US4416992A
Expired / Lapsed
US
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Support matrices and immobilized enzyme systems
Assignee: Honeywell UOP LLC
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Filing: 1982-03-26
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Granted: 1983-11-22
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Expires: 2002-03-26
Abstract
Abstract Support matrices are prepared by titanating the surface hydroxyl groups of refractory inorganic oxides with a titanium tetrahalide, such as TiCl 4 , reacting each of the remaining halogens of the surface-titanated oxide with one of the amino groups of diamine, and thereafter reacting the remaining amino group with one of the functional groups of a dialdehyde or diisocyanate. Titanating is carried out by contacting a refractory inorganic oxide with titanium tetrahalide, preferably in the absence of a solvent for the titanium tetrahalide, removing excess and unreacted titanium tetrahalide and heating the titanated inorganic oxide at a temperature of from about 80° C. to about 200° C. in an inert atmosphere of nitrogen, argon or helium, or in a vacuum. Such support matrices may be used to bind enzymes, affording effective immobilized enzyme systems.
Inventors
- 👤 Blaise J. Arena
- 👤 Ronald P. Rohrbach
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-25 15:24
CPC Classifications
C; C12; C12N; C12N11/00; C12N11/14; C12N11/02; C12N11/08; C12N11/089; C12N11/091; C12N11/093
Claims Analysis
Total Claims: 36
Claim 1
Independent Claim
205 words
A method of preparing a support matrix comprising contacting a porous, refractory inorganic oxide selected from the group consisting of alumina, silica, titania, thoria, and combinations thereof, with titanium tetrahalide in the absence of a solvent for the titanium tetrahalide so as to produce a surface titanated inorganic oxide, removing excess and unreacted titanium tetrahalide, heating the titanated inorganic oxide at a temperature from about 80° to about 200° C. in an inert atmosphere of nitrogen, argon, helium, or in a vacuum, for a time sufficient to volatilize any remaining unreacted titanium tetrahalide, contacting the resulting material with a diamine, selected from the group of alkylene diamines containing from 2 to about 10 carbon atoms and phenylene diamine, or a polyamine of formula H 2 N(CH 2 CH 2 NH) x H, where x is an integer from 2 to about 2300, removing excess amine, treating the resulting material with an excess of a bifunctional reagent selected from the group consisting of phthalaldehyde, toluene diisocyanate, and X(CH 2 ) p X, where X is an aldehyde, CHO, or isocyanate, NCO, functional group and p is an integer from 2 to about 8, removing the excess and unreacted bifunctional reagent, and recovering the resulting support matrix.
Claim 2
Independent Claim
205 words
A method of preparing a support matrix comprising contacting a porous, refractory inorganic oxide selected from the group consisting of alumina, silica, titania, thoria, and combinations thereof, with titanium tetrahalide in the absence of a solvent for the titanium tetrahalide so as to produce a surface titanated inorganic oxide, removing excess and unreacted titanium tetrahalide, heating the titanated inorganic oxide at a temperature from about 80° to about 200° C. in an inert atmosphere of nitrogen, argon, helium, or in a vacuum, for a time sufficient to volatilize any remaining unreacted titanium tetrahalide, contacting the resulting material with a diamine, selected from the group of alkylene diamines containing from 2 to about 10 carbon atoms and phenylene diamine, or a polyamine of formula H 2 N(CH 2 CH 2 NH) x H, where x is an integer from 2 to about 2300, removing excess amine, treating the resulting material with an excess of a bifunctional reagent selected from the group consisting of phthalaldehyde, toluene diisocyanate, and X(CH 2 ) p X, where X is an aldehyde, CHO, or isocyanate, NCO, functional group and p is an integer from 2 to about 8, removing the excess and unreacted bifunctional reagent, and recovering the resulting support matrix.
Claim 3
Dependent Claim
10 words
The method of claim 1 where the oxide is alumina.
Claim 4
Dependent Claim
34 words
The method of claim 1 where the diamine is an alkylene diamine whose formula is H 2 N(CH 2 ) n NH 2 , where n is an integer from 2 to about 10.
Claim 5
Dependent Claim
19 words
The method of claim 3 where the diamine is selected from the group consisting of 1,4-diaminobutane, 1,5-diaminopentane, and 1,6-diaminohexane.
Claim 6
Dependent Claim
11 words
The method of claim 1 where the diamine is a phenylenediamine.
Claim 7
Dependent Claim
22 words
The method of claim 1 where the bifunctional reagent is selected from the group consisting of succindialdehyde, glutaraldehyde, adipaldehyde, phthalaldehyde, and phenylisocyanate.
Claim 8
Dependent Claim
22 words
The method of claim 1 where the halide of titanium tetrahalide is selected from the group consisting of fluorine, chlorine, and bromine.
Claim 9
Dependent Claim
13 words
The method of claim 7 where the halide of titanium tetrahalide is chlorine.
Claim 10
Independent Claim
214 words
The method of preparing an immobilized enzyme system comprising contacting a porous, refractory inorganic oxide selected from the group consisting of alumina, silica, titania, thoria, and combinations thereof, with titanium tetrahalide in the absence of a solvent for the titanium tetrahalide so as to produce a surface-titanated inorganic oxide, removing excess and unreacted titanium tetrahalide, heating the titanated inorganic oxide at a temperature from about 80° to about 200° C. in an inert atmosphere of nitrogen, argon, helium, or in a vacuum, for a time sufficient to volatilize any remaining unreacted titanium tetrahalide, contacting the resulting material with a diamine selected from the group of alkylene diamines containing from 2 to about 10 carbon atoms and phenylene diamine, or a polyamine of formula H 2 N(CH 2 CH 2 NH) x H, where x is an integer from 2 to about 2300, removing excess amine, treating the resulting material with an excess of a bifunctional reagent selected from the group consisting of phthalaldehyde, toluene diisocyanate, and X(CH 2 ) p X, where X is an aldehyde, CHO, or isocyanate, NCO, functional group and p is an integer from z to about 8, removing the excess and unreacted bifunctional reagent, contacting the resulting mass with an enzyme solution, and recovering the formed immobilized enzyme system.
Claim 11
Independent Claim
214 words
The method of preparing an immobilized enzyme system comprising contacting a porous, refractory inorganic oxide selected from the group consisting of alumina, silica, titania, thoria, and combinations thereof, with titanium tetrahalide in the absence of a solvent for the titanium tetrahalide so as to produce a surface-titanated inorganic oxide, removing excess and unreacted titanium tetrahalide, heating the titanated inorganic oxide at a temperature from about 80° to about 200° C. in an inert atmosphere of nitrogen, argon, helium, or in a vacuum, for a time sufficient to volatilize any remaining unreacted titanium tetrahalide, contacting the resulting material with a diamine selected from the group of alkylene diamines containing from 2 to about 10 carbon atoms and phenylene diamine, or a polyamine of formula H 2 N(CH 2 CH 2 NH) x H, where x is an integer from 2 to about 2300, removing excess amine, treating the resulting material with an excess of a bifunctional reagent selected from the group consisting of phthalaldehyde, toluene diisocyanate, and X(CH 2 ) p X, where X is an aldehyde, CHO, or isocyanate, NCO, functional group and p is an integer from z to about 8, removing the excess and unreacted bifunctional reagent, contacting the resulting mass with an enzyme solution, and recovering the formed immobilized enzyme system.
Claim 12
Dependent Claim
10 words
The method of claim 9 where the oxide is alumina.
Claim 13
Dependent Claim
34 words
The method of claim 9 where the diamine is an alkylene diamine whose formula is H 2 N(CH 2 ) n NH 2 , where n is an integer from 2 to about 10.
Claim 14
Dependent Claim
19 words
The method of claim 11 where the diamine is selected from the group consisting of 1,4-diaminobutane, 1,5-diaminopentane, and 1,6-diaminohexane.
Claim 15
Dependent Claim
11 words
The method of claim 9 where the diamine is a phenylenediamine.
Claim 16
Dependent Claim
22 words
The method of claim 9 where the bifunctional reagent is selected from the group consisting of succindialdehyde, glutaraldehyde, adipaldehyde, phthalaldehyde, and phenylisocyanate.
Claim 17
Dependent Claim
22 words
The method of claim 9 where the halide of titanium tetrahalide is selected from the group consisting of fluorine, chlorine, and bromine.
Claim 18
Dependent Claim
13 words
The method of claim 15 where the halide of titanium tetrahalide is chlorine.
Claim 19
Dependent Claim
44 words
The method of claim 9 where the enzyme is selected from the group consisting of glucose isomerase, glucoamylase, cholesteroloxidase, alcohol dehydrogenase, amino acid oxidase, arginase, asparaginase, catalase, chymotrypsin, cellulase, collagenase, deoxyribonuclease, ficin, histidase, glucose oxidase, lactase, peroxidase, lysozyme, amylase, papain, rennin, ribonuclease, and urease.
Claim 20
Dependent Claim
10 words
The support matrix prepared by the method of claim 1.
Claim 21
Dependent Claim
11 words
The support matrix of claim 18 where the oxide is alumina.
Claim 22
Dependent Claim
35 words
The support matrix of claim 18 where the diamine is an alkylene diamine whose formula is H 2 N(CH 2 ) n NH 2 , where n is an integer from 2 to about 10.
Claim 23
Dependent Claim
20 words
The support matrix of claim 20 where the diamine is selected from the group consisting of 1,4-diaminobutane, 1,5-diaminopentane, and 1,6-diaminohexane.
Claim 24
Dependent Claim
12 words
The support matrix of claim 18 where the diamine is a phenylenediamine.
Claim 25
Dependent Claim
23 words
The support matrix of claim 18 where the bifunctional reagent is selected from the group consisting of succindialdehyde, glutaraldehyde, adipaldehyde, phthalaldehyde, and phenylisocyanate.
Claim 26
Dependent Claim
23 words
The support matrix of claim 18 where the halide of titanium tetrahalide is selected from the group consisting of fluorine, chlorine, and bromine.
Claim 27
Dependent Claim
14 words
The support matrix of claim 24 where the halide of titanium tetrahalide is chlorine.
Claim 28
Dependent Claim
11 words
The immobilized enzyme system prepared by the method of claim 9.
Claim 29
Dependent Claim
12 words
The immobilized enzyme system of claim 26 where the oxide is alumina.
Claim 30
Dependent Claim
36 words
The immobilized enzyme system of claim 26 where the diamine is an alkylene diamine whose formula is H 2 N(CH 2 ) n NH 2 , where n is an integer from 2 to about 10.
Claim 31
Dependent Claim
21 words
The immobilized enzyme system of claim 28 where the diamine is selected from the group consisting of 1,4-diaminobutane, 1,5-diaminopentane, and 1,6-diaminohexane.
Claim 32
Dependent Claim
13 words
The immobilized enzyme system of claim 26 where the diamine is a phenylenediamine.
Claim 33
Dependent Claim
24 words
The immobilized enzyme system of claim 26 where the bifunctional reagent is selected from the group consisting of succindialdehyde, glutaraldehyde, adipaldehyde, phthalaldehyde, and phenylisocyanate.
Claim 34
Dependent Claim
24 words
The immobilized enzyme system of claim 26 where the halide of titanium tetrahalide is selected from the group consisting of fluorine, chlorine, and bromine.
Claim 35
Dependent Claim
15 words
The immobilized enzyme system of claim 32 where the halide of titanium tetrahalide is chlorine.
Claim 36
Dependent Claim
46 words
The immobilized enzyme system of claim 26 where the enzyme is selected from the group consisting of glucose isomerase, glucoamylase, cholesteroloxidase, alcohol dehydrogenase, amino acid oxidase, arginase, asparaginase, catalase, chymotrypsin, cellulase, collagenase, deoxyribonuclease, ficin, histidase, glucose oxidase, lactase, peroxidase, lysozyme, amylase, papain, rennin, ribonuclease, and urease.
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1986-11-21 | 1987-05-23 | 1987-11-22 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1990-11-21 | 1991-05-23 | 1991-11-22 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1994-11-21 | 1995-05-23 | 1995-11-22 | $7700.00 | Window Closed / Lapsed |