CN118185052B - Zirconium porphyrin metal organic framework nano-enzyme and preparation method and application thereof - Google Patents
Zirconium porphyrin metal organic framework nano-enzyme and preparation method and application thereof Download PDFInfo
- Publication number
- CN118185052B CN118185052B CN202410615026.0A CN202410615026A CN118185052B CN 118185052 B CN118185052 B CN 118185052B CN 202410615026 A CN202410615026 A CN 202410615026A CN 118185052 B CN118185052 B CN 118185052B
- Authority
- CN
- China
- Prior art keywords
- metal organic
- enzyme
- organic framework
- zirconium
- porphyrin metal
- 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.)
- Active
Links
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 87
- TUUPIFDTVOTCJS-UHFFFAOYSA-N C12=CC=C(N1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2.[Zr] Chemical compound C12=CC=C(N1)C=C1C=CC(=N1)C=C1C=CC(N1)=CC=1C=CC(N1)=C2.[Zr] TUUPIFDTVOTCJS-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 40
- 239000002184 metal Substances 0.000 claims abstract description 40
- -1 4-carboxyphenyl Chemical group 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 15
- 239000002243 precursor Substances 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 12
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims abstract description 12
- 239000002244 precipitate Substances 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 9
- RKCAIXNGYQCCAL-UHFFFAOYSA-N porphin Chemical compound N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 RKCAIXNGYQCCAL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003814 drug Substances 0.000 claims abstract description 5
- 208000035143 Bacterial infection Diseases 0.000 claims abstract description 4
- 208000022362 bacterial infectious disease Diseases 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 26
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 10
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 claims description 8
- QUMITRDILMWWBC-UHFFFAOYSA-N nitroterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C([N+]([O-])=O)=C1 QUMITRDILMWWBC-UHFFFAOYSA-N 0.000 claims description 6
- 239000005711 Benzoic acid Substances 0.000 claims description 5
- 235000010233 benzoic acid Nutrition 0.000 claims description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- 239000003607 modifier Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 15
- 102000004190 Enzymes Human genes 0.000 abstract description 13
- 108090000790 Enzymes Proteins 0.000 abstract description 13
- 102000003992 Peroxidases Human genes 0.000 abstract description 3
- 229940079593 drug Drugs 0.000 abstract description 3
- 108040007629 peroxidase activity proteins Proteins 0.000 abstract description 3
- 239000012620 biological material Substances 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 description 25
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 14
- 239000003446 ligand Substances 0.000 description 7
- 238000010586 diagram Methods 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 description 3
- QPBGNSFASPVGTP-UHFFFAOYSA-N 2-bromoterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(Br)=C1 QPBGNSFASPVGTP-UHFFFAOYSA-N 0.000 description 3
- SMOZAZLNDSFWAB-UHFFFAOYSA-N 4-[10,15,20-tris(4-carboxyphenyl)-21,24-dihydroporphyrin-5-yl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C(C=1C=CC(N=1)=C(C=1C=CC(=CC=1)C(O)=O)C1=CC=C(N1)C(C=1C=CC(=CC=1)C(O)=O)=C1C=CC(N1)=C1C=2C=CC(=CC=2)C(O)=O)=C2N=C1C=C2 SMOZAZLNDSFWAB-UHFFFAOYSA-N 0.000 description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 229940071125 manganese acetate Drugs 0.000 description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 3
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 150000001413 amino acids Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229960003280 cupric chloride Drugs 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 230000002255 enzymatic effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- HHDUMDVQUCBCEY-UHFFFAOYSA-N 4-[10,15,20-tris(4-carboxyphenyl)-21,23-dihydroporphyrin-5-yl]benzoic acid Chemical compound OC(=O)c1ccc(cc1)-c1c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc([nH]2)c(-c2ccc(cc2)C(O)=O)c2ccc(n2)c(-c2ccc(cc2)C(O)=O)c2ccc1[nH]2 HHDUMDVQUCBCEY-UHFFFAOYSA-N 0.000 description 1
- 108010001336 Horseradish Peroxidase Proteins 0.000 description 1
- 102000005741 Metalloproteases Human genes 0.000 description 1
- 108010006035 Metalloproteases Proteins 0.000 description 1
- 108091005804 Peptidases Proteins 0.000 description 1
- 239000004365 Protease Substances 0.000 description 1
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KCNMSAKCTPBRPK-UHFFFAOYSA-N benzoic acid;terephthalic acid Chemical compound OC(=O)C1=CC=CC=C1.OC(=O)C1=CC=C(C(O)=O)C=C1 KCNMSAKCTPBRPK-UHFFFAOYSA-N 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009510 drug design Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000003278 haem Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000005556 structure-activity relationship Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
- A61P31/04—Antibacterial agents
-
- 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
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- 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
-
- 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
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y5/00—Nanobiotechnology or nanomedicine, e.g. protein engineering or drug delivery
-
- 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
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/48—Zirconium
-
- 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
- B01J2531/82—Metals of the platinum group
- B01J2531/827—Iridium
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Pharmacology & Pharmacy (AREA)
- Medical Informatics (AREA)
- General Physics & Mathematics (AREA)
- Biotechnology (AREA)
- Physics & Mathematics (AREA)
- Biophysics (AREA)
- Molecular Biology (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Communicable Diseases (AREA)
- Oncology (AREA)
- General Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Animal Behavior & Ethology (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Composite Materials (AREA)
- Polymers & Plastics (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a nano biological material, in particular to a zirconium porphyrin metal organic framework nano enzyme, a preparation method and application thereof. Mixing MESO-tetra (4-carboxyphenyl) porphin, zirconium tetrachloride, aryl dicarboxylic acid and a morphology regulator in a first solvent, reacting at 120-140 ℃, washing and separating precipitate to obtain a zirconium porphyrin metal organic framework material; dispersing the zirconium porphyrin metal organic framework material in a second solvent, adding a metal precursor solution, reacting at 80-90 ℃, washing and separating precipitate to obtain the zirconium porphyrin metal organic framework nano-enzyme. The zirconium porphyrin metal organic framework nano-enzyme has good peroxidase activity, and can be used for preparing medicines or auxiliary materials for resisting bacterial infection or preventing and treating biological films.
Description
Technical Field
The invention relates to a nano biological material, in particular to a zirconium porphyrin metal organic framework nano enzyme, a preparation method and application thereof.
Background
Natural enzymes are a class of organic molecules synthesized from living bodies, including proteins, DNA or RNA, which have been used in fields including industry, food fermentation, biological medicine, etc., due to their high specificity and superior catalytic activity. But are limited by their high cost of preparation, low environmental tolerance (substantial loss of catalytic activity especially in high temperature, extreme pH, high salt, etc.), and the use of natural enzymes in long-term, complex, extreme environments is severely limited.
Nano-enzyme, which is a new artificial enzyme, is attracting more and more attention from researchers because of its catalytic ability and inherent physicochemical advantages (low preparation cost, high stability) of materials. However, the current considerable nano-enzymes have the problems of blind synthesis, insufficient activity, fuzzy structure-activity relationship and the like, and the development and the high-grade application of the high-activity nano-enzymes are hindered.
Disclosure of Invention
Based on the above, the invention provides a zirconium porphyrin metal organic framework nano-enzyme, a preparation method and application thereof, and at least solves one problem in the prior art.
In a first aspect, the invention provides a method for preparing zirconium porphyrin metal organic framework nano-enzyme, which comprises the following steps:
mixing MESO-tetra (4-carboxyphenyl) porphin (also known as MESO-tetra (4-carboxyphenyl) porphin, TCPP), zirconium tetrachloride, aryl dicarboxylic acid and a morphology regulator in a first solvent, reacting at 120-140 ℃, washing and separating the precipitate to obtain a zirconium porphyrin metal organic framework material;
dispersing the zirconium porphyrin metal organic framework material in a second solvent, adding a metal precursor solution, reacting at 80-90 ℃, washing and separating precipitate to obtain the zirconium porphyrin metal organic framework nano-enzyme.
In a second aspect, the invention provides a zirconium porphyrin metal organic framework nano-enzyme, which is obtained by a preparation method of the zirconium porphyrin metal organic framework nano-enzyme.
In a third aspect, the invention provides application of the zirconium porphyrin metal organic framework nano-enzyme in preparing medicines or auxiliary materials for resisting bacterial infection or preventing and treating biological films.
Due to the adoption of the technical scheme, the embodiment of the invention has at least the following beneficial effects:
(1) The zirconium porphyrin metal organic framework nano-enzyme is synthesized by a two-step method, the method is rapid and simple, the reaction condition is adjustable, the large-scale preparation can be realized, and the precise regulation and control of the nano-enzyme activity and rational design can be realized;
(2) Compared with the traditional nano-enzyme, the zirconium porphyrin metal organic framework nano-enzyme has different metal sites and pore wall microenvironments, has strictly defined active sites and adjustable catalytic microenvironments, and is an ideal model for researching the relationship between the nano-enzyme structure and the activity;
(3) The zirconium porphyrin metal organic framework nano enzyme has excellent stability, and can be stored for a long time, and is resistant to high temperature, acid, salt and various organic solvents.
Drawings
FIG. 1 is a morphology diagram of Zr-TCPP-H MOF in an embodiment of the invention.
FIG. 2 is a morphology diagram of Zr-TCPP-NH 2 MOF in an embodiment of the present invention.
FIG. 3 is a morphology diagram of Zr-TCPP-NO 2 MOF in an embodiment of the present invention.
FIG. 4 is a morphology diagram of Zr-TCPP-Br MOF according to an embodiment of the present invention.
FIG. 5 is a diagram showing the morphology of Zr-TCPP (Ir) -H MOF in the example of the present invention.
FIG. 6 is a morphology diagram of Zr-TCPP (Ir) -NH 2 MOF in an example of the present invention.
FIG. 7 is a graph showing the morphology of Zr-TCPP (Ir) -NO 2 MOF in the example of the present invention.
FIG. 8 is a graph showing the morphology of Zr-TCPP (Ir) -Br MOF in an embodiment of the invention.
FIG. 9 shows the results of evaluation of the catalytic activity of Zr-TCPP (Fe) -H MOF in the examples of the present invention.
FIG. 10 shows the results of evaluation of the catalytic activity of Zr-TCPP (Ir) -H MOF in the examples of the present invention.
FIG. 11 shows the results of evaluation of the catalytic activity of Zr-TCPP (Ir) -NO 2 MOF in the examples of the present invention.
FIG. 12 shows the comparative results of the catalytic activities of Zr-TCPP (Fe) -H MOF, zr-TCPP (Ir) -NO 2 MOF in examples of the present invention.
Detailed Description
The following is a clear and complete description of the conception and technical effects produced thereby to fully illustrate the objects, aspects, and effects of the present invention.
How to synthesize high-performance nano-enzymes from the de novo design is clearly a prerequisite for widening and pushing nano-enzymes in the process of gradually replacing natural enzymes in practical application. Inspired that the catalytic micro-environment consisting of exquisite active sites and amino acids of the metalloprotease jointly determines the catalytic efficiency and the catalytic selectivity of the natural enzyme, the metal organic framework is introduced as a bionic design framework, has adjustable metal nodes and side chain functional groups, and can well simulate the active sites and the amino acid micro-environment of the protease, but the current design of the metal organic framework simulant is concentrated on single metal site regulation or side chain ligand regulation, so that the remarkable improvement of the catalytic activity of the nanoenzyme is fundamentally limited.
In order to solve the problems of high cost, low stability, insufficient activity, fuzzy structure-activity relation and the like of the existing natural enzymes, the development of a dual regulation strategy for metal sites and catalytic microenvironments of the metal organic framework nano-enzyme is an effective way for solving the problem of insufficient catalytic activity of the nano-enzyme, and accordingly, the invention provides a zirconium porphyrin metal organic framework nano-enzyme based on pore wall engineering and metal site synergistic enhancement of catalytic activity, and a preparation method and application thereof.
In a first aspect, the invention provides a method for preparing zirconium porphyrin metal organic framework nano-enzyme, which comprises the following steps:
Mixing MESO-tetra (4-carboxyphenyl) porphin, zirconium tetrachloride, aryl dicarboxylic acid and a morphology regulator in a first solvent, reacting at 120-140 ℃, washing and separating precipitate to obtain a zirconium porphyrin metal organic framework material;
dispersing the zirconium porphyrin metal organic framework material in a second solvent, adding a metal precursor solution, reacting at 80-90 ℃, washing and separating precipitate to obtain the zirconium porphyrin metal organic framework nano-enzyme.
The zirconium porphyrin metal organic frame nano-enzyme is a zirconium porphyrin metal organic frame nano-enzyme obtained by synthesizing a zirconium porphyrin metal organic frame in advance and then introducing different metal precursors through modification after synthesis. Wherein, the pre-synthesized zirconium porphyrin metal organic framework is a multivalent zirconium porphyrin metal organic framework synthesized under the solvothermal condition by taking aryl dicarboxylic acid and MESO-tetra (4-carboxyphenyl) porphin as mixed ligands, zirconium tetrachloride as metal precursors and benzoic acid or formic acid as regulator; and different metal precursors introduced by post-synthesis modification can be iridium chloride, rhodium chloride, ruthenium chloride, ferric chloride, cupric chloride, cobalt chloride or manganese acetate.
The zirconium porphyrin metal organic framework is a multivalent metal organic framework synthesized by two organic ligands (aryl dicarboxylic acid and MESO-tetra (4-carboxyphenyl) porphin) and zirconium chloride under solvothermal conditions, and in order to effectively enhance the enzyme-like catalytic activity of the zirconium porphyrin metal organic framework, a pore wall engineering and metal active site dual regulation strategy is introduced. Wherein pore wall engineering refers to rational screening of aryl dicarboxylic acids with different side chain groups to construct microenvironments with natural enzyme-like active sites; the metal site engineering is to introduce a series of noble metals and transition state metals with catalytic activity through post-modification by utilizing the inherent excellent metal chelating capability of MESO-tetra (4-carboxyphenyl) porphin; thus constructing the zirconium porphyrin metal organic framework nano-enzyme library with adjustable pore wall microenvironment and metal active sites.
In some alternative embodiments, the aryl dicarboxylic acid is at least one of terephthalic acid, 2-amino terephthalic acid, 2-bromo terephthalic acid, and 2-nitro terephthalic acid. Preferably, the aryl dicarboxylic acid is 2-nitroterephthalic acid.
In some alternative embodiments, the metal precursor solution is an iridium chloride solution, rhodium chloride solution, ruthenium chloride solution, ferric chloride solution, cupric chloride solution, cobalt chloride solution, or manganese acetate solution. Preferably, the metal precursor solution is an aqueous iridium chloride solution.
In some alternative embodiments, the morphology modifier is at least one of benzoic acid, formic acid.
In some alternative embodiments, the molar ratio of MESO-tetrakis (4-carboxyphenyl) porphine, zirconium tetrachloride, aryl dicarboxylic acid, and metal precursor solution is (1-3): (18-20): (13-15): (1-2). Preferably, the molar ratio of MESO-tetrakis (4-carboxyphenyl) porphine, zirconium tetrachloride, aryl dicarboxylic acid and metal precursor solution is 2:19:14:1.
In some alternative embodiments, the morphology modifier is used in an amount of 50.9 times (molar amount) the metal precursor and the morphology modifier is used in an amount of 16.5 times (molar amount) the metal precursor.
In some alternative embodiments, the first solvent is N, N-Dimethylformamide (DMF).
In some alternative embodiments, the second solvent is ethanol.
In a second aspect, the invention provides a zirconium porphyrin metal organic framework nano-enzyme, which is obtained by a preparation method of the zirconium porphyrin metal organic framework nano-enzyme.
The obtained zirconium porphyrin metal organic frame nano-enzyme has good peroxidase activity, wherein the zirconium porphyrin metal organic frame nano-enzyme obtained by taking 2-nitroterephthalic acid as a side chain ligand and iridium chloride as a metal source has more excellent catalytic activity compared with zirconium porphyrin metal organic frame nano-enzyme synthesized by other side chain ligands (terephthalic acid, 2-amino terephthalic acid and 2-bromo terephthalic acid) and metal sources (rhodium chloride, ruthenium chloride, ferric chloride, copper chloride, cobalt chloride and manganese acetate).
In a third aspect, the invention provides application of the zirconium porphyrin metal organic framework nano-enzyme in preparing medicines or auxiliary materials for resisting bacterial infection or preventing and treating biological films.
Some exemplary embodiments are described below.
Example 1
Zr-TCPP-H MOF was synthesized according to the following procedure:
(1) Respectively ultrasonically dissolving 45 mg zirconium chloride and 13.8 mg MESO-tetra (4-carboxyphenyl) porphine in 1 mL DMF in advance to prepare MESO-tetra (4-carboxyphenyl) porphine solution and zirconium tetrachloride solution;
(2) Ultrasonic dissolving 1200 mg benzoic acid and 23.7 mg terephthalic acid in 28 mL DMF solution to prepare a benzoic acid-terephthalic acid mixed solution;
(3) Sequentially adding the MESO-tetra (4-carboxyphenyl) porphine solution and the zirconium tetrachloride solution into the mixed solution of benzoic acid and terephthalic acid under intense stirring, dropwise adding 120 mu L of formic acid under intense stirring, and continuing stirring for 20min after the dropwise adding is finished;
(4) Transferring the mixed solution into a 50 mL polytetrafluoroethylene liner, and keeping 12: 12 h at 130 ℃;
(5) After cooling to room temperature, the resulting product was washed three times with DMF and ethanol by centrifugation at 12000 rpm, and finally the precipitate was collected and dried overnight in a vacuum oven at 60℃to give Zr-TCPP-H MOF.
Example 2
This embodiment is substantially the same as embodiment 1, except that: terephthalic acid was replaced with an equimolar amount of 2-amino terephthalic acid (25.8 mg) to give Zr-TCPP-NH 2 MOF.
Example 3
This embodiment is substantially the same as embodiment 1, except that: terephthalic acid was replaced with an equimolar amount of 2-bromoterephthalic acid (34.8 mg) to give Zr-TCPP-Br MOF.
Example 4
This embodiment is substantially the same as embodiment 1, except that: the terephthalic acid was replaced with an equimolar amount of 2-nitroterephthalic acid (30 mg) to give Zr-TCPP-NO 2 MOF.
Example 5
The zirconium porphyrin metal organic framework nano-enzyme (Zr-TCPP (Ir) -H MOF) is synthesized according to the following steps:
(1) Taking Zr-TCPP-H MOF 10 mg synthesized in the example 1, and dispersing the Zr-TCPP-H MOF 10 mg in 10 mL ethanol solution by ultrasonic wave to obtain Zr-TCPP-H MOF dispersion;
(2) An aqueous iridium chloride solution (6.15 mg/mL, 500. Mu.L) was added dropwise to the Zr-TCPP-H MOF dispersion under 500: 500 rpm stirring, and stirring was continued for 20: 20 min;
(3) Transferring the mixed solution into an oil bath kettle preheated to 85 ℃, and continuing to react at 300 rpm for 12 h;
(4) Cooling to room temperature, sequentially centrifugally washing the obtained product with DMF and ethanol for three times by 12000 rpm, finally collecting precipitate and drying the precipitate in a vacuum oven at 60 ℃ for overnight to obtain Zr-TCPP (Ir) -H MOF.
Example 6
This embodiment is substantially the same as embodiment 5, except that: the iridium chloride aqueous solution in example 5 was replaced with an equimolar amount of an aqueous solution of ferric chloride (5.55 mg/mL, 500. Mu.L) to give Zr-TCPP (Fe) -H MOF.
Example 7
This embodiment is substantially the same as embodiment 5, except that: the Zr-TCPP-H MOF synthesized in example 1 was replaced with an equal mass of the Zr-TCPP-NH 2 MOF synthesized in example 2 to give Zr-TCPP (Ir) -NH 2 MOF.
Example 8
This embodiment is substantially the same as embodiment 5, except that: the Zr-TCPP-H MOF synthesized in example 1 was replaced with an equal mass of the Zr-TCPP-Br MOF synthesized in example 3 to give a Zr-TCPP (Ir) -Br MOF.
Example 9
This embodiment is substantially the same as embodiment 5, except that: the Zr-TCPP-H MOF synthesized in example 1 was replaced with an equal mass of the Zr-TCPP-NO 2 MOF synthesized in example 4, to give a Zr-TCPP (Ir) -NO 2 MOF.
The above examples 1-4 gave zirconium porphyrin metal organic framework materials, and examples 5-9 gave zirconium porphyrin metal organic framework nanoezymes with tunable catalytic microenvironment and well defined metal sites, which were used for peroxidase-like activity evaluation as follows.
The method for evaluating the activity of the peroxidase-like comprises the following steps: 100. Mu.L of a zirconium porphyrin metal organic framework nano-enzyme dispersion (100. Mu.g/mL, dissolved in water) and 100. Mu. L H 2O2 (1 mM) were added to 700. Mu.L of TMB solution containing a final concentration of 4 mM for a period of time, the absorbance change at 500-800 nm was monitored, the A652 nm value was used as an index of its peroxidase activity, and the catalytic enzyme kinetics were determined as follows: the concentration of the immobilization material and TMB were 10 μg/mL and 4 mM, the concentration of H 2O2 was varied (0.2 mM, 0.4 mM, 1 mM, 2 mM and 4 mM), and its catalytic kinetics within 1 min were monitored.
As shown in fig. 1-8, the synthesized zirconium porphyrin metal organic frameworks of different side-chain ligands have uniform size distribution and are close in size; after the iridium is chelated, the morphology of the obtained metal organic frame nano enzyme is basically unchanged compared with that of the metal organic frame nano enzyme before chelation, so that the interference of the influence of the size on the catalytic activity is eliminated, and the real contribution of the side chain ligand to the catalytic activity of the metal organic frame nano enzyme is studied.
FIGS. 9-11 show the enzymatic kinetics of Zr-TCPP (Fe) -H MOF, zr-TCPP (Ir) -NO 2 MOF with H 2O2 as substrate. FIG. 12 shows the enzymatic performance comparisons of Zr-TCPP (Fe) -H MOF, zr-TCPP (Ir) -NO 2 MOF. It can be seen that compared with Zr-TCPP (Fe) -H MOF with a structure similar to heme of horseradish peroxidase, the obtained Zr-TCPP (Ir) -NO 2 MOF has remarkable improvement on catalytic efficiency by introducing 2-nitroterephthalic acid and iridium chloride of electron-withdrawing ligand, and the remarkable promotion effect of pore wall engineering and metal sites on the catalytic activity of zirconium porphyrin metallo-organic framework nano-enzyme is proved.
The present invention is not limited to the above embodiments, but is merely preferred embodiments of the present invention, and the present invention should be considered as being within the scope of the present invention as long as the technical effects of the present invention are achieved by the same or equivalent means. Various modifications and variations are possible in the technical solution and/or in the embodiments within the scope of the invention.
Claims (7)
1. The preparation method of the zirconium porphyrin metal organic framework nano-enzyme is characterized by comprising the following steps of:
Mixing MESO-tetra (4-carboxyphenyl) porphin, zirconium tetrachloride, aryl dicarboxylic acid and a morphology regulator in a first solvent, reacting at 120-140 ℃, washing and separating precipitate to obtain a zirconium porphyrin metal organic framework material;
dispersing the zirconium porphyrin metal organic frame material in a second solvent, adding a metal precursor solution, reacting at 80-90 ℃, washing and separating precipitate to obtain zirconium porphyrin metal organic frame nano-enzyme;
wherein the aryl dicarboxylic acid is 2-nitroterephthalic acid, and the metal precursor solution is iridium chloride aqueous solution.
2. The method of claim 1, wherein the morphology modifier is at least one of benzoic acid, formic acid.
3. The method of claim 1, wherein the molar ratio of MESO-tetrakis (4-carboxyphenyl) porphine, zirconium tetrachloride, aryl dicarboxylic acid, and metal precursor solution is (1-3): (18-20): (13-15): (1-2).
4. The method of claim 1, wherein the first solvent is N, N-dimethylformamide.
5. The method of claim 1, wherein the second solvent is ethanol.
6. A zirconium porphyrin metal organic framework nano-enzyme, characterized in that the zirconium porphyrin metal organic framework nano-enzyme is obtained by the preparation method of the zirconium porphyrin metal organic framework nano-enzyme according to any one of claims 1 to 5.
7. The use of the zirconium porphyrin metal organic framework nano-enzyme according to claim 6 for preparing a medicament or an auxiliary material for resisting bacterial infection or preventing and treating a biological film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410615026.0A CN118185052B (en) | 2024-05-17 | 2024-05-17 | Zirconium porphyrin metal organic framework nano-enzyme and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410615026.0A CN118185052B (en) | 2024-05-17 | 2024-05-17 | Zirconium porphyrin metal organic framework nano-enzyme and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN118185052A CN118185052A (en) | 2024-06-14 |
| CN118185052B true CN118185052B (en) | 2024-09-13 |
Family
ID=91406952
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410615026.0A Active CN118185052B (en) | 2024-05-17 | 2024-05-17 | Zirconium porphyrin metal organic framework nano-enzyme and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN118185052B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115598193A (en) * | 2022-10-12 | 2023-01-13 | 华东交通大学（Cn） | Preparation of molecular imprinting photoelectrochemical sensor based on photoexcitation mimic enzyme and method for detecting norfloxacin by using molecular imprinting photoelectrochemical sensor |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017052474A1 (en) * | 2015-09-23 | 2017-03-30 | Nanyang Technological University | A metal-organic framework nanosheet |
| CN109158128B (en) * | 2018-07-24 | 2020-11-03 | 浙江大学 | Method for preparing metal organic framework nano particles simulating peroxidase |
| JP2020054801A (en) * | 2018-09-07 | 2020-04-09 | 旭化成株式会社 | Sorption material, specific substance capture system, and specific substance capture method |
| CN109126877A (en) * | 2018-09-20 | 2019-01-04 | 西北师范大学 | A kind of preparation and application of iron (III) tetracarboxylic phenyl porphyrin implanted metal organic frame |
| CN110025596A (en) * | 2019-04-25 | 2019-07-19 | 上海理工大学 | A kind of Nano composite granules and preparation method thereof |
| CN113457659B (en) * | 2021-06-24 | 2022-08-26 | 四川大学 | Transition metal monoatomic nano enzyme and its preparation method and use |
| CN113694935B (en) * | 2021-06-24 | 2023-11-03 | 南开大学 | Method for improving activity of nano-material peroxidase |
| CN115521470B (en) * | 2022-08-29 | 2023-10-31 | 中国人民解放军国防科技大学 | N-chloro zirconium-porphyrin MOF, N-chloro zirconium-porphyrin MOF/polymer composite material and preparation method |
| CN116478416A (en) * | 2023-04-17 | 2023-07-25 | 合肥工业大学 | Porphyrin-based bimetallic MOFs material and preparation method and application thereof |
-
2024
- 2024-05-17 CN CN202410615026.0A patent/CN118185052B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115598193A (en) * | 2022-10-12 | 2023-01-13 | 华东交通大学（Cn） | Preparation of molecular imprinting photoelectrochemical sensor based on photoexcitation mimic enzyme and method for detecting norfloxacin by using molecular imprinting photoelectrochemical sensor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN118185052A (en) | 2024-06-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Davies et al. | A semisynthetic metalloenzyme based on a protein cavity that catalyzes the enantioselective hydrolysis of ester and amide substrates | |
| Coucouvanis et al. | Reaction of [Fe (SC6H5) 4] 2-with organic trisulfides and implications concerning the biosynthesis of ferredoxins. Synthesis and structure of the [(C6H5) 4P] 2Fe2S12 complex | |
| Song et al. | Exquisitely designed magnetic DNA nanocompartment for enzyme immobilization with adjustable catalytic activity and improved enzymatic assay performance | |
| Pan et al. | Novel aqueous soluble cobalt phthalocyanine: synthesis and catalytic activity on oxidation of 2-mercaptoethanol | |
| CN118185052B (en) | Zirconium porphyrin metal organic framework nano-enzyme and preparation method and application thereof | |
| CN110697758B (en) | Method for constructing multilevel-structure copper sulfide nanoenzyme by biological template method | |
| CN110467641A (en) | A kind of more molybdic acid alcoxyl derivatives of Anderson type and one pot hydrothermal preparing process | |
| CN109772378B (en) | Method for preparing high-activity iron-doped bismuth oxyhalide photo-Fenton catalyst, product and application thereof | |
| Lalioti et al. | New metal-binding modes for 5-aminoorotic acid: preparation, characterization and crystal structures of zinc (II) complexes | |
| Wang et al. | Imide-functionalized Cu-MOF: Biomimetic peroxidase activity and detection of hydrogen peroxide and ascorbic acid | |
| CN112225307B (en) | Catalysis of H by using MIL-100(Fe/Mn) derivative2O2Method for removing PPCPs in water | |
| CN102875458B (en) | Synthesis method of chromium 2-pyridylformate | |
| CN113105646A (en) | Preparation method and application of bimetallic-organic infinite coordination polymer nano-microsphere | |
| CN114874449B (en) | Preparation method and application of metal-organic framework compound containing monoatomic catalytic site | |
| Ang et al. | Synthesis, crystal structures and magnetic properties of one-and two-dimensional copper (II) complexes bridged by succinate | |
| CN113845521B (en) | Method for synthesizing imidazo nitrogen-containing heterocyclic hydrazine derivative by aqueous phase photocatalysis one-pot method | |
| CN113717391B (en) | Boron-containing zirconium-based metal organic framework material and preparation method and application thereof | |
| JP2002047266A (en) | Composition including methionine transition metal complex and amino acids | |
| CN109956981A (en) | A kind of isopolyacid precursor assembling manganese and copper are heteroatomic polyacid material | |
| CN101020692A (en) | Process of preparing organic tin compound | |
| CN112958117A (en) | Fenton cocatalyst, and preparation method and application thereof | |
| CN114522732B (en) | Preparation and application of chiral titanium oxide cluster capable of serving as chiral construction unit | |
| CN115518691A (en) | Artificial enzyme with laccase-like enzyme activity, preparation method and application thereof | |
| CN111662337A (en) | Oxygen-bridged binuclear ruthenium complex and preparation method thereof | |
| CN118812535A (en) | Novel folic acid synthesis method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |