Optically Active Functional Fluid Markers

- THE LUBRIZOL CORPORATION

The present invention relates to a method of identifying in a fluid by measuring the amount of optical rotation the fluid causes in a beam of polarized light. The invention further provides for the use of an optional optically active marker in the fluids in order the impact the amount of rotation the fluid will cause. The invention provides a convenient and reliable means for identifying the fluid before, during and/or after the fluid's use.

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Description
FIELD OF THE INVENTION

The present invention relates to the determination of the identity of a fluid, such as aqueous fluids. The present invention also relates to a system for identifying a fluid by passing a beam of polarized light through a sample of the fluid, and measuring the amount of optical rotation caused by the sample. The invention further provides for the use of optically active markers to increase and/or adjust the amount of rotation that is observed from a sample. The measurement of this rotation, caused by the materials in the fluid being tested, including the optional optically active marker, allows for the identification of the fluid.

BACKGROUND OF THE INVENTION

Various types of fluids are used in numerous and very different applications. In all of the varied types of and uses for fluids, there is often a need to identify a fluid and/or the source of the fluid and a need for the means of identifying the fluid to be convenient and reliable.

Functional fluids, as defined in this application, are fluids employed in a variety of applications, for example personal care, food industry, industrial and institutional, pharmaceutical, and agricultural applications, as well as others. Such fluids include perfumes and various cosmetics, liquors, syrups, alcohols, food stocks, pharmaceuticals, vitamins, cosmetics, pesticides, as well as the ingredients and additives used for making the same. It is often important to know the identity and/or source of a fluid in these varied areas and applications. The need may be related to anti-counterfeiting activities, ensuring proper use, and various other needs. It is therefore desirable to be able to determine the identity of such functional fluids.

Methods exist for the analysis and identification of fluids using various reagents in determining the presence and/or concentration of various constituents of the functional fluids. Specific reagents may be employed for determining the presence and concentration of components in functional fluids. These methods generally analyze for pH, coloring agents, and contaminants using reactive reagents on test strips. These methods also generally require controlled conditions for the reactive reagents to function properly. Further, these methods may be subjective and inaccurate.

Markers have been used to identify fluids. Proton accepting chemical substances, that at a solution concentration of below about 50 milligrams per liter, impart little or no significant color to organic solvents, have been proposed as markers, or taggants, especially for petroleum-derived fuels. The marker is dissolved in a liquid to be identified, and then subsequently detected by performing a chemical test on the marked liquid.

Consumers rely upon product names and quality designations to assure that the products being purchased and used are the quality desired. Thus, it is important to be able to identify a marker in various products. In many situations, the marker must not impact the appearance, smell, or taste of the product. The marker system may also maintain the fluid's ability to be safely used, which may include human consumption (in the case of foods and beverages), skin application (in the case of cosmetics), or other factors.

It would be desirable to have an accurate and easy analytical method to determine the identity of a fluid. It would further be desirable to have an accurate analytical method to determine the identity of the fluid in the field without impacting the fluid's appearance, smell, taste, or ability to be safely consumed and/or used.

It is an object of this invention to provide an easy and convenient delivery system to accurately analyze the identity of a fluid. It is a further object of the invention to provide a method to analyze functional fluids rapidly in the field. It is still the object of the present invention to provide a method to test the identity of a functional fluid in the field rapidly by untrained personnel and without precision measurement. It is still a further object of the invention to provide a diagnostic kit for identification of functional fluids rapidly in the field.

SUMMARY OF THE INVENTION

The invention provides a method to determine the identity of a fluid comprising: (1) adding an optional optically active marker component to a functional fluid; (2) obtaining a sample of the fluid before, during or after its use in an application; (3) passing a beam of polarized light through the sample of fluid; (4) measuring the rotation of the plane of the light after it passes through the sample of fluid by comparing it to the light's original orientation; and (5) determining the identity of the fluid by the amount of rotation observed. The optically active marker component used in the methods of the invention are non-racemic in regards to at least one set of enantiomers.

The invention further provides a diagnostic kit for the analysis of a fluid comprising a source of polarized light, a means for directing a beam of polarized light from said source through a sample of fluid, a means for detecting the amount of rotation in the beam of polarized light after it passes through the sample, and a means of communicating the results from the analyzer to a user wherein the kit also comprises written instruction, pictures, drawings, photographs, or combinations thereof to aid the user in the identification of the fluid.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides for the use of optical markers in identifying and/or confirming the source of a fluid, including a method and a device, such as a kit, for analyzing and monitoring the identity of various fluids.

Fluids to be Identified

The fluids that are suitable for use in the present invention, in that the optically active markers described herein may be used to identify said fluids, are not overly limited. In general, the optically active markers described herein may be used in any liquid or fluid for which there is a need to confirm and/or determine the fluid's source and/or identity. More particularly, the methods of the invention are directed toward personal care and consumable products.

Suitable fluids include personal care fluids such as perfumes, cosmetics, fragrances, essential oils, cleaners, detergents, and soaps, shampoos, lotions, creams and the like; medical industry fluids such pharmaceuticals, medicines, vaccines, ointments, antiseptics, salves and the like; food industry fluids such as liquors, beers, wines, carbonated beverages, energy drinks, syrups, baby formulas, baby foods, food stocks, food additives, food flavorings, food odorants, and the like; Industrial and Institutional fluids such as disinfectants, cleaners, detergents, degreasers, and the like; agricultural industry fluids such as pesticides, fertilizers and the like; as well as the various fluid ingredients and additives used in the making of any of the fluids described above.

Non-fluid materials may also be used with the invention, where the non-fluid material is dissolved into a solvent, melted, or otherwise transferred into a fluid medium in order to be tested.

The invention may be used in pharmaceuticals fluids and materials. Counterfeit drugs and medicines are of serious concern for pharmaceutical companies and public health organizations. Such counterfeits may lack active ingredients, contain an insufficient or inaccurate quantity of active ingredients, or contain different active ingredients and may be sold with inaccurate, incorrect, or fake packaging. Counterfeits can also include falsely-labeled drugs, expired drugs, and diluted drugs.

The invention may be used with perfumes and other fragrances. Such materials include perfumes and colognes sold as well as any of the ingredients used to prepare such materials. Fragrances and perfumes often contain several hundred ingredients, including one or more essential oils, synthetic oils, perfumer's alcohols, artisan's alcohols and water. Such materials include eau de parfum, eau de toilette, eau de toilette has, eau de cologne, and eau fraiche, splashes and aftershaves, and room and linen sprays including air fresheners and aerosols. The methods of the invention may be used to identify the finished products or one or more of the components used in the preparation of these various materials.

The invention may be used with beverages, including distilled beverages, liquors and spirits. These fluids are drinkable liquids containing ethanol produced by means of distilling fermented grain, fruit, or vegetables. Also includes are malted beverages such as beers, wines, whiskeys, bourbons

In some embodiments the fluids used in the invention are aqueous, safe for human consumption, safe for skin application, or combinations thereof.

In some embodiments the fluids are aqueous and are free of any organic materials except small amounts that are commonly caused by contamination. In such embodiments the fluid may contain less than 10% organic material or less than 5%, less than 1% or even less than 0.5% organic material. In other embodiments, the fluids include both organic and aqueous fluids, and mixtures thereof.

Many fluids contain materials that will rotate the plane of polarized light. The measurement of this rotation may be used to verify the identity of the fluid, as described below. Such materials inherently contain optical active materials that may be used as markers in the methods of the invention. The invention includes methods that measure the optical rotation of such materials and uses the observed rotation as a mean to identify the fluid. In some embodiments, a fluid may not provide any significant rotation and/or may not rotate light any more or less than a competing, counterfeit and/or alternative product. In such cases the invention further provides for the use of optically active markers which may be added to the fluid in order to provide a different level of optical rotation. The fluid, which then includes the optional marker, can then be tested by the methods of the present invention and the observed optical rotation, which has been adjusted by the use of the optical markers described herein, may be used to identify and/or verify the identity of the fluid

Solvents to be Used with the Markers

In some embodiments the optical markers of the present invention may simply be added to the fluid with which they are used. In these embodiments the marker is added to a fluid as a neat component. In other embodiments the marker may be present in a mixture comprising one or more optical markers, as described herein, and further comprising one or more solvents, forming a marker concentrate or marker solution, which may then be added to the fluid. This mixture may further comprise additional materials, such as but not limited to, additives designed to enhance and/or improve the performance, appearance, etc, of the fluid it is being added to.

As described above, suitable solvents may be used with the markers, forming a marker solution. The solvent used depends on the type of fluid being tested, the delivery system being used and the marker being used. Combinations of solvents are also useful when the marker, depending on the application and type of analysis desired, is not soluble in the fluid. Solvents or combinations of solvents may be selected by considering desirable properties including good solvency power and miscibility with the fluid and the marker, odor, color, volatility and the like.

Suitable solvents include water and various alcohols. Other solvents include aliphatic, unsaturated and aromatic hydrocarbons, alcohols, glycols, glycol ethers, polyols such as glycerol, lower alcohols, such as methanol, ethanol and propanol, ethers, esters, amides, amines, water and the like. Combinations of solvents may be used. In some embodiments the fluid is free of organic solvents and is an aqueous fluid. In other embodiments the fluid is an aqueous fluid that may contain one or more organic components but not to an extent that the fluid loses its aqueous character.

In some embodiments the marker component, which refers to the mixture of the marker and any optional solvents and/or additional additives that may be present, is free of any materials that would inhibit the optically active nature of the marker compounds. In other embodiments the marker component is free of any materials that would react with the optically active markers present. In other embodiments the marker component is free of any non-chiral and/or non-optically active acids.

It is understood that the term marker and/or the term marker component, when used in the application, unless otherwise indicated, can mean either the marker compound or compounds themselves with no added solvent, or the marker solution comprising a mixture of the marker compound or compounds and one or more solvents or additional additives. The solvent may be present in the marker solution in the range of about 1 wt. % to about 99.99 wt. %, in one embodiment about 5 wt. % to about 98 wt. % and in another embodiment about 1 wt. % to about 95.5 wt. % of the marker solution.

The Optically Active Markers

The marker substance is chosen to be compatible with, or not adverse to, the fluid with which it is used and/or the system in which the fluid will be used.

Markers suitable for use in the present invention may be described as optically active markers. Suitable optically active markers include: one or more compounds comprising chiral molecules; one or more compounds wherein its molecules contains at least one chiral center, axis or plane; one more compounds wherein its molecules contains at least one tetrahedrally-bonded atom in which all four substituents on the tetrahedrally bonded atom are different; or mixtures of one or more of the compounds described above. In all of the embodiments described above, the mixture of markers used must have an overall enantiomeric excess such that an optically active system exists, such that the system rotates the plane of polarized light.

In one embodiment, the marker of the present invention includes one more compounds represented by Formula I shown below:

wherein X is C, N, P, or S; and R1, R2, R3, and R4 are each independently a hydrocarbyl group, and —OR5 group where R5 is a hydrogen or a hydrocarbyl group, an aromatic group, a lone pair of elections when X is N, a double bonded Oxygen atom when X is P or S, with the provisos that each R group is unique and each R group may contain functional groups. That is R1, R2, R3, and R4 are each a unique substituent group wherein R1≠R2≠R3≠R4.

In some embodiments, the optically active marker is: soluble in the fluid being marked; exhibits a measurable optical rotation of an appropriate wavelength of light; causes no harm to the fluid being marked or to the application in which the fluid is used; is colorless in the visible spectrum and/or makes no impact on the color of the fluid being marked; is odorless and/or tasteless and/or has no impact on the odor and/or taste of the fluid being marked; or some combination thereof.

The markers may be soluble in the fluid from 0.00001% up to 10% by weight. Appropriate wavelengths of light for which suitable markers cause rotations include ultraviolet light, visible light, infrared light, or combinations thereof. Sufficient optical rotation may be an amount greater than the margin of error in the measuring device used to evaluate the rotation, and in some embodiments is at least 0.1 degrees of rotation, at least 0.5 degrees, at least 1 degree, or at least 5 degrees of rotation. Optical rotations of greater than 360 degrees are possible but for this invention molecules that rotate light greater than 360 degrees are characterized as having optical rotations of their actual rotation minus 360.

A compound is considered to be optically active if it can rotate the plane of polarized light that passes through it. The amount of optical rotation is determined by the molecular structure and concentration of the optically active molecules in the fluid, the wavelength of the light passing though the fluid, the optical path length involved, and the temperature. Each optically active substance provides its own specific rotation as defined in Biot's law:

[ α ] λ T = α λ T c · l

where [α]=specific rotation, T=temperature, λ=wavelength, α=optical rotation, c=concentration in g/100 ml, l=optical path length in dm. The rotation caused by the optically active compounds results from the interaction of chiral materials with polarized light. Specific enantiomers of a chiral molecule absorb polarized light to differing degrees. Enantiomers can be named by the direction in which it rotates the plane of polarized light. If it rotates the light clockwise (as seen by a viewer towards whom the light is traveling) the enantiomer is labeled (+) or “d-” for dextrorotatory. Its mirror-image is labeled (−) or “l-” for levorotatory.

Optically active compounds may also be labeled by identifying each isomer by the spatial configuration of its atoms using an R/S designation. The R/S system has no fixed relation to the (+)/(−) or d-/l- systems described above. The R/S system labels each chiral center present in a compound with an R or S according to a system in which the chiral center's substituents are assigned a priority, based on atomic number. If the chiral center is oriented such that the lowest-priority substituents is pointed away from a viewer, the viewer will then see two possibilities: if the priority of the other three substituents decreases in a clockwise direction, it is labeled R for Rectus; if the substituents' priority decrease in a counterclockwise direction, it is labeled S for Sinister. This system labels each chiral center (and/or each chiral plane, chiral axis, and/or chiral group) in a molecule and so has greater generality than the other systems described above.

Optically active compounds include chiral molecules. The term chiral is used to describe an object that is non-superimposable on its own mirror image. Chiral molecules can have “point chirality” where the chirality of the molecule is centered around a single atom, usually a carbon atom, which has four different substituents. If all four substituents on the tetrahedrally bonded atom are different, the molecule is chiral. Isotopic differences are enough for chirality.

The above definition for chiral molecules is not limited to tetrahedral carbon atoms, but also includes any other type of central atom with an appropriate set of substituent groups or ligands. Examples include octahedral and other coordination geometries of appropriate substitution, including metal complexes and inorganic structures. In addition, a molecule may have multiple chiral centers. It is also possible for a molecule to be chiral without having point chirality. Common examples include 1,1′-bi-2-naphthol (BINOL) and 1,3-dichloro-allene, which have axial chirality, and (E)-cyclooctene, which has planar chirality.

The stereogenic center of a chiral molecule need not to be located on a specific atom. For example, adamantane derivatives with suitable substituents may also be chiral. In these structures an entire group, as opposed to a single atom, holds four substituents in a spatial arrangement making the compound non-superimposable on its mirror image.

There are many examples where chirality of molecules results from hindered rotation of groups or spatial arrangements of chemical moieties, a few examples of which include 1,2,3,4-tetramethyl-cyclooctatetraene, 2,5-dimethyl-bicyclo-2,2,2-oct-2,5,7-triene, and perchloro-triphenylamine. In addition, catenanes and molecular knots made up from achiral molecules may be chiral.

A chiral substance is considered enantiopure or homochiral when only one of two possible enantiomers is present. A mixture of equal amounts of the two enantiomers is said to be a racemic mixture. A chiral substance is enantioenriched or heterochiral when an excess of one enantiomer is present but not to the exclusion of the other. Enantiomeric excess is a measure for how much of one enantiomer is present compared to the other. A non-racemic chiral mixture may also be called scalemic.

In some embodiments, the present invention uses one or more optically active markers where the marker component and/or mixture is not a racemic mixture. That is, the marker component is scalemic and has an enantiomeric excess, or has less than 100% optical purity. In some embodiments, the present invention requires the mixture of optically active markers to contain at least a 1 percent by weight excess of one enantiomer for each optically active marker present. In still other embodiments the excess must be 10 percent by weight, 50 percent by weight or even 75 percent by weight or more.

The markers of the present invention may include one or more of the following: Abscisic Acid, sulfoximes, sulfonamides, sultams, 1-Acetoxychavicol Acetate, Acenaphthenol, Alfuzosin, Alprenolol, Althiazide, 1-Aminoindan, Amlodipine, Anisoin, 9-anthrylethanol, 9-anthryl trifluoromethyl carbinol, Arginine, Atenolol, Atropine, Azelastine, Bambuterol, Bendroflumethiazide, Benzoin, 1-(4-Benzyloxy) phenyl, Ethanol, Beta Naphthyl Methyl Carbinol, Betaxolol, Bifonazole, 1,1′-Binaphthol Monomethylether, 1-(p-Bromophenyl) Ethanol, Brompheniramine, Buckminsterfullerene-Enone [2+2] Photoadducts, Bufuralol, Bupivacaine, Bupranolol, Calanolide, Carazolol, Carprofen, Carvedilol, Chlorflurecol Methyl Chlormezanone, 4-Chloromandelic acid, 2-(2-Chloro-4-methylphenoxy) Propionic Acid, 2-(3-Chlorophenoxy)Propionic Acid, 1-(m-Chlorophenyl) Ethanol, 1-(o-Chlorophenyl) Ethanol, 1-(p-Chlorophenyl) Ethanol, Chlorthalidone, Cicloprofen, Citalopram, Clenbuterol, Cromakalim, Crotoxyphos, Cyclandelate, 1-Cyclohexyl-1-phenylacetic Acid, 1-Cyclopentyl-1-phenylacetic Acid, Cyclopentyl Benzoyl-Diamide, Cyclophosphamide, Cyclothiazide, Cyclothiazide-1, Combretastatin D-1, Coumachlor, Cypermethrin, Devrinol, Napropamide, Dexmedetomidine, 2,2′-Diaminobinaphthalene, 2,3-Dibenzoyl-Tartaric Acid, Diclofop Methyl, Dihydrotetrabenazine, Diltiazem, Dimethyl (1-acetoxy-3-phenyl-E-prop enyl) phosphonate, Dimethyl (1-hydroxy-3-phenyl-E-propenyl) phosphonate, 3,5-Dimethylanilide-R,S-Ibuprofen, Dinocap, Diperodon, Diperodon-1, Diperodon-2, Diphenylnitroxide, Disopyramide-1, Disopyramide-2, Ditoluoyltartaric Acid, propropizine, Doxazosin, EEDQ, Ethotoin, Ethyl-2-(p-Hydroxyphenoxy) Propionate, Ephedrine, Etodolac, Fenoprofen, Fenoterol, Fenoxaprop-ethyl, Fenvalerate, Flavanone, Flobufen, Flobufen-1,4-Fluorophenylalanine, Fluazifopbutyl, Fluridil, 1-(p-Fluorophenyl) Ethanol, Fluoxetine (Prozac), Flurbiprofen, Formoterol, Glutamine, Glutamic Acid, Haloxyfop-ethoxyethyl, Hanessian's Lignan, Hesperitin, Hesperitin-2, Hexobarbital, Histidine, Homatropine, Homocysteine Thiolactone, Huperzine, Hydratropic Acid, Hydrobenzoin, Hydroxychloroquine, 1-(4-Hydroxyphenyl) Ethanol, p-Hydroxy-Phenylglycine, 2-(4-Hydroxy-Phenoxy)Propionic Acid, Ibuprofen, Ibuprofenol, Idazoxan, Ifenprodil, Ifenprodil-2, Ifosfamide, Indapamide, Indapamide-1, Indoprofen, Ipsdienol, Isoxsuprine, Isradipine, Isradipine-1, Ketamine, Ketoconazole, Ketoprofen, Ketoprofen-1-Naphthylamide, Ketorolac, KP 411, Kynurenine, Lansoprazole, Laudanosine, Leptophos, Phosvel, Leucine, Leucine-1, Lorazepam, Lorglumide, Loxoprofen, Luciferin, Mandelic Acid, McN 5652, Mecoprop, Mephenyloin, Metalaxyl, Methadone, Methadone-1, Methionine, a-Methoxyphenyl Acetic Acid, 2-Methoxyphenyl Phenyl Carbinol, 1-(4-Methoxyphenyl)-2-butanol, 1-(o-Methoxyphenyl) Ethanol, 1-(4-Methoxyphenyl)-2-propanol, Methyl Mandelate, 1-(o-Methylphenyl) Ethanol, 1-(m-Methylphenyl) Ethanol, 1-(p-Methylphenyl) Ethanol, Methyl 3-phenyl-3-azido-2-hydroxypropanoate, 3-Methyl-5-phenylhydantoin, Metolachlor, Metolazone, Metoprolol, Mianserin, Modafinil, Mosapride, Nadifloxacin, Nadolol, 1,1′-bi-2-naphthol, a-naphthol methyl carbinol, 1-Naphthyl-2-butanol, 2-Naphthyl-2-butanol, 1-Naphthylureaphenethylamine, Napropamide, Naproxen Diisopropyl Amide, Naproxen (normal phase), Naproxen (reversed phase), Naproxen (on ULMO CSP), Naproxen Methyl Amide, Naringenin, Nicardipine, N-CBZ-Valine, Nicotine, Nimodipine, Nirvanol, Norleucine, Norvaline, Octopamine, Ofloxacin, Omeprazole, Omeprazole (Prilosec), Omeprazole (Prilosec)-1, Oxazepam, Oxprenolol, Oxybutynin, p-Chloro-Warfarin, Pantoprazole, Pazufloxacin, Permethrin, Pheniramine, Phenyl cyclohexyl Carbinol, 2-Phenylcyclopropane Carboxylate, Phenyl ethyl carbinol, Phenyl Isopropyl Carbinol, Phenyl Methyl Carbinol, 1-[(4-Phenyl) phenyl]Ethanol, Phenyl phenylethyl Carbinol, 1-Phenyl-2-propanol, Phenyl propyl carbinol, Phenyl tribromomethyl carbinol, Phenylalanine, Phenylbutyric acid, Phenylethylene Glycol, Phenylglycine, 1-Phenylpentanol, Phenylsuccinic Acid, Pindolol, Pindolol-1, Pirprofen, PPO Inhibitor, Practolol, Praziquantel, Prilocalne, Proglumide, Proline, Pronethalol, Propafenone, Propiconazole, Tilt, Propranolol, Quizalofop-ethyl, Ranolazine, Rebamipide, Resmethrin, SC 41930, Serine, Sethoxydim, Sotalol, Stilbene Oxide, Styrene Oxide, Sulconazole, Sulfinpyrazone, Sulindac, Sulpiride, Suprofen, Taxifolin, Temazepam, Temazepam-1, Terbutaline, Terfenadine, Terfenadine-2, Tert-butyl-2-(benzamido) Cyclopentyl Carbamat, Separation, Tert Butyl Phenyl Carbinol, Tetrabenazine, Tetrahydrobenzopyrene-7-ol, Tetrahydropalmatine, Tetrahydropalmatine-2, Tetrahydropyrimindine, Tetrahydrozoline, 1,2,3,4-tetrahydro-1-naphthol, 1,2,3,4-tetrahydro-1-naphthylamine, Tetramethrin, Tetramisole, Thalidomide, 2-Thiopheneethanol, 3-Thiopheneethanol, Tiaprofenic Acid, Timolol maleate, Tofisopam, Tolperisone, Trans-2-phenyl-1-cyclohexanol, Trans-11,12-Diamino-9,10-dihydro-9,10-ethanoanthracene, Trichlormethiazide, 4-(Trifluoromethyl)mandelic Acid, 1,1,2-triphenyl-1,2-ethanediol, 1,3,5-triphenylpent-4-yn-1-one, 1-(m-Trifluoromethylphenyl) Ethanol a-Trityl-2-naphthalene propionic acid, Troger's Base, Troglitazone, Trolox, Trolox-1, Trolox-methylether, Tropicamide, Tryptophan, Tulobuterol HCl, Tyrosine, U-100057, U-94863, trans-U-50488H, Valine, Vanilmandelic Acid, Vapol, Verapamil, Verapamil, Viloxazine, Warfarin (normal phase), Warfarin (reverse phase), Warfarin (on ULMO CSP), Zopiclone.

Additional examples of chiral compounds include: D-Alaninol, L-Alaninol, L-(+)-Isoleucinol, L-(+)-Isoleucinol, L-(+)-Leucinol, D-Methioninol, L-Methioninol, D-(+)-Phenylalaninol, L-(−)-Phenylalaninol, D-(−)-alpha-Phenylglycinol, L-(+)-alpha-Phenylglycinol, D-(−)-Prolinol, L-(+)-Prolinol, D-Tryptophanol, L-Tryptophanol, D-Valinol, L-Valinol, R-(−)-2-Amino-2-Phenylethanol, BOC-D-Alaninol, BOC-L-Alaninol, CBZ-D-Alaninol, CBZ-L-Alaninol, FMOC-D-Alaninol, FMOC-L-Alaninol, BOC-D-(+)-Isoleucinol, BOC-L-(+)-Isoleucinol, CBZ-D-(+)-Isoleucinol, CBZ-L-(+)-Isoleucinol, BOC-D-(+)-Leucinol, BOC-L-(+)-Leucinol, CBZ-D-(+)-Leucinol, CBZ-L-(+)-Leucinol, BOC-D-Phenylalaninol, BOC-L-Phenylalaninol, CBZ-D-Phenylalaninol, CBZ-L-Phenylalaninol, FMOC-D-Phenylalaninol, FMOC-L-Phenylalaninol, BOC-D-alpha-Phenylglycinol, BOC-L-alpha-Phenylglycinol, FMOC-D-alpha-Phenylglycinol, FMOC-L-alpha-Phenylglycinol, BOC-D-Prolinol, BOC-L-Prolinol, CBZ-D-Prolinol, FMOC-D-Prolinol, FMOC-L-Prolinol, BOC-D-Valinol, BOC-L-Valinol, FMOC-L-Valinol.

Still further examples of chiral compounds include: S-2-methylpiperazine, R-2-methylpiperazine, S-1-Boc-2-methylpiperazine, R-1-Boc-2-methylpiperazine, S-piperazine-2-carboxylic acid, R-piperazine-2-carboxylic acid, S-4-Boc-piperazine-3-carboxylic acid, R-4-Boc-piperazine-3-carboxylic acid, S-4-Boc-2-methylpiperazine, R-4-Boc-2-methylpiperazine, S-4-Boc-piperazine-2-carboxyl-t-Butylamide, R-4-Boc-piperazine-2-carboxyl-t-Butylamide, L-Malic Acid, D-Malic Acid, Diethyl L-(+)-Tartrate, Diethyl D-(−)-Tartrate, S-2-Amino-1-propanol, R-2-Amino-1-propanol, S-1-Amino-2-propanol, R-1-Amino-2-propanol, S-1,2-Decanediol, R-1,2-Decanediol, S-2-Amino-1-butanol, R-2-Amino-1-butanol, S-Octanol, R-Octanol, S-2-Phenylpropylamine, R-2-Phenylpropylamine, S-2-Heptanol, R-2-Heptanol, S-3-Hydroxy-Gamma-Butyrolactone, R-3-Hydroxy-Gamma-Butyrolactone, S-2-M ethyl-1-butanol, R-2-Methyl-1-butanol, S-Glyceric acid (hemicalcium salt), R-Glyceric acid (hemicalcium salt), S-1-Benzylglycerol, R-1-Benzylglycerol, S-3-Amino-1,2-propanol, R-3-Amino-1,2-propanol, S-3-Methyl-2-butanol, R-3-Methyl-2-butanol, S-Glycidol, R-Glycidol, S-2-Methyl-1,4-butanediol, R-2-Methyl-1,4-butanediol, S-3-Hydroxyisobutyric acid methyl ester, R-3-Hydroxyisobutyric acid methyl ester, S-2-Methoxy-2-phenylethanol, R-2-Methoxy-2-phenylethanol.

Tartrates, tartrimides, and similar materials derived from carboxylic acids such as tartaric acid, citric acid, ascorbic acid, dehydroascorbic acid and the like, may also be chiral, and so may also be suitable markers for use in the present invention. In some embodiments the markers used in the methods of the invention are selected from the group consisting of tartaric acid, glucose, 2-bromobutane, D-alaninol, L-alaninol, L-(+)-isoleucinol, L-(+)-leucinol, D-methioninol, L-methioninol, D-(+)-phenylalaninol, L-(−)-phenylalaninol, D-(−)-alpha-phenylglycinol, L-(+)-alpha-phenylglycinol, D-(−)-prolinol, L-(+)-prolinol, D-tryptophanol, L-tryptophanol, D-valinol, L-valinol, R-(−)-2-amino-2-phenylethanol, 2-pentanol, 2-fluorobutane, 3-methylhexane, 2-bromomethyl-2-chloromethyl-1-fluoropropane, N-ethyl-N-methyl-N-propylbutan-1-aminium, m-dichlorocyclohexane and o-dichlorocyclohexane, amino(hydroxy)acetic acid, 1-aminoethanol, 2-[pyridine-3-yl(pyridine-4-yl)methyl]pyridine, 2-amino-2-hydroxy-3-oxoacetic acid, and combinations thereof.

Tartrates, tartrimides, and similar materials derived from carboxylic acids such as tartaric acid, citric acid, and the like, and the acids themselves, may also be chiral, and so may also be suitable markers for use in the present invention. Markers that fit these categories include tartaric acid derived diesters. The diesters may be derived from tartaric acid and an alcohol and/or a mixture of alcohols (such as Alfol™ 810). Specific examples include D-tartaric acid/Alfol™ 810 diester, L-tartaric acid/Alfol™ 810 diester, D-tartaric acid/Alfol™1214 tridecyl alcohol diester, L-tartaric acid/Alfol™1214 tridecyl alcohol diester, and mixtures thereof, as long as the mixture is non-racemic, that is, contains an excess of at least one enantiomer.

In other embodiments the markers used in the methods of the invention are cholesteryl acetate, L-menthyl lactate, S-(−)-perillaldehyde, 1R-(−)-menthyl acetate, R-(+)-limonene, or combinations thereof.

In some embodiments the markers used in the methods of the invention are chiral sugars, chiral amino acids, chiral carbohydrates, or combinations thereof.

In some embodiments the markers used in the invention are chiral carbohydrate sugars. In such embodiments the markers used may be erythrose, threose, arabinose, ribose, ribulose, xylose, xylulose, lyxose, allose, altrose, fructose, galactose, glucose, gulose, idose, mannose, sorbose, talose, tagatose, sedoheptulose, heptose, hexose, pentose, sucrose, maltose, trehalose, lactose, melibiose, inulin, dextran, amylopectin, Amylose, 1-arabinofuranose, N-Acetyl-d-glucosamine, 13-d-glucuronate, N-acetylgalactosamine-4-sulfate, agarobiose, d-galactose, 3,6-anhydro-1-galactose, 13-d-mannuronic acid, α-1-guluronic acid, d- and l-glyceraldehyde, pyranoses, alpha or beta-d-glucopyranose, cellulose, saccharose, sorbitol, mannitol, xylitol, maltitol, maltitol syrup, lactitol, erythritol, isomalt, sugar alcohols, and combinations or derivatives thereof.

The markers of the invention may also be chiral sugar alcohols, amino sugars and uronic acids. Sugar alcohols, also known as polyols, polyhydric alcohols, or polyalcohols, are the hydrogenated forms of the aldoses or ketoses. For example, glucitol, also known as sorbitol, has the same linear structure as the chain form of glucose, but the aldehyde (—CHO) group is replaced with a —CH2OH group. Other common sugar alcohols include the monosaccharides erythritol and xylitol and the disaccharides lactitol and maltitol. Amino sugars or aminosaccharides replace a hydroxyl group with an amino (—NH2) group. Glucosamine is an amino sugar. Uronic acids have a carboxyl group (—COOH) on the carbon that is not part of the ring, for example, galacturonic acid.

The markers of the invention may also be chiral amino acids and related compounds such as isoleucine, alanine, leucine, asparagine, lysine, aspartate, methionine, cysteine, glutamate, phenylalanine, threonin, glutamine, valine, glycine, tryptophan, praline, serine, tyrosine, arginine, histidine, and derivative and combinations thereof.

In some embodiment the markers of the present invention provide a measurable impact on the optical rotation caused by the fluid in which it is used. In some embodiments this impact is more than the margin of error of the testing method used. In other embodiments the marker causes the optical rotation caused by the fluid to change by at least 5%, at least 10% or at least 20%.

When present, the amount of marker present in the fluid is not overly limited as long as there is enough marker to allow for positive identification and so long as there is not so much marker that it interferes with the performance and/or desired characteristics of the fluid. The markers may be present in the fluid at concentrations of 10 to 10,000 ppm or 10 to 1,000 ppm. In another embodiment the makers are present in the fluid at 20 to 500 ppm; 25 to 350 ppm, 30 to 130 ppm; or to 100 ppm.

The marker compound itself may be soluble in water, substantially soluble in water, substantially insoluble in water or insoluble in water. In other embodiments the marker compound is soluble in organic liquids, such as alcohols or oils, substantially soluble in organic liquids, substantially insoluble in organic liquids or insoluble in organic liquids. The marker compound should be substantially soluble and/or soluble in the fluid with which it is used, or substantially soluble and/or soluble in at least one of the components present in the fluid with which it is used.

The optical markers of the present invention may be used in combination with other markers including non-optically active markers such as markers that react with reagents to provide positive identification of a fluid. The use of multiple types of markers allows for additional levels of protection and accuracy when verifying the identity and/or source of the fluid being tested.

Optional Components

Optional components may be added to the marker solutions or the fluids. These include, for example, surfactants, maskants and fragrances to improve customer appeal, as well as antifoam additives to improve product manufacture and use. These optional components can be used with in the marker solutions either alone or in combination.

The optional component may be used in the range of about 0% to about 20% wt, in one embodiment about 0.01% to about 5% wt, and in another embodiment about 0.1% to about 2% wt of the reagent solution.

Method

The present invention includes a method to determine the identity of a fluid comprising: (1) adding a optional marker component to a fluid; (2) obtaining a sample of the fluid before, during or after the fluid's use; (3) passing a beam of polarized light through the sample; (4) analyze the results by measuring the rotation of the polarized light after it passes through the sample; (5) determining and/or verifying the identity of the fluid. In some embodiments the optical rotation observed is that caused by the fluid itself without the addition of the optional optical markers described herein. In other embodiments one or more of the optically active markers described above are added to the fluid, which causes at least some of the rotation observed in the fluid.

Diagnostic Kit

The diagnostic kit includes a means to generate a polarized beam of light and to direct that light beam through a sample of fluid. The kit further includes a means for measuring the rotation of the beam of polarized light after it passes through the sample of fluid, compared to the beam before it passes through the sample. The measurement of the amount of rotation the polarized light beam experiences, is the means for identifying the fluid being tested.

In one embodiment the present invention excludes the use of reactive markers and/or reactive reagents where a marker-containing fluid sample is reacted with a reagent in order to produce an observable response used to identify the fluid.

In one embodiment the present invention excludes identification by observing a compound removed from the function fluid by a water extraction. A water extraction includes where a compound, such as a dye, in a fluid is removed from the fluid and drawn into an aqueous solution, due to the compound's miscibility in water. The observance of the compound, without any reaction taking place, in the water solution is the only indicator provided.

The marking/identification of a fluid is desirable because counterfeiting and adulteration/dilution of genuine fluids is a large concern of fluid suppliers and results in a loss of profits, customer complaints, and harm to brand name and reputation. A simple, easy to use marker system is beneficial since different fluids can be indistinguishable based on casual inspection. Chemical analyses or physical properties can tell various fluids apart but these analyses require expensive laboratory test equipment and often take too long to be a practical end user identification test. The disclosed methods enable end users to exclude a counterfeit or adulterated product based on optical rotation, in a efficient and convenient way.

Visual Indicia

Analysis of the test sample can be accomplished by visual inspection of the light beam rotation, and may include using a provided visual indicia as a guide.

The visual indicia may include an artistic rendering, a reproduction of a photograph of one or more functional fluids in various conditions with and without the reagent. The visual indicia generally include one representation, two representations or more than two representations of one or more functional fluids and/or a diagram showing the expected light beam, rotation for a fluid of a given source, a given identity, and/or a given condition. In one embodiment the preferred visual indicia is one or more representations showing a positive identification result and one or more representations showing a negative identification result. A descriptive text corresponding to each of these examples may be provided. It is to be understood that a different number of indicia may be provided.

Specific Embodiment

The following data was collected with a JASCO Model DIP-360 digital polarimeter, which was operated according to the manufacturer's directions. 100 mm length test cells were used for all testing.

Example 1

Mineral oil is treated with several optically active markers and tested using a polarimeter. The results are summarized in the table below.

TABLE 1 Mineral Oil Data Marker Conc Rotation None - Oil Alone  0% wt 0.860 Cholesteryl Acetate 10% wt −2.860 L-menthyl lactate 10% wt −5.690 S-(−)-perillaldehyde 10% wt −10.790 1R-(−)-menthyl acetate 10% wt −5.890 R-(+)-limonene 10% wt 11.740 Cholesterol 10% wt Insoluble

The results show that some fluids provide a measurable amount of optical rotation that may be used in the methods of the invention as a means of identifying and/or verifying the identity of the fluid. The results also show that the optically active markers defined above may be used in such fluids to adjust, impact, and/or change the amount of optical rotation caused by the fluid, which may make it easier to identify a fluid. The markers may also be used to achieve an amount of rotation that would not otherwise be present in such a fluid, thus providing a convenient means of identifying and/or verifying the identity of a fluid.

Example 2

Several aqueous fluids are treated with several optically active markers and the samples are tested using a polarimeter. The samples are described in the table below.

TABLE 2 Water Data Marker Fluid 11 Fluid 22 Fluid 33 None - Water Alone  0% wt  0% wt  0% wt sucrose 10% wt 10% wt 10% wt lactose 10% wt 10% wt 10% wt erythritol 10% wt 10% wt 10% wt sorbitol 10% wt 10% wt 10% wt tryptophan 10% wt 10% wt 10% wt 1Fluid 1 is a commercially available fragrance. 2Fluid 2 is a commercially available beverage. 3Fluid 3 is a commercially available pesticide used in agriculture.

Example 2 demonstrates that markers such as chiral sugars, chiral amino acids, and chiral carbohydrates may be used in aqueous functional fluids

While the invention has been explained, it is to be understood that various modifications thereof will become apparent to those skilled in the art upon reading the specification. Therefore, it is to be understood that the invention disclosed herein is intended to cover such modifications as fall within the scope of the appended claims.

Each of the documents referred to above is incorporated herein by reference. Except in the Examples, or where otherwise explicitly indicated, all numerical quantities in this description specifying amounts of materials, reaction conditions, molecular weights, number of carbon atoms, and the like, are to be understood as modified by the word about. Unless otherwise indicated, each chemical or composition referred to herein should be interpreted as being a commercial grade material which may contain the isomers, by-products, derivatives, and other such materials which are normally understood to be present in the commercial grade. However, the amount of each chemical component is presented exclusive of any solvent or diluent oil, which may be customarily present in the commercial material, unless otherwise indicated. Unless otherwise indicated, all percentage values are percents by weight. It is to be understood that the upper and lower amounts, ranges, and ratio limits set forth herein may be independently combined. Similarly, the ranges and amounts for each element of the invention can be used together with ranges or amounts for any of the other elements. As used herein, the expression “consisting essentially of” permits the inclusion of substances that do not materially affect the basic and novel characteristics of the composition under consideration.

Claims

1. A method to determine the identity of a functional fluid comprising:

(1) adding an optional optically active marker component to a functional fluid;
(2) obtaining a sample of the fluid before, during or after its use in an application;
(3) passing a beam of polarized light through the sample of fluid;
(4) measuring the rotation of the plane of the light after it passes through the sample of fluid by comparing it to the light's original orientation;
(5) determining the identity of the fluid by the amount of rotation observed.

2. The method of claim 1 wherein the optically active marker component comprises a chiral molecule that is at least partially soluble in the functional fluid.

3. The method of claim 1 wherein the optically active marker component comprises a compound is of the formula:

wherein X is C, N, P, or S; and R1, R2, R3, and R4 are each independently a hydrocarbyl group, an —OR5 group where R5 is hydrogen or a hydrocarbyl group an aromatic group, a lone pair of elections when X is N, a double bonded Oxygen atom when X is P or S, with the proviso that none of the R groups are identical, wherein the optically active marker component is non-racemic in regards to at least one set of enantiomers.

4. The method of claim 1 wherein the functional fluid is selected from the group consisting of perfumes, cosmetics, fragrances, detergents, soaps, shampoos, lotions, creams, antiseptics, ointments, salves, pharmaceuticals, medicines, vaccines, liquors, beers, wines, carbonated beverages, energy drinks, baby formula, baby food, food stocks, syrups, food additives, food flavorings, essential oils, pesticides, fertilizers, and combinations thereof.

5. The method of claim 1 wherein the marker component is added to the fluid before or during the fluid's use in an application.

6. The method of claim 1 wherein the concentration of the marker component in the in the functional fluid is from 10 to 1000 ppm.

7. The method of claim 1 wherein the optically active marker component comprises a chiral sugar, a chiral amino acid, a chiral carbohydrate, or combinations thereof.

8. The method of claim 1 wherein the optically active marker component comprises cholesteryl acetate, L-menthyl lactate, (S)-(−)-perillaldehyde, (1R)-(−)-menthyl acetate, (R)-(+)-limonene, cholesterol, sucrose, camphor, penicillin V, taxol, bromobutane, cavicularin, or combinations thereof.

9. A diagnostic kit for the analysis of a fluid comprising a source of polarized light, a means for directing a beam of polarized light from said source through a sample of fluid, a means for detecting the amount of rotation in the beam of polarized light after it passes through the sample, and a means of communicating the results from the analyzer to a user wherein the kit also comprises written instruction, pictures, drawings, photographs, or combinations thereof to aid the user in the identification of the fluid.

10. The diagnostic kit of claim 9 wherein the fluid contains at least one optical marker.

Patent History
Publication number: 20110299081
Type: Application
Filed: Dec 10, 2009
Publication Date: Dec 8, 2011
Applicant: THE LUBRIZOL CORPORATION (Wickliffe, OH)
Inventors: John S. Manka (Chardon, OH), Ying Wang (Hudson, OH)
Application Number: 13/139,530
Classifications
Current U.S. Class: By Polarized Light Examination (356/364)
International Classification: G01J 4/00 (20060101);