranging from 1 to 3, and  x denotes an integer ranging from 0 to 2, with z+x =3; or
R.sub.9—Si(OR.sub.8).sub.z(R′.sub.8).sub.x  (II) in which:  R.sub.8 and R′.sub.8, which are identical or different, are i) a hydrogen atom or ii) a linear or branched, optionally substituted (C.sub.1-C.sub.8)alkyl group, and  R.sub.9 is i) a hydrogen atom, ii) a group OR.sub.8, iii) a linear or branched (C.sub.1-C.sub.6)alkyl group, optionally substituted with a thiol or hydroxyl group or with an amino group N(H)R.sub.d with R.sub.d representing a hydrogen atom or a (C.sub.1-C.sub.6)alkyl group, iv) a (hetero)aryl group, or v) (hetero)aryl(C.sub.1-C.sub.6)alkyl,  z=1, 2, or 3, and  x=0, 1, or 2,  with z+x=3; ii) at least one tetra(C.sub.1-C.sub.6)alkoxysilane crosslinking agent; iii) at least porogenic solvent chosen from polar protic solvents and polar aprotic solvents; iv) at least one template molecule chosen from: linear or branched, saturated or unsaturated, and/or optionally substituted C2-C13 aliphatic acids chosen from acetic acid, 2-propenoic acid, propanoic acid, 2-methylpropanoic acid, 2-methylpropenoic acid, 2-butenoic acid, 2-methyl-2-butenoic acid, 3-methyl-2-butenoic acid, butanoic acid, 2-methylbutanoic acid, 3-methylbutanoic acid, 3-hydroxybutanoic acid, 3-hydroxy-3-methylbutanoic acid, 2-pentenoic acid, 2-methyl-2-pentenoic acid, 3-methyl-2-pentenoic acid, pentanoic acid, 2-methylpentanoic acid, 3-methylpentanoic acid, 3-hydroxypentanoic acid, 3-hydroxy-3-methylpentanoic acid, 3-methyl-2-hexenoic acid, 3-hydroxy-3-methylhexanoic acid, 3-hydroxy-4-methyloctanoic acid, 3-hydroxyhexanoic acid, 2-heptenoic acid, 2-methyl-2-heptenoic acid, 3-methyl-2-heptenoic acid, heptanoic acid, 2-methylheptanoic acid, 3-methylheptanoic acid, 3-hydroxyheptanoic acid, 3-hydroxy-3-methylheptanoic acid, 2-octenoic acid, 2-methyl-2-octenoic acid, 3-methyl-2-octenoic acid, octanoic acid, 2-methyloctanoic acid, 3-methyloctanoic acid, 3-hydroxyoctanoic acid, 3-hydroxy-3-methyloctanoic acid, 2-nonenoic acid, 2-methyl-2-nonenoic acid, 3-methyl-2-nonenoic acid, nonanoic acid, 2-methylnonanoic acid, 3-methylnonanoic acid, 3-hydroxynonanoic acid, 3-hydroxy-3-methylnonanoic acid, 2-decenoic acid, 2-methyl-2-decenoic acid, 3-methyl-2-decenoic acid, decanoic acid, 2-methyldecanoic acid, 3-methyldecanoic acid, 3-hydroxydecanoic acid, 3-hydroxy-3-methyldecanoic acid, 10-hydroxydecanoic acid, 2-undecenoic acid, 2-methyl-2-undecenoic acid, 3-methyl-2-undecenoic acid, undecanoic acid, 2-methylundecanoic acid, 3-methylundecanoic acid, 3-hydroxyundecanoic acid, 3-hydroxy-3-methylundecanoic acid, dodecanoic acid, 2-hydroxydodecanoic acid, tridecanoic acid, or mixtures thereof; sulfanylalkanols or mercaptoalkanols; conjugated products of 3-methyl-3-sulfanylhexan-1-ol; sulfo-conjugated steroids; or mixtures thereof; v) at least one basifying agent; and vi) optionally at least one acid; and B) subsequently removing the at least one template molecule to form vacant cavities that are complementary to the at least one template molecule.

19. A composition for reducing body odor, the composition comprising: a physiologically acceptable medium chosen from water, organic solvents, or mixtures thereof, at least one excipient chosen from emulsifiers, oils, structuring agents, waxes, pasty compounds, gelling agents, thickeners, suspension agents, or propellants, at least one molecularly imprinted polymer configured to trap at least one molecule at the surface of keratin materials in order to reduce body odor, and at least one additional agent for reducing body odor chosen from antiperspirant active agents or deodorant active agents other than the at least one molecularly imprinted polymer, wherein the pH of the composition ranges from 3 to 9, and wherein the at least one molecularly imprinted polymer is obtained by: A) sol-gel polymerization of a mixture comprising: i) aminopropyltriethoxysilane (APTES); ii) tetraethoxysilane (TEOS); iii) ethanol; iv) at least one template molecule chosen from acetic acid, 2-propenoic acid, propanoic acid, 2-methylpropanoic acid, 2-methylpropenoic acid, 2-butenoic acid, 2-methyl-2-butenoic acid, 3-methyl-2-butenoic acid, butanoic acid, 2-methylbutanoic acid, 3-methylbutanoic acid, 3-hydroxybutanoic acid, 3-hydroxy-3-methylbutanoic acid, 2-pentenoic acid, 2-methyl-2-pentenoic acid, 3-methyl-2-pentenoic acid, pentanoic acid, 2-methylpentanoic acid, 3-methylpentanoic acid, 3-hydroxypentanoic acid, 3-hydroxy-3-methylpentanoic acid, 3-methyl-2-hexenoic acid, 3-hydroxy-3-methylhexanoic acid, 3-hydroxy-4-methyloctanoic acid, 3-hydroxyhexanoic acid, 2-heptenoic acid, 2-methyl-2-heptenoic acid, 3-methyl-2-heptenoic acid, heptanoic acid, 2-methylheptanoic acid, 3-methylheptanoic acid, 3-hydroxyheptanoic acid, 3-hydroxy-3-methylheptanoic acid, 2-octenoic acid, 2-methyl-2-octenoic acid, 3-methyl-2-octenoic acid, octanoic acid, 2-methyloctanoic acid, 3-methyloctanoic acid, 3-hydroxyoctanoic acid, 3-hydroxy-3-methyloctanoic acid, 2-nonenoic acid, 2-methyl-2-nonenoic acid, 3-methyl-2-nonenoic acid, nonanoic acid, 2-methylnonanoic acid, 3-methylnonanoic acid, 3-hydroxynonanoic acid, 3-hydroxy-3-methylnonanoic acid, 2-decenoic acid, 2-methyl-2-decenoic acid, 3-methyl-2-decenoic acid, decanoic acid, 2-methyldecanoic acid, 3-methyldecanoic acid, 3-hydroxydecanoic acid, 3-hydroxy-3-methyldecanoic acid, 10-hydroxydecanoic acid, 2-undecenoic acid, 2-methyl-2-undecenoic acid, 3-methyl-2-undecenoic acid, undecanoic acid, 2-methylundecanoic acid, 3-methylundecanoic acid, 3-hydroxyundecanoic acid, 3-hydroxy-3-methylundecanoic acid, dodecanoic acid, 2-hydroxydodecanoic acid, tridecanoic acid, or mixtures thereof; v) at least one basifying agent; and vi) optionally at least one acid; and B) subsequently removing the at least one template molecule to form vacant cavities that are complementary to the at least one template molecule.

Description

EXAMPLES

Example 1

Synthesis of MIP1 and Trapping Test

(1) Synthesis of MIP1

(2) TABLE-US-00001 Mole ratio as a function of the imprint molecule Ingredients Amount or template 3-Methyl-2-hexenoic Template 270 mg 1 acid (3M2H) molecule 3-Aminopropyltri- Functional 500 mg 1 ethoxysilane monomer (APTES) Tetraethyl orthosilicate Crosslinking 10 g 24 (TEOS) agent Aqueous ammonia (28% Polymerization 3 ml aqueous solution) initiator Ethanol Solvent 2*50 ml (porogen)

(3) 3M2H, APTES and TEOS are mixed together in the proportions and amounts defined in the above table. Ethanol (50 ml) is added and the mixture is stirred for 5 minutes. Next, the aqueous ammonia is added (dropwise). At the end of the addition, ethanol (50 ml) is added. The mixture is stirred for 18 hours at room temperature and at atmospheric pressure, filtered, washed with ethanol (100 ml), with acetone (100 ml) and then air-dried. The crude white powder is then triturated in the presence of a solution derived from a mixture of acetic acid (4 ml) and ethanol (100 ml), for 15 minutes. The said powder is finally filtered off, washed with ethanol (100 ml) and then air-dried. A white powder is obtained.

(4) The morphology of the particles is characterized using an optical microscopy machine (Morphologi G3 from the company Malvern Instruments). 2 mg of the powder are sonicated in 1 mL of water for 5 minutes and then analysed. The particles have a mean diameter of 1.92 microns and a mean circularity of 0.74.

(5) Synthesis of the Comparative NIP1:

(6) NIP1 is synthesized under the same operating conditions and using the same amounts of ingredients as for MIP1, except that the mixture does not comprise any template. A white powder is obtained (4.5 g).

(7) The morphology of the particles is characterized as in example MIP1. The particles have a mean diameter of 2.53 microns and a mean circularity of 0.76.

Example 2

Synthesis of MIP2

(8) Synthesis of MIP2

(9) TABLE-US-00002 Mole ratio as a function of the imprint molecule Ingredients Amount or template N-[3-Methylhex-2- Template 1.1 g 1 enoyl]glutamic molecule acid (glum3M2H) 3-Aminopropyltri- Functional 1 g 1 ethoxysilane monomer (APTES) Tetraethyl orthosilicate Crosslinking 10 g 10 (TEOS) agent Aqueous ammonia (28% Polymerization 3 ml aqueous solution) initiator Ethanol Solvent 100 ml (porogen)

(10) Glum3M2H, APTES and TEOS are mixed together in the proportions and amounts defined in the above table. Ethanol (100 ml) is added and the mixture is stirred for 5 minutes. A solution of hydrochloric acid (37%, 0.5 ml) in water (50 ml) is added and the mixture is stirred for 15 minutes. Next, the aqueous ammonia is added (dropwise). The mixture is stirred for 18 hours at room temperature and at atmospheric pressure, filtered, washed with ethanol (100 ml) and with acetone (100 ml), and then air-dried. The white powder is triturated with a solution of acetic acid (4 ml) and ethanol (100 ml), for 15 minutes, and then filtered off, washed with ethanol (100 ml) and then air-dried. A white powder is obtained (3.7 g). The morphology of the particles is characterized as in Example MIP1. The particles have a mean diameter of 1.15 microns and a mean circularity of 0.88.

(11) Synthesis of the Comparative NIP2:

(12) NIP2 is synthesized under the same operating conditions and amount as for MIP2, the only difference being that the mixture does not comprise the template. A white powder is obtained (4.1 g).

(13) The morphology of the particles is characterized as in example MIP1. The particles have a mean diameter of 1.16 microns and a mean circularity of 0.53.

(14) Sensory Odour Tests

(15) 100 mg of the MIPs or NIPs are placed in bottles containing an ethanolic solution of the odorous molecule 3M2H (1.5 g %; 5 ml). The bottles are closed and left for 3 hours. Next, the bottles are opened just before performing the sensory test. The bottles are independently held a distance of 2 cm from the nose for 3 seconds. The intensity of the odour is judged by comparing a control bottle containing ethanol (5 ml) and a bottle containing an ethanolic solution of the odorous molecule 3M2H (1.5 g %; 5 ml). A strong odour intensity equivalent to the odour of the bottle containing an ethanolic solution of the odorous molecule (1.5 g %; 5 ml) is given a score of 10. A weak odour intensity equivalent to the odour of the bottle containing ethanol alone is given a score of 1.

(16) Results

(17) TABLE-US-00003 Odour intensity Sample (1 to 10) MIP1 2 NIP1 7 MIP2 5 NIP2 8

(18) In all these examples, the MIPs very significantly reduce the odour intensity compared with the NIPs. The reduction of the odour intensity demonstrates that the MIPs have a much better capacity for trapping the odorous molecules than the NIPs.