CN116396497B - Metal organic framework material, ligand structure thereof and application of metal organic framework material in nano enzyme - Google Patents
Metal organic framework material, ligand structure thereof and application of metal organic framework material in nano enzyme Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 37
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 35
- 239000003446 ligand Substances 0.000 title claims abstract description 22
- 102000004190 Enzymes Human genes 0.000 title abstract description 14
- 108090000790 Enzymes Proteins 0.000 title abstract description 14
- 230000003115 biocidal effect Effects 0.000 claims abstract description 3
- 230000000844 anti-bacterial effect Effects 0.000 claims description 16
- 241000191967 Staphylococcus aureus Species 0.000 claims description 8
- 241000588724 Escherichia coli Species 0.000 claims description 7
- 239000003899 bactericide agent Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 230000002401 inhibitory effect Effects 0.000 claims description 2
- 239000003139 biocide Substances 0.000 claims 1
- 230000000855 fungicidal effect Effects 0.000 claims 1
- 239000000417 fungicide Substances 0.000 claims 1
- 238000012360 testing method Methods 0.000 abstract description 12
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- 238000000034 method Methods 0.000 abstract description 7
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- 238000000338 in vitro Methods 0.000 abstract description 3
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- 230000008569 process Effects 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 39
- 238000006243 chemical reaction Methods 0.000 description 19
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- 238000012512 characterization method Methods 0.000 description 7
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- 238000005481 NMR spectroscopy Methods 0.000 description 6
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- 238000004364 calculation method Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- SZQQTWLBYAKIOT-UHFFFAOYSA-N (3,5-dibromophenyl)-trimethylsilane Chemical compound C[Si](C)(C)C1=CC(Br)=CC(Br)=C1 SZQQTWLBYAKIOT-UHFFFAOYSA-N 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
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- 229910020820 NaAc-HAc Inorganic materials 0.000 description 4
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
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- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 3
- PGUJTLXJHQLAPJ-UHFFFAOYSA-N 2-[2,5-dimethyl-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Chemical compound CC=1C=C(B2OC(C)(C)C(C)(C)O2)C(C)=CC=1B1OC(C)(C)C(C)(C)O1 PGUJTLXJHQLAPJ-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
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- 239000002253 acid Substances 0.000 description 3
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- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- BMIBJCFFZPYJHF-UHFFFAOYSA-N 2-methoxy-5-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine Chemical compound COC1=NC=C(C)C=C1B1OC(C)(C)C(C)(C)O1 BMIBJCFFZPYJHF-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
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- RWSXRVCMGQZWBV-WDSKDSINSA-N glutathione Chemical compound OC(=O)[C@@H](N)CCC(=O)N[C@@H](CS)C(=O)NCC(O)=O RWSXRVCMGQZWBV-WDSKDSINSA-N 0.000 description 2
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- 102000035195 Peptidases Human genes 0.000 description 1
- 108091005804 Peptidases Proteins 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- 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
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/74—Synthetic polymeric materials
- A61K31/80—Polymers containing hetero atoms not provided for in groups A61K31/755 - A61K31/795
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K33/00—Medicinal preparations containing inorganic active ingredients
- A61K33/40—Peroxides
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P17/00—Drugs for dermatological disorders
- A61P17/02—Drugs for dermatological disorders for treating wounds, ulcers, burns, scars, keloids, or the like
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- 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
- A61P31/02—Local antiseptics
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- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C63/00—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings
- C07C63/33—Polycyclic acids
- C07C63/331—Polycyclic acids with all carboxyl groups bound to non-condensed rings
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Abstract
The invention discloses a metal organic framework material, a ligand structure thereof and application thereof in nano-enzyme, and belongs to the technical field of biology. The invention provides nano-enzyme with good sterilization effect based on a metal organic framework material. The invention prepares a carboxylic acid ligand and applies the carboxylic acid ligand to the synthesis of novel metal organic framework materials, the synthesized MOF materials can be used as nano enzymes, have peroxidase activity, show good sterilization capability in vivo and in vitro sterilization tests, are vital to resisting bacterial pathogens and treating infected wounds, and have good application prospects and development potential in the field of antibiosis. In addition, the metal organic framework material synthesis method provided by the invention has the advantages of simple process, mild conditions and the like.
Description
Technical Field
The invention relates to a metal organic framework material, a ligand structure thereof and application thereof in nano enzyme, belonging to the technical field of biology.
Background
The spread of pathogenic bacteria has been a fatal challenge for humans, not only severely threatening the health of humans, but also one of the leading causes of human death worldwide. While antibiotics, metal ions and quaternary ammonium salts are currently effective against bacterial attack, microbial resistance is also greatly increased. As a substitute for these traditional antibiotics, rapid development of nanoenzymes has brought promise to antibacterial technologies. Because the nano enzyme has bactericidal activity and a nano structure generating a photo-thermal effect, drug-resistant bacteria can be inactivated through continuous reaction catalysis, and the nano enzyme has excellent development prospect in biomedicine, and is expected to become an antibacterial disinfectant with more durability and safety.
The nano-enzyme is a nano-material having enzyme-like properties, and exhibits excellent enzymatic activities such as those of peroxidase-like (POD), catalase-like (CAT), superoxide dismutase-like (SOD), glucose oxidase-like (GOx), and glutathione peroxidase-like (GPx). Wherein, the peroxide-like nano-enzyme (POD) can utilize hydrogen peroxide with physiological concentration (3 mmol/L) to activate enzyme-like reaction to locally generate a large amount of bactericidal active oxygen, and can avoid denaturation or proteinase hydrolysis to maintain lasting bactericidal activity, thereby realizing the disinfection treatment sensitive to bacteria and playing a high-level role in pathological parts. However, this antimicrobial therapy is severely challenged by the lack of rational design of nanoenzymes with good catalytic reactivity. Therefore, development of a nanoenzyme with better catalytic reactivity is an important subject facing the field.
Metal organic framework materials (Metal Organic Frameworks, MOFs) as a class of porous materials composed of metal ions and organic ligands have been developed to accurately design de novo or post-synthesis modifications to tailor the abundant and well-defined enzyme mimics, which have become the focus of research in the nanoenzyme research field. And, the metal organic framework material has high similarity with biological enzyme in physical property and chemical property, and has an ordered space structure with a catalytic site taking metal as a center and a site available for substrate adsorption. Therefore, it is necessary to provide a metal organic framework material applied to nano-enzymes and a preparation method thereof.
Disclosure of Invention
The invention provides a metal organic frame material and a preparation method thereof, and the metal organic frame material is used as nano enzyme in order to provide the nano enzyme with good sterilization effect.
The technical scheme of the invention is as follows:
one of the purposes of the present invention is to proposeFor a metal organic framework material, which is abbreviated as MOF-ET13, the chemical formula is [ Cu ] 4 Ce 4 (L) 2 ]Wherein L is C 72 H 50 O 8 。
The second object of the present invention is to provide a method for preparing the above metal organic framework material, which comprises the following steps: ce (NO) 3 ) 3 •6H 2 O and Cu (NO) 3 ) 2 •3H 2 O is dissolved in ethanol solution, the ligand is dissolved in ethanol solution, then the two solutions are mixed, stirred for 2.5 hours at room temperature, and after the reaction is finished, the MOF-ET13 is obtained through centrifugation, washing and drying treatment in sequence.
Further defined, ce (NO 3 ) 3 •6H 2 O、Cu(NO 3 ) 2 •3H 2 The molar ratio of O to ligand was 1:1:1.
Further defined, the volume ratio of ethanol to water in the ethanol solution is 1:1.
Further defined, the reaction is completed and then washed 3 times with water and ethanol.
Further defined, the drying temperature is 333K.
Further defined, the structure of the ligand is:
。
further defined, the method of preparing the ligand comprises the steps of:
s1, adding 3, 5-dibromo-1-trimethylsilyl benzene, 4' - (carboxyl) biphenyl-4-boric acid, 1.4 g palladium carbon and sodium carbonate into absolute ethyl alcohol, heating for reaction under the protection of argon, slowly cooling a reaction system to room temperature after the reaction is finished, adding water for dilution, filtering, acidifying filtrate with hydrochloric acid, filtering, washing precipitate, and drying to obtain white powder, namely an intermediate 1;
s2, heating iodine monochloride to liquid, transferring to a three-mouth bottle placed on ice, adding N, N-dimethylformamide, stirring uniformly, adding the intermediate 1, heating to room temperature for reaction, pouring the reaction liquid into dichloromethane after the reaction is finished, filtering, collecting solids, and drying to obtain light yellow powder, namely the intermediate 2;
s3, adding an intermediate 2, 5-dimethyl-1, 4-phenylene diboronic acid pinacol ester and tetrakis (triphenylphosphine) palladium into a potassium carbonate aqueous solution, heating for reaction under the protection of argon, slowly cooling a reaction system to room temperature after the reaction is finished, adding water for dilution, filtering, acidifying filtrate with hydrochloric acid, centrifuging, collecting a precipitate, washing the precipitate, adding the precipitate into ethanol, rotationally evaporating to remove a solvent, and drying to obtain a tan solid, namely the ligand.
Still further defined, the molar volume ratio of 3, 5-dibromo-1-trimethylsilylbenzene, 4' - (carboxyl) biphenyl-4-boronic acid, 1.4 grams of palladium on carbon, sodium carbonate, and absolute ethanol in S1 is 10mmol:22mmol:80mmol:180mL.
Further defined, the S1 heating reaction temperature is 70 ℃ and the time is 30 hours.
Further defined, the filtrate in S1 is acidified to pH 1 with 2mol/L hydrochloric acid.
Further defined, the precipitate is washed with water in S1.
Further defined, the drying process in S1 is: and placing for 24 hours at the temperature of 50 ℃ under vacuum.
Further defined, the molar ratio of iodine monochloride to intermediate 1 in S2 is 34:6.2.
further defined, the reaction time in S2 is 64h.
Still further defined, the molar ratio of potassium carbonate, intermediate 2, 5-dimethyl-1, 4-phenylene diboronic acid pinacol ester and tetrakis (triphenylphosphine) palladium in S3 is 70:5:2.5:0.25.
further defined, the reaction temperature in S3 is 80℃and the time is 20 hours.
Further defined, the filtrate in S3 is acidified using 6mol/L hydrochloric acid.
Still further defined, the centrifugation speed in S3 is 6000rpm.
Further defined, the precipitate in S3 is washed with water and then with ethanol 3 times.
Further defined, the drying temperature in S3 is 65℃and the time is 24 hours.
The third object of the present invention is to provide an application of the metal organic framework material, which is used as a nano-enzyme bactericide.
The invention also provides a nano-enzyme bactericide based on the metal organic framework material, and the nano-enzyme bactericide is particularly used for inhibiting the growth of escherichia coli and staphylococcus aureus.
The invention has the following beneficial effects:
the MOF material can be used as nano enzyme, has peroxidase activity, shows good sterilization capability in-vivo and in-vitro sterilization tests, is critical to resisting bacterial pathogens and treating infected wounds, and has good application prospect and development potential in the field of antibiosis. In addition, the metal organic framework material synthesis method provided by the invention has the advantages of simple process, mild conditions and the like.
Drawings
FIG. 1 is a synthetic route to ligands for preparing metal organic framework materials;
FIG. 2 is a diagram of intermediate 1 prepared in example 1 1 H-NMR spectrum;
FIG. 3 is a diagram of intermediate 1 prepared in example 1 13 C-NMR spectrum;
FIG. 4 is a mass spectrum of intermediate 1 prepared in example 1;
FIG. 5 is a diagram of intermediate 2 prepared in example 1 1 H-NMR spectrum;
FIG. 6 is a diagram of intermediate 2 prepared in example 1 13 C-NMR spectrum;
FIG. 7 is a mass spectrum of intermediate 2 prepared in example 1;
FIG. 8 shows the ligand prepared in example 1 1 H-NMR spectrum;
FIG. 9 is a diagram of the ligands prepared in example 1 13 C-NMR spectrum;
FIG. 10 is a mass spectrum of the ligand prepared in example 1;
FIG. 11 is a representation of the X-ray structure of the metal organic framework material MOF-ET13 prepared in example 1;
FIG. 12 is a graph showing the results of the antibacterial activity test of the metal organic framework material MOF-ET13 prepared in example 1 against Escherichia coli;
FIG. 13 is a graph showing the antimicrobial activity of MOF-ET13, a metal organic framework material prepared in example 1, against Staphylococcus aureus;
FIG. 14 shows the results of an in vivo antimicrobial activity test of the metal-organic framework material MOF-ET13 prepared in example 1.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. The following description of the embodiments of the present invention will be made apparent and fully in view of the accompanying drawings, in which some, but not all embodiments of the invention are shown. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In addition, the technical features of the different embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
The experimental methods used in the following examples are conventional methods unless otherwise specified. The materials, reagents, methods and apparatus used, without any particular description, are those conventional in the art and are commercially available to those skilled in the art.
3, 5-dibromo-1-trimethylsilylbenzene (CAS: 17878-23-8), 4' - (carboxyl) biphenyl-4-boronic acid (CAS: 872341-95-2) and 2, 5-dimethyl-1, 4-phenylenedioic acid pinacol ester (CAS: 303006-89-5) used in the following examples were all obtained by direct purchase from Sigma-Aldrich corporation.
The elemental analysis of the following examples was performed using a german Elementar UNICUBE elemental analyzer.
Example 1:
the process for preparing the metal organic framework material MOF-ET13 in this example is as follows:
(1) As shown in fig. 1, the ligand was synthesized:
(1) synthetic intermediate 1:
to a three-necked flask were added 180ml of absolute ethanol, 3, 5-dibromo-1-trimethylsilylbenzene (starting material 1,3.08 g, 10 mmol), 4' - (carboxyl) biphenyl-4-boronic acid (starting material 2,5.32 g, 22 mmol), 1.4 g palladium on carbon and sodium carbonate (8.48 g, 80 mmol), and the mixture was evacuated and then backfilled 3 times with argon, heated and stirred at 70 ℃ for 30 hours. After the reaction, the reaction system was cooled slowly to 25 ℃, diluted with 500 ml of water, filtered, the filtrate was acidified to ph=1 with 2mol/l of hydrochloric acid, the precipitate was filtered, washed with water, dried, and finally placed under vacuum at 50 ℃ for 24 hours to give 4.34 g of white powder, intermediate 1, in 80% yield.
The intermediate 1 obtained was structurally characterized:
<1> nuclear magnetic characterization results:
hydrogen spectrum: 1 H NMR (400 MHz, DMSO):δ8.05 (m, 7H), 7.86 (d, 4H), 7.38 (m, 8H), 0.35 (s, 9H), as shown in fig. 2.
Carbon spectrum: 13 C NMR (100 MHz, DMSO):δ167.69, 144.13, 140.90, 140.62, 139.21, 138.55, 132.28, 130.23, 129.63, 127.88, 127.50, 126.96, 126.71, 1.43 as shown in fig. 3.
<2> mass spectrometry characterization results:
ESI(m/z): [M+H] + theoretical calculation C 35 H 30 O 4 Si, 542.71; actual measurement 543.29. As shown in fig. 4.
<3> elemental analysis test results:
theoretical calculation C 35 H 30 O 4 Si, C, 77.46, H, 5.57, O, 11.79; actual measurements of C, 78.23, H, 6.03, O, 12.13.
In summary, the structure of the intermediate 1 obtained is as follows:
。
(2) synthesis of intermediate 2:
iodine monochloride (5.5 g, 34 mmol) was heated to liquid and transferred by pipette into a three-necked flask placed on ice. N, N-dimethylformamide was added thereto, and the solution was stirred for 5 minutes, followed by addition of intermediate 1 (3.36 g, 6.2 mmol). The mixture was heated to 25 ℃, stirred for 64 hours, poured into dichloromethane, filtered, and the white solid was collected and dried to give 3.07 g of pale yellow powder as intermediate 2 in 83% yield.
The intermediate 2 obtained was structurally characterized:
<1> nuclear magnetic characterization results:
hydrogen spectrum: 1 H NMR (400 MHz, DMSO):δ8.17 (d, 2H), 8.11 (d, 4H), 8.04 (d, 1H), 7.88 (d, 4H), 7.39 (m, 8H), as shown in fig. 5.
Carbon spectrum: 13 C NMR (100 MHz, DMSO):δ167.69, 144.13, 141.58, 140.90, 138.49, 136.17, 130.23, 129.63, 127.89, 127.72, 126.85, 126.71, 96.83, as shown in fig. 6.
<2> mass spectrometry characterization results:
ESI(m/z): [M+H] + theoretical calculation C 32 H 21 IO 4 596.42; actual measurement 597.23. As shown in fig. 7.
<3> elemental analysis test results:
theoretical calculation C 32 H 21 IO 4 C, 64.44, H, 3.55, O, 10.73; actual measurements of C, 65.23, H, 4.03, O, 11.46.
In summary, the structure of the intermediate 2 obtained is as follows:
。
(3) synthesizing a ligand:
potassium carbonate (9.7 g, 70 mmol) was dissolved in 30 ml of water, then the solution was transferred to a 250 ml three-necked flask, and intermediate 2 (2.98 g, 5 mmol), 2, 5-dimethyl-1, 4-phenylenedioic acid pinacol ester (raw material 3,0.829 g, 2.5 mmol) and tetrakis (triphenylphosphine) palladium (0.29 g, 0.25 mmol) were sequentially added to the flask, and the mixture was evacuated and then backfilled with argon for 3 times, and then heated and stirred at 80℃for 20 hours. After the reaction was completed, the reaction system was slowly cooled to 25 ℃, the mixture was diluted with water, filtered, acidified with 6 mol/liter hydrochloric acid, centrifuged at 6000rpm, and the precipitate was collected. The precipitate was then washed with water and then ethanol 3 times, 50 ml each. Finally, the mixture is suspended in ethanol, the solvent is removed by rotary evaporation, and finally, the mixture is dried for 24 hours at the temperature of 65 ℃ to obtain 0.83 g of tan solid which is the ligand, and the yield is 92%.
Structural characterization of the ligand obtained:
<1> nuclear magnetic characterization results:
hydrogen spectrum: 1 H NMR (400 MHz, DMSO):δ8.13 (m, 14, H), 7.96 (m, 10H), 7.41 (m, 16, H), 2.60 (s, 6H), as shown in fig. 8.
Carbon spectrum: 13 C NMR (100 MHz, DMSO):δ167.69, 144.13, 140.90, 139.87, 139.35, 139.15, 139.02, 134.85, 130.23, 129.63, 127.89, 127.71, 127.17, 126.94, 126.71, 126.62, 21.45 as shown in fig. 9.
<2> mass spectrometry characterization results:
ESI(m/z): [M+H] + theoretical calculation C 72 H 50 O 8 1042.18; actual measurement 1043.01. As shown in fig. 10.
<3> elemental analysis test results:
theoretical calculation C 72 H 50 O 8 C, 82.90, H,4.83, O, 12.27; actual measurements of C, 83.14, H, 5.68, O, 12.99.
In summary, the structure of ligand 1 obtained was as follows:
。
(2) Synthetic metal organic framework material MOF-ET13:
1 millimole of Ce (NO 3 ) 3 •6H 2 O and 1 mmol Cu (NO) 3 ) 2 •3H 2 O was dissolved in 20 ml of water/ethanol (volume ratio 1:1) solution, and 1 mmol of ligand was dissolved in 5 ml of water/ethanol (volume ratio 1:1) solution. The two solutions were then mixed and magnetically stirred at 25 ℃ for 2.5 hours. After the reaction was completed, the product was collected by centrifugation, washed 3 times with 50 ml of water and ethanol each time. Vacuum drying under 333 and K to obtain MOF-ET13.
The obtained MOF-ET13 is structurally characterized:
<1> the synthesized MOF-ET13 crystals were stored in glass capillaries and tested for crystal structure using single crystal X-rays, the instrument was a Bruker-Apex type ii CCD detector, and were acquired using a Cu ka (λ= 1.54178 a) X-ray source. The data are that the SADABS program corrects for absorption, and not extinction or decay. The test results are shown in FIG. 11, directly solved with the SHELXTL software package.
Antibacterial activity test;
the whole plate was coated with E.coli and Staphylococcus aureus using a sterile coating rod, and then the plate was placed in an incubator and cultured at 36.+ -. 1 ℃ for 1 hour. Five groups were then set:<1>the control group is NaAc-HAc buffer;<2>H 2 O 2 ；<3>MOF-ET13+H 2 O 2 ；<4>H 2 O 2 +illumination;<5>MOF-ET13+H 2 O 2 +light. Wherein the light irradiation time was 15 minutes and the MOF-ET13 concentration was 50. Mu.g/ml. And then the in vitro sterilization effect of 50 microgram/milliliter MOF-ET13 nano enzyme on escherichia coli and staphylococcus aureus under weak acid condition is measured by using a plate counting method.
The test results are shown in fig. 12 and 13, and the MOF-ET13 was found to be at 500 μl of 3 mmol/liter H compared to the control NaAc-HAc, ph=4.0 2 O 2 In the presence, the antibacterial agent has excellent antibacterial effect on escherichia coli or staphylococcus aureus. Then under light conditions and 500. Mu.l of 3mM H 2 O 2 When coexisting, the bactericidal composition has obvious inhibition effect on the growth of escherichia coli and staphylococcus aureus, and the bactericidal rate is 99.87 percent and 99.95 percent respectively.
(4) Taking the metal organic framework material MOF-ET13 prepared by the method as nano enzyme, and performing in-vivo antibacterial activity test on the nano enzyme;
the 12 mice with average weight gain were randomly divided into 3 groups and anesthetized, and then 100 microliters of 1×10 were used 8 The CFU/mL staphylococcus aureus suspension was used to treat the wound of mice, infected for 12 hours,<1>the control group is NaAc-HAc buffer;<2>MOF-ET13+H 2 O 2 ；<3>MOF-ET13+H 2 O 2 +light. Wherein the light irradiation time was 15 minutes and the MOF-ET13 concentration was 50. Mu.g/ml.
The results of the test are shown in FIG. 14, in which the change over time of the wound area of each group was compared with that of the NaAc-HAc buffer blank group, MOF-ET13+ H 2 O 2 The group can significantly reduce the wound area in the same time, which suggests that the addition of MOF-ET13 can significantly increase the antibacterial activity in vivo.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (4)
1. A metal organic framework material is characterized in that the material is simply called MOF-ET13, and the chemical formula is [ Cu ] 4 Ce 4 (L) 2 ]Wherein L is C 72 H 50 O 8 ；
The ligand structure for preparing the metal organic framework material is as follows:
2. use of a metal organic framework material according to claim 1 for the preparation of a nano-enzymatic biocide.
3. Use of a metal organic framework material according to claim 1 as a nano-enzyme fungicide, characterized in that the metal organic framework material is mixed with H 2 O 2 Is compounded for use.
4. A nano-enzyme bactericide, which is the metal-organic framework material of claim 1, and is used for inhibiting the growth of escherichia coli and staphylococcus aureus.
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| CN102942444A (en) * | 2012-11-09 | 2013-02-27 | 烟台海川化学制品有限公司 | Synthesis method of 2,2'-dibromo-9,9'-spirobifluorene |
| CN106867025A (en) * | 2017-03-02 | 2017-06-20 | 张家港市五湖新材料技术开发有限公司 | A kind of efficient flame-retarding agent and preparation method thereof |
| CN111954939A (en) * | 2018-03-07 | 2020-11-17 | 株式会社半导体能源研究所 | Light-emitting element, display device, electronic device, organic compound, and lighting device |
| CN113943318A (en) * | 2021-10-20 | 2022-01-18 | 宁夏大学 | Synthesis method of chiral phenyl silanol and 1, 2-chiral disilicon compound |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102942444A (en) * | 2012-11-09 | 2013-02-27 | 烟台海川化学制品有限公司 | Synthesis method of 2,2'-dibromo-9,9'-spirobifluorene |
| CN106867025A (en) * | 2017-03-02 | 2017-06-20 | 张家港市五湖新材料技术开发有限公司 | A kind of efficient flame-retarding agent and preparation method thereof |
| CN111954939A (en) * | 2018-03-07 | 2020-11-17 | 株式会社半导体能源研究所 | Light-emitting element, display device, electronic device, organic compound, and lighting device |
| CN113943318A (en) * | 2021-10-20 | 2022-01-18 | 宁夏大学 | Synthesis method of chiral phenyl silanol and 1, 2-chiral disilicon compound |
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