CN105749975A - Immobilized metal porphyrin enzyme catalyst and preparation method thereof - Google Patents
Immobilized metal porphyrin enzyme catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN105749975A CN105749975A CN201610121991.8A CN201610121991A CN105749975A CN 105749975 A CN105749975 A CN 105749975A CN 201610121991 A CN201610121991 A CN 201610121991A CN 105749975 A CN105749975 A CN 105749975A
- Authority
- CN
- China
- Prior art keywords
- enzyme
- preparation
- metalloporphyrin
- meso
- molecular sieve
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/003—Catalysts comprising hydrides, coordination complexes or organic compounds containing enzymes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
- B01J2531/025—Ligands with a porphyrin ring system or analogues thereof, e.g. phthalocyanines, corroles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/42—Tin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
- B01J2531/72—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention provides an immobilized metal porphyrin enzyme catalyst and a preparation method thereof. The catalyst can oxidatively catalyze hydroxymethyl furfural (HMF) to generate a furandicarboxylic acid (FDCA) on presence of a selective oxidant.
Description
Technical field
The invention belongs to biocatalysis technology field, relate to immobilization metal porphyrin enzyme Catalysts and its preparation method, the method further relating to utilize this oxydasis catalysis Hydroxymethylfurfural (HMF) to generate FDCA (FDCA).
Background technology
First, along with the progress of petrochemical technology, drive the development of the macromolecular material being raw material with petrochemical derivative, but this kind of macromolecular material is because having degraded, and then the environmental problem caused causes the attention of the public gradually, define global " White Revolution ".In order to alleviate the impact on environment of the dependence on fossil resource and macromolecular material, in recent years biomass resource be developed into the focus that various countries are competitively studied.FDCA (FDCA) is one of 12 biomass-based platform chemicals of USDOE's proposition, its structure and character similar to p-phthalic acid (PTA).Therefore can as the substitute of PTA.If so FDCA can become the substitute of the PTA of the accounting high market share, having huge application prospect and social meaning.Therefore developing low-cost FDCA becomes the key capturing new bio base polyester material application problem.Owing to FDCA can be obtained by Hydroxymethylfurfural (HMF) selective oxidation, and HMF oxidant direct oxidation easily produces a large amount of by-product and corrosivity is strong, it is difficult to become the green production process of FDCA, thus the efficient catalyst of developing green becomes particularly important.
Secondly, along with progress and the expanding economy of society, the quality of the life of people steps up, and the attention degree of food safety is also more and more higher.Hydroxymethylfurfural (HMF) is a kind of material formed after glucide degraded in food, energy inducing cell and gene mutation, has potential carcinogenecity, therefore as an index of food heat treatment or long time stored quality destructiveness.Generally, it is considered that Hydroxymethylfurfural (HMF) is the cytotoxin of a kind of weak carcinogenecity, in higher concentrations, eyes, respiratory tract, skin and mucosa can be injured.The research such as researcher Anese finds that Hydroxymethylfurfural (HMF) can suddenly change by modificator gene in mouse body, causes that mouse suffers from colon cancer and hepatocarcinoma.Hydroxymethylfurfural (HMF) toxicity is primarily due to it can form sulfonic acid oxygen methyl furfural (SMF with external in vivo respectively, and 5-chloromethyl furfural (5-Chloromethylfurfural Sulfoxymethylfurfural), 5-CMF), and these materials have stronger carcinogenecity and genotoxicity.So it is all a problem hiding, that have menace for the mankind that Hydroxymethylfurfural (HMF) exists in food.Therefore the Hydroxymethylfurfural (HMF) removed in food is very necessary, and selecting the catalyst of a kind of green high-efficient to remove Hydroxymethylfurfural (HMF) is a very worth problem that we explore and study.
In sum, efficient catalyst oxidation conversion of hydroxymethyl methyl furfural (HMF) of exploitation one is one and significantly explores.
In prior art; Hydroxymethylfurfural (HMF) can be converted into other materials by catalytic oxidation mechanism and remove; the representative product of Hydroxymethylfurfural (HMF) is 5-HMFA (HMFCA), DFF, 5-formoxyl furancarboxylic acid and FDCA (FDCA).
Chinese patent CN201210390203.7 report is a kind of with 5 hydroxymethyl furfural for raw material, use catalytic oxidation means synthesis 2, the method of 5-furandicarboxylic acid, utilize catalyst prepared by noble-metal-supported basic supports, with oxygen or air for oxidant, can efficiently high selective catalysis 5 hydroxymethyl furfural oxidative synthesis FDCA.
The concrete grammar that Chinese patent CN201510395096.0 sets forth is that oxygen, hydrogen peroxide or air are oxidant, be heated to 80-120 DEG C, 5 hydroxymethyl furfural is selectively oxidized under alkaline environment with molybdic acid quaternary ammonium salt and wolframic acid quaternary ammonium salt for catalyst.This invention utilizes ammonium salt and molybdic acid or wolframic acid structure regulating catalyst activity and selectivity of product.The oxidant environmental friendliness that oxidizing process adopts, green non-pollution, just can obtain the high yield of FDCA and high selectivity at low temperatures, the conversion ratio of 5 hydroxymethyl furfural has reached more than 90%.
The concrete operations content of Chinese patent CN201310572055.5 is: under the effect of nickel system metallic catalyst, and 5 hydroxymethyl furfural (HMF) is carried out hydrogenolysis in a solvent, obtains 2,5-dimethyl furans (DMF).Described nickel system metallic catalyst is load type bimetal catalyst, and its effective active composition includes nickel and tungsten.The method that this invention provides is to adopt to carry out hydrogenolysis with the nickel system metallic catalyst catalysis HMF that nickel and tungsten are effective ingredient, obtains DMF, and nickel composition has good hydrogenation capability, it is possible to make aldehyde groups hydrogenation become methylol groups；It is acid that tungsten composition has good Louis (Lewis), it is possible to promotes the fracture of carbon-oxygen bond in HMF hydrogenolysis process, makes methylol groups change into methyl group；Under the dual function of nickel and tungsten, it is possible to HMF is efficient, height is optionally converted into DMF, and the productivity making DMF is higher.
But, the exploration of new catalyst for improving catalytic efficiency, strengthen catalyst stability, reduce catalyst cost and then to realize reacting still meaning on a large scale huge.
Summary of the invention
The technical problem to be solved is in that to improve the catalytic efficiency of catalyst in 5 hydroxymethyl furfural (HMF) catalytic oxidation, and improves catalyst stability, reduces catalyst cost.
In order to solve the technical problem of the present invention, technical scheme provided by the invention is:
A kind of preparation method of immobilization metal porphyrin enzyme catalyst, including, the meso-porous molecular sieve material through finishing is obtained with Ionic Liquid Modified meso-porous molecular sieve material, carry out complexation reaction in organic solvent with the porphyrin compound containing different substituents and slaine and generate metal porphyrins, by physical absorption, metal porphyrins is immobilized onto the meso-porous molecular sieve material surface through finishing, forms specific immobilization metal porphyrin enzyme.
In preparation method of the present invention, described ionic liquid is the glyoxaline ion liquid with functional group, and ionic liquid with anionic functional groups be-OH ,-NH2Basic group.
In preparation method of the present invention, ionic liquid with cationic functional groups be the one in amino, sulfydryl, methyl, ethyl, isopropyl.
In preparation method of the present invention, meso-porous molecular sieve material is SiO2, activated carbon, one in Graphene.
In preparation method of the present invention, the substituent group in the described porphyrins with substituted radical is the one in pyridine radicals, hydroxyl, carboxyl, aldehyde radical, carbonyl, phenyl.
In preparation method of the present invention, the metal in slaine is the one in cobalt, manganese, copper, zinc, ferrum, stannum.
In preparation method of the present invention, also include the step by obtaining the embedding of immobilized metalloporphyrin enzyme.
A kind of method preparing immobilization metal porphyrin enzyme catalyst, also includes concretely comprising the following steps of its making:
(1) porphyrins containing different substituents is carried out complexation reaction with slaine in organic solvent, it is thus achieved that there is the metal porphyrins of different metal center and substituent group；
(2) in toluene solution, under 110 DEG C of conditions, 24h is reacted with the glyoxaline ion liquid with functional group with meso-porous molecular sieve material；It is filtrated to get carrier, and with dichloromethane surname extraction 20h, it is thus achieved that through the meso-porous molecular sieve material of finishing；
(3) meso-porous molecular sieve material through finishing that metalloporphyrin step (1) obtained obtains with step (2) mixes in 0.0125MTris-HCl buffer solution and contacts, and stabilizes the PH of reaction system under the effect of buffer solution.Afterwards by stirring under the mixed solution temperature at 30 DEG C and 150rpm rotating speed until sample reaches physical absorption balance, filter and obtain immobilized metalloporphyrin enzyme.
(4) the immobilized metalloporphyrin enzyme that step (3) obtains is immersed in CaCl2In solution and stir 1h, mixed liquor is injected into 2%w/v sodium alginate soln carries out aging, it is thus achieved that the metalloporphyrin enzyme of calcium alginate gel embedding.
Immobilization metal porphyrin enzyme is prepared according to said method.
The present invention provides a kind of method of catalytic oxidation Hydroxymethylfurfural (HMF), wherein, is dissolved by Hydroxymethylfurfural (HMF), and at O2、NaIO4、H2O2, in TBHP under arbitrary oxidant existent condition, contact with prepared immobilization metal porphyrin enzyme, catalytic oxidation generates FDCA (FDCA).
The beneficial effects of the present invention is:
(1) have selected porphyrins in the present invention, it is natural biological oxidase, has that mild condition, specificity be strong, the characteristic of green non-pollution.
(2) present invention proposes and builds with enzyme active center structure is similar, have the chemistry bionical immobilization metal porphyrin catalyst with biocatalyzer advantage concurrently, it is achieved HMF green high-efficient catalytic oxidation.
(3) present invention is with mesoporous material for structural framework, utilize ionic liquid designability that material surface is carried out functional modification, the ionic liquid cation of albuminoid functionalization group is introduced in the slewing of mesoporous material surface, there is provided bionical microenvironment for metalloporphyrin, improve the ability of analogue enztme anakmetomeres oxygen.
(4) in the present invention, in conjunction with in HMF oxidation technology, under alkaline environment, aldehyde radical can be rapidly converted into the feature that polyhydroxy intermediate is conducive to FDCA to generate, and by the Acidity of Aikalinity in ionic liquid anion modulation reaction environment, has promoted the rapid conversion of substrate.
(5) metal material that the catalyst of the present invention adopts is the one in cobalt, manganese, copper, zinc, ferrum, stannum, and price, relative to prior art, cheap is easy to get.
Detailed description of the invention
Embodiment 1 this example demonstrates that the catalyst method of synthesis metalloporphyrin enzyme
By the porphyrin compound of pyridine radicals at CoCl2With FeCl in solution2Complexation reaction forms metalloporphyrin enzyme；
With being hydroxyl with anionic functional groups and ionic liquid that cationic functional groups is amino reacts 24h with mesoporous activated carbon molecular screen material in toluene solution under 110 DEG C of conditions；It is filtrated to get carrier.It is filtrated to get carrier again with dichloromethane surname extraction 20h, afterwards metalloporphyrin enzymatic solution is put into (50mL in 0.0125MTris-HCl buffer solution, PH7.0), and introduce the mesoporous activated carbon molecular screen material after finishing, by stirring under the mixed solution temperature at 30 DEG C and 150rpm rotating speed until sample reaches adsorption equilibrium.
Embodiment 2 this example demonstrates that embedding
Immobilization metal porphyrin enzyme solution is immersed in CaCl2In solution and stir 1h, being injected into by mixed liquor and carry out aging in 2%w/v sodium alginate soln, finally this enzyme is wrapped up by calcium alginate gel, it is thus achieved that the immobilization metal porphyrin enzyme of calcium alginate gel embedding, drying for standby afterwards.
Embodiment 3 this example demonstrates that the catalyst utilizing immobilization metal porphyrin enzyme oxidation Hydroxymethylfurfural (HMF) is furandicarboxylic acid (FDCA) method
Take in the round-bottomed flask of acetonitrile solution addition 10mL of 1.0g Hydroxymethylfurfural and 5mL, and agitating solution to solution clarify, add the TBHP oxidant of 50mg immobilization metal porphyrin enzyme catalyst and 70% afterwards, and the 60h that reacts at 110 DEG C, afterwards oxidant, catalyst are reclaimed in order to can use in the future.Finally by VarianProstar efficient liquid phase chromatographic analysis reaction conversion ratio and product purity.
Embodiment 4 this example demonstrates that the catalyst method of synthesis immobilization metal porphyrin enzyme
By the porphyrin compound of hydroxyl at CoCl2With CuCl in solution2Complexation reaction forms metalloporphyrin enzyme.
With with the mesoporous SiO that cationic functional groups is sulfydryl and ionic liquid that anionic functional groups is amino and low cost2Molecular screen material reacts 24h in toluene solution under 110 DEG C of conditions, it is filtrated to get carrier, it is filtrated to get carrier with dichloromethane surname extraction 20h, afterwards metalloporphyrin enzymatic solution is put into (50mL in 0.0125MTris-HCl buffer solution, PH7.0), and introduce the mesoporous activated carbon molecular screen material after finishing, by stirring under the mixed solution temperature at 30 DEG C and 150rpm rotating speed until sample reaches adsorption equilibrium.
Again immobilization metal porphyrin enzyme solution is immersed in CaCl2In solution and stir 1h, being injected into by mixed liquor and carry out aging in 2%w/v sodium alginate soln, finally this enzyme is wrapped up by calcium alginate gel, it is thus achieved that the immobilization metal porphyrin enzyme of calcium alginate gel embedding, drying for standby afterwards.
Embodiment 5 this example demonstrates that the catalyst method of synthesis immobilization metal porphyrin enzyme
By the porphyrin compound of carboxyl at MnCl2With CoCl in solution2Complexation reaction forms metalloporphyrin enzyme.
With with the mesoporous SiO that cationic functional groups is methyl and ionic liquid that anionic functional groups is hydroxyl and low cost2Molecular screen material reacts 24h in toluene solution under 110 DEG C of conditions, it is filtrated to get carrier, it is filtrated to get carrier with dichloromethane surname extraction 20h, afterwards metalloporphyrin enzymatic solution is put into (50mL in 0.0125MTris-HCl buffer solution, PH7.0), and introduce the mesoporous activated carbon molecular screen material after finishing, by stirring under the mixed solution temperature at 30 DEG C and 150rpm rotating speed until sample reaches adsorption equilibrium.
Immobilization metal porphyrin enzyme solution is immersed in CaCl2In solution and stir 1h, being injected into by mixed liquor and carry out aging in 2%w/v sodium alginate soln, finally this enzyme is wrapped up by calcium alginate gel, it is thus achieved that the immobilization metal porphyrin enzyme of calcium alginate gel embedding, drying for standby afterwards.
Embodiment 6 this example demonstrates that the catalyst method of synthesis immobilization metal porphyrin enzyme
By the porphyrin compound of aldehyde radical at MgCl2With MnCl in solution2Complexation reaction forms metalloporphyrin enzyme.
With being ethyl and ionic liquid that anionic functional groups is hydroxyl with cationic functional groups and the mesoporous graphene molecules sieve material of low cost reacts 24h in toluene solution under 110 DEG C of conditions, it is filtrated to get carrier, it is filtrated to get carrier with dichloromethane surname extraction 20h, afterwards metalloporphyrin enzymatic solution is put into (50mL in 0.0125MTris-HCl buffer solution, PH7.0), and introduce the mesoporous activated carbon molecular screen material after finishing, by stirring under the mixed solution temperature at 30 DEG C and 150rpm rotating speed until sample reaches adsorption equilibrium.
Immobilization metal porphyrin enzyme solution is immersed in CaCl2 solution and stirs 1h, mixed liquor is injected into 2%w/v sodium alginate soln carries out aging, finally this enzyme is wrapped up by calcium alginate gel, it is thus achieved that the immobilization metal porphyrin enzyme of calcium alginate gel embedding, drying for standby afterwards.
Embodiment 7 this example demonstrates that the catalyst method of synthesis immobilization metal porphyrin enzyme
By the porphyrin compound of carbonyl at MnCl2With ZnCl in solution2Complexation reaction forms metalloporphyrin enzyme.
With with the mesoporous SiO that cationic functional groups is isopropyl and ionic liquid that anionic functional groups is hydroxyl and low cost2Molecular screen material reacts 24h in toluene solution under 110 DEG C of conditions, it is filtrated to get carrier, it is filtrated to get carrier with dichloromethane surname extraction 20h, afterwards metalloporphyrin enzymatic solution is put into (50mL in 0.0125MTris-HCl buffer solution, PH7.0), and introduce the mesoporous activated carbon molecular screen material after finishing, by stirring under the mixed solution temperature at 30 DEG C and 150rpm rotating speed until sample reaches adsorption equilibrium.
Immobilization metal porphyrin enzyme solution is immersed in CaCl2 solution and stirs 1h, mixed liquor is injected into 2%w/v sodium alginate soln carries out aging, finally this enzyme is wrapped up by calcium alginate gel, it is thus achieved that the immobilization metal porphyrin enzyme of calcium alginate gel embedding, drying for standby afterwards.
Embodiment 8 this example demonstrates that the catalyst method of synthesis immobilization metal porphyrin enzyme
By the porphyrin compound of phenyl at MnCl2With SnCl in solution2Complexation reaction forms metalloporphyrin enzyme.
With with the mesoporous SiO that cationic functional groups is methyl and ionic liquid that anionic functional groups is hydroxyl and low cost2Molecular screen material reacts 24h in toluene solution under 110 DEG C of conditions, it is filtrated to get carrier, it is filtrated to get carrier with dichloromethane surname extraction 20h, afterwards metalloporphyrin enzymatic solution is put into (50mL in 0.0125MTris-HCl buffer solution, PH7.0), and introduce the mesoporous activated carbon molecular screen material after finishing, by stirring under the mixed solution temperature at 30 DEG C and 150rpm rotating speed until sample reaches adsorption equilibrium.
Immobilization metal porphyrin enzyme solution is immersed in CaCl2In solution and stir 1h, being injected into by mixed liquor and carry out aging in 2%w/v sodium alginate soln, finally this enzyme is wrapped up by calcium alginate gel, it is thus achieved that the immobilization metal porphyrin enzyme of calcium alginate gel embedding, drying for standby afterwards.
Embodiment:
Adopt the system used by embodiment 3, the catalyst then utilizing different embodiment to obtain, carry out the catalytic oxidation of Hydroxymethylfurfural (HMF).Concrete outcome is shown in list 1.
The catalytic result table of table 1 different catalysts catalytic oxidation Hydroxymethylfurfural
| Catalyst is numbered | HMF conversion ratio | FDCA yield | DFF yield | HMFCA yield |
| Embodiment 1 | 84.2 | 73.5 | 5.4 | 1.7 |
| Embodiment 2 | 94.7 | 82.8 | 5.8 | 1.5 |
| Embodiment 4 | 92.3 | 81.4 | 6.2 | 0.9 |
| Embodiment 5 | 96.4 | 83.1 | 5.4 | 1.3 |
| Embodiment 6 | 93.5 | 86.5 | 4.9 | 1.2 |
| Embodiment 7 | 97.3 | 85.6 | 6.9 | 1.5 |
| Embodiment 8 | 95.8 | 84.7 | 4.6 | 1.6 |
Claims (10)
1. the preparation method of an immobilization metal porphyrin enzyme catalyst, it is characterized in that: obtain the meso-porous molecular sieve material through finishing with Ionic Liquid Modified meso-porous molecular sieve material, carry out complexation reaction in organic solvent with the porphyrin compound containing different substituents and slaine and generate metal porphyrins, by physical absorption, metal porphyrins is immobilized onto the meso-porous molecular sieve material surface through finishing, it is thus achieved that specific immobilization metal porphyrin enzyme.
2. preparation method according to claim 1, it is characterised in that described ionic liquid is the glyoxaline ion liquid with functional group, and ionic liquid with anionic functional groups be-OH ,-NH2Basic group.
3. preparation method according to claim 2, it is characterised in that ionic liquid with cationic functional groups be the one in amino, sulfydryl, methyl, ethyl, isopropyl.
4. preparation method according to claim 1, it is characterised in that meso-porous molecular sieve material is SiO2, activated carbon, one in Graphene.
5. preparation method according to claim 1, it is characterised in that the substituent group in the described porphyrins with substituted radical is the one in pyridine radicals, hydroxyl, carboxyl, aldehyde radical, carbonyl, phenyl.
6. preparation method according to claim 1, it is characterised in that the metal in slaine is the one in cobalt, manganese, copper, zinc, ferrum, stannum.
7. preparation method according to claim 1, it is characterised in that also include the step by obtaining the embedding of immobilized metalloporphyrin enzyme.
8. the method preparing immobilization metal porphyrin enzyme catalyst, it is characterised in that concretely comprising the following steps of making:
(1) porphyrins containing different substituents is carried out complexation reaction with slaine in organic solvent, it is thus achieved that there is the metal porphyrins of different metal center and substituent group；
(2) in toluene solution, under 110 DEG C of conditions, 24h is reacted with the glyoxaline ion liquid with functional group with meso-porous molecular sieve material；It is filtrated to get carrier, and with dichloromethane surname extraction 20h, it is thus achieved that through the meso-porous molecular sieve material of finishing；
(3) meso-porous molecular sieve material through finishing that metalloporphyrin step (1) obtained obtains with step (2) mixes in 0.0125MTris-HCl buffer solution and contacts, and stabilizes the PH of reaction system under the effect of buffer solution.Afterwards again by stirring under the mixed solution temperature at 30 DEG C and 150rpm rotating speed until sample reaches physical absorption balance, filter and obtain immobilized metalloporphyrin enzyme.
(4) the immobilized metalloporphyrin enzyme that step (3) obtains is immersed in CaCl2In solution and stir 1h, mixed liquor is injected into 2%w/v sodium alginate soln carries out aging, it is thus achieved that the metalloporphyrin enzyme of calcium alginate gel embedding.
9. the method described in any of the above-described claim prepares immobilization metal porphyrin enzyme.
10. the method for a catalytic oxidation Hydroxymethylfurfural (HMF), it is characterised in that Hydroxymethylfurfural (HMF) is dissolved, and at O2、NaIO4、H2O2, in TBHP under arbitrary oxidant existent condition, contact with the metalloporphyrin enzyme described in claim 9, catalytic oxidation generates FDCA (FDCA).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610121991.8A CN105749975A (en) | 2016-03-04 | 2016-03-04 | Immobilized metal porphyrin enzyme catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610121991.8A CN105749975A (en) | 2016-03-04 | 2016-03-04 | Immobilized metal porphyrin enzyme catalyst and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105749975A true CN105749975A (en) | 2016-07-13 |
Family
ID=56332455
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610121991.8A Pending CN105749975A (en) | 2016-03-04 | 2016-03-04 | Immobilized metal porphyrin enzyme catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105749975A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105685774A (en) * | 2016-01-14 | 2016-06-22 | 江苏大学 | Method for removing hydroxymethyl furfural in food |
| CN106925349A (en) * | 2017-03-20 | 2017-07-07 | 江南大学 | A kind of solid supported type metal porphyrin catalyst and its application in terms of maleic acid is prepared |
| CN109234263A (en) * | 2018-09-27 | 2019-01-18 | 福建海峡石墨烯产业技术研究院有限公司 | A method of the crosslinked action immobilized enzyme based on adenosine monophosphate and graphene |
| WO2019083452A1 (en) * | 2017-10-25 | 2019-05-02 | National University Of Singapore | An oxidant activator |
| CN110201717A (en) * | 2019-05-21 | 2019-09-06 | 南京工业大学 | Preparation method and application of copper-based metal organic polyhedral composite material |
| CN110372650A (en) * | 2019-07-03 | 2019-10-25 | 南京先进生物材料与过程装备研究院有限公司 | A method of 2,5-furandicarboxylic acid is prepared using micro flow field reaction technology |
| CN110904014A (en) * | 2019-12-23 | 2020-03-24 | 南京林业大学 | Pseudomonas marginalis and application thereof in preparation of 2, 5-furandicarboxylic acid |
| CN112844487A (en) * | 2021-02-20 | 2021-05-28 | 南京工业大学 | Alkali lignin supported metalloporphyrin catalyst and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8481756B1 (en) * | 2007-09-04 | 2013-07-09 | Cornell Research Foundation, Inc. | Succinic anhydrides from epoxides |
| CN103724314A (en) * | 2013-12-16 | 2014-04-16 | 中山大学 | Method for preparing inner ester through composite catalysis of ketone compounds |
| CN103776781A (en) * | 2014-02-14 | 2014-05-07 | 中国石油大学(华东) | Nano material for detecting dimethoate and preparation method thereof |
| CN103467434B (en) * | 2013-09-16 | 2015-06-10 | 中山大学 | Method for preparing eta-caprolactone by composite catalysis |
-
2016
- 2016-03-04 CN CN201610121991.8A patent/CN105749975A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8481756B1 (en) * | 2007-09-04 | 2013-07-09 | Cornell Research Foundation, Inc. | Succinic anhydrides from epoxides |
| CN103467434B (en) * | 2013-09-16 | 2015-06-10 | 中山大学 | Method for preparing eta-caprolactone by composite catalysis |
| CN103724314A (en) * | 2013-12-16 | 2014-04-16 | 中山大学 | Method for preparing inner ester through composite catalysis of ketone compounds |
| CN103776781A (en) * | 2014-02-14 | 2014-05-07 | 中国石油大学(华东) | Nano material for detecting dimethoate and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| LANGCHANG GAO ET AL.: ""Efficient oxidation of biomass derived 5-hydroxymethylfurfural into 2,5-furandicarboxylic acid catalyzed by Merrifield resin supported cobalt porphyrin"", 《CHEMICAL ENGINEERING JOURNAL》 * |
| 邹彬等: ""离子液体修饰的SBA-16材料在猪胰脂肪酶固定化中的应用"", 《生物加工过程》 * |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105685774A (en) * | 2016-01-14 | 2016-06-22 | 江苏大学 | Method for removing hydroxymethyl furfural in food |
| US10525454B2 (en) | 2017-03-20 | 2020-01-07 | Jiangnan University | Immobilized metalloporphyrin catalyst and its utilization in maleic acid preparation |
| CN106925349A (en) * | 2017-03-20 | 2017-07-07 | 江南大学 | A kind of solid supported type metal porphyrin catalyst and its application in terms of maleic acid is prepared |
| WO2018171251A1 (en) * | 2017-03-20 | 2018-09-27 | 江南大学 | Solid-supported metalloporphyrin catalyst and application thereof in preparation of maleic acid |
| CN106925349B (en) * | 2017-03-20 | 2019-07-02 | 江南大学 | A kind of solid supported type metal porphyrin catalyst and its application in terms of preparing maleic acid |
| WO2019083452A1 (en) * | 2017-10-25 | 2019-05-02 | National University Of Singapore | An oxidant activator |
| CN111344061A (en) * | 2017-10-25 | 2020-06-26 | 新加坡国立大学 | Oxidant activator |
| CN109234263A (en) * | 2018-09-27 | 2019-01-18 | 福建海峡石墨烯产业技术研究院有限公司 | A method of the crosslinked action immobilized enzyme based on adenosine monophosphate and graphene |
| CN110201717A (en) * | 2019-05-21 | 2019-09-06 | 南京工业大学 | Preparation method and application of copper-based metal organic polyhedral composite material |
| CN110201717B (en) * | 2019-05-21 | 2021-11-23 | 南京工业大学 | Preparation method and application of copper-based metal organic polyhedral composite material |
| CN110372650A (en) * | 2019-07-03 | 2019-10-25 | 南京先进生物材料与过程装备研究院有限公司 | A method of 2,5-furandicarboxylic acid is prepared using micro flow field reaction technology |
| CN110372650B (en) * | 2019-07-03 | 2022-12-20 | 南京先进生物材料与过程装备研究院有限公司 | Method for preparing 2, 5-furandicarboxylic acid by adopting micro-flow field reaction technology |
| CN110904014A (en) * | 2019-12-23 | 2020-03-24 | 南京林业大学 | Pseudomonas marginalis and application thereof in preparation of 2, 5-furandicarboxylic acid |
| CN110904014B (en) * | 2019-12-23 | 2021-04-30 | 南京林业大学 | Pseudomonas marginalis and application thereof in preparation of 2, 5-furandicarboxylic acid |
| CN112844487A (en) * | 2021-02-20 | 2021-05-28 | 南京工业大学 | Alkali lignin supported metalloporphyrin catalyst and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105749975A (en) | Immobilized metal porphyrin enzyme catalyst and preparation method thereof | |
| Yi et al. | Purification of biomass‐derived 5‐hydroxymethylfurfural and its catalytic conversion to 2, 5‐furandicarboxylic acid | |
| El Kadib | Chitosan as a sustainable organocatalyst: a concise overview | |
| Niakan et al. | Efficient glucose-to-HMF conversion in deep eutectic solvents over sulfonated dendrimer modified activated carbon | |
| Sun et al. | Lysine functional heteropolyacid nanospheres as bifunctional acid–base catalysts for cascade conversion of glucose to levulinic acid | |
| Liu et al. | Squaramide functionalized ionic liquids with well-designed structures: Highly-active and recyclable catalyst platform for promoting cycloaddition of CO2 to epoxides | |
| Degirmenci et al. | Towards a selective heterogeneous catalyst for glucose dehydration to 5‐hydroxymethylfurfural in water: CrCl2 catalysis in a thin immobilized ionic liquid layer | |
| Delbecq et al. | Microwave assisted efficient furfural production using nano-sized surface-sulfonated diamond powder | |
| Verma et al. | Recent developments in heterogeneous catalytic routes for the sustainable production of succinic acid from biomass resources | |
| Zhang et al. | Production of HMF from glucose using an Al3+-promoted acidic phenol-formaldehyde resin catalyst | |
| Dhakshinamoorthy et al. | Pristine and modified chitosan as solid catalysts for catalysis and biodiesel production: A minireview | |
| Ke et al. | Spatially ordered arrangement of multifunctional sites at molecule level in a single catalyst for tandem synthesis of cyclic carbonates | |
| Xu et al. | Selective oxidation of 5-hydroxymethylfurfural to 5-formyl-2-furancar-boxylic acid over a Fe-Anderson type catalyst | |
| Li et al. | Fabrication of Trifunctional Polyoxometalate‐Decorated Chitosan Nanofibers for Selective Production of 2, 5‐Diformylfuran | |
| Modugno et al. | Influence of reaction conditions on hydrothermal carbonization of fructose | |
| Sampani et al. | Solvent-free synthesis and key intermediate isolation in Ni2Dy2 catalyst development in the domino ring-opening electrocyclization reaction of furfural and amines | |
| Sun et al. | An Anderson-type polyoxometalate triggers aerobic oxidation of 5-hydroxymethylfurfural to 2, 5-diformylfuran | |
| Shi et al. | Multiple-SO3H functionalized ionic liquid as efficient catalyst for direct conversion of carbohydrate biomass into levulinic acid | |
| Niakan et al. | Sulfonated ionic liquid immobilized SBA-16 as an active solid acid catalyst for the synthesis of biofuel precursor 5-hydroxymethylfurfural from fructose | |
| Chang et al. | Production of 5-hydroxymethylfurfural from glucose by recyclable heteropolyacid catalyst in ionic liquid | |
| CN106345530A (en) | Magnetic core-shell nanocatalyst, preparation method thereof and application thereof in catalyzing 5-hydroxymethylfurfural to prepare 2, 5-diformyl furan | |
| Kochetkov et al. | (1R, 2R)‐Bis [(S)‐prolinamido] cyclohexane Modified with Ionic Groups: The First C2‐Symmetric Immobilized Organocatalyst for Asymmetric Aldol Reactions in Aqueous Media | |
| Zhao et al. | Sevelamer as an efficient and reusable heterogeneous catalyst for the Knoevenagel reaction in water | |
| CN110283147A (en) | The method that formic acid hydrogen supply, base metal load azepine carbon catalysis 5-HMF transfer hydrogenation prepare 2,5- furyl dimethyl carbinol | |
| Ortiz-Bustos et al. | Prolinate-based heterogeneous catalyst for Knoevenagel condensation reaction: Insights into mechanism reaction using solid-state electrochemical studies |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20160713 |
|
| WD01 | Invention patent application deemed withdrawn after publication |