CN112225893A - Porphyrin and hydantoin-based porous organic polymer and preparation method and application thereof - Google Patents
Porphyrin and hydantoin-based porous organic polymer and preparation method and application thereof Download PDFInfo
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- CN112225893A CN112225893A CN202010948748.XA CN202010948748A CN112225893A CN 112225893 A CN112225893 A CN 112225893A CN 202010948748 A CN202010948748 A CN 202010948748A CN 112225893 A CN112225893 A CN 112225893A
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- hydantoin
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- organic polymer
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- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 title claims abstract description 133
- 229920000620 organic polymer Polymers 0.000 title claims abstract description 31
- 150000004032 porphyrins Chemical class 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229940091173 hydantoin Drugs 0.000 title claims abstract description 14
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 21
- 239000002245 particle Substances 0.000 claims abstract description 6
- 239000012798 spherical particle Substances 0.000 claims abstract description 5
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
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- VRLDVERQJMEPIF-UHFFFAOYSA-N dbdmh Chemical compound CC1(C)N(Br)C(=O)N(Br)C1=O VRLDVERQJMEPIF-UHFFFAOYSA-N 0.000 claims description 13
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- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 9
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- YIROYDNZEPTFOL-UHFFFAOYSA-N 5,5-Dimethylhydantoin Chemical compound CC1(C)NC(=O)NC1=O YIROYDNZEPTFOL-UHFFFAOYSA-N 0.000 description 2
- 206010059866 Drug resistance Diseases 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
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- UAIUNKRWKOVEES-UHFFFAOYSA-N 3,3',5,5'-tetramethylbenzidine Chemical compound CC1=C(N)C(C)=CC(C=2C=C(C)C(N)=C(C)C=2)=C1 UAIUNKRWKOVEES-UHFFFAOYSA-N 0.000 description 1
- ZBQCCTCQUCOXBO-UHFFFAOYSA-N 4-(4-aminophenyl)-2,2,6,6-tetramethylcyclohex-3-en-1-amine Chemical compound CC1(C)C(N)C(C)(C)CC(C=2C=CC(N)=CC=2)=C1 ZBQCCTCQUCOXBO-UHFFFAOYSA-N 0.000 description 1
- 108020000946 Bacterial DNA Proteins 0.000 description 1
- 125000006416 CBr Chemical group BrC* 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
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- RGHNJXZEOKUKBD-SQOUGZDYSA-N Gluconic acid Natural products OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
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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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0605—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0616—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only two nitrogen atoms in the ring
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
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- 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
- B01J31/184—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine mixed aromatic/aliphatic ring systems, e.g. indoline
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- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- 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
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- 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
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Abstract
The invention provides a porous organic polymer based on porphyrin and hydantoin, and a preparation method and application thereof, and belongs to the technical field of porous organic polymers. The porous organic polymer is composed of spherical particles with the particle size being aggregated within the range of 200-300 nm. The porous organic polymer of the invention has positive charges, is more beneficial to interact with negatively charged bacteria so as to enable the bacteria to be combined on a bacterial membrane, and is beneficial to eliminating the bacteria within the damage range of active oxygen. At the same time, porphyrin and hydantoin units and their extended conjugated structures provide the material with excellent peroxidase-like catalysisChemical activity, near infrared enhanced light Fenton performance and chemical antibacterial activity, and has good reusability. Proved by experiments, under the near infrared irradiation, FePPOPHydantoinThe antibacterial efficiency of the antibacterial agent is over 99.999 percent. Meanwhile, the material preparation method is simple and has strong controllability, so that the material has good practical application value.
Description
Technical Field
The invention belongs to the technical field of porous organic polymers, and particularly relates to a porous organic polymer based on porphyrin and hydantoin, and a preparation method and application thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Bacterial infections are an increasingly serious health problem worldwide. Antibiotics are considered the most widely accepted therapeutic measures. However, bacteria have begun to develop resistance to antibiotics due to overuse and abuse. Antibiotic resistance causes about 70 million deaths worldwide each year, and becomes a huge economic burden impeding social development, especially in underdeveloped countries. Therefore, the development of efficient novel antibacterial drugs, particularly antibacterial drugs with low drug resistance tendency, is very important for preventing and treating bacterial infection.
To date, significant efforts have been made to design alternative nanomaterials for antimicrobial applications. Different from the traditional antibiotics for preserving the form of bacteria, the nano material has a multi-modal antibacterial effect, and the nano material has good stability, is easy to manufacture and reuse, so that the drug resistance is not easy to generate. The cell membrane of the whole bacterium can be completely decomposed by the treatment of the nano material. Therefore, it is difficult for bacteria to repair physically damaged cell membranes, thereby slowing down the evolution of antibacterial resistance. To date, a large number of nanomaterials, such as metal oxide nanoparticles, noble metal nanoparticles and transition metals, have been reported to exhibit good antibacterial properties. Among them, nanoenzymes provide unprecedented opportunities for antibacterial activity. They gain inspiration from the natural antibacterial mechanism and can catalyze H2O2Converted into highly toxic Reactive Oxygen Species (ROS) and cause irreversible damage to bacteria. E.g. Fe3O4Nanoparticles of V2O5Nanowires, nitrogen-doped carbon nanomaterials (N-CNMs), CeO2Nanoparticles and the like have been found to be able to combat bacteria with their superior peroxidase mimetic activity.
Despite their promising antibacterial applications, nanoenzymes still face some challenges. First, some nanoenzymesHave toxicity which prevents their widespread use. Secondly, the diffusion distance of ROS is about 20nm, and its lifetime is less than 200 ns. Unfortunately, most nanoenzymes do not effectively capture bacteria within the effective range of reactive oxygen species damage, thereby reducing their effect against bacteria. Third, nanoenzymes typically have lower catalytic efficiency than native enzymes, exhibiting pH-dependent catalytic properties. Thus, to obtain a sufficiently high concentration of ROS, a higher concentration of H is required2O2. These fatal defects limit their use in biological systems where the pH is neutral and the allowable H is2O2The highest biologically relevant concentration was 100. mu.M. To address these challenges faced by nanoenzymes, a typical strategy is to construct multifunctional materials with synergistic effects. For example, the just-in-the-morning task group reported a positively charged microporous MoS2The hydrogel can capture bacteria in the damage range of active oxygen. In addition, the photo-thermal effect of the molybdenum disulfide is combined to achieve the synergistic sterilization effect. To avoid direct use of high concentrations of toxic H2O2A self-activating (2D Cu-TCPP (Fe)/GOx) nano-catalyst is prepared. The glucose oxidase can convert glucose into gluconic acid and H2O2Not only can provide rich H2O2And the pH value of the system can be reduced to 3-4, so that the antibacterial efficiency of the 2D Cu-TCPP (Fe) is obviously improved. Au/g-C is also reported3N4Multifunctional material, and MoS2@ PDA-Ag and the like are against bacteria. Despite these tremendous advances, new and effective strategies against bacteria remain urgently needed.
Among many reported biological systems, porphyrins have good biocompatibility and efficient catalytic performance, and are typical representatives of functional molecular materials. In recent years, porphyrin-based porous organic polymers (POPPs) have become one of the most interesting nanoenzymology. Due to the following advantages: 1) the POPPs serving as a porous material has larger surface area, hierarchical pore structure and abundant surface active sites, and is beneficial to H2O2Close to the active site and diffusion of ROS. 2) The POPPs can be given various structures due to the structure's modifiabilityAnd a function. However, the inventors found that, to date, studies on the activity of POPPs peroxidase-like enzymes have been mainly focused on biosensors, but since strong acidic conditions are also required for optimal expression of peroxidase-like enzyme activity, there are few people who apply it to the biomedical field.
Disclosure of Invention
In order to overcome the technical problems, the invention provides a porous organic polymer FePPOP based on porphyrin and hydantoinHydantoinThe invention utilizes cross-coupling reaction to construct FePPOP (FePPOP)HydantoinIt has a positive charge, facilitating its interaction with negatively charged bacteria and thus binding to the bacterial membrane, facilitating bacterial clearance in the range of reactive oxygen species destruction. At the same time, FePPOPHydantoinThe porphyrin and hydantoin units and the enlarged conjugated structure thereof enable the material to have excellent peroxidase-like catalytic activity, near-infrared enhanced light Fenton performance and chemical antibacterial activity, thereby having good practical application value.
In order to achieve the technical purpose, the technical scheme adopted by the invention is as follows:
in a first aspect of the invention, a porous organic polymer FePPOP based on porphyrin and hydantoin is providedHydantoinHaving a repeating structural unit represented by the following formula I,
in a second aspect of the present invention, there is provided the above-mentioned porous organic polymer FePPOPHydantoinThe production method of (2), the production method comprising: the compound is prepared by taking 1, 3-dibromo-5, 5-dimethylhydantoin and a monomer 5,10,15, 20-tetra (4-bromophenyl) ferriporphyrin (FeTBrPP) as raw materials based on cross-coupling reaction.
In a third aspect of the invention, the porous organic polymer FePPOP is providedHydantoinUse in any one of:
1) antibacterial agents and/or preparation of antibacterial agents;
2) nano enzyme and/or nano enzyme preparation.
In a fourth aspect of the invention, there is provided an antibacterial agent comprising the above porous organic polymer, FePPOPHydantoinThe antibacterial agent can exhibit bacteriostatic and bactericidal effects on various bacteria including staphylococcus aureus.
In a fifth aspect of the invention, a nanoenzyme is provided, wherein the nanoenzyme comprises the porous organic polymer FePPOPHydantoinThe nano enzyme has peroxidase mimic activity.
In a sixth aspect of the present invention, there is provided a bacteriostasis and/or sterilization method, comprising: adding the porous organic polymer FePPOP into a sample to be treatedHydantoinAntibacterial agents and/or nanoenzymes.
The beneficial technical effects of one or more technical schemes are as follows:
the technical scheme is used for preparing the porous porphyrin-based organic polymer FePPOP with positive charge for the first timeHydantoinIt is more favorable for interacting with negatively charged bacteria to bind on the bacterial membrane, and is favorable for eliminating bacteria in the damage range of active oxygen. Meanwhile, the porphyrin and hydantoin units and the enlarged conjugated structures thereof enable the material to have excellent peroxidase-like catalytic activity, near-infrared enhanced light Fenton performance and chemical antibacterial activity, and have good reusability. Proved by experiments, under the near infrared irradiation, FePPOPHydantoinThe antibacterial efficiency of the antibacterial agent is over 99.999 percent. Meanwhile, the material preparation method is simple and has strong controllability, so that the material has good practical application value.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 shows FePPOP prepared by the example of the present inventionHydantoinThe infrared spectrogram of (1) is shown in the specification, wherein a is Hydantoin, b is FeTBrPP, and c is FePPOPHydantoin；
FIG. 2 shows FePPOP prepared by the embodiment of the present inventionHydantoinA solid carbon spectrum of (a);
FIG. 3 shows FePPOP prepared by the embodiment of the present inventionHydantoinThermogravimetric analysis curve of (a);
FIG. 4 shows FePPOP prepared by the embodiment of the present inventionHydantoinScanning electron microscope pictures;
FIG. 5 shows FePPOP prepared by the embodiment of the present inventionHydantoinThe nitrogen adsorption and desorption curve diagram;
FIG. 6 shows FePPOP prepared by the example of the present inventionHydantoinWherein A is FePPOPHydantoinThe ultraviolet-visible absorption spectrogram of Hydantoin and FeTBrPP, B is FePPOPHydantoinThe band gap energy spectrum schematic diagram C is FePPOPHydantoinHydantoin and FeTBrPP fluorescence spectrograms, D is FePPOPHydantoinGraph of photocurrent versus time;
FIG. 7 shows FePPOP prepared by the example of the present inventionHydantoinThe peroxidase activity condition of (1) is a characteristic diagram, wherein A is a transformation diagram of TMB and oxTMB, and B is FePPOP under different conditionsHydantoinC is FePPOPHydantoinD is H2O2Concentration, E is pH, F is temperature;
FIG. 8 shows FePPOP prepared by the present inventionHydantoinA is H2O2The curve of the initial velocity of the substrate and the concentration of the substrate, B is a simulation standard curve of the initial velocity of A and the double reciprocal of the concentration of the substrate, C is a curve of the initial velocity of the TMB substrate and the concentration of the substrate, and D is a simulation standard curve of the initial velocity of C and the double reciprocal of the concentration of the substrate;
FIG. 9 shows FePPOP prepared by an embodiment of the present inventionHydantoinThe photo-Fenton activity test chart of (1);
FIG. 10 shows FePPOP prepared by an embodiment of the present inventionHydantoinZeta potential test chart and antibacterial activity chart of (1); wherein, A is a Zeta potential test chart, and B is an antibacterial activity chart;
FIG. 11 is a graph of a polymer prepared according to an embodiment of the present inventionFePPOPHydantoinWherein A is FePPOPHydantoinXPS graph before use, B is FePPOPHydantoinXPS graph after use, C is FePPOPHydantoinXPS plot of O1s before use, plot D is FePPOPHydantoinXPS plots of post-use O1 s;
FIG. 12 shows FePPOP prepared by the example of the present inventionEPAInfrared spectrograms before and after use;
FIG. 13 is an SEM image of Staphylococcus aureus treated under different conditions, wherein A is PBS and B is H2O2C is FePPOPHydantoinD is FePPOPHydantoin+ NIR, E is FePPOPHydantoin+H2O2F is FePPOPHydantoin+H2O2+NIR。
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise. It is to be understood that the scope of the invention is not to be limited to the specific embodiments described below; it is also to be understood that the terminology used in the examples is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the present invention.
As mentioned previously, porphyrins have good biocompatibility and efficient catalytic properties and are typical representatives of functional molecular materials. However, studies on the activity of POPPs peroxidase-like enzymes have so far focused on biosensors, but since strong acidic conditions are also required for optimal expression of peroxidase-like activities, few have been applied to the biomedical field.
On the other hand, 1, 3-dibromo-5, 5' dimethylhydantoin has attracted considerable interest as an antibiotic. Studies have shown that they exhibit low bacterial resistance, probably because they have a mixed multi-modal biocidal mechanism of destroying bacterial DNA, interfering with cellular metabolism by reacting with cellular material, etc. However, having only moderate antibacterial activity will seriously affect its practical application. Therefore, it is necessary to combine other antibacterial groups with 1, 3-dibromo-5, 5' dimethylhydantoin to overcome the inefficiency, minimize the risk of undesirable effects, and achieve synergistic antibacterial performance. In addition, the polymer structure containing hydantoin functional groups is more stable than the monomer structure from a recycling point of view.
Based on the consideration, the invention firstly prepares the porous porphyrin-based organic polymer FePPOP with positive chargeHydantoinIt can be used as an effective antibacterial agent. Thus, in one embodiment of the present invention, there is provided a porphyrin and hydantoin based porous organic polymer, FePPOPHydantoinWhich is composed of spherical particles having a particle diameter of 200 to 300nm, has good thermal stability, and has a repeating structural unit represented by the following formula I,
in still another embodiment of the present invention, there is provided the above porous organic polymer, FePPOPHydantoinThe production method of (2), the production method comprising: the compound is prepared by taking 1, 3-dibromo-5, 5-dimethylhydantoin and a monomer 5,10,15, 20-tetra (4-bromophenyl) ferriporphyrin (FeTBrPP) as raw materials based on cross-coupling reaction.
Wherein the molar ratio of the 1, 3-dibromo-5, 5-dimethylhydantoin to the FeTBrPP is 0.5-5: 1, such as 0.5: 1. 1: 1. 2: 1. 5: 1, more preferably 0.47: 0.24;
specifically, the preparation method comprises the following steps: under the atmosphere of inert gas, 1, 3-dibromo-5, 5-dimethylhydantoin and FeTBrPP are placed in a mixed solution for heating; and (3) after the heating reaction is finished, adding propionic acid into the solution, and stirring and purifying to obtain the propionic acid.
Wherein the inert gas is nitrogen or argon, preferably argon;
the mixed solution is a mixture of 2, 2' -bipyridine, bis (1, 5-cyclooctadiene) nickel (0), 1, 5-cyclooctadiene and N, N-Dimethylformamide (DMF), and is used when the mixed solution is purple after being stirred.
Wherein the molar volume ratio of the 2, 2' -bipyridine to the bis (1, 5-cyclooctadiene) nickel (0) to the 1, 5-cyclooctadiene to DMF is 1-5 mmol: 1-5 mmol: 1-4 mmol: 50-100 mL; preferably 4.09 mmol: 4.09 mmol: 3.96 mmol: 65 mL.
The heating reaction specifically comprises the following steps: reacting for 1-15 h at 70-90 ℃, preferably for 12h at 80 ℃; by controlling the heating temperature and time, the reaction progress is accelerated, and the yield is improved.
The molar volume ratio of FeTBrPP to DMF to propionic acid is 0.1-0.5 mmol: 50-100 mL: 5-15 mL; preferably 0.24 mmol: 65mL of: 10 mL.
The propionic acid is added in a stirring mode, and the stirring time is controlled to be 0.1-1 h, preferably 0.5 h.
The purification step includes filtration, washing and drying.
The washing method comprises the following specific steps: washing with chloroform, tetrahydrofuran and water respectively;
the drying method comprises the following specific steps: and (3) carrying out vacuum drying on the washed product at 70-90 ℃.
In still another embodiment of the present invention, there is provided the above porous organic polymer, FePPOPHydantoinUse in any one of:
1) antibacterial agents and/or preparation of antibacterial agents;
2) nano enzyme and/or nano enzyme preparation.
In yet another embodiment of the present invention, there is provided an antimicrobial agent comprising the above-described porous organic polymer, FePPOPHydantoinThe antibacterial agent can exhibit bacteriostatic and bactericidal effects on various bacteria including staphylococcus aureus.
In another embodiment of the invention, a nanoenzyme is provided, which comprises the above porous organic polymer FePPOPHydantoinThe nano enzyme has peroxidase mimic activity.
In another embodiment of the present invention, there is provided a method of bacteriostasis and/or sterilization, comprising: adding the porous organic polymer FePPOP into a sample to be treatedHydantoinAntibacterial agents and/or nanoenzymes.
In another embodiment of the present invention, the method further comprises irradiating the sample to be treated with near infrared light and/or adding H to the sample to be treated2O2。
The present invention will be further described with reference to specific examples for better illustrating the objects, technical solutions and advantages of the present invention.
Examples
HydantoinFePPOP material synthesis
1) Synthesis of monomer 5,10,15, 20-tetrakis (4-bromophenyl) ferriporphyrin (FeTBrPP):
in a 250mL three-necked flask, H was added2TBrPP (300mg,0.32mmol) was dissolved in 150mL DMF and FeCl was added3·6H2O (60.48mg,0.37mmol), was heated under reflux with stirring for 4 h. Then distilling under reduced pressure to remove DMF solvent, cooling to room temperature, adding a large amount of water for washing, and filtering to remove FeCl3Until the wash solution is colorless, at which point the filter cake is purple, i.e., the monomer 5,10,15, 20-tetrakis (4-bromophenyl) ferriporphyrin (MALDI-TOF MS: calcd. for C)44H26Br4N4Fe[M+H]+:983.06；found m/z 986.32)。
2)FePPOPHydantoinPreparation of
FePPOPHydantoinThe preparation of (A) is carried out in two stages. One is a reaction process in the glove box and the other is a post-treatment process. Firstly, 2' -dipyridyl(0.64g,4.09mmol), bis (1, 5-cyclooctadiene) nickel (0) (1.13g,4.09mmol) and 1, 5-cyclooctadiene (0.5mL,3.96mmol) were dissolved in dry DMF (65mL) and stirred to a purple color. 1, 3-dibromo-5, 5-dimethylhydantoin (134.66mg,0.47mmol) and iron (III)5,10,15, 20-tetrabromo- (4' -bromophenyl) porphyrin (FeTBrPP,232.40mg,0.24mmol) were mixed with the above solution, and the temperature was maintained at 80 ℃. The solution was kept at this temperature for 12 hours under argon protection and then allowed to cool naturally. A defined amount of 10mL of propionic acid was gradually added to the purple suspension, stirred for 0.5h and filtered to give the crude product. Then washed with chloroform, tetrahydrofuran and water, respectively, to give the product, the reaction formula is shown below, and finally the black solid was dried in a vacuum oven at 80 ℃ (yield 78.1%).
HydantoinFePPOP infrared spectroscopy and solid nuclear magnetism characterization
It was first characterized by infrared spectroscopy. Compared with the monomer, the C-Br and N-Br stretching vibration of FeTBrPP and 1, 3-dibromo-5, 5-dimethylhydantoin respectively appears at 467cm-1And 720cm-1Almost disappeared after polymerization, indicating that the monomer had been completely condensed, FIG. 1. At the same time, the main fingerprint peaks of the monomers were observed in the polymer. At 2960cm-1And 1640cm-1In which-CH of 1, 3-dibromo-5, 5-dimethylhydantoin is present3And C-H and C ═ O vibrate telescopically. At 1001cm-1The peak is caused by the N-Fe stretching vibration band formed by FeTBrPP. In addition, use is made of13FePPOP was further verified by C CP/MAS solid-state NMRHydantoinFIG. 2. The characteristic peaks δ of 20ppm and δ of 60ppm can be assigned to CH in 1, 3-dibromo-5, 5-dimethylhydantoin3And sp3 hybridized carbon. The peaks centered at 162ppm and 180ppm are due to the C ═ O group of the methoxy group. And FePPOPHydantoinThe aromatic carbon in the medium from FeTBrPP reaches a peak value between 109 and 159 ppm. From the above results, it can be seen that 1, 3-dibromo-5, 5-dimethylhydantoin and FeTBrPP remain expected in the polymerThe structure of (1).
HydantoinThe stability and the morphology of FePPOP are characterized as follows:
the thermogravimetric analysis (TGA) results show that the compound has good heat resistance. In N2Under the protection of (3), when the temperature reaches 100 ℃, the weight loss rate is only 7.02 percent, which is shown in figure 3. FePPOPHydantoinHas good stability, which is probably related to more nitrogen-containing groups. The high stability ensures FePPOPHydantoinCan bear severe environmental conditions. FIG. 4 is a diagram of synthetic FePPOPHydantoinThe morphological characteristics of (1). FePPOPHydantoinIs composed of spherical particles with the particle diameter being gathered in the range of 200-300 nm. It was further observed that the particle surface was clearly rough, which may be the result of aggregation of spherical particles.
HydantoinPorosity characterization of FePPOP
FIG. 5 shows FePPOPHydantoinThe inner graph is a pore diameter distribution graph. Adsorption of nitrogen gas at different pressure ranges confirmed FePPOPHydantoinSatisfying a combination of type I and type iv adsorption isotherms. FePPOP materialHydantoinHas a Brunauer-Emmett-Teller (BET) surface area of 301.41m2 g-1And through the calculation of a non-density functional theory, FePPOPHydantoinMainly concentrated at 1.5, 5, 9nm, which fully demonstrates the FePPOPHydantoinThe hierarchical pore structure of (1). The high BET surface area and hierarchical pore structure provide rich active sites for peroxidase-like performance, facilitating accessibility and diffusion of reactants and products to catalytic centers.
HydantoinOptical property characterization of FePPOP
Research of FePPOP by using ultraviolet-visible diffuse reflectance spectrum, fluorescence spectrum and photocurrentHydantoinSee fig. 6. 1, 3-dibromo-5, 5-dimethylhydantoin monomer (Hydantoin) absorbs light having a wavelength of 272 nm. The FeTBrPP shows a strong and narrow absorption band only at the wavelength 417nm, both with relatively low efficiency for visible light, fig. 6, a. After polymerization, light absorption edgeSharply broadened and the absorption tail extended to 1000 nm. In combination with a narrow band gap (1.06eV) estimated based on the starting wavelength of the uv diffuse reflectance spectrum, this clearly means that the dipyrrolidone can utilize more visible and near infrared light to enhance its photocatalytic activity, thanks to the extended coupled framework, fig. 6, B. In addition, FePPOPHydantoinThe fluorescence response is obviously weakened, and fig. 6 and C show that the recombination rate of the photoexcited electron-hole pair is reduced, which is beneficial to FePPOPHydantoinImprove the photocatalytic activity. The photocurrent response test shows that the photocurrent response of the ITO sample is obviously enhanced, the generated photocurrent is about 31nA, and the ITO sample can be repeatedly switched on and off without obvious deterioration, and the graph is shown in figure 6 and D. This may be due to FePPOPHydantoinThe expanded coupling structure not only improves the near infrared absorption capability, but also promotes the mobility of current carriers, thereby slowing down the recombination of charges.
HydantoinPeroxidase Activity of FePPOP
FePPOP was evaluated by oxidation of 3,3,5, 5-Tetramethylbenzidine (TMB) as a colorimetric substrateHydantoinFig. 7, B. With FePPOPHydantoin+TMB、H2O2+ TMB, TMB and other control experiments compared with no color change, FePPOPHydantoinCan be at H2O2When present, accelerated the conversion of TMB to oxTMB, appearing dark blue. FePPOPHydantoinThe large specific surface area and the expanded coupling framework promote TMB and FePPOP by means of clusteringHydantoinIn combination with (1). And the abundant surface catalytic active sites and the multi-stage porous structure are beneficial to H2O2Accessibility of and diffusion of generated ROS. In addition, FePPOP was recovered by 5 consecutive timesHydantoinSustainability analysis was performed, as shown in fig. 7, C, indicating good recyclability. Further experiments show that FePPOPHydantoinCatalytic performance of with H2O2Concentration, pH and temperature (FIG. 7, D-F) were related, consistent with most peroxidase-like mimetic enzymes reported previously. The best performance occurs at pH 3.77 and 30 ℃ respectively. In addition, FePPOPHydantoinAlso at pH 7.0The catalytic activity of 50% is shown in FIG. 7, E, which provides the possibility for the practical application of the catalyst in normal tissues and bacterial infection sites.
HydantoinReaction kinetics of FePPOP
To better understand FePPOPHydantoinBy fixing TMB concentration and varying H2O2Concentrations were analyzed for steady state kinetics and vice versa. The kinetics of the catalytic reaction is determined by ultraviolet-visible spectrophotometry. The reaction is carried out by maintaining H2O2The Michaelis constant was determined by varying the concentration of TMB (0.5mM) and by maintaining the concentration of TMB and varying the concentration of hydrogen peroxide. Then, a series of initial reaction rates were obtained, as shown in FIG. 8. Km and Vmax are calculated by using a Lineweaver-Burk double reciprocal formula, which is shown as the following formula:
1/v＝(Km/Vmax)×(1/[C])+1/Vmax Eq.(1)
in the formula, V is the initial velocity, C is the substrate concentration, VmaxAnd KmThe maximum reaction rate and the mie constant, respectively. The maximum reaction rate of the material and the mie constant are shown in table 1.
TABLE 1 maximum reaction rates and Mie's constants
Hydantoinphoto-Fenton catalytic activity of FePPOP
The MB is degraded by near infrared radiation, and FePPOP is determinedHydantoinThe photo-Fenton catalytic activity of (1). FePPOP (FePPOP)HydantoinStirring the mixed solution with MB vigorously in dark for 80min to reach adsorption-desorption equilibrium, and adding H2O2Added to the solution and irradiated with 808nm near infrared light. As shown in FIG. 9, about 97% of MB changed color within 40 minutes of irradiation (FePPOPHYydantoin + H)2O2+ NIR group). FePPOP without irradiationHydantoin+H2O2Group, only 66% of MB discoloured at the same time. However, by a series of NIR, H2O2、NIR+H2O2、NIR+FePPOPHydantoinThe control experiment of (2) shows that neither can effectively photodegrade MB. These results clearly demonstrate the FePPOPHydantoinHas excellent photo-Fenton performance such as high specific surface area, abundant active sites, effective near-infrared absorption and the like.
Detection of active oxygen
The photo-assisted fenton process starts with a classical reaction, generating hydroxyl radicals. At the same time, Fe (III) can be converted into Fe (II), possibly in H, with the aid of light2O2With the help of (2), further complete the continuous cycle in Fe (III)/Fe (II). On the other hand, the catalytic properties of peroxidase-like nanoenzymes are generally capable of degrading H2O2Hydroxyl radicals are generated. Terephthalic Acid (TA) was used to verify the catalytic mechanism of the material as an indicator to monitor hydroxyl radical generation. As shown in FIG. 10, A, the fluorescence intensity shows a FePPOPHydantoinConcentration dependence indicates that OH is produced in large amounts. All these results indicate that the FePPOP is due toHydantoinThe light and peroxide properties of (2) significantly enhance catalytic activity.
Antibacterial experiments are carried out on staphylococcus aureus by considering the enzyme catalytic capability and the photocatalytic capability of ferriporphyrin and the chemical antibacterial property of hydantoin. Before the test, FePPOP was monitoredHydantoinZeta potential of (c) to evaluate its antibacterial ability. From FIG. 10, A, it can be seen that the Zeta potential value of the polymer of FeTBrPP is-15.7 mV. However, when Hydantoin cells are introduced into the system, FePPOPHydantoinThe potential value of the positive charge material is obviously improved to +26mV, and the capture efficiency of the bacteria can be effectively improved due to the electronic interaction between the positive charge material and the negative charge bacterial cell membrane. When bacteria react with FePPOPHydantoinAfter combination, the oxidation resistance potential value is obviously reduced, which indicates that FePPOPHydantoinThere is an interaction with staphylococcus aureus. In addition, different concentrations of FePPOPHydantoinAnd is different fromThe effect of the treatment under the conditions is shown in fig. 10, B.
Mechanism exploration
To clarify the antibacterial mechanism, two antibacterial methods were investigated using X-ray photoelectron spectroscopy (XPS) and fourier transform infrared spectroscopy (FT-IR), as shown in fig. 11 and 12. FePPOPHydantoinThe XPS survey spectra of (a) showed C1s, N1s, O1s, and Fe2p peaks at 284.7, 398.4, 531.7, and 711.2, respectively. Among them, O1s species belong to FePPOPHydantoinHydantoin cell of (1). The peak remains unchanged after sterilization. Binding of FePPOP before and after antibacteriumHydantoinSimilar FT-IR spectrum clearly demonstrates FePPOPHydantoinStability during the antibacterial process. Studies have shown that the antibacterial mechanism of Hydantoin can be divided into contact kill, release kill and transfer kill. Based on the stability of the above structure, the Hydantoin unit antimicrobial mechanism may be contact kill. Meanwhile, the damage of the staphylococcus aureus cell membrane under different conditions is revealed by using SEM pictures, as shown in FIG. 13. When FePPOPHydantoinAfter incubation with staphylococcus aureus, FePPOP is foundHydantoinDue to electrostatic interaction, it binds tightly to staphylococcus aureus. With FePPOP separatelyHydantoin、FePPOPHydantoin+ NIR and FePPOPHydantoin+H2O2After incubation, there was a small amount of cell surface disruption, but the outer membrane structure remained unchanged, indicating that these modes were less effective at inhibiting bacteria. FePPOPHydantoin+NIR+H2O2The bacterial surface was more severely damaged by the 20 minute treatment. Demonstration of FePPOPHydantoin+NIR+H2O2The system has synergistic antibacterial ability. In this process, OH generated by the photo-Fenton reaction destroys cell membrane, and the permeability of cell membrane increases, accelerating the growth of nutrient substance and FePPOPHydantoinMedium Hydantoin cell contact. Plus FePPOPHydantoinCatalytic decomposition of H2O2The resulting OH attacks further, leading to bacterial death.
It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and the present invention is not limited thereto, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications and equivalents can be made in the technical solutions described in the foregoing embodiments, or equivalents thereof. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention. Although the present invention has been described with reference to the specific embodiments, it should be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
Claims (10)
1. Porphyrin and hydantoin based porous organic polymer FePPOPHydantoinHaving a repeating structural unit represented by the following formula I,
2. the porous organic polymer FePPOP as claimed in claim 1HydantoinThe particle size distribution method is characterized by comprising spherical particles with the particle size being aggregated within the range of 200-300 nm.
3. The porous organic polymer FePPOP as claimed in claim 1 or 2HydantoinThe method for producing (a), characterized by comprising: the compound is obtained by taking 1, 3-dibromo-5, 5-dimethylhydantoin and monomer 5,10,15, 20-tetra (4-bromophenyl) ferriporphyrin as raw materials based on cross-coupling reaction.
4. The preparation method according to claim 3, wherein the molar ratio of the 1, 3-dibromo-5, 5-dimethylhydantoin to the FeTBrPP is 0.5 to 5: 1, preferably 0.47: 0.24.
5. the method of claim 3 or 4, comprising: under the atmosphere of inert gas, 1, 3-dibromo-5, 5-dimethylhydantoin and FeTBrPP are placed in a mixed solution for heating; and (3) after the heating reaction is finished, adding propionic acid into the solution, and stirring and purifying to obtain the propionic acid.
6. The method according to claim 5, wherein the inert gas is nitrogen or argon, preferably argon;
the mixed solution is a mixture of 2, 2' -bipyridine, bis (1, 5-cyclooctadiene) nickel (0), 1, 5-cyclooctadiene and N, N-Dimethylformamide (DMF);
preferably, the molar volume ratio of the 2, 2' -bipyridine to the bis (1, 5-cyclooctadiene) nickel (0) to the 1, 5-cyclooctadiene to DMF is 1-5 mmol: 1-5 mmol: 1-4 mmol: 50-100 mL; further preferably 4.09 mmol: 4.09 mmol: 3.96 mmol: 65 mL;
the heating reaction is specifically 70-90 ℃ for 1-15 h, preferably 80 ℃ for 12 h;
the molar volume ratio of FeTBrPP to DMF to propionic acid is 0.1-0.5 mmol: 50-100 mL: 5-15 mL; preferably 0.24 mmol: 65mL of: 10 mL;
the propionic acid is added in a stirring mode, and the stirring time is controlled to be 0.1-1 h, preferably 0.5 h;
the purification step comprises filtration, washing and drying;
preferably, the washing specific method is as follows: washing with chloroform, tetrahydrofuran and water respectively;
preferably, the drying method comprises the following steps: and (3) carrying out vacuum drying on the washed product at 70-90 ℃.
7. The porous organic polymer FePPOP as claimed in claim 1 or 2HydantoinUse in any one of:
1) antibacterial agents and/or preparation of antibacterial agents;
2) nano enzyme and/or nano enzyme preparation.
8. An antibacterial agent characterized in thatCharacterized in that the antibacterial agent comprises the porous organic polymer FePPOP of claim 1 or 2Hydantoin。
9. Nanoenzyme comprising the porous organic polymer FePPOP according to claim 1 or 2Hydantoin。
10. A method of bacteriostasis and/or sterilization, comprising: adding the porous organic polymer FePPOP into a sample to be treatedHydantoinAntibacterial agents and/or nanoenzymes;
preferably, the method further comprises irradiating the sample to be treated with near infrared light and/or adding H to the sample to be treated2O2。
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