CA1291638C - Use of water-soluble polymers in aqueous chemical light formulations - Google Patents
Use of water-soluble polymers in aqueous chemical light formulationsInfo
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- CA1291638C CA1291638C CA000491292A CA491292A CA1291638C CA 1291638 C CA1291638 C CA 1291638C CA 000491292 A CA000491292 A CA 000491292A CA 491292 A CA491292 A CA 491292A CA 1291638 C CA1291638 C CA 1291638C
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
- C09K11/07—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials having chemically interreactive components, e.g. reactive chemiluminescent compositions
Abstract
29,559 THE USE OF WATER-SOLUBLE POLYMERS IN
AQUEOUS CHEMICAL LIGHT FORMULATIONS
Abstract of the Disclosure Aqueous chemiluminescent systems have been found to exhibit improved chemiluminescence due to the presence of minor amounts of a water-soluble polymer.
AQUEOUS CHEMICAL LIGHT FORMULATIONS
Abstract of the Disclosure Aqueous chemiluminescent systems have been found to exhibit improved chemiluminescence due to the presence of minor amounts of a water-soluble polymer.
Description
12~8 29, J
THE USE OF WATER-SOLUBLE POLYMERS I~
AQUEOUS CHEMICAL LIGHT FORMULATIONS
BACKGROUND OF THE INVENTION
The invention described herein was made in the performance of work supported by the Office of Naval Research (Contract No. N-0014-82-C-0202).
The generation of chemiluminescence by the re-action of an ester or amide of an oxalic acid with a source of hydrogen peroxide in the presence of a fluorescer compound in aqueous solution is disclosed and claimed in U.S. Patent Nos. 4,053,430 and 4,282,357. Recently, U.S.
Patent No. 4,462,931 has issued which discloses an improvement over the previous systems whereby a surfactant is added in mi~or amounts to the aqueous solution, or to solid mixtures which are then mixed with water, in order to enhance the emission intensity of the resultant system. While the use of a surfactant in such systems has enhanced the emission intensity thereof, industry is still continuously on the lookout for ways and means of further enhancing the emission intensities, light capaci-ties and efficiencies of chemiluminescent systems.
SUMMARY OF THE INVENTION
It has now been found, in accordance with the present invention, that the emission intensities of chemiluminescent systems based on oxalic acid esters or amides, fluorescers and a source of hydrogen peroxide can be materially enhanced by the incorporation of minor amounts of a water-soluble polymer into an aqueous solution 1~9~
containing these ingredients or solid mixtures thereof which may be added to water to generate chemiluminescense.
The water-soluble polymers are more effective in this regard than the surfactants described in U.S. 4,462,931 alone in that the quantum yield of light emitted is 15-35% higher when the polymers are employed vis-a-vis the surfactants.
The employment of polymeric additives in organic solvent based chemiluminescent systems is disclosed in U.S. Patent Nos. 3,377,291; 3,816,325 and 3,994,820. The compositions produced in U.S. 3,377,291 are, however, gels which may be used to spread on porous cloth etc.
wherein the polymer functions as a thickening agent. In U.S. 3,816,3250polymeric materials are employed so as to render the final composition immune to adverse environ-mental conditions such as water. Additionally, the materials can be formulated into a dry system which will not be absorbed into porous surfaces or can be molded into specific shapes. There is no evidence, however, that the presence of the polymeric additive enhances the ultimate emission intensities of either of the systems.
In U.S. 3,994,820, the light capacity of organic ox~late ester chemiluminescent systems is increased by the addi-tion of certain polymeric materials to the system. These polymers include homopolymers and copolymers of a) poly-~alkylene oxides), b) poly(vinylalkylethers and esters), and c) maleic anhydride and cellulose esters whereas the polymers useful in the present invention exhibit high binding capacity, in aqueous solution, especially for substrates that possess negative charges, and function, in the present invention, in that manner. The function of the polymers in the organic systems is unknown.
DESCRIPTION OF THE INVENTION
INCLUDING PREFERRED EMBODIMENTS
In accordance with the present invention, there is provided a composition for generating chemiluminescent ~9~638 emission comprising an aqueous solution of (a) a water-soluble reactant, (b) a water-soluble organic fluorescer having a spectral emission in the range from about 330 to 1000 nanometers, and (c) a water-soluble polymer, in proportions capable of producing enhanced chemiluminescence on reaction with hydrogen peroxide.
More particularly, the invention provides a composition for generating chemiluminescence comprising, in aqueous solution, a) 10 to 5 molar concentration of a water-soluble reactant which generates light by reaction with hydrogen peroxide, b) 10 5 to 1 molar concentration of a water-soluble or water-dispersible organic fluorescer having spectral emission in the range about 300 to 1000 nanometers and c) from about 10 2 to about 50%, by weight, based on the total weight of the solution, of a water-soluble polymer which render the biomolecular chemiluminescent reaction monomolecular selected from alkylene oxide polymerization products, vinyl acetate polymers, vinyl pyrrolidone polymers, vinyl pyridene polymers, styrene sulfonate polymers, acrylamide polymers, or copolymers of the above.
The present in~ention further provides a dry composi-tion for generating chemiluminescence comprising a dry mixture of (a) water-soluble reactant, (b) a solid hydrogen peroxide source e.g. sodium perborate, potassium perborate, sodium carbonate peroxyhydrate, histidine perhydrate, etc., (c) a solid water-soluble fluorescer having a spectral emission in the range from about 330 to 1000 nanometers, and (d) a water-soluble polymer, ~,~
1'~91638 - 3a - 61109-7422 in proportions capable of producing enhanced chemiluminescence when added to water.
More particularly, the invention provides a dry mixture of components for making a chemiluminescent reaction by addition of the dry mixture to water, said dry mixture comprising amounts sufficient to obtain, in solution, of a) a water-soluble reactant which generates light by reaction with hydrogen peroxide, in an initial molar concentration of about 10 3 to 5, b) a water-soluble or water-dispersible organic fluorescer having spectral emission in the range of from about 300 to about 1000 nanometers, in a molar concentration of about 10 5 to 1, c) a water-soluble polymer which render the biomolecular chemiluminescent reaction monomolecular selected from alkylene oxide polymerization products, vinyl acetate poly-mers, vinyl pyrrolidone polymers, vinyl pyridene polymers, styrene sulfonate polymers, acrylamide polymers, or copoly-mers of the above, from about 10 ~ to 50~ by weight based on total solution weight, and d) a solid hydrogen peroxide source in an initial molar con-centration of about 10 3 to 10.
In the above compositions the reactant is preferably a water-soluble ester, or amide, of oxalic acid.
The present invention also provides processes for generating chemiluminescence by adding effective amounts of the ~91638 - 3b - 61109-7422 aforedescribed by dry compositions to water or adding to the aqueous solutions an aqueous solution of hydrogen peroxide, or source of hydrogen peroxide.
The aqueous chemiluminescent systems of the present invention provide enhanced emission of light which is useful in a wide variety of applications, particular]y for providing emergency light at home, on highways r and at sea.
The chemiluminescent reaction mixture contains a water-soluble reactant which generates light by reacting with hydrogen peroxide, or a source of hydrogen peroxide, in the presence of a fluorescer compound and a water-soluble polymer.
Suitable water-soluble esters of oxalic acid which may be used in the present invention as reactants are disclosed by Mohan in United States Patent No. 4,053,430, discussed above.
Illustrative examples of suitable water-soluble 1~9~i3~
esters of oxalic acid include the dihydrochlorides, dihy-drobromides, dihydrofluorides, di(trifluoromethane) sul-fonates, dimethanesulfonates, di-p-toluenesulfonates, di-methosulfates and diquaternary ammonium salts of the following compounds:
bis(2,6-dichloro-4-[~2-dimethylaminoethyl)methylsulfamoyl]-- phenyl)oxalate.
bis(2,4-dichloro-6-[(2-dimethylaminoethyl)methylsulfamoyl]-phenyl)oxalate.
bis(2-chloro-4-[(2-dimethylaminoethyl)methylsulfamoyl]phen-yl)oxalate.
bis(2-bromo-4-[(2-dimethylaminoethyl)methylsulfamoyl]phen-yl)oxalate.
bis(2,6-dibromo-4-[(2-dimethylaminoethyl)methylsulfamoyl]-phenyl)oxalate.
bis(3-fluoro-4-[(2-dimethylaminoethyl)methylsulfamoyl]-phenyl)oxalate.
bis(2,4-dibromo-6-[(2-dimethylaminoethyl)methylsulfamoyl]-phenyl)oxalate.
bis(2-fluoro-4-[(2-dimethylaminoethyl)methylsulfamoyl]phen-yl)oxalate, and the like.
The preferred water-soluble ester of oxalic acid is the dihydrochloride of bis(2,4-dich1Oro-6-[(2-dimethyl-aminoethyl)methylsulfamoyl]phenyl)oxalate.
Suitable water-soluble amides of oxalic acid which may be used in the processes and compositions of this invention are disclosed in U.S. Pat. No. 4,282,357 and in U.S. Pat. No. 4,338,213.
Illustrative examples of suitable water-soluble amides of oxalic acid include the dihydrochlorides, di-hydrobromides, dihydrofluorides, di(trifluoromethane) sulfonates, dimethanesulfonates, dimethosulfates, and ditetrafluoroborates of the following compounds:
N,N'-bis(2-morpholinoethyl)-N,N'-bis-(trifluoromethylsul-fonyl)oxamide, N,N'-bis(3-morpholinopropyl)-N,N'-bis(trifluoromethylsul-- fonyl)oxamide, 12916~8 N,N'-bis[2-(2-pyridyl)ethyl]-N,N'-bis(trifluoromethyl-sulfonyl)oxamide, N,N'-bis[3-(2-pyridyl)propyl]-N,N'-bis(trifluoromethyl-sulfonyl)oxamide, N,N'-bis(6-morpholinohexyl)-N,N'-bis(trifluoromethylsul-fonyl)oxamide, N,N'-bis[2-(4-pyridyl)ethyl]-N,N'-bis(trifluoromethyl-sulfonyl)oxamide, N,N'-bis[5-(3-pyridyl)pentyl]-N,N'-bis(trifluoromethyl-sulfonyl)oxamide,and the like.
The preferred water-soluble oxamide is 4,4'-(oxalyl-bis[[(trifluoromethyl)sulfonyl]imino]ethylene)-bis(4-methylmorpholinium trifluoromethanesulfonate).
The water-soluble fluorescer compounds, useful in the chemiluminescent compositions of this invention, may be defined broadly as compounds, having an emission spectral maximum between 330 and 1000 nanometers, which do not react with a hydrogen peroxide compound, or the amide, or ester, of oxalic acid, on contact. The water-soluble fluorescer may be anionic, cationic, or nonionic.
Illustrative examples of suitable fluorescers including the following:
Sulfonated 5,6,11,12-tetraphenylnaphthacene sodium salts, 4-methyl-4-[2-[1-oxo-4-tl-pyrenyl)butoxy]ethyl~morpholinium methyl sulfate, 4,4'-[9, 10-anthracenediylbis~l, 2-ethanediyl)]bisbenzene-sulfonic acid disodium salt, 4,4'-~9,10-anthracenediylbisll,2-ethanediyl)]bisbenzenemeth-anol bis (monosodium sulfate).
4,4'-[9, 10-anthracenediylbis(l, 2-ethynediyl)]bisbenzene-carboxylic acid dilithium salt, 4,4'-[6, 12-diphenyl-5, 11-tetracenediylbis(4, l-phenyl-enemethylene~bis (4-methylmorpholinium methyl sulfate), 4,4'-[6, 12-diphenyl-5, 11-tetracenediylbis(4, l-phenyl enemethylene)]bis (4-trifluoromethylmorpholinium trifluor-omethyl sulfate), 2, 8-bis[(3, 6, 9-trioxadecyl)oxy]~5, 1l-bis[[3~ 6, 9-trioxadecyl)oxyl)phenyl]-6, 12-diphenylnaphthacene, and the like; see also U.S. Patent No. 4,366,079.
The preferred water-soluble fluorescer, referred to herein as sulfonated rubrene, is a mixture of sodium salts of sulfonated 5,6, 11, 12-tetraphenylnaphthacene.
Illustrative examples of suitable fluorescers which are not water-soluble include the following com-pounds:
5, 6, 11, 12-tetraphenylnaphthacene, 9, 10-bis(phenylethynyl)anthracene, 5, 12-bis(phenylethynyl)tetracene, 9, 10-diphenylanthracene, perylene, pyrene, l-chloro-9, 10-bis(phenylethynyl)anthracene, 2-chloro-9, 10-bis(phenylethynyl)anthracene, 1, 5-dichloro-9, 10-bis(phenylethynyl)anthracene, 1, 8-dichloro-9, 10-bis(phenylethynyl)anthracene, l-bromo-9, 10-bis(phenylethynyl)anthracene, l-fluoro-9, 10-bis(phenylethynyl)anthracene, 2-methyl-9, 10-bis(phenylethynyl)anthracene, fluorescein, rhodamine, 2, 3-benæanthracene, 5, 11-bis(4-(n-hexyl)phenyl)-6, 12-diphenylnaphthacene, 5, 11-bis[4-(n-dodecyl)phenyl]-6, 12-diphenylnaphthacene, 5, 11-bis[~-(2, 5, 8, 11, 14, 17-hexaoctadec-1-yl)phenyl]-6, 12-diphenylnaphthacene, and the like.
Any water-soluble polymer may be employed to produce the novel compositions of the present invention.
Examples of suitable polymers falling within the scope of the present invention include the polymerization products ~ f alkylene oxides such as ethylene oxide, propylene oxide, hexylene oxide and mixtures thereof; polymers of vinyl acetate; polymers of vinyl pyrolidone alone or as copolymers with comonomers such as vinyl acetate, etc.;
,_ polyvinyl pyridenes, polystyrene sulfonates, polyacrylo-mides copolymers thereof~ and the like.
The molar concentrations (moles per liter of solution) of the reactant e.g. the oxalic acid ester, or S amide, may vary considerably. It is only necessary that it be present in sufficient concentration to obtain chemiluminescence. The initial molar concentration is in the range of 10-3 to 5, preferably about 10-2 to 1Ø
The molar concentration of the fluorescer compound used is about 10-5 to 1, preferably about 10-3 to 10-1.
The initial molar concentration of the hydrogen peroxide compound used is from about 10-3 to 10.~, preferably about 10-1 to 4Ø The mole ratio of hydrogen peroxide to reactant used ranges from about 0.5 to 100, preferably about 20 to 60.
The amount of water-soluble polymer employed should range from about 10-2 to about 50 percent by weight, based on the total weight of the solution.
When dry admixtures are prepared, the amounts of the ingredients should vary such that they fall within the above ranges when added to water.
The ingredients of the chemiluminescent composi-tions of this invention are kept separated until chemiluminescence is desired, when they may be admixed in a single step or in a series of steps. The order of admixing of the ingredients is usually not critical. The hydrogen peroxide compound, polymer and fluorescer compound may be dissolved in water and the reactant, added thereto as a solid, or in a suitable inert diluent, to initiate chemiluminescence. Alternatively, the reactant, polymer and fluorescer compound may be dissolved in water, and the hydrogen peroxide compound added thereto to initiate chemiluminescence. Optionally, a solution of the hydrogen peroxide compound in water may be added to a solid mixture of reactant, polymer and fluorescer compound to initiate chemiluminescence.
6~
An illustrative example of a suitable dry mixture contains the following: 13.23%, by weight, of 4,4'-(ox-alylbis [(trifluoromethylsulfonyl)imino3ethylene~bis(4-methyl- morpholinium trifluoromethanesulfonate), 2.12%, by weight of sulfonated rubrene, 1.0% by weight of poly(vi-nyl pyrolidone) and 83.65% by weight of sodium perborate.
If the fluorescer compound is water-insoluble, such as rubrene, it may be dissolved in a suitable inert water-immiscible organic solvent, such as cyclohexane, and the solution added to an aqueous mixture of a hydro-gen peroxide source, an effective amount of a polymer and a water-soluble reactant to produce a chemiluminescent emulsion.
The hydrogen peroxide source employed in the compositions and processes of this invention may be an aqueous solution of hydrogen peroxide per se, or a solid hydrogen peroxide-producing compound, such as sodium perborate, potassium perborate, sodium carbonate peroxhydrate, histidine perhydrate, and the like. When a solid hydro-gen peroxide-producing compound is used, it is preferred that an acid having a pKa of from about 1-5 also be added to assist in the hydrogen peroxide generation in amounts equivalent to the amount of solid hydrogen peroxide-producing compound used. Preferred acids are the solid polycarboxylic acids such as oxalic acid, tartaric acid, citric acid, malonic acid, tricarballylic acid, adipic acid, citraconic acid, fumanic acid, glutaric acid, maleic acid, malic acid, malonic acid, succinic acid, phthalic acid and the like.
The following examples are set forth for purposes of illustration only and are not to be construed as limita-tions on the present invention except as set forth in the appended claims. All parts and percentages are by weight unless otherwise specified.
1~9~63~ 61109-7~22 Example 1 An aqueous solution containing 0.01 mole/liter of 4,4'-[oxalylbis~(trifluoromethylsulfonyl)imino]ethylene~-bisl4-methylmorpholinium trifluoromethane-sulfonate], hereafter referred to as METQ, is mixed with 1~ of poly-(vinylpyrrolidone) and 0.005 mole/liter of the fluorescer rubrene sulfonate. Aqueous hydrogen peroxide is then added. The emission intensity is then measured at the wavelength of maximum emission by means of a spectroradio-meter-luminometer similar to that described by Roberts and Hirt [Appl. Spectrosc., 21, 250 (1967)] modified with a Jarrell-Ash*Model 82-410 grating monochromator and an ~CA C31034 photomultiplier with a gallium arsenide photo-cathode operated at 1300 V with dry ice cooling. Raw data are recorded digitally on a Hewlett-Packard 5150A
thermal printer. Spectral response is corrected by calibra-tion against a standard tungsten lamp. Absolute light intensities are obtained by deriving calibration constants based on the accepted fluorescence quantum yield (0.55) for quinine sulfate, as reported by Melhuish (N.Z. Sci.
Tech., B, 37, 142 ~1955)], in 0.1~ ~2SO4 , and by ferri-oxalate actinometry lHatchard et al., Proc. R. Soc. ~ondon, Ser. A, 235, 518 (1956)] of the exciting light.
The light capacity (the light output in lumen hours per liter of emitting solution) is related to the chemiluminescence brightness and lifetime as described in U.S. Patent No. 3,816,326.
Chemiluminescence percent quantum yields (einsteins per mole of reactant xlO0) are calculated by monitoring the intensity decay at the emission maximum and calculating the intensity at each time interval in einsteins per second from the chemiluminescence spectrum.
Chemiluminescence spectra are then corrected for intensity decay. The total area under the decay curve is calculated by using a combination of a Simpson's rule integration and an exponential extrapolation to infinite time as Trademark 1~,91638 described by Roberts and Hirt. Data are processed by a Digital Equipment Corp. PDP-11/40 computer.
A comparison determination is also carried out, in the manner described above, without the polymer. The results obtained are shown below in Table I.
TABLE
Relative Chemical Light Yield Product of Bxample 1 ~.13 Product of Example 1 0.05 without Polymer Example 2 The procedure of Example 1 is again followed except that trisodium-8-hydroxy-1,3,6-pyrenetrisulfonate is used in place of the METQ. Similar results are obtained.
Example 3 The replacement of the METQ of Example 1 by 2,2'-[oxalyl bis[[(trifluoromethylsulfonyl)imino]ethylene]]
bis[l-methyl-pyridinium trifluoromethanesulfonate] again results in an increase in the relative chemical light yield as compared to a similar composition without polymer.
Example 4 Following the procedure of Example 1, except that rubrene sulonate is replaced by rubrene, similar 2S results are achieved.
Example 5 The METQ of Example 1 is replaced by 4-methyl-4[2-[1-oxo-4-(1-pyrenyl) butoxy]ethyl] morpholinium methyl sulfate. Similar improved results are observed.
Example 6 Example 1 is again followed except that the METQ
is replaced by bis(2,4-dichloro-6- [(dimethylaminoethyl) methylsulfamoyl]phenyl)oxalate. Again, increased relative chemical light yield is realized.
1~,9~
Example 7 The bis(tetramethylammonium) salt of bis(2,3,6-trichloro-4-sulfophenyl) oxalate is used to replace METQ
in accordance with Example 1. Excellent results are achieved.
Example 8 The poly(vinylpyrrolidone) of Example 1 is replaced by a copolymer of vinylpyrrolidone and vinyl acetate (6~/90). Excellent results are achieved.
Example 9 A polyethyleneoxide-polypropyleneoxide copolymer is used to replace the polymer of Example 1. Results are equivalent.
Example 10 When the polymer of Example 1 is replaced by poly(styrene sulfonate), excellent results are obtained.
Example 11 Polyacrylamide is used to replace the polymer of Example 1 with equivalent results.
Example 12 A solid mixture is prepared by blending the METQ, poly(vinylpyrridone) and rubrene sulfonate of Example 1 together with solid sodium perborate and an equivalent amount of oxalic acid. Addition of the solid mixture to water substantially immediately produces a strong colored light.
THE USE OF WATER-SOLUBLE POLYMERS I~
AQUEOUS CHEMICAL LIGHT FORMULATIONS
BACKGROUND OF THE INVENTION
The invention described herein was made in the performance of work supported by the Office of Naval Research (Contract No. N-0014-82-C-0202).
The generation of chemiluminescence by the re-action of an ester or amide of an oxalic acid with a source of hydrogen peroxide in the presence of a fluorescer compound in aqueous solution is disclosed and claimed in U.S. Patent Nos. 4,053,430 and 4,282,357. Recently, U.S.
Patent No. 4,462,931 has issued which discloses an improvement over the previous systems whereby a surfactant is added in mi~or amounts to the aqueous solution, or to solid mixtures which are then mixed with water, in order to enhance the emission intensity of the resultant system. While the use of a surfactant in such systems has enhanced the emission intensity thereof, industry is still continuously on the lookout for ways and means of further enhancing the emission intensities, light capaci-ties and efficiencies of chemiluminescent systems.
SUMMARY OF THE INVENTION
It has now been found, in accordance with the present invention, that the emission intensities of chemiluminescent systems based on oxalic acid esters or amides, fluorescers and a source of hydrogen peroxide can be materially enhanced by the incorporation of minor amounts of a water-soluble polymer into an aqueous solution 1~9~
containing these ingredients or solid mixtures thereof which may be added to water to generate chemiluminescense.
The water-soluble polymers are more effective in this regard than the surfactants described in U.S. 4,462,931 alone in that the quantum yield of light emitted is 15-35% higher when the polymers are employed vis-a-vis the surfactants.
The employment of polymeric additives in organic solvent based chemiluminescent systems is disclosed in U.S. Patent Nos. 3,377,291; 3,816,325 and 3,994,820. The compositions produced in U.S. 3,377,291 are, however, gels which may be used to spread on porous cloth etc.
wherein the polymer functions as a thickening agent. In U.S. 3,816,3250polymeric materials are employed so as to render the final composition immune to adverse environ-mental conditions such as water. Additionally, the materials can be formulated into a dry system which will not be absorbed into porous surfaces or can be molded into specific shapes. There is no evidence, however, that the presence of the polymeric additive enhances the ultimate emission intensities of either of the systems.
In U.S. 3,994,820, the light capacity of organic ox~late ester chemiluminescent systems is increased by the addi-tion of certain polymeric materials to the system. These polymers include homopolymers and copolymers of a) poly-~alkylene oxides), b) poly(vinylalkylethers and esters), and c) maleic anhydride and cellulose esters whereas the polymers useful in the present invention exhibit high binding capacity, in aqueous solution, especially for substrates that possess negative charges, and function, in the present invention, in that manner. The function of the polymers in the organic systems is unknown.
DESCRIPTION OF THE INVENTION
INCLUDING PREFERRED EMBODIMENTS
In accordance with the present invention, there is provided a composition for generating chemiluminescent ~9~638 emission comprising an aqueous solution of (a) a water-soluble reactant, (b) a water-soluble organic fluorescer having a spectral emission in the range from about 330 to 1000 nanometers, and (c) a water-soluble polymer, in proportions capable of producing enhanced chemiluminescence on reaction with hydrogen peroxide.
More particularly, the invention provides a composition for generating chemiluminescence comprising, in aqueous solution, a) 10 to 5 molar concentration of a water-soluble reactant which generates light by reaction with hydrogen peroxide, b) 10 5 to 1 molar concentration of a water-soluble or water-dispersible organic fluorescer having spectral emission in the range about 300 to 1000 nanometers and c) from about 10 2 to about 50%, by weight, based on the total weight of the solution, of a water-soluble polymer which render the biomolecular chemiluminescent reaction monomolecular selected from alkylene oxide polymerization products, vinyl acetate polymers, vinyl pyrrolidone polymers, vinyl pyridene polymers, styrene sulfonate polymers, acrylamide polymers, or copolymers of the above.
The present in~ention further provides a dry composi-tion for generating chemiluminescence comprising a dry mixture of (a) water-soluble reactant, (b) a solid hydrogen peroxide source e.g. sodium perborate, potassium perborate, sodium carbonate peroxyhydrate, histidine perhydrate, etc., (c) a solid water-soluble fluorescer having a spectral emission in the range from about 330 to 1000 nanometers, and (d) a water-soluble polymer, ~,~
1'~91638 - 3a - 61109-7422 in proportions capable of producing enhanced chemiluminescence when added to water.
More particularly, the invention provides a dry mixture of components for making a chemiluminescent reaction by addition of the dry mixture to water, said dry mixture comprising amounts sufficient to obtain, in solution, of a) a water-soluble reactant which generates light by reaction with hydrogen peroxide, in an initial molar concentration of about 10 3 to 5, b) a water-soluble or water-dispersible organic fluorescer having spectral emission in the range of from about 300 to about 1000 nanometers, in a molar concentration of about 10 5 to 1, c) a water-soluble polymer which render the biomolecular chemiluminescent reaction monomolecular selected from alkylene oxide polymerization products, vinyl acetate poly-mers, vinyl pyrrolidone polymers, vinyl pyridene polymers, styrene sulfonate polymers, acrylamide polymers, or copoly-mers of the above, from about 10 ~ to 50~ by weight based on total solution weight, and d) a solid hydrogen peroxide source in an initial molar con-centration of about 10 3 to 10.
In the above compositions the reactant is preferably a water-soluble ester, or amide, of oxalic acid.
The present invention also provides processes for generating chemiluminescence by adding effective amounts of the ~91638 - 3b - 61109-7422 aforedescribed by dry compositions to water or adding to the aqueous solutions an aqueous solution of hydrogen peroxide, or source of hydrogen peroxide.
The aqueous chemiluminescent systems of the present invention provide enhanced emission of light which is useful in a wide variety of applications, particular]y for providing emergency light at home, on highways r and at sea.
The chemiluminescent reaction mixture contains a water-soluble reactant which generates light by reacting with hydrogen peroxide, or a source of hydrogen peroxide, in the presence of a fluorescer compound and a water-soluble polymer.
Suitable water-soluble esters of oxalic acid which may be used in the present invention as reactants are disclosed by Mohan in United States Patent No. 4,053,430, discussed above.
Illustrative examples of suitable water-soluble 1~9~i3~
esters of oxalic acid include the dihydrochlorides, dihy-drobromides, dihydrofluorides, di(trifluoromethane) sul-fonates, dimethanesulfonates, di-p-toluenesulfonates, di-methosulfates and diquaternary ammonium salts of the following compounds:
bis(2,6-dichloro-4-[~2-dimethylaminoethyl)methylsulfamoyl]-- phenyl)oxalate.
bis(2,4-dichloro-6-[(2-dimethylaminoethyl)methylsulfamoyl]-phenyl)oxalate.
bis(2-chloro-4-[(2-dimethylaminoethyl)methylsulfamoyl]phen-yl)oxalate.
bis(2-bromo-4-[(2-dimethylaminoethyl)methylsulfamoyl]phen-yl)oxalate.
bis(2,6-dibromo-4-[(2-dimethylaminoethyl)methylsulfamoyl]-phenyl)oxalate.
bis(3-fluoro-4-[(2-dimethylaminoethyl)methylsulfamoyl]-phenyl)oxalate.
bis(2,4-dibromo-6-[(2-dimethylaminoethyl)methylsulfamoyl]-phenyl)oxalate.
bis(2-fluoro-4-[(2-dimethylaminoethyl)methylsulfamoyl]phen-yl)oxalate, and the like.
The preferred water-soluble ester of oxalic acid is the dihydrochloride of bis(2,4-dich1Oro-6-[(2-dimethyl-aminoethyl)methylsulfamoyl]phenyl)oxalate.
Suitable water-soluble amides of oxalic acid which may be used in the processes and compositions of this invention are disclosed in U.S. Pat. No. 4,282,357 and in U.S. Pat. No. 4,338,213.
Illustrative examples of suitable water-soluble amides of oxalic acid include the dihydrochlorides, di-hydrobromides, dihydrofluorides, di(trifluoromethane) sulfonates, dimethanesulfonates, dimethosulfates, and ditetrafluoroborates of the following compounds:
N,N'-bis(2-morpholinoethyl)-N,N'-bis-(trifluoromethylsul-fonyl)oxamide, N,N'-bis(3-morpholinopropyl)-N,N'-bis(trifluoromethylsul-- fonyl)oxamide, 12916~8 N,N'-bis[2-(2-pyridyl)ethyl]-N,N'-bis(trifluoromethyl-sulfonyl)oxamide, N,N'-bis[3-(2-pyridyl)propyl]-N,N'-bis(trifluoromethyl-sulfonyl)oxamide, N,N'-bis(6-morpholinohexyl)-N,N'-bis(trifluoromethylsul-fonyl)oxamide, N,N'-bis[2-(4-pyridyl)ethyl]-N,N'-bis(trifluoromethyl-sulfonyl)oxamide, N,N'-bis[5-(3-pyridyl)pentyl]-N,N'-bis(trifluoromethyl-sulfonyl)oxamide,and the like.
The preferred water-soluble oxamide is 4,4'-(oxalyl-bis[[(trifluoromethyl)sulfonyl]imino]ethylene)-bis(4-methylmorpholinium trifluoromethanesulfonate).
The water-soluble fluorescer compounds, useful in the chemiluminescent compositions of this invention, may be defined broadly as compounds, having an emission spectral maximum between 330 and 1000 nanometers, which do not react with a hydrogen peroxide compound, or the amide, or ester, of oxalic acid, on contact. The water-soluble fluorescer may be anionic, cationic, or nonionic.
Illustrative examples of suitable fluorescers including the following:
Sulfonated 5,6,11,12-tetraphenylnaphthacene sodium salts, 4-methyl-4-[2-[1-oxo-4-tl-pyrenyl)butoxy]ethyl~morpholinium methyl sulfate, 4,4'-[9, 10-anthracenediylbis~l, 2-ethanediyl)]bisbenzene-sulfonic acid disodium salt, 4,4'-~9,10-anthracenediylbisll,2-ethanediyl)]bisbenzenemeth-anol bis (monosodium sulfate).
4,4'-[9, 10-anthracenediylbis(l, 2-ethynediyl)]bisbenzene-carboxylic acid dilithium salt, 4,4'-[6, 12-diphenyl-5, 11-tetracenediylbis(4, l-phenyl-enemethylene~bis (4-methylmorpholinium methyl sulfate), 4,4'-[6, 12-diphenyl-5, 11-tetracenediylbis(4, l-phenyl enemethylene)]bis (4-trifluoromethylmorpholinium trifluor-omethyl sulfate), 2, 8-bis[(3, 6, 9-trioxadecyl)oxy]~5, 1l-bis[[3~ 6, 9-trioxadecyl)oxyl)phenyl]-6, 12-diphenylnaphthacene, and the like; see also U.S. Patent No. 4,366,079.
The preferred water-soluble fluorescer, referred to herein as sulfonated rubrene, is a mixture of sodium salts of sulfonated 5,6, 11, 12-tetraphenylnaphthacene.
Illustrative examples of suitable fluorescers which are not water-soluble include the following com-pounds:
5, 6, 11, 12-tetraphenylnaphthacene, 9, 10-bis(phenylethynyl)anthracene, 5, 12-bis(phenylethynyl)tetracene, 9, 10-diphenylanthracene, perylene, pyrene, l-chloro-9, 10-bis(phenylethynyl)anthracene, 2-chloro-9, 10-bis(phenylethynyl)anthracene, 1, 5-dichloro-9, 10-bis(phenylethynyl)anthracene, 1, 8-dichloro-9, 10-bis(phenylethynyl)anthracene, l-bromo-9, 10-bis(phenylethynyl)anthracene, l-fluoro-9, 10-bis(phenylethynyl)anthracene, 2-methyl-9, 10-bis(phenylethynyl)anthracene, fluorescein, rhodamine, 2, 3-benæanthracene, 5, 11-bis(4-(n-hexyl)phenyl)-6, 12-diphenylnaphthacene, 5, 11-bis[4-(n-dodecyl)phenyl]-6, 12-diphenylnaphthacene, 5, 11-bis[~-(2, 5, 8, 11, 14, 17-hexaoctadec-1-yl)phenyl]-6, 12-diphenylnaphthacene, and the like.
Any water-soluble polymer may be employed to produce the novel compositions of the present invention.
Examples of suitable polymers falling within the scope of the present invention include the polymerization products ~ f alkylene oxides such as ethylene oxide, propylene oxide, hexylene oxide and mixtures thereof; polymers of vinyl acetate; polymers of vinyl pyrolidone alone or as copolymers with comonomers such as vinyl acetate, etc.;
,_ polyvinyl pyridenes, polystyrene sulfonates, polyacrylo-mides copolymers thereof~ and the like.
The molar concentrations (moles per liter of solution) of the reactant e.g. the oxalic acid ester, or S amide, may vary considerably. It is only necessary that it be present in sufficient concentration to obtain chemiluminescence. The initial molar concentration is in the range of 10-3 to 5, preferably about 10-2 to 1Ø
The molar concentration of the fluorescer compound used is about 10-5 to 1, preferably about 10-3 to 10-1.
The initial molar concentration of the hydrogen peroxide compound used is from about 10-3 to 10.~, preferably about 10-1 to 4Ø The mole ratio of hydrogen peroxide to reactant used ranges from about 0.5 to 100, preferably about 20 to 60.
The amount of water-soluble polymer employed should range from about 10-2 to about 50 percent by weight, based on the total weight of the solution.
When dry admixtures are prepared, the amounts of the ingredients should vary such that they fall within the above ranges when added to water.
The ingredients of the chemiluminescent composi-tions of this invention are kept separated until chemiluminescence is desired, when they may be admixed in a single step or in a series of steps. The order of admixing of the ingredients is usually not critical. The hydrogen peroxide compound, polymer and fluorescer compound may be dissolved in water and the reactant, added thereto as a solid, or in a suitable inert diluent, to initiate chemiluminescence. Alternatively, the reactant, polymer and fluorescer compound may be dissolved in water, and the hydrogen peroxide compound added thereto to initiate chemiluminescence. Optionally, a solution of the hydrogen peroxide compound in water may be added to a solid mixture of reactant, polymer and fluorescer compound to initiate chemiluminescence.
6~
An illustrative example of a suitable dry mixture contains the following: 13.23%, by weight, of 4,4'-(ox-alylbis [(trifluoromethylsulfonyl)imino3ethylene~bis(4-methyl- morpholinium trifluoromethanesulfonate), 2.12%, by weight of sulfonated rubrene, 1.0% by weight of poly(vi-nyl pyrolidone) and 83.65% by weight of sodium perborate.
If the fluorescer compound is water-insoluble, such as rubrene, it may be dissolved in a suitable inert water-immiscible organic solvent, such as cyclohexane, and the solution added to an aqueous mixture of a hydro-gen peroxide source, an effective amount of a polymer and a water-soluble reactant to produce a chemiluminescent emulsion.
The hydrogen peroxide source employed in the compositions and processes of this invention may be an aqueous solution of hydrogen peroxide per se, or a solid hydrogen peroxide-producing compound, such as sodium perborate, potassium perborate, sodium carbonate peroxhydrate, histidine perhydrate, and the like. When a solid hydro-gen peroxide-producing compound is used, it is preferred that an acid having a pKa of from about 1-5 also be added to assist in the hydrogen peroxide generation in amounts equivalent to the amount of solid hydrogen peroxide-producing compound used. Preferred acids are the solid polycarboxylic acids such as oxalic acid, tartaric acid, citric acid, malonic acid, tricarballylic acid, adipic acid, citraconic acid, fumanic acid, glutaric acid, maleic acid, malic acid, malonic acid, succinic acid, phthalic acid and the like.
The following examples are set forth for purposes of illustration only and are not to be construed as limita-tions on the present invention except as set forth in the appended claims. All parts and percentages are by weight unless otherwise specified.
1~9~63~ 61109-7~22 Example 1 An aqueous solution containing 0.01 mole/liter of 4,4'-[oxalylbis~(trifluoromethylsulfonyl)imino]ethylene~-bisl4-methylmorpholinium trifluoromethane-sulfonate], hereafter referred to as METQ, is mixed with 1~ of poly-(vinylpyrrolidone) and 0.005 mole/liter of the fluorescer rubrene sulfonate. Aqueous hydrogen peroxide is then added. The emission intensity is then measured at the wavelength of maximum emission by means of a spectroradio-meter-luminometer similar to that described by Roberts and Hirt [Appl. Spectrosc., 21, 250 (1967)] modified with a Jarrell-Ash*Model 82-410 grating monochromator and an ~CA C31034 photomultiplier with a gallium arsenide photo-cathode operated at 1300 V with dry ice cooling. Raw data are recorded digitally on a Hewlett-Packard 5150A
thermal printer. Spectral response is corrected by calibra-tion against a standard tungsten lamp. Absolute light intensities are obtained by deriving calibration constants based on the accepted fluorescence quantum yield (0.55) for quinine sulfate, as reported by Melhuish (N.Z. Sci.
Tech., B, 37, 142 ~1955)], in 0.1~ ~2SO4 , and by ferri-oxalate actinometry lHatchard et al., Proc. R. Soc. ~ondon, Ser. A, 235, 518 (1956)] of the exciting light.
The light capacity (the light output in lumen hours per liter of emitting solution) is related to the chemiluminescence brightness and lifetime as described in U.S. Patent No. 3,816,326.
Chemiluminescence percent quantum yields (einsteins per mole of reactant xlO0) are calculated by monitoring the intensity decay at the emission maximum and calculating the intensity at each time interval in einsteins per second from the chemiluminescence spectrum.
Chemiluminescence spectra are then corrected for intensity decay. The total area under the decay curve is calculated by using a combination of a Simpson's rule integration and an exponential extrapolation to infinite time as Trademark 1~,91638 described by Roberts and Hirt. Data are processed by a Digital Equipment Corp. PDP-11/40 computer.
A comparison determination is also carried out, in the manner described above, without the polymer. The results obtained are shown below in Table I.
TABLE
Relative Chemical Light Yield Product of Bxample 1 ~.13 Product of Example 1 0.05 without Polymer Example 2 The procedure of Example 1 is again followed except that trisodium-8-hydroxy-1,3,6-pyrenetrisulfonate is used in place of the METQ. Similar results are obtained.
Example 3 The replacement of the METQ of Example 1 by 2,2'-[oxalyl bis[[(trifluoromethylsulfonyl)imino]ethylene]]
bis[l-methyl-pyridinium trifluoromethanesulfonate] again results in an increase in the relative chemical light yield as compared to a similar composition without polymer.
Example 4 Following the procedure of Example 1, except that rubrene sulonate is replaced by rubrene, similar 2S results are achieved.
Example 5 The METQ of Example 1 is replaced by 4-methyl-4[2-[1-oxo-4-(1-pyrenyl) butoxy]ethyl] morpholinium methyl sulfate. Similar improved results are observed.
Example 6 Example 1 is again followed except that the METQ
is replaced by bis(2,4-dichloro-6- [(dimethylaminoethyl) methylsulfamoyl]phenyl)oxalate. Again, increased relative chemical light yield is realized.
1~,9~
Example 7 The bis(tetramethylammonium) salt of bis(2,3,6-trichloro-4-sulfophenyl) oxalate is used to replace METQ
in accordance with Example 1. Excellent results are achieved.
Example 8 The poly(vinylpyrrolidone) of Example 1 is replaced by a copolymer of vinylpyrrolidone and vinyl acetate (6~/90). Excellent results are achieved.
Example 9 A polyethyleneoxide-polypropyleneoxide copolymer is used to replace the polymer of Example 1. Results are equivalent.
Example 10 When the polymer of Example 1 is replaced by poly(styrene sulfonate), excellent results are obtained.
Example 11 Polyacrylamide is used to replace the polymer of Example 1 with equivalent results.
Example 12 A solid mixture is prepared by blending the METQ, poly(vinylpyrridone) and rubrene sulfonate of Example 1 together with solid sodium perborate and an equivalent amount of oxalic acid. Addition of the solid mixture to water substantially immediately produces a strong colored light.
Claims (12)
1. A composition for generating chemiluminescence com-prising, in aqueous solution, a) 10-3 to 5 molar concentration of a water-soluble reactant which generates light by reaction with hydrogen peroxide, b) 10-5 to 1 molar concentration of a water-soluble or water-dispersible organic fluorescer having spectral emission in the range about 300 to 1000 nanometers and c) from about 10 to about 50%, by weight, based on the total weight of the solution, of a water-soluble polymer which render the bimolecular chemiluminescent reaction monomole-cular selected from alkylene oxide polymerization products, vinyl acetate polymers, vinyl pyrrolidone polymers, vinyl pyridene polymers, styrene sulfonate polymers, acrylamide polymers, or copolymers of the above.
2. A composition according to Claim 1 wherein the react-ant is 4,4'-[oxalylbis[(trifluoromethylsulfonyl)imino]ethylene]bis [4-methylmorpholinium trifluoromethane sulfonate].
3. A composition according to Claim 1 wherein the fluo-rescer is sulfonated rubrene.
4. A dry mixture of components for making a chemi-luminescent reaction by addition of the dry mixture to water, said dry mixture comprising amounts sufficient to obtain, in solution, of a) a water-soluble reactant which generates light by reaction with hydrogen peroxide, in an initial molar concentration of about 10-3 to 5.
b) a water-soluble or water-dispersible organic fluorescer having spectral emission in the range of from about 300 to about 1000 nanometers, in a molar concentration of about 10-5 to 1, c) a water-soluble polymer which render the biomolecular chemi-luminescent reaction monomolecular selected from alkylene oxide polymerization products, vinyl acetate polymers, vinyl pyrrolidone polymers, vinyl pyridene polymers, styrene sul-fonate polymers, acrylamide polymers, or copolymers of the above, from about 10-2 to 50% by weight based on total solution weight, and d) a solid hydrogen peroxide source in an initial molar concen-tration of about 10-3 to 10.
b) a water-soluble or water-dispersible organic fluorescer having spectral emission in the range of from about 300 to about 1000 nanometers, in a molar concentration of about 10-5 to 1, c) a water-soluble polymer which render the biomolecular chemi-luminescent reaction monomolecular selected from alkylene oxide polymerization products, vinyl acetate polymers, vinyl pyrrolidone polymers, vinyl pyridene polymers, styrene sul-fonate polymers, acrylamide polymers, or copolymers of the above, from about 10-2 to 50% by weight based on total solution weight, and d) a solid hydrogen peroxide source in an initial molar concen-tration of about 10-3 to 10.
5. A mixture according to Claim 4 wherein the reactant is 4,4'-[oxalylbis[(trifluoromethylsulfonyl)imino]ethylene]bis-[4-methylmorpholinium trifluoromethanesulfonate].
6. A mixture according to Claim 4 wherein the fluorescer is sulfonated rubrene.
7. A composition according to Claim 1 wherein the polymer is poly(vinyl pyrrolidone).
8. A mixture according to Claim 4 wherein the polymer is poly(vinyl pyrrolidone).
9. A composition according to Claim 1 wherein the polymer is a copolymer of vinyl pyrrolidone and vinyl acetate.
10. A mixture according to Claim 4 wherein the polymer is a copolymer of vinyl pyrrolidone and vinyl acetate.
11. A method for producing chemiluminescence comprising dispersing the dry mixture of Claim 4 in water.
12. A method for producing chemiluminescence comprising combining the composition of Claim 1 with hydrogen peroxide or a source of hydrogen peroxide in aqueous solution.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/653,405 US4859369A (en) | 1984-09-24 | 1984-09-24 | Use of water-soluble polymers in aqueous chemical light formulations |
| US653,405 | 1984-09-24 |
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| CA (1) | CA1291638C (en) |
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| US5298197A (en) * | 1988-10-06 | 1994-03-29 | The United States Of America As Represented By The Secretary Of The Navy | Chemiluminescent microemulsions |
| BE1003403A7 (en) * | 1989-11-28 | 1992-03-17 | Continental Photo | SUBSTITUTED ANTIHRACENE-BASED CHEMILUMINESCENT SOLUTION. |
| US5173218A (en) * | 1990-12-24 | 1992-12-22 | American Cyanamid Company | Preparation of chemiluminescent vinyl halide or vinylidene halide polymer structures |
| US5279940A (en) * | 1992-08-03 | 1994-01-18 | Eastman Kodak Company | Chemiluminescent composition containing cationic surfactants or polymers and 4'-hydroxyacetanilide, test kits and their use in analytical methods |
| BE1009224A6 (en) * | 1995-03-31 | 1997-01-07 | Continental Photo | Improved solution chemiluminescent. |
| US5705103A (en) * | 1996-11-22 | 1998-01-06 | Jame Fine Chemicals, Inc. | Composition for producing chemiluminescent light of controllable duration |
| KR100480628B1 (en) * | 2002-11-11 | 2005-03-31 | 삼성전자주식회사 | Chip pick-up method and device for manufacturing semiconductor device using air blowing |
| US20060214141A1 (en) * | 2005-03-23 | 2006-09-28 | Yankielun Norbert E | Luminescent illumination adjunct for night vision |
| US20070134513A1 (en) * | 2005-12-13 | 2007-06-14 | Binney & Smith | Chemiluminescent system |
| US20080128666A1 (en) * | 2005-12-13 | 2008-06-05 | Crayola, Llc | Chemiluminescent system |
| CN102482573A (en) | 2009-06-24 | 2012-05-30 | 克禄美科技股份有限公司 | Blue/violet diphenylanthracene chemiluminescent fluorescers |
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| US3392123A (en) * | 1962-10-17 | 1968-07-09 | Du Pont | Chemiluminescent formulations |
| US3816325A (en) * | 1970-04-15 | 1974-06-11 | American Cyanamid Co | Chemical lighting system comprising a polymeric chemiluminescent composition and an activating liquid comprising hydrogen peroxide |
| US3718599A (en) * | 1970-06-29 | 1973-02-27 | American Cyanamid Co | Stabilization of oxalate ester solutions during storage |
| US3691085A (en) * | 1970-07-13 | 1972-09-12 | American Cyanamid Co | Method of controlling the lifetime of oxalate ester chemiluminescent reactions |
| US3994820A (en) * | 1972-06-19 | 1976-11-30 | American Cyanamid Company | Polymers in oxalate chemiluminescent systems |
| US4053430A (en) * | 1976-07-16 | 1977-10-11 | American Cyanamid Company | Aqueous chemiluminescent systems |
| IL59263A (en) * | 1980-01-29 | 1982-11-30 | Yeda Res & Dev | Chemiluminescent reaction systems |
| NL8201713A (en) * | 1982-04-26 | 1983-11-16 | Impexa International B V | Chemiluminescent systems with extended light emission period - in which one or both reactants are associated in micelles for gradual release on mixing the components |
| US4462931A (en) * | 1982-06-16 | 1984-07-31 | American Cyanamid Company | Enhanced aqueous chemiluminescent systems |
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