CN101182362A - Method for preparing cyclodextrin-phthalocyanine binary combination - Google Patents

Method for preparing cyclodextrin-phthalocyanine binary combination Download PDF

Info

Publication number
CN101182362A
CN101182362A CNA2007101647057A CN200710164705A CN101182362A CN 101182362 A CN101182362 A CN 101182362A CN A2007101647057 A CNA2007101647057 A CN A2007101647057A CN 200710164705 A CN200710164705 A CN 200710164705A CN 101182362 A CN101182362 A CN 101182362A
Authority
CN
China
Prior art keywords
cyclodextrin
phthalocyanine
add
weight
carboxyl
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.)
Granted
Application number
CNA2007101647057A
Other languages
Chinese (zh)
Other versions
CN100556918C (en
Inventor
胡智文
温会涛
高国琴
万军民
陈文兴
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang University of Technology ZJUT
Original Assignee
Zhejiang University of Technology ZJUT
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Zhejiang University of Technology ZJUT filed Critical Zhejiang University of Technology ZJUT
Priority to CNB2007101647057A priority Critical patent/CN100556918C/en
Publication of CN101182362A publication Critical patent/CN101182362A/en
Application granted granted Critical
Publication of CN100556918C publication Critical patent/CN100556918C/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

The invention relates to a preparation method of a cyclodextrin-phthalocyanine dualistic combination. The method is that the cyclodextrin and cobalt phthalocyanine are used to prepare for the cyclodextrin-phthalocyanine dualistic combination by synthesis. The cyclodextrin provides necessary hydrophobic space for mimetic enzyme, and the cobalt phthalocyanine provides effective reaction position for the mimetic enzyme, which does not exist in other single cyclodextrin and phthalocyanine mimetic enzyme. The covalent bonds of the cobalt phthalocyanine and the cyclodextrin are combined together directly, and the phthalocyanine and the cyclodextrin can take effect on substrate by the concerted reaction. The invention can be applied to catalyze purifying organic pollutants, remedy cancer etc.

Description

A kind of preparation method of cyclodextrin-phthalocyanine binary combination
Technical field
That the present invention relates to is a kind of preparation method of cyclodextrin-phthalocyanine binary combination.
Background technology
Enzyme catalysis is compared with the general chemistry catalyzer, have advantages such as high efficiency, specificity and reaction conditions gentleness, and natural enzyme is too responsive to environment, operational condition is required harsh, easily inactivation costs an arm and a leg, so people attempt to keep the advantage of natural enzyme, change the shortcoming of its volatility inactivation, begin to carry out the modeling effort of enzyme function.This class enzyme model molecule that is used to make up analogue enztme at present has cyclodextrin, crown ether, cave ether, cage ether, porphyrin etc.Cyclodextrin is a more satisfactory enzyme model, and the catalytic characteristics of cyclodextrin are: the substrate molecule that participates in reaction is connect by the cyclodextrin molecular bag earlier, reacts with it again, and is quite similar with enzymatic reaction.Phthalocyanine is a plane macrocylc compound, one hole is arranged in the ring, can hold iron, copper, cobalt, aluminium, nickel, calcium, sodium, magnesium, zinc etc. are planted multiple metallic element, the metal phthalocyanine that contains metallic element has the structure similar to metalloporphyrin, studies show that, the many organic reactions of metal phthalocyanine energy catalysis, particularly can effectively activate oxygen molecule, and the autoxidation of catalyzing organic at ambient temperature, therefore metal phthalocyanine can be used as the model of simulation biological enzyme, tetracarboxylic cobalt phthalocyanine is one of them, studies have shown that tetracarboxylic cobalt phthalocyanine can catalyzed oxidation mercaptan etc. objectionable impurities.
As the existing many researchs of imitative enzyme catalyst, then belong to the problem of studying about cyclodextrin, metal phthalocyanine but utilize cyclodextrin and metal phthalocyanine to prepare cyclodextrin-phthalocyanine binary combination.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of cyclodextrin-phthalocyanine binary combination, it is that cyclodextrin and cobalt phthalocyanine are prepared cyclodextrin-phthalocyanine binary combination by synthesizing.The goods of this preparation gained can be used for the photodynamic therapy of catalytic purification organic pollutant, cancer etc.
Method of the present invention is: A) be that potassium hydroxide/cyclodextrin mixt of 1/25 is 1: 12~20 to add in the mixed solution that the volume ratio of componentss are tetrahydrofuran (THF)/water of 7/10 by weight with the weight ratio of components, after treating most of dissolving, by cyclodextrin and Tosyl chloride weight ratio is 1: 0.1~0.2 slowly to drip the tetrahydrofuran solution that weight percent concentration is 6% Tosyl chloride, vigorous stirring 2~6 hours, add acetone, separate out white solid, filter, with the ether washing, obtain 6 p-toluenesulfonyl modification cyclodextrins with the distilled water secondary recrystallization;
B) be 1: 10~17 to join in the new polyamine compounds that steamed by weight with 6 p-toluenesulfonyl modification cyclodextrins; Stir under nitrogen protection, after treating to dissolve fully, be warming up to 70~90 ℃, reacted 8-9 hour, underpressure distillation removes and desolvates, and the gained solid is dissolved in a small amount of hot water; Under agitation be added to an amount of volume ratio and be in 10/1 the acetone solution, collect white precipitate, repeat aforesaid operations 3~5 times,, after vacuum-drying, obtain 6 polyamines modification cyclodextrins with the mixed solvent recrystallization of alcohol-water 1-5 time;
C) be 1: 152: 2500 with mol ratio: 440 ammonium molybdate: cobalt chloride hexahydrate: urea: the mixture that the four class materials such as mixture of phthalic anhydride compounds are formed is transferred in the container after grinding evenly, is added a cover, be heated to 100~150 ℃ of insulations 1-60 minute, after treating bubble collapse, continue to be warming up to 170~200 ℃, react and obtain black-and-blue solid after 1~12 hour; Fragmentation is after hydrochloric acid/sodium chloride saturated solution is handled, and alkalization then, acidifying obtain carboxyl cobalt phthalocyanine for several times after centrifugation, collection, the drying;
D) be 1: 10~30 to join in the dimethyl formamide by weight with the polyamines modification cyclodextrin, temperature is controlled at-5~5 ℃, by being to add the carboxyl phthalocyanine at 0.5~1.5: 1 with polyamines modification cyclodextrin mol ratio; By being to add dicyclohexylcarbodiimide at 1.5~0.5: 1 with carboxyl phthalocyanine mol ratio, be to add I-hydroxybenzotriazole at 1.5~0.5: 1 with carboxyl phthalocyanine mol ratio, stir, in bathing, stirred 1~3 day-15~-5 ℃ of cryosels, at room temperature reacted then 3~5 days; Leave standstill, the elimination insolubles, filtrate splashes in the acetone, and collecting precipitation is with obtaining cyclodextrin-phthalocyanine binary combination behind the chromatogram purification.
Cyclodextrin of the present invention is alpha-cylodextrin or beta-cyclodextrin or γ-Huan Hujing.
The present invention compared with prior art has following outstanding advantage: 1) cyclodextrin provides necessary hydrophobic space for analogue enztme, and the cobalt phthalocyanine provides effective reactive site for analogue enztme, and this is that other single cyclodextrin, phthalocyanine analogue enztme are unexistent; 2) cobalt phthalocyanine, cyclodextrin directly combine with covalent linkage, can be by concerted reaction etc. to substrate generation effect between cobalt phthalocyanine, the cyclodextrin; 3) goods can be used for the photodynamic therapy of catalytic purification organic pollutant, cancer etc.
Embodiment
The present invention will be described in detail below in conjunction with embodiment:
Embodiment 1:A) be that potassium hydroxide/alpha-cylodextrin mixture of 1/25 is to add at 1: 12 in the mixed solution that the volume ratio of components is tetrahydrofuran (THF)/water of 7/10 by weight with the weight ratio of components, after treating most of dissolving, by alpha-cylodextrin and Tosyl chloride weight ratio is slowly to drip the tetrahydrofuran solution that weight percent concentration is 6% Tosyl chloride at 1: 0.1, vigorous stirring 2 hours, add acetone, separate out white solid, filter, with the ether washing, obtain 6 p-toluenesulfonyl modification cyclodextrins with the distilled water secondary recrystallization;
B) be to join in the new polyamine compounds that steamed at 1: 10 by weight with 6 p-toluenesulfonyl modification cyclodextrins;
Stir under nitrogen protection, after treating to dissolve fully, be warming up to 70 ℃, reacted 8 hours, underpressure distillation removes and desolvates, and the gained solid is dissolved in a small amount of hot water; Under agitation be added to an amount of volume ratio and be in 10/1 the acetone solution, collect white precipitate, repeat aforesaid operations 3 times,, after vacuum-drying, obtain 6 polyamines modification cyclodextrins with the mixed solvent recrystallization of alcohol-water 1 time;
C) be 1: 152: 2500 with mol ratio: 440 ammonium molybdate: cobalt chloride hexahydrate: urea: the mixture that the four class materials such as mixture of phthalic anhydride compounds are formed is transferred in the container after grinding evenly, is added a cover, be heated to 100 ℃ of insulations 1 minute, after treating bubble collapse, continue to be warming up to 170 ℃, react and obtain black-and-blue solid after 1 hour; Fragmentation is after hydrochloric acid/sodium chloride saturated solution is handled, and alkalization then, acidifying obtain carboxyl cobalt phthalocyanine for several times after centrifugation, collection, the drying;
D) be to join in dimethyl formamide at 1: 10 by weight with the polyamines modification cyclodextrin, temperature is controlled at-5 ℃, by being to add the carboxyl phthalocyanine at 0.5: 1 with polyamines modification cyclodextrin mol ratio; By being to add dicyclohexylcarbodiimide at 1.5: 1 with carboxyl phthalocyanine mol ratio, be to add I-hydroxybenzotriazole at 1.5: 1 with carboxyl phthalocyanine mol ratio, stir, in bathing, stirred 1 day-15 ℃ of cryosels, at room temperature reacted then 3 days; Leave standstill, the elimination insolubles, filtrate splashes in the acetone, and collecting precipitation is with obtaining cyclodextrin-phthalocyanine binary combination behind the chromatogram purification.
Embodiment 2, A) be that potassium hydroxide/beta-cyclodextrin mixture of 1/25 is to add at 1: 20 in the mixed solution that the volume ratio of components is tetrahydrofuran (THF)/water of 7/10 by weight with the weight ratio of components, after treating most of dissolving, by beta-cyclodextrin and Tosyl chloride weight ratio is slowly to drip the tetrahydrofuran solution that weight percent concentration is 6% Tosyl chloride at 1: 0.2, vigorous stirring 6 hours, add acetone, separate out white solid, filter, with the ether washing, obtain 6 p-toluenesulfonyl modification cyclodextrins with the distilled water secondary recrystallization;
B) be to join in the new polyamine compounds that steamed at 1: 17 by weight with 6 p-toluenesulfonyl modification cyclodextrins; Stir under nitrogen protection, after treating to dissolve fully, be warming up to 90 ℃, reacted 9 hours, underpressure distillation removes and desolvates, and the gained solid is dissolved in a small amount of hot water; Under agitation be added to an amount of volume ratio and be in 10/1 the acetone solution, collect white precipitate, repeat aforesaid operations 5 times,, after vacuum-drying, obtain 6 polyamines modification cyclodextrins with the mixed solvent recrystallization of alcohol-water 5 times;
C) be 1: 152: 2500 with mol ratio: 440 ammonium molybdate: cobalt chloride hexahydrate: urea: the mixture that the four class materials such as mixture of phthalic anhydride compounds are formed is transferred in the container after grinding evenly, is added a cover, be heated to 150 ℃ of insulations 60 minutes, after treating bubble collapse, continue to be warming up to 200 ℃, react and obtain black-and-blue solid after 12 hours; Fragmentation is after hydrochloric acid/sodium chloride saturated solution is handled, and alkalization then, acidifying obtain carboxyl cobalt phthalocyanine for several times after centrifugation, collection, the drying;
D) be to join in dimethyl formamide at 1: 30 by weight with the polyamines modification cyclodextrin, temperature is controlled at 5 ℃, by being to add the carboxyl phthalocyanine at 1.5: 1 with polyamines modification cyclodextrin mol ratio; By being to add dicyclohexylcarbodiimide at 0.5: 1 with carboxyl phthalocyanine mol ratio, be to add I-hydroxybenzotriazole at 0.5: 1 with carboxyl phthalocyanine mol ratio, stir, in bathing, stirred 3 days-5 ℃ of cryosels, at room temperature reacted then 5 days; Leave standstill, the elimination insolubles, filtrate splashes in the acetone, and collecting precipitation is with obtaining cyclodextrin-phthalocyanine binary combination behind the chromatogram purification.
Embodiment 3, A) be that potassium hydroxide/γ-Huan Hujing mixture of 1/25 is to add at 1: 16 in the mixed solution that the volume ratio of components is tetrahydrofuran (THF)/water of 7/10 by weight with the weight ratio of components, after treating most of dissolving, by γ-Huan Hujing and Tosyl chloride weight ratio is slowly to drip the tetrahydrofuran solution that weight percent concentration is 6% Tosyl chloride at 1: 0.17, vigorous stirring 3 hours, add acetone, separate out white solid, filter, with the ether washing, obtain 6 p-toluenesulfonyl modification cyclodextrins with the distilled water secondary recrystallization;
B) be to join in the new polyamine compounds that steamed at 1: 14 by weight with 6 p-toluenesulfonyl modification cyclodextrins; Stir under nitrogen protection, after treating to dissolve fully, be warming up to 80 ℃, reacted 7 hours, underpressure distillation removes and desolvates, and the gained solid is dissolved in a small amount of hot water; Under agitation be added to an amount of volume ratio and be in 10/1 the acetone solution, collect white precipitate, repeat aforesaid operations 4 times,, after vacuum-drying, obtain 6 polyamines modification cyclodextrins with the mixed solvent recrystallization of alcohol-water 3 times;
C) be 1: 152: 2500 with mol ratio: 440 ammonium molybdate: cobalt chloride hexahydrate: urea: the mixture that the four class materials such as mixture of phthalic anhydride compounds are formed is transferred in the container after grinding evenly, is added a cover, be heated to 130 ℃ of insulations 1-60 minute, after treating bubble collapse, continue to be warming up to 185 ℃, react and obtain black-and-blue solid after 6 hours; Fragmentation is after hydrochloric acid/sodium chloride saturated solution is handled, and alkalization then, acidifying obtain carboxyl cobalt phthalocyanine for several times after centrifugation, collection, the drying;
D) be to join in dimethyl formamide at 1: 14 by weight with the polyamines modification cyclodextrin, temperature is controlled at 0 ℃, by being to add the carboxyl phthalocyanine at 1: 1 with polyamines modification cyclodextrin mol ratio; By being to add dicyclohexylcarbodiimide at 1: 1 with carboxyl phthalocyanine mol ratio, be to add I-hydroxybenzotriazole at 1: 1 with carboxyl phthalocyanine mol ratio, stir, in bathing, stirred 2 days-10 ℃ of cryosels, at room temperature reacted then 4 days; Leave standstill, the elimination insolubles, filtrate splashes in the acetone, and collecting precipitation is with obtaining cyclodextrin-phthalocyanine binary combination behind the chromatogram purification.

Claims (2)

1. the preparation method of a cyclodextrin-phthalocyanine binary combination, this method is: A) be that potassium hydroxide/cyclodextrin mixt of 1/25 is 1: 12~20 to add in the mixed solution that the volume ratio of componentss are tetrahydrofuran (THF)/water of 7/10 by weight with the weight ratio of components, after treating most of dissolving, by cyclodextrin and Tosyl chloride weight ratio is 1: 0.1~0.2 slowly to drip the tetrahydrofuran solution that weight percent concentration is 6% Tosyl chloride, vigorous stirring 2~6 hours, add acetone, separate out white solid, filter, with the ether washing, obtain 6 p-toluenesulfonyl modification cyclodextrins with the distilled water secondary recrystallization;
B) be 1: 10~17 to join in the new polyamine compounds that steamed by weight with 6 p-toluenesulfonyl modification cyclodextrins; Stir under nitrogen protection, after treating to dissolve fully, be warming up to 70~90 ℃, reacted 8-9 hour, underpressure distillation removes and desolvates, and the gained solid is dissolved in a small amount of hot water; Under agitation be added to an amount of volume ratio and be in 10/1 the acetone solution, collect white precipitate, repeat aforesaid operations 3~5 times,, after vacuum-drying, obtain 6 polyamines modification cyclodextrins with the mixed solvent recrystallization of alcohol-water 1-5 time;
C) be 1: 152: 2500 with mol ratio: 440 ammonium molybdate: cobalt chloride hexahydrate: urea: the mixture that the four class materials such as mixture of phthalic anhydride compounds are formed is transferred in the container after grinding evenly, is added a cover, be heated to 100~150 ℃ of insulations 1-60 minute, after treating bubble collapse, continue to be warming up to 170~200 ℃, react and obtain black-and-blue solid after 1~12 hour; Fragmentation is after hydrochloric acid/sodium chloride saturated solution is handled, and alkalization then, acidifying obtain carboxyl cobalt phthalocyanine for several times after centrifugation, collection, the drying;
D) be 1: 10~30 to join in the dimethyl formamide by weight with the polyamines modification cyclodextrin, temperature is controlled at-5~5 ℃, by being to add the carboxyl phthalocyanine at 0.5~1.5: 1 with polyamines modification cyclodextrin mol ratio; By being to add dicyclohexylcarbodiimide at 1.5~0.5: 1 with carboxyl phthalocyanine mol ratio, be to add I-hydroxybenzotriazole at 1.5~0.5: 1 with carboxyl phthalocyanine mol ratio, stir, in bathing, stirred 1~3 day-15~-5 ℃ of cryosels, at room temperature reacted then 3~5 days; Leave standstill, the elimination insolubles, filtrate splashes in the acetone, and collecting precipitation is with obtaining cyclodextrin-phthalocyanine binary combination behind the chromatogram purification.
2. the preparation method of cyclodextrin-phthalocyanine binary combination according to claim 1 is characterized in that described cyclodextrin is alpha-cylodextrin or beta-cyclodextrin or γ-Huan Hujing.
CNB2007101647057A 2007-12-06 2007-12-06 A kind of preparation method of cyclodextrin-phthalocyanine binary combination Expired - Fee Related CN100556918C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CNB2007101647057A CN100556918C (en) 2007-12-06 2007-12-06 A kind of preparation method of cyclodextrin-phthalocyanine binary combination

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNB2007101647057A CN100556918C (en) 2007-12-06 2007-12-06 A kind of preparation method of cyclodextrin-phthalocyanine binary combination

Publications (2)

Publication Number Publication Date
CN101182362A true CN101182362A (en) 2008-05-21
CN100556918C CN100556918C (en) 2009-11-04

Family

ID=39447801

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB2007101647057A Expired - Fee Related CN100556918C (en) 2007-12-06 2007-12-06 A kind of preparation method of cyclodextrin-phthalocyanine binary combination

Country Status (1)

Country Link
CN (1) CN100556918C (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103446969A (en) * 2013-06-07 2013-12-18 南开大学 Micro-nano reactor based on phthalocyanine bridging methylation cyclodextrin and preparation of micro-nano reactor
CN111943989A (en) * 2020-07-20 2020-11-17 青岛职业技术学院 Cluster-phthalocyanine binary molecule photosensitizer and preparation method and application thereof
CN115140788A (en) * 2022-08-02 2022-10-04 王兵雷 Processing method of water pollution control agent
CN116731294A (en) * 2022-08-17 2023-09-12 四川大学 Conjugated polymer biocatalysis material and preparation method and application thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100415980C (en) * 2006-09-21 2008-09-03 浙江理工大学 Production of cyclodextrin-phthalocyanine double analog enzyme functional fibre

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103446969A (en) * 2013-06-07 2013-12-18 南开大学 Micro-nano reactor based on phthalocyanine bridging methylation cyclodextrin and preparation of micro-nano reactor
CN103446969B (en) * 2013-06-07 2015-02-11 南开大学 Micro-nano reactor based on phthalocyanine bridging methylation cyclodextrin and preparation of micro-nano reactor
CN111943989A (en) * 2020-07-20 2020-11-17 青岛职业技术学院 Cluster-phthalocyanine binary molecule photosensitizer and preparation method and application thereof
CN111943989B (en) * 2020-07-20 2023-08-01 青岛职业技术学院 Cluster-phthalocyanine binary molecule photosensitizer and preparation method and application thereof
CN115140788A (en) * 2022-08-02 2022-10-04 王兵雷 Processing method of water pollution control agent
CN116731294A (en) * 2022-08-17 2023-09-12 四川大学 Conjugated polymer biocatalysis material and preparation method and application thereof

Also Published As

Publication number Publication date
CN100556918C (en) 2009-11-04

Similar Documents

Publication Publication Date Title
Kovacs Tuning the relative stability and reactivity of manganese dioxygen and peroxo intermediates via systematic ligand modification
Bauer Iron catalysis: Historic overview and current trends
CN100556918C (en) A kind of preparation method of cyclodextrin-phthalocyanine binary combination
CN106925349B (en) A kind of solid supported type metal porphyrin catalyst and its application in terms of preparing maleic acid
Leng et al. Organometallic-polyoxometalate hybrid based on V-Schiff base and phosphovanadomolybdate as a highly effective heterogenous catalyst for hydroxylation of benzene
Shen et al. An efficient silica supported Chitosan@ vanadium catalyst for asymmetric sulfoxidation and its application in the synthesis of esomeprazole
CN102020308A (en) Nano copper oxide analogue enzyme and method for measuring hydrogen peroxide by using nano copper oxide analogue enzyme as peroxide analogue enzyme
Majumdar Bioinorganic modeling chemistry of carbon monoxide dehydrogenases: description of model complexes, current status and possible future scopes
Tao et al. Dicopper μ-Oxo, μ-Nitrosyl Complex from the Activation of NO or Nitrite at a Dicopper Center
Laskar et al. Cellulose as recyclable organocatalyst for ipso-hydroxylation of arylboronic acids
Zhong et al. The influence of a peripheral functional group of diiron hexacarbonyl complexes on their electrochemistry and electrocatalytic reduction of proton
Yan Poon et al. How metal ion lewis acidity and steric properties influence the barrier to dioxygen binding, peroxo O–O bond cleavage, and reactivity
Krüger What can we learn from nature about the reactivity of coordinated phenoxyl radicals?—a bioinorganic success story
Boll et al. Novel bacterial molybdenum and tungsten enzymes: three-dimensional structure, spectroscopy, and reaction mechanism
Maurya Structural models of vanadate-dependent haloperoxidases, their reactivity, immobilization on polymer support and catalytic activities
Herbert et al. Olefin epoxidations in the ionic liquid [C4mim][PF6] catalysed by oxodiperoxomolybdenum species in situ generated from molybdenum trioxide and urea–hydrogen peroxide: The synthesis and molecular structure of [Mo (O)(O2) 2 (4-MepyO) 2]· H2O
CN105642325A (en) Supported vanadium-based catalyst and preparation method thereof
Hou et al. Recent Advances in Visible Light‐induced Asymmetric Transformations of Carbonyl Compounds into Chiral Alcohols
Özkan et al. Influence of load on the recycling stability of nanospheres attached platinium ion for determination of glucose
Amao et al. Visible-light induced hydrogen and formic acid production from biomass and carbon dioxide with enzymatic and artificial photosynthesis system
CN114908127B (en) enzyme-TiO (TiO) utilization method 2 Method for catalyzing and synthesizing nanotube-quantum dot co-assembly
CN108435256B (en) Preparation method of metal (II) functionalized graphene oxide catalyst
Gan et al. Biomimetic complexes for production of dihydrogen and reduction of CO 2
Bora et al. Ammonia from dinitrogen at ambient conditions by organometallic catalysts
CN110801866A (en) Method for preparing monatomic copper artificial simulation peroxidase

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C17 Cessation of patent right
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20091104

Termination date: 20121206