CN109206595B

CN109206595B - Silver-carrying nano composite antibacterial material and preparation method thereof

Info

Publication number: CN109206595B
Application number: CN201710515614.7A
Authority: CN
Inventors: 吴梦娇; 陈于蓝
Original assignee: Tianjin University
Current assignee: Tianjin University
Priority date: 2017-06-29
Filing date: 2017-06-29
Publication date: 2020-11-06
Anticipated expiration: 2037-06-29
Also published as: CN109206595A

Abstract

The invention discloses a silver-carrying nano composite antibacterial material and a preparation method thereof, wherein a conjugated microporous polymer SN1-CMP or SN2-CMP is sequentially and respectively represented by a formula (I) or a formula (IV):

Description

Silver-carrying nano composite antibacterial material and preparation method thereof

Technical Field

The invention belongs to the field of organic porous materials, and particularly relates to a preparation method of a silver-loaded nano composite antibacterial material.

Background

In recent years, the synthesis and application of Conjugated Microporous Polymers (CMPs) have been receiving attention. As an important organic porous material, the conjugated microporous polymer has an application value in the traditional fields of adsorption, separation, heterogeneous catalysis and the like by virtue of a conjugated rigid structure and a permanent microporous property of the conjugated microporous polymer, and also has potential application in the fields of photoelectricity, energy storage, sensing and the like. The design idea is to change the CMPs constructed by different synthetic methods from the initial selection of different monomers into the post-modification and functionalization of the CMPs, and gradually has more and new application fields.

As an important aza-condensed ring, the 1, 10-phenanthroline and the derivative thereof have important values in the aspects of complexing metal ions, photoelectric devices and the like.

Inorganic antibacterial agents, that is, antibacterial agents of metals such as silver, copper, etc., which are supported by porous materials and have antibacterial effects, have been widely studied on the basis of their characteristics such as good heat resistance, no generation of drug resistance, low toxicity, etc., which are superior to natural antibacterial agents and organic antibacterial agents.

There is a need for novel CMPs and their use in antimicrobial vectors.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provide a conjugated microporous polymer SN1-CMP or SN 2-CMP.

The second purpose of the invention is to provide a preparation method of the conjugated microporous polymer SN1-CMP or SN 2-CMP.

The third purpose of the invention is to provide the silver-loaded nano composite antibacterial material prepared by using the conjugated microporous polymer SN1-CMP or SN2-CMP as the raw material.

The fourth purpose of the invention is to provide a preparation method of the silver-loaded nano composite antibacterial material.

The technical scheme of the invention is summarized as follows:

the conjugated microporous polymer SN1-CMP or SN2-CMP, SN1-CMP represented by formula I, SN2-CMP represented by formula IV;

formula I is prepared from compound III-Br and compound II by Sonogashira coupling reaction type A2B 4:

formula IV is prepared from compound V-Br and compound II by Sonogashira coupling reaction type A2B 4:

wherein R is₁Is a tert-butyl group.

The preparation method of the conjugated microporous polymer SN1-CMP or SN2-CMP comprises the following steps:

under the argon atmosphere, adding a palladium catalyst and a ligand into an organic solvent, uniformly stirring at room temperature, adding a compound III-Br or V-Br, a compound II, cuprous iodide and triethylamine, freezing to remove oxygen for 2-4 times, heating to 80-120 ℃, reacting for 24-72 hours, cooling to room temperature, filtering, washing and drying to obtain a conjugated microporous polymer SN1-CMP or SN 2-CMP;

the preparation of the SN1-CMP is shown in a reaction formula 1:

reaction formula 1:

the preparation of the SN2-CMP is shown in a reaction formula 2:

reaction formula 2:

wherein R is₁Is a tert-butyl group.

The palladium catalyst is preferably dicyanobenzene palladium dichloride or tetratriphenylphosphine palladium, and other palladium catalysts can be selected for catalysis.

The ligand is preferably tri (o-tolyl) phosphine or triphenylphosphine.

The organic solvent is N, N-dimethylformamide or tetrahydrofuran, and other organic solvents can be selected.

The preparation method of the silver-loaded nano composite antibacterial material comprises the following steps:

dissolving silver salt in alcohol, adding conjugated microporous polymer SN1-CMP or SN2-CMP, stirring at room temperature in dark for 8-12 hours, filtering, washing with alcohol to obtain solid, putting into a Soxhlet extractor filled with methanol, washing to remove unadsorbed silver salt, and drying to obtain the silver-loaded nano composite antibacterial material Ag-SN1-CMP or Ag-SN 2-CMP.

The mass ratio of the silver salt to the conjugated microporous polymer SN1-CMP or SN2-CMP is preferably 2: 1.

the silver salt is preferably silver tetrafluoroborate or silver nitrate.

The alcohol is methanol or ethanol, and other alcohols can be used.

The silver-loaded nano composite antibacterial material prepared by the method.

The invention has the advantages that:

the invention synthesizes two conjugated microporous polymers SN1-CMP or SN2-CMP, and the silver-loaded nano composite antibacterial material Ag-SN1-CMP or Ag-SN2-CMP is prepared by taking the two conjugated microporous polymers as carriers and loading silver ions. The application range of the conjugated microporous polymer material is expanded, the silver-loaded nano composite antibacterial material Ag-SN1-CMP or Ag-SN2-CMP has good antibacterial effect, and has potential application value in the field of biological antibacterial.

Drawings

FIG. 1 is a solid nuclear magnetic map of a conjugated microporous polymer SN 1-CMP.

FIG. 2 is a solid nuclear magnetic map of a conjugated microporous polymer SN 2-CMP.

FIG. 3 is an infrared spectrum of a conjugated microporous polymer SN1-CMP and its synthetic monomers.

FIG. 4 is an infrared spectrum of a conjugated microporous polymer SN2-CMP and its synthetic monomers.

FIG. 5 is a Scanning Electron Micrograph (SEM) of conjugated microporous polymer SN 1-CMP.

FIG. 6 is a Scanning Electron Micrograph (SEM) of conjugated microporous polymer SN 2-CMP.

FIG. 7 is a Transmission Electron Micrograph (TEM) of conjugated microporous polymer SN 1-CMP.

FIG. 8 is a Transmission Electron Micrograph (TEM) of conjugated microporous polymer SN 2-CMP.

FIG. 9 is a Transmission Electron Micrograph (TEM) of Ag-SN1-CMP of the Ag-loaded nanocomposite antibacterial material.

FIG. 10 is a Transmission Electron Micrograph (TEM) of Ag-SN2-CMP of Ag-loaded nanocomposite antibacterial material.

FIG. 11 shows N of conjugated microporous polymer SN1-CMP₂Adsorption and desorption curves.

FIG. 12 shows N of conjugated microporous polymer SN2-CMP₂Adsorption and desorption curves.

FIG. 13 shows the antibacterial experiment of Ag-SN1-CMP as the Ag-carrying nano composite antibacterial material.

FIG. 14 shows the antibacterial experiment of Ag-SN2-CMP as the Ag-carrying nano composite antibacterial material.

Detailed Description

The present invention will be further described with reference to the following examples. The following description is a specific description of the invention in order to facilitate understanding thereof and should not be construed as limiting the invention.

Example 1

Synthesis of monomer SN1-Br (III-Br): (the preparation of example 1 is merely exemplary and does not limit the invention in any way.)

(1) Compound A1(16.79mmol,4.5g), tert-butyryl chloride (31.45mmol,4.23g), and triethylamine (4mL) were added to 100mL of a tetrahydrofuran solution, and the mixture was stirred at room temperature for 12 hours. The solvent was spun off under reduced pressure, dichloromethane and water were added for extraction washing, and then dried over anhydrous magnesium sulfate, and finally spun dry. Performing column chromatography purification, wherein an eluent is dichloromethane: petroleum ether is 2: 3 to give compound B1(6.17g, 84%) as a white solid.

(2) Compound B1(2.29mmol,1g), phenylboronate (5.28mmol,1.11g), sodium bicarbonate (95.22mmol,8g), tetrakis (triphenylphosphine) palladium (0.07mmol,0.08g) were added to a 250mL two-necked flask, degassed three times with suction, added to a mixed solution of tetrahydrofuran (75mL) and water (30mL), degassed three times with suction, and finally heated to 70 ℃ under nitrogen and refluxed for 24 hours. Cooling to room temperature, removing the solvent under reduced pressure, adding dichloromethane and water for extraction washing, drying with anhydrous magnesium sulfate, and finally spin-drying. Performing column chromatography purification, wherein an eluent is dichloromethane: petroleum ether is 1: 1 to give compound C1(0.61g, 61%) as a white solid.

(3) Compound C1(1.13mmol,0.5g), phosphorus oxychloride (15mL), phosphorus pentoxide (23.25mmol,3.3g) was charged into a 50mL single neck round bottom flask, heated to 116 deg.C and refluxed for 30 hours. After cooling to room temperature, the mixture was slowly poured into ice water, and the pH was adjusted to 10 with potassium hydroxide, followed by cooling. Dichloromethane was added for extraction, followed by drying over anhydrous magnesium sulfate and finally spin-drying. After passing through a neutral alumina column, it was finally recrystallized from dichloro and petroleum ether to give SN1(0.32g, 71%) as a pale yellow solid.

(4) Adding diisopropylamine (1mL) into tetrahydrofuran (20mL), freezing to remove oxygen, slowly adding n-butyllithium (2.5mL) at-78 deg.C, maintaining the temperature for 1 hr, taking out, stirring at room temperature for 1 hr to obtain yellow solution; then, SN1(0.25mmol,0.1g) was added at-78 deg.C, the temperature was maintained at low for 1 hour, and the mixture was taken out and stirred at room temperature for 1 hour until the solution became green; then, carbon tetrabromide (2.6mmol,0.86g) was added at-78 ℃ and the solution was brown overnight with natural warming. The reaction was quenched by addition of water, the solvent was decanted, dichloromethane was added for extraction, dried over anhydrous magnesium sulfate and finally spun dried. After passing through a neutral alumina column, final recrystallization from dichlorine and petroleum ether gave the pure white solid compound SN1-Br (III-Br) (0.12g, 84%) of the formula:

wherein R is₁Is a tert-butyl group.

Example 2

Synthesis of monomer SN2-Br (V-Br): (the preparation of example 2 is merely illustrative and not limitative)

(1) Compound A2(3.6mmol,1g), tert-butyryl chloride (8.6mmol,1.05g), and triethylamine (3mL) were added to a 35mL dichloromethane solution, and the mixture was stirred at room temperature for 24 hours. Cooling to room temperature, pouring into water, adding ethyl acetate and water for extraction washing, drying by anhydrous magnesium sulfate, and finally spin-drying. Performing column chromatography with dichloromethane as eluent to obtain white solid compound B2(1.5g, 93%);

(2) compound B2(2.24mmol,1g) was added to 30mL of DMF, followed by dropwise addition of a solution of N-bromosuccinimide (5mmol,0.9g) in 30mL of DMF, which was then heated to 50 ℃ overnight. Cooled to room temperature, poured into water, extracted with dichloromethane, dried over anhydrous magnesium sulfate and then spin dried. Column chromatography was performed using dichloromethane as eluent to give compound C2(1.04g, 77%) as a pale yellow solid.

(3) C2(0.16mmol,0.1g), phosphorus oxychloride (8mL), phosphorus pentoxide (4.95mmol,0.71g) was charged into a 50mL single neck round bottom flask, heated to 116 deg.C and refluxed for 30 hours. After cooling to room temperature, the mixture was slowly poured into ice water, and the pH was adjusted to 10 with potassium hydroxide, followed by cooling. Dichloromethane was added for extraction, followed by drying over anhydrous magnesium sulfate and finally spin-drying. After passing through a neutral alumina column, it was finally recrystallized from dichloro and petroleum ether to give SN2-Br (V-Br) (0.085g, 91%) as an off-white solid.

Wherein R is₁Is a tert-butyl group.

Example 3

Preparation of conjugated microporous Polymer SN1-CMP (I)

Under argon atmosphere, PdCl₂(PhCN)₂(0.0075mmol,2.88mg) and tri (o-tolyl) phosphine (0.015mmol,4.56mg)After stirring at room temperature for 10min, 4mL of DMF was added with SN1-Br (III-Br) (0.1mmol,56.44mg), tetrakis (4-ethynylphenyl) -methane (TPM, Compound II), (0.075mmol,31.45mg), cuprous iodide (0.00075mmol,0.14mg), triethylamine (2mL), and was cooled 3 times to remove oxygen, heated to 100 ℃ and reacted for 72 hours. Cooled to room temperature, filtered, washed with chloroform, acetone, methanol, and water in this order, repeated three times to remove unreacted monomers and catalyst, and the filtered solid was placed in a vacuum oven and dried at 80 ℃ for 24 hours to obtain a yellow powder (67mg, 87% yield).

FIG. 1 is a solid NMR spectrum of a conjugated microporous polymer SN1-CMP (I) of this example, wherein 164.0-121.8ppm of aromatic carbon, 95.8 and 84.2ppm of carbon having triple bonds between carbon and carbon, demonstrating the effective linkage of two monomers, 66.0ppm of quaternary carbon of tetrakis (4-ethynylphenyl) -methane (TPM), 40.8ppm of quaternary carbon of t-butyl, and 30.3ppm of methyl carbon. The test was performed on a Bruker WB AVANCE II 400MHz nuclear magnetic spectrometer.

The IR spectrum of the monomer SN1-Br and tetrakis (4-ethynylphenyl) -methane (TPM) and the conjugated microporous polymer (SN1-CMP) obtained in this example is shown in FIG. 3, wherein the TPM is 3283cm^-1The absorption peak is the stretching vibration peak of alkynyl hydrogen, and the peak disappears in the infrared curve of the obtained conjugated microporous polymer, which indicates that alkynyl hydrogen disappears after the reaction, and simultaneously, the monomer SN1-Br is 495cm^-1The absorption peak of C-Br disappears in the infrared curve of the conjugated microporous polymer, and the two points verify the structure of the conjugated microporous polymer of the product of the embodiment. The infrared spectrum test adopts a Bruker alphaspectrometer infrared spectrometer, tabletting and sample preparation are carried out, and the conjugated microporous polymer is dried in advance.

The Scanning Electron Micrograph (SEM) of the conjugated microporous polymer SN1-CMP (I) is shown in FIG. 5 and the Transmission Electron Micrograph (TEM) is shown in FIG. 7, and a qualitatively uniform porous structure can be seen. Specific surface area analysis of FIG. 11, SN1-CMP specific surface area of 1003m²·g^-1NLDFT fitting meanThe pore size is about 1.4nm, and micropores are taken as the main pore size. The scanning electron microscope used was a Hitachi Limited model S-4800microscope, the transmission electron microscope used was a JEOL model JEM-2100Fmicroscope, and the specific surface area analysis used was Bel Japan Inc. model BELSOPR-mini II analyzer.

The conjugated microporous polymer SN1-CMP was prepared by using tetratriphenylphosphine palladium to replace PdCl2(PhCN)2 in the example, triphenylphosphine to replace tri (o-tolyl) phosphine in the example, tetrahydrofuran to replace DMF in the example, freezing to remove oxygen for 2 times to replace freezing to remove oxygen for 3 times, heating to 80 ℃ to replace 100 ℃, and reacting for 24 hours to replace reaction 72 in the same way as the example.

Example 4

Preparation of conjugated microporous Polymer SN2-CMP (IV)

Under argon atmosphere, PdCl₂(PhCN)₂(0.0075mmol,2.88mg) and tri (o-tolyl) phosphine (0.015mmol,4.56mg) were added to a solution of 4mL DMF and stirred at room temperature for 10min, SN2-Br (V-Br) (0.1mmol,56.84mmol), tetrakis (4-ethynylphenyl) -methane (TPM, Compound II) (0.075mmol,31.45mg), cuprous iodide (0.00075mmol,0.14mg), triethylamine (2mL) were added, the oxygen was removed by freezing 3 times, heated to 100 ℃ and reacted for 72 h. Cooled to room temperature, filtered, washed with chloroform, acetone, methanol, and water in this order, repeated three times to remove unreacted monomers and catalyst, and the filtered solid was placed in a vacuum oven and dried at 80 ℃ for 24 hours to obtain a yellow powder (73mg, 94% yield).

FIG. 2 is a solid NMR spectrum of the conjugated microporous polymer SN2-CMP (IV) of this example, wherein 163.6-121.8ppm are aromatic carbons, 98.1 and 83.8ppm are carbons with triple bonds between carbons, demonstrating the effective attachment of two monomers, 65.8ppm is quaternary carbon of tetrakis (4-ethynylphenyl) -methane (TPM), 39.9ppm is quaternary carbon of t-butyl, and 30.0ppm is methyl carbon. The test was performed on a Bruker WB AVANCE II 400MHz nuclear magnetic spectrometer.

Monomers SN2-Br and tetrakis (4-ethyl)The infrared spectrum of alkynyl phenyl) -methane (TPM) and the conjugated microporous polymer (SN2-CMP) obtained in this example is shown in FIG. 4, wherein the TPM is 3283cm^-1The absorption peak is the stretching vibration peak of alkynyl hydrogen, and the peak disappears in the infrared curve of the obtained conjugated microporous polymer, which shows that alkynyl hydrogen disappears after the reaction, and simultaneously, monomer SN2-Br is 491cm^-1The absorption peak of C-Br disappears in the infrared curve of the conjugated microporous polymer, and the two points verify the structure of the conjugated microporous polymer of the product of the embodiment. The infrared spectrum test adopts a Bruker alphaspectrophotometer infrared spectrometer, tabletting and sample preparation are carried out, and the conjugated microporous polymer is dried in advance.

Scanning Electron Micrographs (SEM) of the yoke microporous polymer SN2-CMP (IV) are FIG. 6 and Transmission Electron Micrographs (TEM) are FIG. 8, showing a qualitatively uniform porous structure. Specific surface area analysis of FIG. 12, SN2-CMP a specific surface area of 925m²·g^-1The NLDFT fitting average pore size is 1.4nm, and micropores are taken as the main pore size. The scanning electron microscope used was a Hitachi Limited model S-4800microscope, the transmission electron microscope used was a JEOL model JEM-2100Fmicroscope, and the specific surface area analysis used was Bel Japan Inc. model BELSOPR-mini II analyzer.

Replacement of PdCl in this example with Tetratriphenylphosphine Palladium₂(PhCN)₂The conjugated microporous polymer SN2-CMP is prepared by the same steps as the embodiment except that triphenylphosphine is used for replacing tri (o-tolyl) phosphine in the embodiment, tetrahydrofuran is used for replacing DMF in the embodiment, frozen oxygen removal is used for replacing 4 times, frozen oxygen removal is used for replacing 3 times, heating is carried out to 120 ℃ for replacing 100 ℃, and reaction is carried out for 48 hours instead of 72 hours.

Example 5

The preparation method of the Ag-SN1-CMP nano composite antibacterial material comprises the following steps:

dissolving silver tetrafluoroborate (10mg) in 5mL of anhydrous methanol, adding a conjugated microporous polymer SN1-CMP (5mg), stirring at room temperature in the dark for 8 hours, repeatedly washing with methanol to remove unadsorbed silver tetrafluoroborate, separating to obtain a solid, putting the solid into a Soxhlet extractor filled with methanol, washing to remove unadsorbed silver salt, and drying to obtain the silver-loaded nano composite antibacterial material Ag-SN 1-CMP.

The mass fraction of silver was determined by ICP-MS to be 12.32 wt% (Ag-SN 1-CMP).

FIG. 9 is a transmission electron micrograph of Ag-SN1-CMP showing the presence of silver nanoparticles. A transmission electron microscope was used with a JEOL model JEM-2100F microscope.

Classical antibacterial agar assay tests As shown in FIG. 13, equal amounts of E.coli colonies were cultured on agar plates 80mm in diameter and left for the same time, with increasing concentration of the added antibacterial agent, the bacterial mortality rate increased, i.e., the antibacterial ability increased.

Experiments prove that silver nitrate is used for replacing silver tetrafluoroborate in the embodiment, ethanol is used for replacing methanol in the embodiment, and other similar embodiments can prepare the silver-loaded nano composite antibacterial material Ag-SN1-CMP and have similar antibacterial effects.

Example 6

The preparation method of the Ag-SN2-CMP nano composite antibacterial material comprises the following steps:

dissolving silver tetrafluoroborate (10mg) in 5mL of anhydrous methanol, adding a conjugated microporous polymer SN2-CMP (5mg), stirring at room temperature in the dark for 12 hours, repeatedly washing with methanol to remove unadsorbed silver tetrafluoroborate to obtain a solid, putting the solid into a Soxhlet extractor filled with methanol, washing to remove unadsorbed silver salt, and drying to obtain the silver-loaded nano composite antibacterial material Ag-SN 2-CMP.

The mass fraction of silver was determined by ICP-MS to be 6.22 wt% (Ag-SN 2-CMP).

FIG. 10 is a transmission electron micrograph of Ag-SN2-CMP, in which the presence of silver nanoparticles can be seen. A transmission electron microscope was used with a JEOL model JEM-2100F microscope.

Classical antibacterial agar assay tests As shown in FIG. 14, equal amounts of E.coli colonies were cultured on agar plates 80mm in diameter and left for the same time, with increasing concentration of the added antibacterial agent, the bacterial mortality rate increased, i.e., the antibacterial ability increased.

Experiments prove that silver nitrate is used for replacing silver tetrafluoroborate in the embodiment, ethanol is used for replacing methanol in the embodiment, and other similar embodiments can prepare the silver-loaded nano composite antibacterial material Ag-SN2-CMP and have similar antibacterial effects.

Through agar antibacterial experiments, Ag-SN-CMP with different concentrations is dispersed in agar bacteria culture dishes, and the antibacterial condition is observed by standing. The antibacterial effect is enhanced along with the increase of the concentration of the added antibacterial agent under the condition of the same time.

Claims

1. The conjugated microporous polymer SN1-CMP or SN2-CMP is characterized in that SN1-CMP is shown by formula (I) and SN2-CMP is shown by formula (IV); the formula (I) is prepared from a compound (III-Br) and a compound (II) through a Sonogashira coupling reaction of A2B4 type:

the formula (IV) is prepared from a compound (V-Br) and a compound (II) through a Sonogashira coupling reaction of A2B4 type:

wherein R is₁Is a tert-butyl group.

2. A method for preparing the conjugated microporous polymer SN1-CMP or SN2-CMP according to claim 1, characterized by comprising the steps of:

the preparation of the SN1-CMP is shown in a reaction formula 1:

reaction formula 1:

the preparation of the SN2-CMP is shown in a reaction formula 2:

reaction formula 2:

wherein R is₁Is a tert-butyl group.

3. The process as set forth in claim 2 wherein the palladium catalyst is dicyanobenzene palladium dichloride or tetratriphenylphosphine palladium.

4. The process as claimed in claim 2, wherein the ligand is tri (o-tolyl) phosphine or triphenylphosphine.

5. The process as set forth in claim 2, characterized in that the organic solvent is N, N-dimethylformamide or tetrahydrofuran.

6. The preparation method of the silver-loaded nano composite antibacterial material is characterized by comprising the following steps:

dissolving silver salt in alcohol, adding the conjugated microporous polymer SN1-CMP or SN2-CMP described in claim 1, stirring at room temperature in the dark for 8-12 hours, filtering, washing with alcohol to obtain a solid, putting the solid into a Soxhlet extractor filled with methanol, washing to remove unadsorbed silver salt, and drying to obtain the silver-loaded nano composite antibacterial material Ag-SN1-CMP or Ag-SN 2-CMP.

7. The method of claim 6, wherein the mass ratio of the silver salt to the conjugated microporous polymer SN1-CMP or SN2-CMP is 2: 1.

8. the method according to claim 6 or 7, characterized in that the silver salt is silver tetrafluoroborate or silver nitrate.

9. The method according to claim 6 or 7, characterized in that the alcohol is methanol or ethanol.

10. A silver-loaded nanocomposite antimicrobial material prepared by the method of any one of claims 6 to 9.