CN115612114A - Copolymer membrane and enzymatic self-assembly synthesis method and application thereof - Google Patents

Copolymer membrane and enzymatic self-assembly synthesis method and application thereof Download PDF

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CN115612114A
CN115612114A CN202110797790.0A CN202110797790A CN115612114A CN 115612114 A CN115612114 A CN 115612114A CN 202110797790 A CN202110797790 A CN 202110797790A CN 115612114 A CN115612114 A CN 115612114A
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CN115612114B (en
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姜文侠
田晓丽
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Tianjin Institute of Industrial Biotechnology of CAS
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Abstract

The copolymer membrane and the enzymatic self-assembly synthesis method thereof provided by the invention are characterized in that a film-forming monomer containing phenolic hydroxyl, a film-forming monomer containing at least two amino groups and a catalyst are subjected to an enzymatic reaction to prepare the copolymer membrane at the interface of two liquid phases. The method has the advantages of simple operation steps, mild reaction conditions and wide selection range of film forming monomers, and can select the film forming monomers to prepare the copolymer film with corresponding functions according to application requirements. The preparation method of the invention is easy to upgrade from laboratory to industrialized mass production, and has better application prospect.

Description

Copolymer membrane, enzymatic self-assembly synthesis method thereof and application thereof
Technical Field
The invention belongs to a novel high polymer material, belongs to the fields of modern chemistry, biology, material science and application science and engineering thereof, and particularly relates to a copolymer membrane and a method for enzymatic self-assembly synthesis of the copolymer membrane at a liquid-liquid interface and application thereof.
Background
There are millions of organic substances, but the types of monomers that can be used as raw materials for synthesizing polymers are limited, at most, hundreds, so how to use two or more monomers to co-polymerize in different ways and in different proportions to obtain a wide variety of copolymers with different properties to meet different requirements [ Robinia pseudoacacia III, koukang polymer chemistry "M ]. Beijing: scientific publishing, 2007:213] is still an important direction of development. The design and enzymatic synthesis of novel functional polymer materials, and the synthesis and application of nano polymers are the leading edges of polymer research and development.
The two-dimensional material and the quasi two-dimensional material have wide application prospects in the fields of quantum information, artificial intelligence, integrated circuits, life health, brain science, aerospace science and technology and the like, and the fields of sensors, logic switches, pharmaceutical preparations, medical diagnosis, electronic information, flexible wearable equipment, intelligent clothing, food safety detection, environmental protection and intelligent packaging. Films with a thickness of the order of nanometers (1 to 100 nm) are referred to as "nanofilms" and exhibit properties of nanomaterials.
The large-scale synthesis of high-quality thin films with wide adjustability will promote the development of artificial solids with designed functions. However, many "bottom-up" polymer film fabrication techniques still have significant drawbacks in controllability and the like. The control of the thickness of many film layers, especially the thickness and uniformity of nano-film, remains a difficult point in process implementation. The uncontrollable reaction is difficult to realize large-scale industrial production, and the method for preparing the organic polymer composite ultrathin multilayer film is less.
The stability of the membrane is very important for the application of the membrane. The LB film (a monomolecular or polymolecular film with ordered molecular arrangement, prepared by Langmuir-Blodgett film-forming technique) is uniformly and completely regularly arranged at the molecular level. However, the LB film deposited with small molecules has low mechanical strength (the LB film deposited on the substrate can be scratched by a force of only several newtons), and has poor heat resistance, solvent resistance and environmental resistance, and thus has limited practical applications. In order to overcome these weaknesses, an effective method is to introduce a group capable of further performing polymerization reaction into a film-forming organic small molecule compound to make it high molecular [ he sheng, polymerization in a two-dimensional state: polymerization of monomolecular film and Langmuir-Blodgett film [ M ]. Fertilizer combination: china university of science and technology publishing, 2008:58.]. However, since the LB film requires amphiphilic molecules of the film-forming organic compound, the molecular chain length is limited by suitable conditions, and the like, the selection range of the LB film-forming monomer is greatly limited, which brings difficulties to the design of the LB film-forming material. Moreover, since the polymerization of monomers into polymers is a transition from van der waals interaction distance to chemical bond distance, the shortening of the distance between molecules causes the shrinkage of the formed monomolecular film polymer or polymerized LB film, and the overall order of the film is not guaranteed [ how, hessian, polymerization in two-dimensional state: polymerization of monomolecular film and Langmuir-Blodgett film [ M ]. Fertilizer combination: china university of science and technology publishing, 2008:61.].
Supramolecular materials are a modern new material in the development stage, which are based on supramolecular chemistry, materials prepared by intermolecular non-covalent bonding (e.g. hydrogen bonding interactions, electron donor-acceptor interactions, ionic interactions, etc.) [ zhangshijmaterial physico-chemistry [ M ]. Beijing: chemical industry publishers, 2020:53.]. The self-assembled film is an ordered supermolecular system formed by active molecules spontaneously adsorbed on a heterogeneous interface through chemical bonds.
The development of a wider variety of copolymer films and a simple preparation method thereof can meet specific application requirements, and become the direction of efforts of researchers.
Disclosure of Invention
The invention provides a synthetic method of a copolymer film, the copolymer film prepared by the method and application.
The invention uses catalyst to catalyze two types of film-forming monomers to polymerize and self-assemble to generate an organic copolymer film at two immiscible liquid phase interfaces (liquid-liquid interfaces), wherein one type of film-forming monomer is an organic compound containing phenolic hydroxyl, and the other type of film-forming monomer is an organic compound containing at least two amino groups. The organic copolymer film can introduce other molecules and/or atoms into the surface of the film through secondary and/or multiple chemical and/or enzymatic reactions, obtain expected chemical composition, molecular structure, physical property and chemical property, realize the performance of the film and meet the application requirements.
In order to improve the technical problem, the invention provides a method for synthesizing a copolymer film, which comprises the following steps:
dissolving a film-forming monomer containing phenolic hydroxyl, a film-forming monomer containing at least two amino groups and a catalyst in a water phase and/or a liquid phase which is not mutually soluble with the water phase, and polymerizing at the interface of the two phases to form the copolymer film.
Preferably, the copolymer film is obtained by dissolving a film-forming monomer containing a phenolic hydroxyl group and a film-forming monomer containing at least two amino groups in a solvent, adding a catalyst, mixing to obtain an aqueous phase, contacting the aqueous phase with a liquid phase which is immiscible with the aqueous phase, and polymerizing at the interface of the two phases to form the film.
Preferably, the copolymer film is obtained by dissolving a film-forming monomer containing phenolic hydroxyl in a solvent, adding a catalyst, mixing to obtain an aqueous phase, dissolving a film-forming monomer containing at least two amino groups in a liquid phase immiscible with the aqueous phase, contacting the aqueous phase with the liquid phase immiscible with the aqueous phase to perform an enzymatic reaction, and polymerizing at the interface of the two phases to form the film.
Preferably, the copolymer film is obtained by dissolving a film-forming monomer containing at least two amino groups in a solvent, adding a catalyst, mixing to obtain an aqueous phase, dissolving a film-forming monomer containing a phenolic hydroxyl group in a liquid phase immiscible with the aqueous phase, contacting the aqueous phase with the liquid phase immiscible with the aqueous phase, and polymerizing at the interface of the two phases to form a film.
Preferably, the copolymer film is obtained by dissolving a catalyst in an aqueous phase, dissolving a film-forming monomer containing a phenolic hydroxyl group and a film-forming monomer containing at least two amino groups in a liquid phase immiscible with the aqueous phase, contacting the aqueous phase and the liquid phase immiscible with the aqueous phase to perform an enzymatic reaction, and polymerizing at the interface of the two phases to form a film.
According to an embodiment of the invention, the aqueous phase is an aqueous solution having a water content of not less than 50% by mass; the film forming monomer can be dissolved, and a certain amount of organic solvent which is dissolved in water can be contained, wherein the organic solvent can be at least one of methanol, ethanol, isopropanol, acetone, methyl formate, ethyl acetate, acetonitrile, tetrahydrofuran, N-dimethylformamide, 1, 4-dioxane, dimethyl sulfoxide, diethylene glycol butyl ether and diethylene glycol;
according to an embodiment of the present invention, the solvent is selected from water or a buffer solution, the buffer and buffer pair of which is a pH buffer suitable for supporting the polymerization reaction, without being limited to any particular pH buffer. The buffer solution is preferably a sodium acetate-acetic acid buffer solution, a disodium hydrogen phosphate-citric acid buffer solution, a potassium hydrogen phthalate-sodium hydroxide buffer solution, a tartaric acid-sodium tartrate buffer solution, a sodium citrate-citric acid buffer solution, a trisodium phosphate-phosphoric acid buffer solution, a sodium malonate-malonic acid buffer solution, a sodium succinate-succinic acid buffer solution, a phthalic acid-hydrochloric acid buffer solution, a disodium hydrogen phosphate-sodium dihydrogen phosphate buffer solution, a disodium hydrogen phosphate-potassium dihydrogen phosphate buffer solution, a dipotassium hydrogen phosphate-sodium hydroxide buffer solution, a Tris-hydrochloric acid buffer solution, a boric acid-borax buffer solution, or a glycine-sodium hydroxide buffer solution.
According to an embodiment of the present invention, the liquid phase immiscible with the aqueous phase may be an oil that is liquid at normal temperature, an oil that is solid at a set temperature, or a liquid metal. The oil which is liquid at normal temperature can be at least one of vegetable oil, mineral oil and artificially synthesized water-insoluble liquid. The vegetable oil can be peanut oil, soybean oil, linseed oil, castor oil, rapeseed oil, corn oil, olive oil, linseed oil, cinnamon oil, essential oil, etc. The mineral oil can be petroleum (crude oil), condensate oil, gasoline, kerosene, diesel oil, lubricating oil, transformer oil, engine oil, liquid paraffin, paraffin and coal tar. The artificially synthesized water-insoluble liquid includes at least one of various silicone oils, aromatic hydrocarbons (e.g., benzene, toluene, xylene, dichlorotoluene, bromobenzene, etc.), alkanes (e.g., pentadecane, tetradecane, tridecane, dodecane, undecane, nonane, isooctane, hexane, trichloromethane, tetrachloromethane, carbon tetrachloride, carbon disulfide, etc.), cycloalkanes (e.g., cyclohexane, cyclopentane, cycloheptane, etc.), ethers (e.g., petroleum ether, butyl ether, etc.), esters (e.g., butyl oleate, butyl acetate, butyl palmitate, etc.), ketones (e.g., 2-nonanone, methyl isobutyl ketone, 3-hexanone, etc.), organic acids (e.g., octanoic acid, etc.). The oil that is solid at a set temperature, such as at least one of paraffin, cocoa butter, coconut oil, palm oil, and animal oil. The animal oil can be derived from pig, cattle, sheep, horse, chicken, whale, insect (such as beeswax, insect wax, etc.), etc. The liquid metal is gallium, mercury or low melting point alloy.
According to an embodiment of the invention, the catalyst may be at least one of a peroxidase and/or an oxidoreductase with laccase activity and/or an artificial enzyme with the aforementioned catalytic activity;
according to an embodiment of the present invention, the peroxidase may be selected from at least one of Manganese peroxidase (mangase peroxidase, mnP, EC 1.11.1.13), lignin peroxidase (lin peroxidase, liP, EC 1.11.1.14), chloroperoxidase (CPO, EC 1.11.1.10), and Plant peroxidase (Plant peroxidase); the plant peroxidase may be Horseradish peroxidase (HRP, EC 1.11.1.7), soybean peroxidase (Soybean peroxidase, SBP, EC 1.11.1.7), rice peroxidase (Rice peroxidase), cotton peroxidase (Cotton peroxidase), red bean peroxidase (Runner beans peroxidase), chickpea peroxidase (Garbanzo beans peroxidase), guar bean peroxidase (Guar beans peroxidase), pea peroxidase (Pea peroxidase) and the like.
According to an embodiment of the invention, the oxidoreductase with Laccase activity is at least one of the enzymes from plant, animal, fungus, bacterium, yeast, or any Laccase obtained by biotechnology (laccae), and/or any fragment exhibiting Laccase activity derived therefrom, and/or an enzyme exhibiting similar activity, such as phenol catecholase (cathecoxidase, CO, EC 1.10.3.1) or any fragment exhibiting Catechol oxidase activity derived therefrom, monophenol monooxygenase (monophenoxygen, EC 1.14.18.1), or any fragment exhibiting Monophenol monooxygenase activity derived therefrom, bilirubin (Bilirubin, bilirubin 3.5) exhibiting BOD activity, or any fragment exhibiting BOD activity from Bilirubin, bilirubin (Bilirubin, bilirubin 3.3.1, bilirubin 3.5) exhibiting BOD activity, contained in the enzyme classification EC 1.10.3.2 specified by the Nomenclature Committee of the International Union of Biochemistry and molecular Biology, IUBMB.
According to an embodiment of the invention, the plant-derived laccase is selected from the group consisting of laccases in extracts of Anacardiaceae (Anacardiaceae), podocarpaceae (Podocarpaceae), aesculus (Aesculus sp.), acer pseudo-maple (Acer pseudo latinum), catharanthus roseus (Catharanthus roseus), carrot (Daucus carota), dichromitis squalens, ginkgo biloba (Gingko biloba), apple (Malus pumila), panicum songaricum (Monotrophy), avocado (Persea americana), peach (Prunus persica), potato (Solanum tuberosum), rosemary (Rosmarinus officinalis), vinca minor (Vinca minor).
According to an embodiment of the invention, the laccase is preferably a fungal laccase. The fungal laccase is selected from the group consisting of Agaricus bisporus (Agaricus bisporus), aspergillus nidulans (Aspergillus nidulans), botrytis cinerea (Botrytis cinerea), ceriporiopsis subvermispora (Ceriporiopsis subvermispora), ceriporiopsis versicolor (Ceriporiopsis unicolor), chaetomium thermophilum (Chaetomium thermophilum), cladosporium cladosporioides (Cladosporium sporophores), coprinus cinerea (Coprinus cinerea), coriolus versicolor (Coriolus hirsutus), coriolus versicolor (Coriolus versicolor), fomes fomentarius (Fomeyersinius), ganoderma lucidum (Ganodermaria lucidum), pleurotus circineus (Glreophilus cingulate), isobasidium pine root (Heterobasidium anisopliae), lactarius flavus (Lactarius), pleurotus thermophilus versicolor (Melicoccus serous), leptospirillus purpureus (Melicoccus purpureus), leptomyces trichoderma viride (Melicoccus purpureus (Melilotus), leptomyces trichoderma viridis (Melilotus), mycelius (Melilotus) and Mylophora purpureus solani (Melilotus) strain (Melilotus) and Myelomycelii (Melilotus) Neurospora crassa (Neurospora crassa), pleurotus discoidea (Panaeolous papilonensis), pleurotus ostreatus (Pleurotus ostreatus), pleurospora crassa (Podospora anserina), polyporus farinosus (Polyporus vulgaris), polyporus pinsitus, polyporus versicolor (Polyporus versicolor), pycnoporus cinnabarinus (Pycnoporus cinus), pyricularia oryzae (Pyricularia orizae), rhizoctonia pratensis, rhizoctonia solani (Rhizoctonia solani), rhizoctonia solani (Rhizoctonia lignosus), hypsizygus marmoreus (Rhizopus lignosus), pleurotus ruscus (Russulcus), schizophyllum commune (Schizophyllum), thermococcus (Thielavia), thielavia terrestris (Thielavia), thielavia trichotheca (Thielavia), mycospora (Thielavia terrestris), mylophora crassa (Thielavia terrestris), mycolecida (Thielavia cornus) and Mycosporea (Thielavia terreus strain (Thielavia terrestris), mycolecida) and Mycoleus, laccase from trametes versicolor (Tramates versicolor) and its variants.
Preferably, the fungal laccase is a Polyporus hibernalis (preservation number of the strain is CCTCC NO: M2020809) laccase.
The laccase may also be an enzyme produced by a process comprising the steps of: culturing a host cell transformed with a recombinant DNA vector carrying a DNA sequence encoding a function of said laccase in a culture medium under conditions allowing expression of the laccase, and recovering the laccase from the culture.
Fungal laccases have the following advantages over other enzymes: (1) The catalytic substrates are wide, and the enhancer added with the enzyme can catalyze more substrates; (2) high redox potential compared to bacterial laccase; (3) the industrial preparation is easy to realize; (4) the cost is lower; (5) coenzyme is not required; (6) The oxidant is molecular oxygen, so hydrogen peroxide does not need to be added in the reaction; (7) Water is the only by-product and does not form an useless enzyme-substrate complex; (8) glycosylation modification is carried out, so that the stability of the enzyme is better; (9) low sensitivity to metal ions in the medium; (10) has a certain resistance to many organic solvents.
According to an embodiment of the present invention, the structure of the compound containing a phenolic hydroxyl group is represented by formula I:
Figure BDA0003163388000000071
wherein each R is 1 Identical or different, independently of one another, from H, halogen, CN, NO 2 OH, SH, COOH, unsubstituted or substituted by one, two or more R a1 Substituted of the following groups: c 1-40 Alkyl radical, C 2-40 Alkenyl radical, C 2-40 Alkynyl, C 3-40 Cycloalkyl radical, C 3-40 Cycloalkenyl radical, C 3-40 Cycloalkynyl group, C 6-20 Aryl, 5-20 membered heteroaryl, 3-20 membered heterocyclyl, -OR 1-2 、-SR 1-3 、-NR 1-4 R 1-5 、-C(O)R 1-6 、-OC(O)R 1-7 、-S(O) 2 R 1-8 、-OS(O) 2 R 1-9 、-P(O)R 1-10 R 1-11 、-N＝NR 1-12 ；
A 1 Presence or absence; when A is 1 When present, selectFrom unsubstituted or substituted by one, two or more R b1 Substituted C attached to a benzo ring 6-20 Aryl, 5-20 membered heteroaryl, 5-20 membered heterocyclyl; or A 1 Selected from a chemical bond, unsubstituted or optionally substituted by one, two or more R c1 Substituted O, C (O) O, S (O) 2 、N、C 1-6 Alkylene, CH = N, N = N, CH = N-N = CH, CH = CH-CO-CH 2 -CO-CH＝CH；
m is an integer of 0 to 5.
Each R a1 、R b1 、R c1 Identical or different, independently of one another, from H, halogen, CN, OH, SH, oxo (= O), NO 2 、COOH、-OR 1-2 、-SR 1-3 、-NR 1-4 R 1-5 、-C(O)R 1-6 、-OC(O)R 1-7 、-S(O) 2 R 1-8 、-OS(O) 2 R 1-9 、P(O)R 1- 10 R 1-11 Unsubstituted or optionally substituted by one, two or more R 1-12 Substituted C 1-40 Alkyl radical, C 2-40 Alkenyl radical, C 2-40 Alkynyl, C 3-40 Cycloalkyl radical, C 3-40 Cycloalkenyl radical, C 3-40 Cycloalkynyl group, C 6-20 Aryl, 5-20 membered heteroaryl, 3-20 membered heterocyclyl;
each R 1-2 、R 1-3 、R 1-4 、R 1-5 、R 1-6 、R 1-7 、R 1-8 、R 1-9 、R 1-10 、R 1-11 、R 1-12 Identical or different, independently of one another, from H, halogen, CN, OH, SH, oxo (= O), NO 2 、COOH、C 1-40 Alkyl radical, C 2-40 Alkenyl radical, C 2-40 Alkynyl, C 3-40 Cycloalkyl radical, C 3-40 Cycloalkenyl radical, C 3-40 Cycloalkynyl group, C 6-20 Aryl, 5-20 membered heteroaryl, 3-20 membered heterocyclyl.
According to an embodiment of the invention, formula I has the structure shown in formulas I-1 to I-13:
Figure BDA0003163388000000081
wherein R is 1 M and R c1 Having the definitions described above; b is selected from O or by R 1 Substituted N; D. d 1 、D 2 And D 3 Identical or different, independently of one another, from the group consisting of a bond, unsubstituted or optionally substituted by one, two or more R c1 Substituted O, CH 2 C (O) or N-CO-CH 3 (ii) a E and E 1 Identical or different, independently of one another, from a bond, unsubstituted or optionally substituted by one, two or more R c1 Substituted O, C (O) O, S (O) 2 、N、Se、P、C 1-6 Alkylene, CH = CH, CH = N, N = N, CH = N-N = CH, CH = CH-CO-CH 2 -CO-CH = CH; n is an integer of 0 to 5; f 1 And F 2 Identical or different, independently of one another, from N, CH or O + ；R 1 ’、R 1 And R 1 Are defined the same.
<xnotran> , I-1 (CAS: 120-80-9), 3- (CAS: 488-17-5), 3,4- (CAS: 452-86-8), 4- (CAS: 1124-39-6), 4- -1,2- (CAS: 98-29-3), 3,5- -1,2- (CAS: 1020-31-1), 3- (CAS: 934-00-9), 3,4- (CAS: 139-85-5), 3,4- (CAS: 6053-02-7), 2',4' - (CAS: 89-84-9), (CAS: 10597-60-1), (CAS: 51-61-6) ,3- (CAS: 471915-89-6), (CAS: 51-43-4), , (CAS: 51-30-9), (CAS: 2150-43-8) , (CAS: 149-45-1), 3- -5- -1,2- , </xnotran> <xnotran> 3,4- (CAS: 3943-89-3) ,2,3- ,4- (CAS: 3316-09-4), , suillin (CAS: 103538-03-0), grifolin (CAS: 6903-07-7), ilicicolin B (CAS: 22581-07-3), (CAS: 108-46-3), 4- (CAS: 95-88-5), 2,6- (CAS: 608-25-3), 2,4- (CAS: 1995-1-2), 2',4' - (CAS: 89-84-9), 2',6' - (CAS: 699-83-2), 4- (CAS: 136-77-6), (Cardol), (CAS: 23031-32-5), (CAS: 123-31-9), (CAS: 1948-33-0), 2- (CAS: 615-67-8), (CAS: 451-13-8), 3,6- (CAS: 4733-50-0), 2,6- (CAS: 15233-65-5), </xnotran> <xnotran> (CAS: 20123-80-2), (CAS: 25654-31-3), (CAS: 5874-97-5), (CAS: 13956-29-1), (CAS: 6099-90-7), 2,4,6- (CAS: 487-70-7), 2,4,6- (CAS: 90536-74-6) , -6- (CAS: 28094-15-7), 6- (CAS: 636-00-0), 2,4,5- (CAS: 23358-64-7), (CAS: 87-66-1), 2',3',4' - (CAS: 528-21-2), 2,3,4- (CAS: 2144-08-3), (CAS: 99-24-1) ,4- (CAS: 106-41-2), (CAS: 51-67-2), 4- (CAS: 106-44-5), 4- (CAS: 106-48-9), 4- (CAS: 150-76-5), 2,3- (CAS: 5150-42-5), </xnotran> Esters such as 4-ethylphenol (CAS: 123-07-9), vanillin (CAS: 121-33-5), isovanillin (CAS: 621-59-0), vanillyl alcohol (CAS: 498-00-0), guaiacol (CAS: 90-05-1), o-acetaminophenol (CAS: 614-80-2), p-acetaminophenol (CAS: 103-90-2), 3,4, 5-trimethoxyphenol (CAS: 642-71-7), 4- (2' -thiazolylazo) resorcinol (CAS: 2246-46-0), ethyl 2,3, 4-trihydroxybenzoate, and benserazide hydrochloride (CAS: 14919-77-8).
<xnotran> , I-2 3',4- (CAS: 4143-64-0), 6,7- (CAS: 38183-04-9), 7,8- (CAS: 38183-03-8), (CAS: 480-44-4), (CAS: 480-40-0), (CAS: 491-54-3), (CAS: 520-12-7), (CAS: 480-19-3), (CAS: 520-34-3), (CAS: 4423-37-4), (CAS: 491-71-4), (CAS: 480-15-9), (CAS: 529-51-1), (CAS: 603-61-2), 5,7- -2- (4- ) -6,8- -4H-1- -4- (CAS: 4323-80-2), (CAS: 528-48-3), (CAS: 18398-74-8), (CAS: 520-36-5), (CAS: 548-83-4), (CAS: 491-67-8), </xnotran> Quercetin dihydrate (CAS: 6151-25-3), 6-methoxyluteolin (CAS: 520-11-6), 3-O-methylquercetin (CAS: 1486-70-0), morin (CAS: 480-16-0), luteolin (CAS: 491-70-3), quercetin (CAS: 117-39-5), myricetin (CAS: 529-44-2), daphne genkwanin (CAS: 437-64-9), 5, 7-dihydroxy-6, 8,4' -trimethoxyflavone (CAS: 10176-66-6), hamanoxin (CAS: 56003-01-1), kaempferol (CAS: 520-18-3), scutellarein (CAS: 529-53-3), 7,3',4' -trihydroxy-3, 8-dimethoxyflavone, 3,7,3',4' -tetrahydroxy-8-methoxyflavone, 3,7,8,3',4' -pentahydroxyflavone, and the like.
Preferably, the compound of I-3 is selected from texas (CAS: 897-46-1), daidzein (CAS: 486-66-8), biochanin A (CAS: 491-80-5), 4',6, 7-trihydroxyisoflavone (CAS: 17817-31-1), genistein (CAS: 446-72-0), olobol (CAS: 480-23-9), caffeine (CAS: 20575-57-9), prunetin (CAS: 552-59-0), and the like.
Preferably, the compound of I-4 is selected from esculetin (CAS: 305-01-1), 4-methylesculetin (CAS: 529-84-0), and the like.
<xnotran> , I-5 (CAS: 520-33-2), (CAS: 67604-48-2), (CAS: 20725-03-5), (CAS: 480-41-1), (CAS: 24808-04-6), (CAS: 4382-33-6), (CAS: 480-18-2), (CAS: 27200-12-0), (CAS: 552-58-9), (CAS: 490-49-3), (+) -Rhobidanol (CAS: 17445-90-8), (CAS: 3371-27-5), 4',7- (CAS: 531-95-3), (CAS: 2545-00-8), (+) - (CAS: 154-23-4), (CAS: 970-74-1), , , , , , , , , , , , ,7,8,4' - ,3,4- . </xnotran>
Preferably, the compound of I-6 is selected from the group consisting of anthocyanins (CAS: 528-58-5), chloridized delphinidin (CAS: 528-53-0), pelargonidin (CAS: 134-04-3), farnesyl chloride (CAS: 23130-31-6), petunia (CAS: 1429-30-7), malvidin (CAS: 643-84-5), and the like.
Preferably, the compound of I-7 is selected from the group consisting of p-phenylphenol (CAS: 92-69-3), azoviolet (CAS: 74-39-5), 2, 4-dihydroxybenzophenone (CAS: 131-56-6), phenethylresorcinol (CAS: 85-27-8), xanthohumol (CAS: 6754-58-1), resveratrol (CAS: 501-36-0), rosmarinic acid (CAS: 20283-92-5), phloretin (CAS: 60-82-2), nordihydroguaiaretic acid (CAS: 500-38-9), tetrahydroxystilbene, piceatannol (CAS: 10083-24-6), curcumin (CAS: 458-37-7), bisphenol A (CAS: 80-05-7), 2' -dihydroxybiphenyl (CAS: 1806-29-7), 4' -dihydroxybiphenyl (CAS: 92-88-6), phenolphthalein (CAS: 81-90-3), thiobischlorophenol (CAS: 97-18-7), bischlorophenol (CAS: 97-23-4), 2' -dihydroxybenzophenone (CAS: 11-835-0), dihydroxybenzophenone (CAS: 4: 611-90-3), azobenzophenone (CAS: 4: 611-3, 3: 4-96-3, azobenzophenone, 3: 4-96-3, and azobenzophenone (CAS: 4: 11-3, 3: 4-3, 4-96-3) <xnotran>, (CAS: 35354-74-6), (CAS: 528-43-8), (CAS: 5635-50-7), (CAS: 6898-97-1), 3,3',5,5' - () 4,4'- (CAS: 2416-95-7), 2,2' - (CAS: 15764-52-0), (CAS: 49745-95-1), (CAS: 469-32-9), 2,3,3', 4,4',5- ,3,3',4,4',5,5 '- ,2,2', 3,3',4,4' - , . </xnotran>
<xnotran> , I-8 2,3- (CAS: 92-44-4), 1,2- (CAS: 574-00-5), 1,3- (CAS: 132-86-5), 1,5- (CAS: 83-56-7), 1,6- (CAS: 575-44-0), 1,7- (CAS: 575-38-2), 1,4- (CAS: 571-60-8), 2,7- (CAS: 582-17-2), 6,7- -2- (CAS: 135-53-5), 3,5- -2- (CAS: 89-35-0), (CAS: 3737-95-9), (CAS: 3147-14-6), R (CAS: 2538-85-4), 2R (CAS: 4197-07-3), (CAS: 130-85-8), Ⅱ (CAS: 51550-25-5), (CAS: 148-25-4), (CAS: 5808-22-0), (CAS: 3810-39-7), B (CAS: 3564-14-5), </xnotran> Ireland blue SE (CAS: 1058-92-0), and the like.
Preferably, the compound of I-9 is selected from alkannin (CAS: 517-89-5) and the like.
Preferably, the compound of I-10 is selected from aloesin (CAS: 481-72-1), dithranol (CAS: 1143-38-0), 1, 5-dihydroxyanthraquinone (CAS: 117-12-4), 1, 4-dihydroxyanthraquinone (CAS: 81-64-1), 1, 8-dihydroxyanthraquinone (CAS: 117-10-2), 10-acetyl-3, 7-dihydroxyphenazine (CAS: 119171-73-2), anthracene crinol (CAS: 117-12-4), chrysophanol (CAS: 481-74-3), rhein (CAS: 478-43-3), 1,2, 3-trihydroxyanthraquinone (CAS: 602-64-2), rhodopsin (CAS: 81-54-9), alizarin red (CAS: 130-22-3), alizarin complex indicator (CAS: 3952-78-1), alizarin (CAS: 72-48-0), alizarin red S (CAS: 130-22-3), mitoxantrone hydrochloride (CAS: 70476-82-3), fluorescein (CAS: 518-44-5), emodin (CAS: 518-82-1), laccaic acid (CAS: 60687-93-6), quinizarin (CAS: 81-61-8), alpha-mangostin (CAS: 6147-11-1), and the like.
Preferably, the compound of I-11 is selected from the group consisting of bisabolol blue (CAS: 1562-85-2), azure blue (CAS: 1562-90-9), and the like.
Preferably, the compound of I-12 is selected from 1,8, 9-trihydroxyanthracene (CAS: 480-22-8) and the like.
Preferably, the compound of I-13 is selected from the group consisting of para-hydroxybenzoic acid (CAS: 99-96-7), m-hydroxybenzoic acid (CAS: 99-06-9), vanillic acid (CAS: 121-34-6), isovanillic acid (CAS: 645-08-9), 4-hydroxy-2-methoxybenzoic acid (CAS: 90111-34-5), 3-hydroxy-5-methoxybenzoic acid (CAS: 19520-75-3), salicylic acid (CAS: 69-72-7), p-aminosalicylic acid (CAS: 65-49-6), m-aminosalicylic acid (CAS: 89-57-6), 3-methylsalicylic acid (CAS: 83-40-9), 5-methylsalicylic acid (CAS: 89-56-5), 3-methoxysalicylic acid (CAS: 877-22-5), 4-methoxysalicylic acid (CAS: 2237-36-7), 5-methoxysalicylic acid (CAS: 2612-02-4), 6-methoxysalicylic acid (CAS: 3147-64-6), 3, 5-diiodosalicylic acid (CAS: 22391-133-5), cardol (CAS: 552-5), eugenol (CAS: 552-60-910-55-5), eugenol (CAS: 1265, CAS: 85-5, 55-5-6), and the like, diflunisal (CAS: 22494-42-4), gentisic acid (CAS: 490-79-9), pyrocatechoic acid (CAS: 303-38-8), resorcylic acid (CAS: 89-86-1), 3, 5-dihydroxybenzoic acid (CAS: 99-10-5), 2, 6-dihydroxybenzoic acid (CAS: 303-07-1), gallic acid (CAS: 149-91-7), ferulic acid (CAS: 1135-24-6), p-coumaric acid (CAS: 501-98-4), tyrosine, sinapic acid (CAS: 530-59-6), 4-hydroxymandelic acid (CAS: 1198-84-1), 2-hydroxyphenylglycine (CAS: 25178-38-5), caffeic acid (CAS: 331-39-5), diphenolic acid (CAS: 126-00-1), protocatechuic acid (CAS: 99-50-3), danshensu (CAS: 764-21-4), dopa (CAS: 555-30-6), 2, CAS 4-83-30-6-benzoic acid (CAS: 7, etc.
According to an embodiment of the invention, formula I also includes substances in which two or more structural units of formulae I-1 to I-13 are present in the structure, such as sciadopitysin (CAS: 521-34-6), cinnamon tannin (CAS: 86631-38-1), 2 '-dihydroxy-1, 1' -binaphthyl (CAS: 602-09-5), 6 '-dithio-dinaphthol (CAS: 6088-51-3), hypericin (CAS: 548-04-9), pyrantel pamoate (CAS: 22204-24-6), 2, 3-dihydro-sciadopitysin (CAS: 34421-19-7), amentoflavone (CAS: 1617-53-4), isoginkgetin (CAS: 548-19-6), demethylginkgetin (CAS: 521-32-4), 5' -methoxy ginkgetin (CAS: 77053-35-1), ginkgetin (CAS: 481-46-9), procyanidin B1 (CAS: 20315-25-7), procyanidin B2 (CAS: 29106-49-8), procyanidin B3 (CAS: 67-23-9), procyanidin B4 (CAS: 1274-57-51-58), procyanidin B2 (CAS: 1275-58-6), procyanidin (CAS: 23598-51-58-6), procyanidin (CAS: 1275: 1271: 1275-19-6), procyanidin B8 (CAS: 12798-60-6), (-) -epigallocatechin gallate (CAS: 989-51-5), epicatechin gallate (CAS: 1257-08-5), catechin gallate (CAS: 130405-40-2), gallocatechin gallate (CAS: 4233-96-9), prodelphinidin B2-3' -O-gallic acid, dehydrocatechin B, tetrabrominated tannin, protocyanidin B-2,3' -O-gallate, protocyanidin B-2,3' -di-O-gallate, prodelphinidin B1 (CAS: 78362-04-6), prodelphinidin B2 (CAS: 87392-61-8), prodelphinidin B3 (CAS: 78362-05-7), prodelphinidin B4 (CAS: 68964-95-4), and the like.
According to an embodiment of the invention, the compounds of formula I further comprise: saxifragin (CAS: 477-90-7), baicalein (CAS: 632-85-9), tectorigenin (CAS: 548-77-6), licoflavone (CAS: 59870-68-7), ellagic acid (CAS: 476-66-4), catalpa toxin (CAS: 82-08-6), caesin J (CAS: 99217-67-1), hematoxylin oxide (CAS: 475-25-2), rhodotriphenol (CAS: 569-77-7), gnetin A (CAS: 82084-87-5), pyrogallol red (CAS: 32638-88-3), hematoxylin (CAS: 517-28-2), catechol violet (CAS: 115-41-3), 1-naphtholphthalein (CAS: 596-01-0), azoarsine I (CAS: 520-10-5), azoarsine III (CAS: 1668-00-4), phenolphthalein (CAS: 77-09-8), phenol red (CAS: 143-74-8), tetrakisol (CAS: 24-10-5), crocin pigment (CAS: 2324-338-125-1), fluorescein (CAS: 3607-4-2', 365), and fluorescein (CAS: 3607-3-4-3), <xnotran> (CAS: 633-00-1), (CAS: 76-61-9), (CAS: 2103-64-2), (CAS: 60008-03-9), , , , heimiolA, balanicarpol α -H, A, (CAS: 479-66-3) , (CAS: 24280-93-1), S (CAS: 66675-89-6), (CAS: 41372-20-7), (4E) -6- (4,6- -7- -3- -1,3- -5- ) -4- -4- 2- ( -4- ) (CAS: 1322681-36-6), (+) - (CAS: 476-70-0), (CAS: 125-24-6), (CAS: 57-94-3), (CAS: 22888-70-6), (CAS: 13292-53-0), (CAS: 20830-81-3), (CAS: 13292-46-1), 3- SV (CAS: 13292-22-3), </xnotran> Rifamycin SV, rifaximin (CAS: 80621-81-4), doxorubicin hydrochloride (CAS: 25316-40-9), epirubicin hydrochloride (CAS: 56390-09-1), rifapentine (CAS: 61379-65-5), doxorubicin (CAS: 54193-28-1), rifamide (CAS: 2750-76-7), vancomycin and salts thereof, norvancomycin hydrochloride (CAS: 213997-73-0), flav-3-en-3-ol, teicoplanin (CAS: 61036-62-2), malibatol A, malibatol B (CAS: 204644-72-4), suffrutinosol A, suffrutinosol B, vaticanol C, and the like.
According to an embodiment of the invention, the compounds of formula I further comprise: a polyphenol.
According to an embodiment of the invention, the polyphenols comprise: procyanidins (CAS: 4852-22-6), procyanidin A1 (CAS: 103883-03-0), procyanidin A2 (CAS: 41743-41-3), procyanidin A4 (CAS: 111466-29-6), procyanidin C1 (CAS: 37064-30-5), procyanidin C2 (CAS: 37064-31-6), cinnamyl tannin B1 (CAS: 88082-60-4), cinnamyl tannin B2 (CAS: 88038-12-4), theaflavin (CAS: 4670-05-7), tea polyphenol (CAS: 84650-60-2), tannic acid (CAS: 1401-55-4), casuarinin (CAS: 79786-01-9), saxietin (CAS: 819-27-7), davuricin T1 (CAS: 13786-9), tannic acid (CAS: 65995-64-4), gemin A (CAS: 137371-86-9), sanguisorbain H2 (CAS: 200-04-1249), aesculin (CAS: 4151-64-9), aesculin (CAS: 898-31), aescine (CAS: 898-31-47), aescine (CAS: 898-31-9), geraniin A-9), geraniol (CAS: 31-9), geraniol, aescine, alpha-viniferin (CAS: 62218-13-7), epsilon-viniferin (CAS: 62218-08-0), delta-viniferin, gnetin C (CAS: 84870-54-2), gnetin D (CAS: 84870-53-1), gnetin J (CAS: 152511-23-4), pallidol (CAS: 105037-88-5), gongol C (CAS: 109605-83-6), salvianolic acid B (CAS: 115939-25-8), humic acid (CAS: 1415-93-6) and its salts, nitrohumic acid (Nitro humic acid), xanthol, dehydro-ellagic acid, valonia acid and its esters, bisflavan theanin, oolong tea essence, punicin, polygenic emeraldine, and the like.
According to an embodiment of the invention, the compounds of formula I further comprise: compounds of formulae I-1 to I-13 in combination with quinic acid and/or a sugar and/or sugar acid, such as arbutin (CAS: 497-76-7), scutellarin (CAS: 27740-01-8), rhaponticin (CAS: 155-58-8), chlorogenic acid (CAS: 327-97-9), narcissus (CAS: 604-80-8), puerarin (CAS: 3681-99-0), hesperidin (CAS: 520-26-3), neohesperidin (CAS: 13241-33-3), diosmin (CAS: 520-27-4), aloin (CAS: 5133-19-7), forsythiaside E (CAS: 93675-88-8), angoroside C (CAS: 115909-22-3), kaempferol-7-O-D-glucoside (CAS: 16290-07-6), naringin (CAS: 10236-47-2), apigenin-7-glucoside (CAS: 578-74-5), paeonol-3, 5-diglucoside (CAS: 482-37-6), astragalin (CAS: 480-10-4), apigenin-7-glucoside (CAS: 17684-4), kaempferol-3-5-diglucoside (CAS: 482-37-6), kaempferol-3-84-O-3-5), kaempferol (CAS: 482-3-84-3-5) <xnotran> CAS: 142451-65-8), (CAS: 55804-74-5), -3-O-D- (CAS: 5041-82-7), -3-O-D- (CAS: 53430-50-5), -4' - (CAS: 6920-38-3), (CAS: 29838-67-3), (CAS: 6906-39-4), -3-O- (CAS: 30113-37-2), -3-O- (CAS: 28500-04-1), (CAS: 60-81-1), (CAS: 20702-77-6), (CAS: 153-18-4), Ⅱ (CAS: 81571-72-4), -7,3' -O- β -D , -7-O-D- (Ginkgetin-7-O-D-glucopyranoside), -7-O-D- (Isoginkgetin-7-O-D-glucopyranoside), -4- -3' -D- , </xnotran> Catechin-4 '-O-beta-D-glucose, tericin II, agrimonine, geraniin phenazine, gallocatechin, prairisin, corilagin, polyflavanonoside, quercetin-3-O-beta-D-glucose, 3-O- {2-O- [6-O- (P-D-glucosyl) -O-trans-coumaroyl ] -D-glucose } - (L-rhamnosyl) quercetin, rosmarin A, rosmarin B, rosmarin C, rosmarin D, rosmarin E, rosmarin F, rosmarin G, luteolin 7-O-rhamnose-glucoside, luteolin 7-O-glucoside, genistein 7-O-rhamnose glucoside, genistein-3-O-glucoside, olol-7-O-rhamnose glucoside, oloside, olol-2-O, 6-O bis (L-rhamnosyl) -D-glucosyl ] isorhamnetin, quercetin-4' -O-beta-D-glucose-6 "-gallate, quercetin-3-O-alpha-arabinose-2" -gallate, 2,3-O hexahydroxybiphenyl diacyl glucose, etc. The glycosyl group comprises glucose, xylose, galactose, arabinose, rhamnose, mannose, glucuronic acid, rutinose, gentiobiose, sophorose, neohesperose, robiose, lactose, sophoriose, caffeoyl glucose, 2-acetyl glucose and combinations thereof.
Preferably, the film-forming monomer having a phenolic hydroxyl group is selected from at least one of 1, 3-dihydroxynaphthalene, p-hydroxybenzoic acid, ferulic acid, 1, 6-dihydroxynaphthalene, alkannin, 3-methylsalicylic acid, p-coumaric acid, 4 '-dihydroxybiphenyl, bisphenol a, chlorogenic acid, 3-methoxysalicylic acid, gallic acid, 4',6, 7-trihydroxyisoflavone, diosmetin, tannic acid, 3, 5-diiodosalicylic acid, gentisic acid, resveratrol, esculetin, p-aminosalicylic acid, caffeic acid, ellagic acid, sciadopitysin, anthocyanins, syringic acid, tyrosine, guaiacol, 2, 6-dihydroxytoluene, catechol, hydroxytyrosol, hesperetin, 2,4, 6-trihydroxybenzaldehyde, irigenin, narcissin, rhein, bisabolone, 1,8, 9-trihydroxyanthracene, urushiol, and tert-butyl hydroquinone.
According to an embodiment of the invention, the film-forming monomer containing at least two amino groups is of formula II:
Figure BDA0003163388000000171
each R 2 Identical or different, independently of one another, from H, halogen, CN, NO 2 NO, OH, SH, COOH, unsubstituted or substituted by one, two or more R a2 Substituted of the following groups: c 1-40 Alkyl radical, C 2-40 Alkenyl radical, C 2-40 Alkynyl, C 3-40 Cycloalkyl radical, C 3-40 Cycloalkenyl radical, C 3-40 Cycloalkynyl group, C 6-20 Aryl, 5-20 membered heteroaryl, 3-20 membered heterocyclyl, -OR 2-2 、-SR 2-3 、-NR 2-4 R 2-5 、-C(O)R 2-6 、-OC(O)R 2-7 、-S(O) 2 R 2-8 、-OS(O) 2 R 2-9 、P(O)R 2-10 R 2-11 ；
A 2 Selected from unsubstituted or substituted by one, two or more R b2 Substituted C attached to a benzo ring 1-40 Alkyl radical, C 2-40 Alkenyl radical, C 2-40 Alkynyl, C 3-40 Cycloalkyl, C 3-40 Cycloalkenyl radical, C 3-40 Cycloalkynyl, C 6-20 Aryl, 5-20 membered heteroaryl, 3-20 membered heterocyclyl; or A 2 Selected from a chemical bond, unsubstituted or optionally substituted by one, two or more R c2 Substituted O, C (O) O, S (O) 2 、N、C 1-6 Alkylene, CH = N, N = N, CH = N-N = CH, CH = CH-CO-CH 2 -CO-CH＝CH；
p is an integer of 0 to 12;
each R a2 、R b2 、R c2 Identical or different, independently of one another, from H, halogen, CN, OH, SH, oxo (= O), = NH, NO 2 、COOH、C 1-40 Alkyl radical, C 2-40 Alkenyl radical, C 2-40 Alkynyl, C 3-40 Cycloalkyl radical, C 3-40 Cycloalkenyl radical, C 3-40 Cycloalkynyl group, C 6-20 Aryl, 5-20 membered heteroaryl, 3-20 membered heterocyclyl, -OR 2-2 、-SR 2-3 、-NR 2-4 R 2-5 、-C(O)R 2-6 、-OC(O)R 2-7 、-S(O) 2 R 2-8 、-OS(O) 2 R 2-9 、P(O)R 2-10 R 2-11 ；
Each R 2-2 、R 2-3 、R 2-4 、R 2-5 、R 2-6 、R 2-7 、R 2-8 、R 2-9 、R 2-10 、R 2-11 Identical or different, independently of one another, from H, halogen, NH 2 CN, OH, SH, oxo (= O), NO 2 、COOH、C 1-40 Alkyl radical, C 2-40 Alkenyl radical, C 2-40 Alkynyl, C 3-40 Cycloalkyl radical, C 3-40 Cycloalkenyl radical, C 3-40 Cycloalkynyl, C 6-20 Aryl, 5-20 membered heteroaryl, 3-20 membered heterocyclyl.
According to an embodiment of the present invention, formula II has the structure shown in formulas II-1 to II-10:
Figure BDA0003163388000000181
wherein R is 2 P and R c2 Having the definitions described above; q is an integer of 0 to 12; r 2 ’、R 2 And R 2 The definitions of (A) are the same; and R is 2 、R 2 ’、R 2 "there are at least two amino groups;
each D 2 、D 3 、D 4 Identical or different, independently of one another, from N, unsubstituted or substituted by R 2 Substituted CH, N + ；
Each E 2 、E 3 、E 4 Identical or different, independently of one another, from the group consisting of a bond, unsubstituted or optionally substituted by one, two or more R c2 Substituted O, C (O), C (S), C (O) O, S (O) 2 、N、C 1-6 Alkylene, CH = N, N = N, CH = N-N = CH, C 0-6 alkylene/alkenyl-CO-C 1-6 alkylene-CO-C 0-6 Alkylene/alkenyl, C 0-6 alkylene/alkenyl-CO-NH-C 0-6 alkylene-CO-C 0-6 Alkylene/alkenyl, C 0-6 alkylene/alkenyl-NH-C 0-6 alkylene-NH-C 0-6 Alkylene/alkenyl, C 0-6 alkylene/alkenyl-C (O) O-C 0-6 alkylene-C (O) O-C 0-6 Alkylene/alkenyl groups.
Each F 2 Identical or different, independently of one another, from O, S.
<xnotran> , II-1 (CAS: 106-50-3) , (CAS: 95-70-5), 2,3- - (2,3-Dimethyl-1,4-benzenediamine), 2,6- - (2,6-Dimethyl-1,4-benzenediamine), 2,3- - (2,3-Diethyl-1,4-benzenediamine), 2,5- - (CAS: 6393-01-7), 2- (CAS: 93841-25-9), 2- - (2-Fluoro-1,4-benzenediamine), 2- (2-Isopropyl-1,4-benzenediamine), 2- (2-Hydroxymethyl-1,4-benzenediamine), 2- - (2-Hydroxyethoxy-1,4-benzenediamine), 2- - (2-Acetylaminoethoxy-1,4-benzenediamine), N- (4- ) ,2- -1,4- (CAS: 5307-14-2), 2- -1,4- (CAS: 615-66-7), 2,5- -1,4- (CAS: 20103-09-7), </xnotran> <xnotran> 2,5- (CAS: 615-50-9), (CAS: 95-54-5) ,4- -1,2- (CAS: 95-83-0), (CAS: 2016-88-8), 4,5- -1,2- (CAS: 5348-42-5), 3,4- (CAS: 496-72-0), 3- -1,2- (CAS: 3694-52-8), 4- -1,2- (CAS: 99-56-9), 3,4- (CAS: 619-05-6), (CAS: 108-45-2) ,4- -1,3- (CAS: 5131-60-2), 2,6- (CAS: 823-40-5), 2,4- (CAS: 615-05-4) ,3,5- (CAS: 535-87-5) , 2,4- (CAS: 137-09-7), 2,4- (CAS: 88-63-1), 2,3- (CAS: 452-58-4), 2,4,6- (CAS: 1004-38-2), </xnotran> 2, 4-diamino-6-methyl-1, 3, 5-triazine (CAS: 542-02-9), melamine (CAS: 108-78-1), 6-phenyl-1, 3, 5-triazine-2, 4-diamine (CAS: 91-76-9), dianiline (CAS: 5355-16-8), 2,4, 5-triamino-6-hydroxypyrimidine sulfate (CAS: 35011-47-3), trimethoprim (CAS: 738-70-5), phenazopyridine hydrochloride (CAS: 136-40-3), pyrimethamine (CAS: 58-14-0), issorafen maleate (CAS: 84504-69-8), trimethoprim (CAS: 738-70-5), 4-amino-6-chlorobenzene-1, 3-disulfonamide (CAS: 121-30-2), metanilino, and the like.
<xnotran> , II-2 3,4- (CAS: 39070-63-8), 2 (CAS: 532-82-1), (CAS: 119-93-7) ,3,3' - (CAS: 91-95-2) ,4,4' - (CAS: 92-87-5) , 3,3',5,5' - (CAS: 54827-17-7), (4- -3- ) (CAS: 101-14-4), 4,4' - (CAS: 101-77-9), 4,4' - (CAS: 101-80-4), 4,4' - (CAS: 139-65-1), 4,4' - (CAS: 611-98-3), 4,4' - (CAS: 621-95-4), 4,4' - (CAS: 80-08-0), 4,4' - ,3,3- (CAS: 91-94-1), 3,3` - (CAS: 119-90-4), 3,3` - -4,4` - (CAS: 838-88-0), </xnotran> 4,5' -diaminodiphenyl sulfide and the like.
<xnotran> , II-3 (CAS: 107-15-3) ,1,2- (CAS: 78-90-0), 1,3- (CAS: 109-76-2), 1,4- (CAS: 110-60-1), 1,5- (CAS: 462-94-2), 1,6- (CAS: 124-09-4), 1,7- (CAS: 646-19-5), 1,8- (CAS: 373-44-4), 1,10- (CAS: 646-25-3), (CAS: 111-40-0), (CAS: 112-24-3), (CAS: 112-57-2), (CAS: 4067-16-7), , (CAS: 124-20-9), (CAS: 4427-76-3), (CAS: 56-19-9), (CAS: 56-18-8), (CAS: 71-44-3), (CAS: 70862-11-2), (CAS: 13274-42-5), (CAS: 84807-66-9), </xnotran> Thermophilic hexylamine (CAS: 63833-74-9), thermophilic isohexylamine (CAS: 133416-04-3), 3 '-iminodipropylamine (CAS: 56-18-8), N' -bis (3-aminopropyl) -1, 3-propanediamine (CAS: 4605-14-5), urea (CAS: 57-13-6), thiourea, biuret (CAS: 108-19-0), thiosemicarbazide (CAS: 79-19-6), acrylamidomethyleneurea, guanidine (CAS: 90332-86-8), nitrate (CAS: 22817-07-8), glycylglutamine (CAS: 13115-71-4), alanylglutamine (CAS: 39537-23-0), glutamine, N- (2-guanylethyl) guanidine (CAS: 44956-51-6), 2, 6-diaminopimelic acid (CAS: 583-93-7), 2, 4-diaminobutyric acid dihydrochloride, aminyl guanidine (CAS: 57-53), aminoguanidine (CAS: 57-53-515), triaminoguanidine (Triaminoguanidine), triaminoguanidine hydrochloride (CAS: 22aminoguanidine), triaminoguanidine (CAS: 22817-60), triaminoguanidine (Triaminoguanidine), triaminoguanidine (CAS: 22cyanamide), etc.).
Preferably, the compound of II-4 is selected from the group consisting of proflavine (CAS: 92-62-6) and salts thereof, safranin T (CAS: 477-73-6), and the like.
Preferably, the compound of II-5 is selected from 6-hydroxy-2, 4, 5-triaminopyrimidine (CAS: 1004-75-7), 2, 4-diamino-6-hydroxypyrimidine (CAS: 1956-6-4), and the like.
Preferably, the compound of II-6 is selected from 5, 6-diamino-1, 3-dimethyluracil (CAS: 5440-00-6), 4, 5-diamino-6-hydroxy-2-mercaptopyrimidine (CAS: 1004-76-8), and the like.
Preferably, the compound of II-7 is selected from 2, 3-diaminonaphthalene (CAS: 771-97-1), 1, 8-diaminonaphthalene (CAS: 479-27-6), 1, 5-diaminonaphthalene (CAS: 2243-62-1), triamterene (CAS: 396-01-0), methotrexate (CAS: 59-05-2), dihydralazine sulfate (CAS: 7327-87-9), and the like.
Preferably, the compound of II-8 is selected from 1, 2-diaminocyclohexane (CAS: 694-83-7), streptomycin (CAS: 488-52-8), and the like.
Preferably, the compound of II-9 is selected from 4,4' -diaminodicyclohexylmethane (CAS: 1761-71-3) and the like.
Preferably, the compound of II-10 is selected from 1, 2-diaminoanthraquinone (CAS: 1758-68-5), 1, 5-diaminoanthraquinone (CAS: 129-44-2), 1, 4-diaminoanthraquinone (CAS: 128-95-0), and the like.
According to an embodiment of the present invention, the compound of formula II also includes a substance in which two or more structural units represented by formulae II-1 to II-10 are present in the structure, such as 4,4 '-binaphthylamine (CAS: 481-91-4), 3' -dimethylbinaphthylamine (CAS: 13138-48-2), and the like.
According to an embodiment of the invention, the compounds of formula II also include polymers containing multiple amino groups in the structure, such as: polyvinylamine (CAS: 49553-92-6), polyethyleneimine (CAS: 9002-98-6), and the like.
According to an embodiment of the invention, the compound of formula II further comprises: direct brown 44 (CAS: 6252-62-6), direct blue 1 (CAS: 2610-05-1), mecobalamin (CAS: 13422-55-4), vitamin B 12 <xnotran> (CAS: 68-19-9), (CAS: 1239-45-8), 3,5- -1,2,4- (CAS: 1455-77-2), (CAS: 3248-91-7), (CAS: 467-62-9), , (CAS: 37691-11-5), ), , , , , , ,2,7- (CAS: 525-64-4), (CAS: 573-58-0), (CAS: 136489-37-7), (CAS: 69558-55-0), 4',4 ″ (5 ″) - -15- -5 (CAS: 245086-08-2), (CAS: 13870-90-1), (Z) -2- (2- -4- ) -2- ( ) (CAS: 1450758-21-0), B (CAS: 1404-26-8) , (CAS: 1405-87-4) , (CAS: 37517-28-5), (CAS: 55658-47-4), </xnotran> Streptomycin sulfate (CAS: 3810-74-0), neomycin sulfate (CAS: 1405-10-3), bleomycin sulfate (CAS: 11056-06-7), kanamycin, mitomycin (CAS: 50-07-7), sisomicin sulfate (CAS: 53179-09-2), gentamicin sulfate, isepamicin sulfate (CAS: 67814-76-0), capreomycin sulfate (CAS: 1405-37-4), nisin (CAS: 3930-19-6),5, 6-diamino-2, 4-dihydroxypyrimidine sulfate dihydrate (CAS: 63981-35-1), famotidine (Famotidine), 4', 6-diamidino-2-phenylindole dihydrochloride, and the like.
<xnotran> , , (PEI), ,2- - ,2,3- - , , ,3- -1,2- , ,2,3- , ,2,3- ,2,3- - ,2,4- , ,1,6- , ,2- ,2- - ,5,6- -1,3- , , ,3,4- , ,4,4'- ,3,4- ,2,4- , ,4,4' - ,4,4'- , , ,6- -2,4,5- ,1,2- ,2,4- -6- -1,3,5- ,4,4' - ,1,4- ,2,4,6- . </xnotran>
According to an embodiment of the present invention, when the catalyst is at least one of laccase, bilirubin oxidase, and peroxidase, the combination of the film-forming monomer containing a phenolic hydroxyl group and the film-forming monomer containing at least two amino groups may be: the combination is as follows: r is 1 And/or A 1 A combination of a compound of formula I and a compound of formula II wherein there is at least one phenolic hydroxyl group in the structure; or a combination of two: a compound of formula I-13 and 2 is as a quilt R 2 Substituted CH, and R 2 、R 2 ’、R 2 "a combination of compounds of formula II-1 wherein there are at least two amino groups.
According to an embodiment of the present invention, when the catalyst is a monophenol monooxygenase, the combination of the film-forming monomer containing a phenolic hydroxyl group and the film-forming monomer containing at least two amino groups may be: a combination of a compound of formula i and a compound of formula ii.
According to an embodiment of the invention, when the catalyst is a catechol oxidationWhen used enzymatically, the combination of the film-forming monomer containing a phenolic hydroxyl group and the film-forming monomer containing at least two amino groups may be: r 1 A combination of a compound of formula I and a compound of formula II in the case of an ortho-positioned phenolic hydroxyl group.
According to the embodiment of the present invention, the film-forming monomer containing a phenolic hydroxyl group and the film-forming monomer containing at least two amino groups may be one, two or more, respectively, in the reaction system.
According to an embodiment of the present invention, the enzymatic reaction may further include at least one of an enhancer of an enzyme, hydrogen peroxide, a metal ion, a buffer ion pair;
preferably, the first and second liquid crystal display panels are, the enzyme enhancer includes alpha-clavulanic acid, beta-clavulanic acid, gamma-clavulanic acid, cinnamic acid, 4-hydroxycinnamic acid, goethiol, ethyl vanillin, caffeic acid, ferulic acid, 2, 4-pentanedione, 4' -dihydroxybenzophenone, benzoic acid, sodium benzoate, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 3-hydroxyanthranilic acid, 3-hydroxy-2-aminobenzoic acid, 4-amino-3-hydroxybenzoic acid, 2, 3-hydroxybenzoic acid, 3, 4-dihydroxybenzoic acid, dimethoxybenzoic acid, 2,4, 6-trihydroxybenzoic acid, p-hydroxyphenylacetic acid, salicylic acid, salicylate, 4-amino-salicylic acid, pyruvic acid, pyruvate, nicotinic acid, ascorbic acid, ascorbate, guanidine, cyanuric acid, imidazole, and benzoic acid 2, 6-dimethylphenol, 2,4, 6-trimethylphenol, 2-acetamidophenol, p-coumaric acid, 7-hydroxycoumarin, sinapic acid, syringaldehyde, syringic acid, methyl syringate, ethyl syringate, propyl syringate, butyl syringate, hexyl syringate, octyl syringate, vanillic acid, isovanillic acid, vanillin, vanillylazine, acetosyringone, acetovanillone, vanillyl alcohol, homovanillic acid, catechol, epicatechin, naringin, tyrosine, 2-thiouracil, ethyl 3- (4-hydroxy-3, 5-dimethoxyphenyl) acrylate, quercetin, 2' -Azino-bis- (3-ethylbenzodihydrophthaloline-6-sulfonic acid) diammonium salt (2, 2' -Azino-bis (3-ethylbenzothiazoline-6-sulfonic acid- <xnotran> 6-sulfonic acid) diammonium salt, ABTS), , , N- , N- -N- , N- - , N- -N- , N- ,4,4' - -N- - ,4,4' - , , , N- -4- ,3,3' - ,3,3' - ,3,3', 5,5' - ,4,4' - ,4' - -4- , ,2,2 ',6,6' - ,1- (3 ' - ) -3- -5- , , ,1,5- ,7- -2- ,6- -2- ,7- -2- ,5- -2- ,7- -1,2- ,1- ,10- ,10- (2- ) ,10- , -10- ,10- (2- ) ,10- ,10- (3- ) , </xnotran> 2-acetyl-10-methylphenothiazine, 10-ethyl-4-phenothiazinecarboxylic acid, 10-ethylphenothiazine, 10-propylphenothiazine, 10-isopropylphenothiazine, 10-phenothiazine methyl propionate, 10-methylphenothiazine, 10-phenothiazine-propionic acid, phenothiazine-10-propionic acid (phenothiazine-10-propionicacid, PPT), N-hydroxysuccinimide-10-phenothiazine-propionic acid, 10- (3- (4-methyl-1-piperazinyl) propylphenothiazine, promazine, chlorpromazine, 3-hydroxy-1, 2, 3-benzotriazine-4 (3H) -one, N- (4-cyanophenyl) acetylhydroxamic acid, iminostilbene, 4-amino-4 ' -methoxystilbene, 4' -diaminostilbene-2, 2' -disulfonic acid, 2, 7-diaminofluorene, 2- (p-methylbenzothiazole) -6-sulfonic acid, N- (4- (dimethylamino) benzil) -p-anisaldehyde, 3-methylbenzothiazine-7-sulfonic acid, N- (4- (dimethylamino) benzil-p-anisaldehyde, 3-methyl-benzothiazolinone (4-aminothiazoline) lignosulphonate, hardwood, lignosulphonate, and mixtures thereof.
According to an embodiment of the invention, the catalyst is used in the reaction system in an amount of 0.01U/L to 600U/L, for example 0.5U/L to 200U/L, illustratively 1U/L, 2U/L, 6U/L, 12U/L, 24U/L, 40U/L, 60U/L, in terms of enzyme activity.
According to an embodiment of the invention, the mass concentration of the film forming monomer in the reaction system may be 0.002 to 380g/L, such as 0.1 to 20g/L, exemplary 0.5g/L, 0.8g/L, 1g/L, 2g/L, 3g/L, 4g/L.
According to embodiments of the invention, the film formation temperature may be 4 to 90 ℃, e.g., 10 to 60 ℃, exemplary 20 ℃,30 ℃, 35 ℃, 37 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃;
according to an embodiment of the present invention, the film forming time may be 0.01 to 72 hours, for example 2 to 48 hours, exemplary 3 hours, 5 hours, 6 hours, 8 hours, 10 hours, 12 hours, 20 hours, 24 hours, 36 hours;
according to an embodiment of the invention, the pH of the aqueous phase may be 2 to 10, e.g. 3,4,5, 6, 6.5, 7, 8.
According to an embodiment of the invention, when the catalyst is a laccase, a bilirubin oxidase, a monophenol monooxygenase or a catechol oxidase, the reaction requires oxygen to be involved. The oxygen source can be pure oxygen or a mixed gas containing oxygen, further, the oxygen can be oxygen in the air, can be oxygen dissolved in the surface of the solution, and the oxygen-containing gas can be slowly dissolved into the reaction system through the flow of the solution, mechanical stirring, oscillation, a blower and an air compressor to provide oxygen for the reaction. An oxygen-enriched liquid may be added to the liquid.
For reactions requiring hydrogen peroxide, the source of hydrogen peroxide in solution can be at least one of the following: (1) adding a hydrogen peroxide solution to the solution; (2) Adding to the solution a hydrogen peroxide generating enzyme system, such as glucose oxidase and glucose, which oxidizes glucose to produce hydrogen peroxide; galactose oxidase and galactose, galactose oxidase oxidizes galactose to produce hydrogen peroxide; a sugar alcohol oxidase which oxidizes glycerol to produce hydrogen peroxide; amino acid oxidase, flavin Adenine (FAD) and amino acid, wherein the amino acid oxidase uses the FAD as a prosthetic group to oxidize the amino acid to generate hydrogen peroxide; l-glutamate oxidase and L-glutamic acid, L-glutamate oxidase oxidizes L-glutamic acid to produce hydrogen peroxide; (3) To the solution is added a source of hydrogen peroxide, i.e., a compound that generates hydrogen peroxide when dissolved in water or a suitable water-based medium, including but not limited to metal peroxides, t-butyl hydroperoxide, cumene hydroperoxide, percarbonate, persulfate, peroxodisulfate, perphosphate, peracetic acid, perborate, perbenzoic acid, peroxy acids, alkyl peroxides, acyl peroxides, peroxy esters, urea peroxide, and peroxy carboxylic acids or salts thereof, possibly supplemented with catalase.
The interface of the two phases can be an oil-lower phase (reaction solvent) interface where the upper phase is liquid at normal temperature, an oil (such as carbon tetrachloride, carbon disulfide, and butyl palmitate) interface where the upper phase (reaction solvent) -lower phase is liquid at normal temperature, an oil (such as paraffin, beeswax, insect wax, spermaceti wax, cocoa butter, coconut oil, beef tallow, and mutton tallow) interface where the upper phase (reaction solvent) -lower phase is solid at a set temperature, an aqueous phase (reaction solvent) -lower phase (such as gallium, mercury, and low-melting-point alloy) interface, an interface between droplets of the aqueous phase (reaction solvent) suspended in the oil and the oil, and an interface between droplets of the aqueous phase (reaction solvent) suspended in the oil and the aqueous phase.
The invention also provides copolymer particles or a copolymer film prepared by the synthesis method.
According to embodiments of the present invention, the copolymer film comprises the following types: according to the phase of the catalyst and the film-forming monomer, the following three types can be distinguished: (1) The catalyst and the film-forming monomer are completely dissolved in the water phase to form a film; (2) A film formed by the catalyst and at least one film-forming monomer dissolved in the water phase and another or more film-forming monomers in the oil phase; (3) The catalyst is dissolved in the water phase, and the film-forming monomer is dissolved in the oil phase to form a film. According to the interface forming the film, the following can be classified: a membrane of an interface of an upper layer normal temperature oil-a lower layer water phase, a membrane of an interface of an upper layer water phase-a lower layer normal temperature oil, a membrane of an interface of an upper layer water phase-a lower layer liquid metal, a membrane of an interface of a water phase-an oil that is solid at a set temperature (the oil phase that is solid at a set temperature such as paraffin, beeswax, insect wax, spermaceti wax, cacao butter, coconut oil, beef tallow, etc.), an oil-water interface membrane of a water-in-oil emulsion, a water-oil interface membrane of an oil-in-water emulsion.
The invention also provides the application of the copolymer particles or the copolymer membrane, such as the application in preparing multilayer membranes, preparing vesicles, preparing conductive membranes and constructing supermolecular functional materials; and the application in reducing metal and coating; use in secondary reactions, for example, further modification of copolymer films;
preferably, the modification introduces sorbitol, quaternary ammonium salt and dye molecules on the surface of the copolymer film.
The copolymer membranes of the present invention also include vesicles. The Vesicles (Vesicles) are a kind of assembly with a closed structure and surrounded by a copolymer membrane.
The invention also provides a preparation method of the vesicle, which comprises the following steps: (1) And dissolving a catalyst and a film-forming monomer in a water phase, and adding the water phase into the oil-in-water emulsion to obtain the vesicle with the surface of the copolymer film. (2) Dissolving a catalyst and a film-forming monomer in a water phase, pouring the water phase and the film-forming monomer into oil, stirring to obtain a water-in-oil emulsion, and reacting for a period of time to obtain vesicles with the copolymer on the surface. (3) Dissolving a catalyst and a water-soluble film-forming monomer in a water phase, dissolving another oil-soluble monomer in oil to prepare an emulsion, and reacting for a period of time to obtain the copolymer film serving as the vesicle wall.
The selection of the film-forming monomer has significant influence on the characteristics of the copolymer film such as chemical composition, molecular structure, physicochemical properties and performance, and the like, so that the chemical composition, the molecular structure, the physicochemical properties and the performance of the copolymer film can be designed on the molecular level by selecting a proper film-forming monomer and a proper proportion thereof. Such as: general organic polymer is good insulator, and suitable film-forming monomer is selected, such as hydroquinone, ferulic acid, catechol, p-phenylenediamine, benzidine and other film-forming monomers with conjugated pi bonds, so that the copolymer film has highly delocalized pi electrons in the structure, and can be used for preparing films with conductive performance, organic polymer full-color flat display materials and devices, optical limiting materials, sensor sensing materials, electrode materials and microwave absorbing materials.
The invention also provides a multilayer film comprising at least one layer of the copolymer film.
According to an embodiment of the present invention, the thickness of the membrane can also be increased by replenishing the raw material for the enzymatic reaction and/or replacing the enzyme-catalyzed reaction system with fresh one.
Those skilled in the art will appreciate that the reaction rate, the thickness of the membrane, and the reactive functional groups on the surface of the membrane can be easily controlled by changing the type and amount of enzyme, the type and concentration of the membrane-forming monomer, the pH, temperature, the type and concentration of the ion pair in the buffer, the metal ion and concentration thereof, the concentration of the oxidizing agent (e.g., dissolved oxygen, hydrogen peroxide), the duration of the enzymatic reaction, the enhancer of the enzyme, the inhibitor of the enzymatic activity, whether or not the organic solvent is contained and the type and concentration of the organic solvent, the composition of the liquid medium constituting the interface, whether or not the reaction solution is renewed, whether or not the reaction is terminated, and how the reaction is terminated. The thickness of the film, the thickness of the deposit/bond on the film, can be controlled individually at the nanoscale.
The reaction system may employ any buffer, pH, ion, and any combination thereof that may be sufficient for the copolymerization reaction in accordance with the principles of the present invention. Other aspects of the enzymatic reaction conditions of the present invention may be optimized by routine experimentation. For example, pH and temperature are non-limiting examples of optimizable factors.
By selecting suitable film-forming monomers, copolymer films can be designed and prepared on a molecular level that expose specific reactable functional groups, i.e., residual reactive and affinity groups on the copolymer film obtained after polymerization of the monomers, which groups can be: halogen, unsubstituted or substituted by halogen, OH, COOH, NH 2 、CN、SH、NO 2 Alkyl, alkoxy, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl, heteroaryl substituted by: OH, COOH, NH 2 SH, alkyl, alkoxy, alkenyl, alkynyl, aryl, sulfone, sulfonic acid, amide, acid halide, phosphoryl, azo. The active groups on the copolymer film can introduce functional molecules and/or atoms and/or ions into the surface of the copolymer film through two or more reactions, so that the further functionalization of the surface of the copolymer film is realized, the surface of the copolymer film has extremely strong designability, and the application range of the film is further expanded.
According to embodiments of the present invention, the copolymer membrane can be designed and prepared to expose specific reactable functional groups on a molecular level by varying the type and concentration of the membrane-forming monomers, and the functional groups on the membrane can be chemically or enzymatically reacted. Modification and/or modification of the membrane is achieved by attaching the desired target molecule/atom to the membrane by chemical or enzymatic reactions, such as radical reactions, grafting reactions. Such group reactions include, but are not limited to: michael-type addition reaction, schiff base reaction (Schiff base reaction), friedel-Crafts reaction, mannich reaction, substitution reaction, addition reaction, polymerization reaction, condensation reaction, oxidation reaction, reduction reaction, esterification reaction, sulfonation reaction, nitration reaction, diazotization reaction, azidation reaction, amidation reaction, acylation reaction, alkylation reaction, glycoside formation reaction, ether formation reaction, etherification reaction, coupling reaction, complexation reaction, displacement reaction, nucleophilic elimination reaction, surface atom transfer radical polymerization (SI-ATRP) reaction, reversible addition-fragmentation chain transfer polymerization (RAFT) reaction.
Such as: the proper monomers are selected to make the prepared copolymer film contain abundant phenolic hydroxyl groups. Under certain conditions, phenolic hydroxyl is oxidized into quinoid structure, so that the quinoid structure can be combined with a compound containing sulfhydryl (-SH) and amino (-NH) 2 ) The hydrophilic or hydrophobic organic molecules are subjected to Michael addition and Schiff base reaction, functional molecules are introduced to the surface of the copolymer membrane, and Self-assembled monolayer modification (Self-assembled monolayers) on the surface of the copolymer membrane can be realized.
Such as: the phenolic hydroxyl groups in the copolymer film are capable of forming coordinate bonds with metal ions in the metal oxide. Dipping the copolymer film into ammonium hexafluorotitanate ((NH) 4 ) 2 TiF 6 ) And boric acid (H) 3 BO 3 ) (NH) 4 ) 2 TiF 6 And H 3 BO 3 Titanium dioxide (TiO) produced by hydrolysis 2 ) The nanoparticles are chelated with the copolymer film to form uniform TiO on the surface of the copolymer film 2 A film.
Those skilled in the art will appreciate that: the surface of the copolymer membrane can contain active groups, so that different types of functional substances and target molecules can be combined, such as metal atoms, metal oxide nanoparticles, graphene oxide, functional living cells, proteins, enzymes, polypeptides, metal binding polypeptides, fluorescent dyes, antibodies, anti-antibodies, haptens, immunogens, DNA, oligonucleotides, growth factors, drug macromolecules, ligands, amino and/or sulfhydryl and/or aldehyde group and/or carboxyl group-terminated polyethylene glycol, carbohydrate substances, fatty amines and other substances with amino and/or sulfhydryl and/or aldehyde group and/or carboxyl group in the structure, and the like.
The copolymer film and the multilayer film prepared by the invention have rich types of selectable film forming monomers, and the components and molecular structures of the film which can be designed and prepared are rich and diverse, so that the composition, structure, performance and service performance of the copolymer film are rich and diverse, and therefore, the copolymer film and the multilayer film can be selected according to the application requirements.
The copolymer film prepared by selecting proper film-forming monomers can be combined with quaternary ammonium salt molecules for antibiosis.
The copolymer film can be used for constructing a supermolecular functional material, assembling a two-dimensional and smaller structural material and constructing a multi-layer functional polymer material; the bound or supported catalyst becomes a reactive polymer.
According to embodiments of the present invention, the copolymer membrane may be used for catalysis of biological and chemical reactions by the incorporation of catalysts, including biological enzymes, chemical catalysts.
The copolymer film prepared by selecting proper film-forming monomers can be connected with dye molecules to express corresponding colors.
According to an embodiment of the present invention, the copolymer film may have an inorganic substance (silver, hydroxyapatite, calcium carbonate, silica, etc.) deposited on the surface thereof to form a nano layer, from which an organic-inorganic derived film may be prepared. For example, a metal-modified vesicle is prepared by adding the vesicle to a metal salt solution.
According to an embodiment of the present invention, the metal salt includes, but is not limited to, silver nitrate, chloroauric acid, chloroplatinic acid, or palladium nitrate.
The metal cations are reduced from the metal salt solution and deposited on the surface of the copolymer film, thereby effecting electroless metallization of the film surface.
In addition, copolymer particles can be generated in the water phase while the copolymer film is prepared, and the copolymer particles contain high-density active groups such as amino groups, quinonyl groups, phenolic hydroxyl groups and the like, so that the copolymer particles have the characteristic of being capable of reacting again on one hand, and can be added into plastics as a filler to improve the performance of the plastics on the other hand.
Advantageous effects
The copolymer membrane and the enzymatic self-assembly synthesis method thereof provided by the invention have the advantages of simple operation steps, no need of air isolation, no need of external potential, mild reaction conditions, normal temperature, normal pressure, neutral or nearly neutral pH, and low energy consumption; the reaction is carried out in liquid, the chemical uniformity is good, the multi-component uniformity can reach the molecular level, and the composition and the structure are uniform; the reaction is easy to control, the reproducibility is good, and the structure of the compound can be regulated and controlled at the molecular level. The thickness of the copolymer film, the thickness of the deposit/bond on the film, can be controlled individually at the nanoscale.
The method for preparing the copolymer film has wide selection range of film forming monomers, can use various film forming monomers, and can polymerize monomers containing catechol structures, monomers with resorcinol structures, monomers with hydroquinone structures, and even compounds with high redox potentials such as bisphenols, biphenyls and the like. On one hand, different film forming monomers can obtain films with different molecular structures through laccase catalytic polymerization and crosslinking, and the films with different molecular structures have different properties, performances and applications, so that the design of the films has high degree of freedom and strong designability, and copolymer films with corresponding functions can be selected and prepared according to application requirements. On the other hand, the surface of the copolymer membrane prepared by selecting a proper membrane-forming monomer can carry a selected active group, corresponding activity and properties are shown, target molecules and/or atoms can be introduced to the surface of the membrane through two times/multiple times of chemical or/and enzymatic reactions, the purpose of functional modification of the membrane surface is achieved, the surface of the polymer membrane has extremely strong designability, and the application range of the membrane is further expanded.
The copolymer film has higher crosslinking degree, so the copolymer film has better mechanical property and good tolerance to water, acid, alkali, organic solvent and heat. Therefore, the vesicle prepared by the invention has better stability compared with the vesicle prepared by the surfactant and the protein.
Based on the characteristics, the preparation method provided by the invention is easy to upgrade from a laboratory to industrial mass production, the design time is short, the start and stop of production are easy, products can be quickly and flexibly replaced on the same production line, the method is suitable for small-batch production process and distributed manufacturing, the adaptability is strong, and the flexibility of products, production plans and scheduling is high. It is particularly noteworthy that the base membranes of the present invention are prepared enzymatically, many of which are chemically difficult to achieve.
The invention has the outstanding beneficial effects that the characteristics of the copolymer film can be artificially controlled under the condition of more freedom degrees, and the material meeting the requirement is obtained, so that the invention has great potential in technical application.
Term definition and interpretation
Unless otherwise indicated, the definitions of radicals and terms described in the specification and claims of the present application, including definitions thereof as examples, exemplary definitions, preferred definitions, definitions described in tables, definitions of specific compounds in the examples, and the like, may be arbitrarily combined and coupled with each other. The definitions of the groups and the structures of the compounds in such combinations and after the combination are within the scope of the present specification.
The term "film-forming monomer" refers to a molecule or group of molecules of an organic compound that becomes a copolymer film by polymerization.
The film-forming monomer containing phenolic hydroxyl is a compound which is composed of one or more hydroxyl groups directly bonded on an aromatic ring in the same molecule.
The film-forming monomer containing at least two amino groups refers to a compound which is a substance containing at least two amino groups in the same molecule.
The low-melting-point alloy is a metal alloy material which has a melting point of 1-96 ℃, is not easy to volatilize, has stable properties and does not react with a water phase below 120 ℃.
The artificial enzyme is an enzyme analogue which simulates the biological catalysis function of natural enzyme according to the catalysis mechanism of the enzyme and has a special catalysis function and is synthesized by organic chemistry and biological methods, and the artificial enzyme comprises metalloenzyme.
The metalloenzyme is a conjugated enzyme containing one or more metal ions as auxiliary groups.
Unless otherwise indicated, the numerical ranges set forth in the specification and claims are equivalent to at least each specific integer recited therein. For example, the numerical range of "1 to 40" corresponds to the description of each integer value of the numerical range of "1 to 10", i.e., 1,2,3, 4,5, 6,7, 8,9, 10, and each integer value of the numerical range of "11 to 40", i.e., 11, 12, 13, 14, 15, 35, 36, 37, 38, 39, 40. It is to be understood that "more" in one, two, or more of the substituents used herein when describing substituents shall mean an integer ≧ 3, such as 3,4,5, 6,7, 8,9, or 10. Further, when certain numerical ranges are defined as "numbers," it should be understood that the two endpoints of the range, each integer within the range, and each decimal within the range are recited. For example, "a number of 0 to 10" should be understood to not only recite each integer of 0, 1,2,3, 4,5, 6,7, 8,9, and 10, but also to recite at least the sum of each integer with 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, respectively.
The term "halogen" denotes fluorine, chlorine, bromine and iodine.
The term "C 1-40 Alkyl "is understood to mean a straight-chain or branched saturated monovalent hydrocarbon radical having from 1 to 40 carbon atoms. For example, "C 1-10 Alkyl "denotes straight-chain and branched alkyl groups having 1,2,3, 4,5, 6,7, 8,9 or 10 carbon atoms," C 1-6 Alkyl "denotes straight and branched chain alkyl groups having 1,2,3, 4,5 or 6 carbon atoms. The alkyl group is, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutylA group, a sec-butyl group, a tert-butyl group, an isopentyl group, a 2-methylbutyl group, a 1-ethylpropyl group, a1, 2-dimethylpropyl group, a neopentyl group, a1, 1-dimethylpropyl group, a 4-methylpentyl group, a 3-methylpentyl group, a 2-methylpentyl group, a 1-methylpentyl group, a 2-ethylbutyl group, a 1-ethylbutyl group, a 3, 3-dimethylbutyl group, a2, 2-dimethylbutyl group, a1, 1-dimethylbutyl group, a2, 3-dimethylbutyl group, a1, 3-dimethylbutyl group, or a1, 2-dimethylbutyl group, or isomers thereof.
The term "C 2-40 Alkenyl "is understood to preferably mean a straight-chain or branched monovalent hydrocarbon radical comprising one or more double bonds and having from 2 to 40 carbon atoms, preferably" C 2-10 Alkenyl ". ' C 2-10 Alkenyl "is understood to preferably mean a straight-chain or branched monovalent hydrocarbon radical which contains one or more double bonds and has 2,3,4, 5,6, 7,8, 9 or 10 carbon atoms, for example having 2,3,4, 5 or 6 carbon atoms (i.e. C) 2-6 Alkenyl) having 2 or 3 carbon atoms (i.e., C) 2-3 Alkenyl). It is understood that where the alkenyl group contains more than one double bond, the double bonds may be separated from each other or conjugated. The alkenyl group is, for example, vinyl, allyl, (E) -2-methylvinyl, (Z) -2-methylvinyl, (E) -but-2-enyl, (Z) -but-2-enyl, (E) -but-1-enyl, (Z) -but-1-enyl, pent-4-enyl, (E) -pent-3-enyl, (Z) -pent-3-enyl, (E) -pent-2-enyl, (Z) -pent-2-enyl, (E) -pent-1-enyl, (Z) -pent-1-enyl, hex-5-enyl, (E) -hex-4-enyl, (Z) -hex-4-enyl, (E) -hex-3-enyl, (Z) -hex-3-enyl, (E) -hex-2-enyl, (Z) -hex-2-enyl, (E) -hex-1-enyl, (Z) -hex-1-enyl, isopropenyl, 2-methylprop-2-enyl, 1-methylprop-2-enyl, 2-methylprop-1-enyl, (E) -1-methylprop-1-enyl, (Z) -1-methylprop-1-enyl, 3-methylbut-3-enyl, 2-methylbut-3-enyl, 1-methylbut-3-enyl, 3-methylbut-2-enyl, (E) -2-methylbut-2-enyl, (Z) -2-methylbut-2-enyl, (E) -1-methylbut-2-enyl, (Z) -1-methylbut-2-enyl, (E) -3-methylbut-1-enyl, (Z) -3-methylbut-1-enyl, (E) -2-methylbut-1-enyl, (Z) -2-methylbut-1-enyl, (E) -1-methylbut-1-enyl, (Z) -1-methylbut-1-enyl, 1-dimethylprop-2-enyl, 1-ethylbut-3-enylProp-1-enyl, 1-propylvinyl, 1-isopropylvinyl.
The term "C 2-40 Alkynyl "is understood to mean a straight-chain or branched monovalent hydrocarbon radical comprising one or more triple bonds and having from 2 to 40 carbon atoms, preferably" C 2-10 Alkynyl ". The term "C 2-10 Alkynyl "is understood as preferably meaning a straight-chain or branched, monovalent hydrocarbon radical which contains one or more triple bonds and has 2,3,4, 5,6, 7,8, 9 or 10 carbon atoms, for example having 2,3,4, 5 or 6 carbon atoms (i.e." C ") 2-6 Alkynyl ") having 2 or 3 carbon atoms (" C) 2-3 Alkynyl "). <xnotran> , -1- , -2- , -1- , -2- , -3- , -1- , -2- , -3- , -4- , -1- , -2- , -3- , -4- , -5- ,1- -2- ,2- -3- ,1- -3- ,1- -2- ,3- -1- ,1- -2- ,3- -4- ,2- -4- ,1- -4- ,2- -3- ,1- -3- ,4- -2- ,1- -2- ,4- -1- ,3- -1- ,2- -3- ,1- -3- ,1- -2- ,1- -2- ,1- -2- ,2,2- -3- , </xnotran> 1, 1-dimethylbut-3-ynyl, 1-dimethylbut-2-ynyl or 3, 3-dimethylbut-1-ynyl. In particular, the alkynyl group is ethynyl, prop-1-ynyl or prop-2-ynyl.
The term "C 3-40 Cycloalkyl "is understood to mean a saturated monovalent monocyclic, bicyclic hydrocarbon ring or bridged cycloalkane having from 3 to 40 carbon atoms, preferably" C 3-10 Cycloalkyl ". The term "C 3-10 Cycloalkyl "is understood to mean a saturated monovalent monocyclic, bicyclic hydrocarbon ring or bridged cycloalkane having 3,4,5, 6,7, 8,9 or 10 carbon atoms. Said C is 3-10 Cycloalkyl can be monocyclic, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl or cyclodecyl, or bicyclic, such as decahydroA naphthalene ring.
The term "3-20 membered heterocyclyl" means a saturated monovalent monocyclic, bicyclic hydrocarbon ring or bridged cycloalkane group containing from 1 to 5 heteroatoms independently selected from N, O and S in an aggregate ring number of from 3 to 20 (e.g., 3,4,5, 6,7, 8,9, 10, etc.), preferably a "3-10 membered heterocyclyl", and is preferably a non-aromatic cyclic group. The term "3-to 10-membered heterocyclyl" means a saturated monovalent monocyclic, bicyclic hydrocarbon ring or bridged cycloalkane comprising 1 to 5, preferably 1 to 3 heteroatoms selected from N, O and S. The heterocyclic group may be attached to the rest of the molecule through any of the carbon atoms or nitrogen atom (if present). In particular, the heterocyclic group may include, but is not limited to: 4-membered rings such as azetidinyl, oxetanyl; 5-membered rings such as tetrahydrofuranyl, dioxolyl, pyrrolidinyl, imidazolidinyl, pyrazolidinyl, pyrrolinyl; or a 6-membered ring such as tetrahydropyranyl, piperidinyl, morpholinyl, dithianyl, thiomorpholinyl, piperazinyl, or trithianyl; or a 7-membered ring such as diazepanyl. Optionally, the heterocyclic group may be benzo-fused. The heterocyclyl group may be bicyclic, for example but not limited to a 5,5 membered ring such as a hexahydrocyclopenta [ c ] pyrrol-2 (1H) -yl ring, or a 5,6 membered bicyclic ring such as a hexahydropyrrolo [1,2-a ] pyrazin-2 (1H) -yl ring. The nitrogen atom containing ring may be partially unsaturated, i.e., it may contain one or more double bonds, such as, but not limited to, 2, 5-dihydro-1H-pyrrolyl, 4H- [1,3,4] thiadiazinyl, 4, 5-dihydrooxazolyl or 4H- [1,4] thiazinyl, or it may be benzo-fused, such as, but not limited to, dihydroisoquinolyl. According to the invention, the heterocyclic group is non-aromatic. When the 3-20 membered heterocyclic group is linked with other groups to form the compound of the present invention, the carbon atom on the 3-20 membered heterocyclic group may be linked with other groups, or the heterocyclic atom on the 3-20 membered heterocyclic ring may be linked with other groups. For example, when the 3-to 20-membered heterocyclic group is selected from piperazinyl, it is possible that the nitrogen atom on the piperazinyl group is bonded to another group. Or when the 3-20 membered heterocyclyl group is selected from piperidinyl, it may be that the nitrogen atom on the piperidinyl ring and the carbon atom in the para position are attached to other groups.
Term "C 6-20 Aryl "is understood to preferably mean a monocyclic, bicyclic or tricyclic hydrocarbon ring of monovalent or partial aromaticity having from 6 to 20 carbon atoms, preferably" C 6-14 Aryl ". The term "C 6-14 Aryl "is to be understood as preferably meaning a mono-, bi-or tricyclic hydrocarbon ring having a monovalent or partially aromatic character with 6,7, 8,9, 10, 11, 12, 13 or 14 carbon atoms (" C 6-14 Aryl group "), in particular a ring having 6 carbon atoms (" C 6 Aryl "), such as phenyl; or biphenyl, or is a ring having 9 carbon atoms ("C 9 Aryl), such as indanyl or indenyl, or a ring having 10 carbon atoms ("C) 10 Aryl radicals), such as tetralinyl, dihydronaphthyl or naphthyl, or rings having 13 carbon atoms ("C 13 Aryl radicals), such as the fluorenyl radical, or a ring having 14 carbon atoms ("C) 14 Aryl), such as anthracenyl. When said C is 6-20 When the aryl group is substituted, it may be mono-or polysubstituted. And, the substitution site thereof is not limited, and may be, for example, ortho-, para-or meta-substitution.
The term "5-20 membered heteroaryl" is understood to include such monovalent monocyclic, bicyclic or tricyclic aromatic ring systems: having 5 to 20 ring atoms and containing 1 to 5 heteroatoms independently selected from N, O and S, such as "5-to 14-membered heteroaryl". The term "5-to 14-membered heteroaryl" is understood to include such monovalent monocyclic, bicyclic or tricyclic aromatic ring systems: which has 5,6, 7,8, 9, 10, 11, 12, 13 or 14 ring atoms, in particular 5 or 6 or 9 or 10 carbon atoms, and which contains 1 to 5, preferably 1 to 3, heteroatoms each independently selected from the group consisting of N, O and S and, in addition, can be benzo-fused in each case. In particular, heteroaryl is selected from thienyl, furyl, pyrrolyl, oxazolyl, thiazolyl, imidazolyl, pyrazolyl, isoxazolyl, isothiazolyl, oxadiazolyl, triazolyl, thiadiazolyl, thia-4H-pyrazolyl and the like and their benzo derivatives, such as benzofuryl, benzothienyl, benzoxazolyl, benzisoxazolyl, benzimidazolyl, benzotriazolyl, indazolyl, indolyl, isoindolyl and the like; or pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl and the like, and benzo derivatives thereof, such as quinolyl, quinazolinyl, isoquinolyl and the like; or azocinyl, indolizinyl, purinyl and the like and benzo derivatives thereof; or cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, naphthyridinyl, pteridinyl, carbazolyl, acridinyl, phenazinyl, phenothiazinyl, phenoxazinyl, and the like. When the 5-to 20-membered heteroaryl group is linked to another group to form the compound of the present invention, the carbon atom on the 5-to 20-membered heteroaryl ring may be linked to another group, or the heteroatom on the 5-to 20-membered heteroaryl ring may be linked to another group. When the 5-to 20-membered heteroaryl group is substituted, it may be mono-or poly-substituted. And, there is no limitation on the substitution site thereof, and for example, hydrogen bonded to a carbon atom on a heteroaryl ring may be substituted, or hydrogen bonded to a heteroatom on a heteroaryl ring may be substituted.
As used herein, the term "derivative" (derivative) refers to a chemical substance that is structurally related to another substance that is "native" and may also be referred to as a "parent" compound. "derivatives" may be prepared from structurally related parent compounds in one or more steps.
Unless otherwise indicated, heterocyclyl, heteroaryl or heteroarylene include all possible isomeric forms thereof, e.g., positional isomers thereof. Thus, for some illustrative non-limiting examples, forms may be included that are substituted at one, two or more of their 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11-, 12-positions, etc. (if present) or bonded to other groups, including pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, and pyridin-4-yl; thienyl or thienylene includes thien-2-yl, thien-3-yl and thien-3-yl; pyrazol-1-yl, pyrazol-3-yl, pyrazol-4-yl, pyrazol-5-yl.
The term "oxo" refers to an oxy substitution (= O) formed after oxidation of a carbon atom, a nitrogen atom, or a sulfur atom in a substituent.
The polyphenol refers to a natural, synthetic and semi-synthetic organic compound characterized by the presence of a large number of repeating phenolic building blocks. Polyphenols are generally compounds having a molecular weight of 400 to 4000Da, greater than or equal to 5 phenolic hydroxyl groups.
The term "enhancer of the enzyme" refers to a diffusible molecule activated by the oxidase and diffusing from the active site on the enzyme to a sensitive structure, and is some organic small molecule compounds with low redox potential that can act as carriers for electron transfer during laccase catalyzed oxidation.
The multilayer film is a film composed of at least one copolymer film. In order to distinguish the initially formed film from a film prepared by continuing the reaction two or more times on the basis thereof, the initially formed copolymer film is referred to as a "base film" in the present invention. The copolymer membrane, prepared by two or more chemical or/and enzymatic reactions of the base membrane, is referred to as the "derivatized membrane". The new membrane layer can be generated on one side or both sides of the basic membrane through enzymatic polymerization, the chemical composition and the structure of the new membrane layer can be different from those of the basic membrane, and the new membrane layer can be generated continuously. The base film and the new film layer together constitute a "multilayer film". The derivatized film continues to form a new polymer film, referred to as a "derivatized multilayer film".
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
The Polyethyleneimine (PEI) in the present invention has an average relative molecular mass (average molecular weight) of 600, and is manufactured by michelin biochemical technologies, ltd. The paraffin is refined paraffin with a melting point of 58-60 ℃ and is produced by Jiangsu Shitai laboratory instruments Co. Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
Definition of laccase enzyme activity: the enzyme amount required for oxidizing 1. Mu. Mol of 2,2 '-Azino-bis- (3-ethylchromanone-6-sulfonic acid) diammonium salt (2, 2' -Azino-bis (3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt, ABTS) per minute was 1 enzyme activity unit (U).
Definition of manganese peroxidase enzymatic Activity: the enzyme amount required to oxidize 1. Mu. Mol of ABTS per minute was 1 enzyme activity unit (U).
Definition of enzyme activity of horseradish peroxidase: the amount of enzyme required to oxidize 1. Mu. Mol of ABTS per minute was 1 enzyme activity unit (U).
Definition of lignin peroxidase enzymatic activity: the enzyme amount required to oxidize 1. Mu. Mol of ABTS per minute was 1 enzyme activity unit (U).
Definition of soybean peroxidase enzyme activity: the amount of enzyme required to oxidize 1. Mu. Mol of ABTS per minute was 1 enzyme activity unit (U).
Definition of enzyme Activity of chloroperoxidase: the enzyme amount required for oxidizing 1. Mu. Mol of 2-chloro-5, 5-dimethyl-1, 3-cyclohexanedione per minute to form 2, 2-dichloro-5, 5-dimethyl-1, 3-cyclohexanedione is 1 enzyme activity unit (U).
Definition of enzymatic Activity of Monophenol Mono-oxidase: the enzyme amount required for oxidizing 1. Mu. Mol of L-DOPA (L-DOPA) per minute was 1 enzyme activity unit (U).
Definition of the enzymatic activity of catechol oxidase: the amount of enzyme required to oxidize 1. Mu. Mol of catechol per minute was 1 enzyme activity unit (U).
Definition of bilirubin oxidase enzyme activity: the enzyme amount required to oxidize 1. Mu. Mol of ABTS per minute was 1 enzyme activity unit (U).
Example 1: preparation of laccase
(1) Liquid seed culture medium: 30g/L of corn flour, 15g/L of bean cake powder, 54U/L of alpha-amylase and NaH 2 PO 4 2.6g/L，KCl 2.25g/L，MgSO 4 ·7H 2 O1.5 g/L, water in balance, pH 6.0,0.1MPa and sterilizing for 25min.
Fermentation medium: fructose 48g/L, corn flour 12g/L, soybean peptone 9g/L, (NH) 4 ) 2 SO 4 0.5g/L，KCl 1g/L，NaH 2 PO 4 1.8g/L，MgSO 4 ·7H 2 O 0.25g/L，CuSO 4 ·5H 2 O 1mmol/L，VB 1 0.03g/LTween-80.5g/L, vanillin 1mmol/L, water in balance, pH 6.5, and sterilization at 0.1MPa for 25min.
(2) Liquid seed culture: collecting Polyporus fomentarius (Polyporus brutalis) (preservation number of strain CCTCC NO: M2020809) with slant lawn of about 3cm 2 Inoculating into 500mL triangular flask, bottling liquid seed culture medium 150mL, shaking table at 30 deg.C, and culturing at 150rpm for 4 days to obtain seed liquid.
And (3) shake flask fermentation culture: inoculating the seed solution to a fermentation medium according to the inoculation amount of 6% in volume ratio, wherein the liquid loading amount of the fermentation medium in a 500mL triangular flask is 150mL, performing shaking culture at 30 ℃, the rotation speed of a shaking table is 150rpm in 1-3 days of fermentation, and the rotation speed of the shaking table is 200rpm after 3 days of fermentation.
(3) Preparation of crude enzyme solution: the fermentation liquor is centrifuged for 10min at 10000 Xg at 4 ℃, and the supernatant is crude enzyme liquid of laccase.
(4) And (3) laccase purification:
100mL of crude laccase solution is taken, ammonium sulfate is slowly added in stages while stirring, the concentration of the ammonium sulfate solution gradually reaches 60%, after full precipitation, the solution is centrifuged at 12000 Xg at 4 ℃ for 10min, the precipitate is collected and dissolved in a proper volume of citric acid-disodium hydrogen phosphate buffer solution with the pH value of 7.0 and 0.02mol/L, and salting-out solution is obtained. And (3) putting the salting-out solution into the same buffer solution for dialysis overnight, and replacing the dialysate every 10h until the conductivity and pH of the liquid inside and outside the dialysis bag are the same, so as to obtain the dialysate of the laccase.
A chromatographic column packed with DEAE-Sepharose Fast Flow ion exchange medium was equilibrated with citric acid-disodium hydrogen phosphate buffer solution (solution A) having a pH of 7.0,0.02mol/L. The enzyme solution obtained by dialysis was filtered through a filter having a pore size of 0.22 μm, and then the solution was sampled at a flow rate of 2mL/min to give a sample volume of 10mL. After sampling, the solution A is firstly used for balancing until the baseline returns to zero, then citric acid-disodium hydrogen phosphate buffer solution (solution B) containing 0-0.5 mol/L of NaCl is respectively used for continuous gradient elution, the flow rate is 1mL/min, the absorbance at the wavelength of 280nm is recorded, active components are collected for later use, and 2mL of active components are collected in each tube. And (3) measuring the laccase activity and the protein concentration of the collected sample, combining the eluates with the laccase activity to obtain the laccase purified by the chromatographic column (called as pure enzyme solution in the invention), and storing at-20 ℃ for later use.
Example 2: preparation of copolymer membrane by enzymatic polymerization at liquid paraffin-aqueous solution interface
(1) Preparing a chrysin-arginine copolymer membrane by laccase catalysis:
dissolving 0.050g of chrysin, 0.050g of arginine and 5.0mg of vanillin in a mixed solvent of 35mL of 0.05mol/L sodium succinate-succinic acid buffer solution (pH 2.0) and 15mL of acetone, adding 7.5U of laccase, and fully and uniformly mixing to obtain a laccase catalytic system (aqueous phase). The aqueous phase was covered with liquid paraffin of 3mm thickness and left to stand in an incubator (Zhicheng, ZSD-1090, china) at 30 ℃ for 3 hours, and a "chrysin-arginine copolymer film" was formed at the interface between the liquid paraffin and the aqueous phase. The transfer process of the "chrysin-arginine copolymer film" is as follows: sucking out most of the liquid paraffin on the upper side of the chrysin-arginine copolymer membrane and the water phase on the lower side of the chrysin-arginine copolymer membrane by using an injector, injecting distilled water on the lower side of the chrysin-arginine copolymer membrane again, and repeating the operations of liquid suction, liquid injection and liquid suction for multiple times; and (3) inserting the cover glass into the water phase under the membrane, carefully moving the cover glass to the position below the "chrysin-arginine copolymer membrane", gently scooping the cover glass, sucking residual liquid paraffin on the surface of the membrane by using filter paper, and airing at room temperature.
(2) Preparing tectorigenin-PEI copolymer membrane by laccase catalysis:
0.250g of tectorigenin, 0.250g of PEI and 12.5mg of ABTS are dissolved in 175mL of mixed solvent of 0.05mol/L potassium hydrogen phthalate-sodium hydroxide buffer solution (pH 5.0) and 75mL of ethanol, 50U of laccase is added, and the laccase solution and the mixed solvent are mixed uniformly to obtain a laccase catalytic system (aqueous phase). The aqueous phase was covered with liquid paraffin of 5mm thickness and left to stand in an oven (Zhicheng, ZFD-5090, china) at 60 ℃ for 8 hours to form an "tectorigenin-PEI copolymer film" at the interface between the liquid paraffin and the aqueous phase.
The transfer method of the film comprises the following steps: the bottom aqueous phase was slowly drained to allow the film to fall to the surface of the substrate at the bottom of the vessel, and the upper layer of liquid wax was removed.
(3) Preparing rhein-2, 4-diamino-6-methyl-1, 3, 5-triazine copolymer film by laccase catalysis:
dissolving 0.125g of rhein, 0.125g of 2, 4-diamino-6-methyl-1, 3, 5-triazine and 20mg of syringaldehyde in 175mL of a mixed solvent of 0.05mol/L sodium acetate-acetic acid buffer solution (pH 4.0) and 75mL of methanol, adding 5U of laccase, and uniformly mixing to obtain a laccase catalytic system (aqueous phase). The aqueous phase was covered with liquid paraffin of 5mm thickness and left to react in an oven (Zhicheng, ZFD-5090, china) at 50 ℃ for 10h. At the interface between the liquid paraffin and the aqueous phase, a "rhein-2, 4-diamino-6-methyl-1, 3, 5-triazine copolymer film" was formed.
(4) Preparing a1, 6-dihydroxynaphthalene-diethylenetriamine copolymer film under catalysis of manganese peroxidase:
0.125g of 1, 6-dihydroxynaphthalene and 0.250g of diethylenetriamine were dissolved in 200mL of a mixed solvent of 0.05mol/L disodium hydrogenphosphate-citric acid buffer solution (pH 4.0) and 50mL of acetone, and 12U of manganese peroxidase, 40. Mu.L of 5% hydrogen peroxide and 0.1mol/L MnSO were added 4 3.5mL, and mixing to obtain a manganese peroxidase catalytic system (water phase). The surface of the aqueous phase was covered with liquid paraffin 5mm thick by a pipette and allowed to stand in an incubator (Zhicheng, ZSD-1090, china) at 37 ℃ for 10 hours, during which time the reaction system was replenished with 5% hydrogen peroxide 40. Mu.L each time. The interface between the liquid paraffin and the aqueous phase formed a "film of 1, 6-dihydroxynaphthalene-diethylenetriamine copolymer".
(5) Preparing the alkannin-lysine copolymer membrane by using manganese peroxidase as an enzyme:
dissolving 0.125g alkannin and 0.125g lysine in 175mL of mixed solvent of 0.05mol/L disodium hydrogen phosphate-citric acid buffer solution (pH 3.0) and 75mL ethanol, adding manganese peroxidase 10U, 5% hydrogen peroxide 40 μ L, and 0.1mol/L MnSO 4 3.5mL, and mixing to obtain a manganese peroxidase catalytic system (water phase). Covering the surface of a manganese peroxidase catalytic system with liquid paraffin with the thickness of 5mm by using a pipette, standing in an oven (Zhicheng, ZFD-5090, china) at 45 ℃ for 6 hours, and supplementing 5 percent of hydrogen peroxide into the reaction system for a plurality of times during the standing period, wherein each time is 40 mu L. The interface of the liquid paraffin and the aqueous phase forms a "shikonin-lysine copolymer film".
(6) Preparing a 3-methyl salicylic acid-3-nitro-1, 2-phenylenediamine copolymer membrane under catalysis of manganese peroxidase:
0.010g of 3-methylsalicylic acid and 0.010g of 3-nitro-1, 2-phenylenediamine were dissolved in 50mL of a 0.05mol/L sodium succinate-succinic acid buffer solution (pH 5.0),adding manganese peroxidase 0.05U, 5% hydrogen peroxide 8 μ L and 0.1mol/L MnSO 4 0.7mL, and mixing to obtain a manganese peroxidase catalytic system (water phase). Covering liquid paraffin with the thickness of 5mm on the surface of a manganese peroxidase catalytic system by using a suction pipe, standing and reacting for 12 hours in an incubator (Zhicheng, ZSD-1090, china) at 20 ℃, and supplementing 5 percent of hydrogen peroxide into the reaction system for multiple times in the period, wherein 8 mu L of hydrogen peroxide is added each time. The "3-methylsalicylic acid-3-nitro-1, 2-phenylenediamine copolymer film" was formed at the interface between the liquid paraffin and the aqueous phase.
(7) Preparation of a copolymer membrane of bisaccharin blue-2, 4, 6-triaminopyrimidine catalyzed by manganese peroxidase:
dissolving 0.250g of Commiphora blue and 0.250g of 2,4, 6-triaminopyrimidine in 250mL of 0.05mol/L potassium hydrogen phthalate-sodium hydroxide buffer solution (pH 5.0), adding manganese peroxidase 10U, 5% hydrogen peroxide 40. Mu.L and 0.1mol/L MnSO 4 3.5mL, and mixing to obtain a manganese peroxidase catalytic system (water phase). Covering liquid paraffin with the thickness of 5mm on the surface of a manganese peroxidase catalytic system by using a suction pipe, standing and reacting for 15 hours in an oven (Zhicheng, ZFD-5090, china) at the temperature of 40 ℃, and supplementing 5 percent of hydrogen peroxide into the reaction system for multiple times during the reaction, wherein each time is 40 mu L. The interface between the liquid paraffin and the aqueous phase formed a "bisabolol blue-2, 4, 6-triaminopyrimidine copolymer film".
(8) Preparation of 4,4' -dihydroxybiphenyl-2, 3-diaminonaphthalene copolymer film catalyzed by horseradish peroxidase:
dissolving 0.125g of 4,4' -dihydroxybiphenyl and 0.125g of 2, 3-diaminonaphthalene in 215mL of a mixed solvent of 0.05mol/L glycine-sodium hydroxide buffer solution (pH 10.0) and 35mL of acetone, adding 6U of horseradish peroxidase and 40 μ L of 5% hydrogen peroxide, and mixing to obtain a horseradish peroxidase catalytic system (aqueous phase). Covering liquid paraffin with the thickness of 10mm on the surface of a horseradish peroxidase catalytic system by using a pipette, standing in an oven (Zhicheng, ZFD-5090, china) at 40 ℃ for 24 hours, and supplementing 5 percent of hydrogen peroxide into the reaction system for multiple times during the standing, wherein each time is 40 mu L. The "4,4' -dihydroxybiphenyl-2, 3-diaminonaphthalene copolymer film" is formed at the interface between the liquid paraffin and the aqueous phase.
(9) Preparation of bisphenol a-proflavine copolymer membrane catalyzed by horseradish peroxidase:
0.250g of bisphenol A and 0.250g of proflavine are dissolved in 175mL of a mixed solvent of 0.1mol/L Tris-hydrochloric acid buffer solution (pH8.0) and 75mL of ethanol, a proper amount of horseradish peroxidase 3U and 5% of hydrogen peroxide 40 mu L are added, and the mixture is mixed uniformly to obtain a horseradish peroxidase catalytic system (aqueous phase). Covering liquid paraffin with the thickness of 5mm on the surface of a horseradish peroxidase catalytic system by using a pipette, standing for 5 hours in an oven (Zhicheng, ZFD-5090, china) at 45 ℃, and supplementing 5 percent of hydrogen peroxide into the reaction system for multiple times in the period of time, wherein each time is 40 mu L. A "film of bisphenol A-proflavin copolymer" is formed at the interface between the liquid paraffin and the aqueous phase.
(10) Preparing a1, 8, 9-trihydroxy anthracene-4, 4' -diamino diphenyl sulfone copolymer membrane by using horseradish peroxidase:
dissolving 0.040g 1,8, 9-trihydroxy anthracene and 0.060g 4,4' -diaminodiphenyl sulfone in 140mL 0.05mol/L disodium hydrogen phosphate-citric acid buffer solution (pH 6.0) and a mixed solvent of 60mL ethanol, adding 12U of horseradish peroxidase and 40 μ L of 5% hydrogen peroxide, and uniformly mixing to obtain a horseradish peroxidase catalytic system (water phase). Covering liquid paraffin with the thickness of 5mm on the surface of a horseradish peroxidase catalytic system by using a pipette, standing in an oven (Zhicheng, ZFD-5090, china) at 45 ℃ for 17 hours, and supplementing 5 percent of hydrogen peroxide into the reaction system for multiple times in the period of time, wherein each time is 40 mu L. At the interface between the liquid paraffin and the aqueous phase, a "1,8, 9-trihydroxyanthracene-4, 4' -diaminodiphenyl sulfone copolymer film" was formed.
(11) Preparation of 4',6, 7-trihydroxyisoflavone-parafuchsin copolymer film catalyzed by lignin peroxidase:
0.750g of 4',6, 7-trihydroxyisoflavone and 1.500g of parafuchsin are dissolved in 175mL of a mixed solvent of 0.05mol/L sodium citrate-citric acid buffer solution (pH 5.0) and 75mL of ethanol, 1.5U of lignin peroxidase and 40 mu L of 5% hydrogen peroxide are added, and the mixture is mixed uniformly to obtain a lignin peroxide catalytic system (aqueous phase). Covering liquid paraffin with the thickness of 5mm on the surface of a lignin peroxide catalytic system by using a suction pipe, standing and reacting for 12 hours in an oven (Zhicheng, ZFD-5090, china) at the temperature of 45 ℃, and supplementing 5 percent of hydrogen peroxide into the reaction system for multiple times during the reaction, wherein each time is 40 mu L. A "4',6, 7-trihydroxyisoflavone-parafuchsin copolymer film" was formed at the interface between the liquid paraffin and the aqueous phase.
(12) The diosmetin-1, 6-hexanediamine copolymer membrane is prepared by catalysis of lignin peroxidase:
0.025g of diosmetin and 0.050g of 1, 6-hexanediamine are dissolved in 225mL of a mixed solvent of 0.05mol/L trisodium phosphate-phosphoric acid buffer solution (pH 4.0) and 25mL of dimethyl sulfoxide, lignin peroxidase 6U and 40 mu L of 5% hydrogen peroxide are added, and the mixture is mixed uniformly to obtain a lignin peroxide catalytic system (aqueous phase). Covering liquid paraffin with the thickness of 5mm on the surface of a lignin peroxide catalytic system by using a suction pipe, standing and reacting for 8 hours in an incubator (Zhicheng, ZSD-1090, china) at the temperature of 30 ℃, and supplementing 5 percent of hydrogen peroxide into the reaction system for multiple times during the reaction, wherein each time is 40 mu L. A "diosmetin-1, 6-hexanediamine copolymer film" was formed at the interface between the liquid paraffin and the aqueous phase.
(13) Preparing a resveratrol-5, 6-diamino-1, 3-dimethyl uracil copolymer film by using soybean peroxidase:
0.025g of resveratrol, 0.025g of 5, 6-diamino-1, 3-dimethyluracil are dissolved in a mixed solvent of 35mL of 0.05mol/L trisodium phosphate-phosphoric acid buffer solution (pH 6.0) and 15mL of ethanol, 0.6U of soybean peroxidase and 8 mu L of 5% hydrogen peroxide are added, and the mixture is uniformly mixed to obtain a soybean peroxidase catalytic system (aqueous phase). Covering liquid paraffin with the thickness of 5mm on the surface of a soybean peroxidase catalytic system by using a suction pipe, standing and reacting for 5 hours in a 65 ℃ oven (Zhicheng, ZFD-5090, china), and supplementing 5% of hydrogen peroxide into the reaction system for multiple times in the period of time, wherein each time is 8 mu L. At the interface of the liquid paraffin and the aqueous phase, a "resveratrol-5, 6-diamino-1, 3-dimethyluracil copolymer film" was formed.
(14) Preparing esculetin-melamine-1, 4-diaminoanthraquinone copolymer film by using soybean peroxidase:
dissolving 0.075g of esculetin, 0.125g of melamine and 0.075g of 1, 4-diaminoanthraquinone in a mixed solvent of 175mL of 0.05mol/L trisodium phosphate-phosphoric acid buffer solution (pH 5.0) and 75mL of ethanol, adding 15U of soybean peroxidase and 40 microliter of 5% hydrogen peroxide, and uniformly mixing to obtain a soybean peroxidase catalytic system (aqueous phase). Covering liquid paraffin with the thickness of 5mm on the surface of a soybean peroxidase catalytic system by using a pipette, standing and reacting for 4 hours in a 75 ℃ oven (Zhicheng, ZFD-5090, china), and supplementing 5 percent hydrogen peroxide into the reaction system for multiple times in the period of time, wherein each time is 40 mu L. At the interface between the liquid paraffin and the aqueous phase, a "esculetin-melamine-1, 4-diaminoanthraquinone copolymer film" was formed.
(15) Preparation of ellagic acid-PEI copolymer membranes catalyzed by chloroperoxidase:
0.025g of ellagic acid and 0.050g of PEI are dissolved in 250mL of 0.05mol/L sodium citrate-citric acid buffer solution (pH 3.0), 11.25U of chloroperoxidase and 40 mu L of 5% hydrogen peroxide are added, and the mixture is mixed uniformly to obtain a chloroperoxidase catalytic system (aqueous phase). Covering liquid paraffin with the thickness of 5mm on the surface of a chloroperoxidase catalytic system by using a suction pipe, standing and reacting for 4 hours in an incubator (Zhicheng, ZSD-1090, china) at the temperature of 35 ℃, and supplementing 5 percent of hydrogen peroxide into the reaction system for multiple times during the reaction, wherein each time is 40 mu L. At the interface of the liquid paraffin and the aqueous phase, a "ellagic acid-PEI copolymer film" was formed.
(16) Preparing sciadopitysin-spermine copolymer membrane by catalysis of chloroperoxidase:
0.050g of sciadopitysin and 0.100g of spermine are dissolved in 70mL of a mixed solvent of 0.05mol/L trisodium phosphate-phosphoric acid buffer solution (pH 3.0) and 30mL of ethanol, 3U of chloroperoxidase and 16 mu L of 5% hydrogen peroxide are added, and the mixture is uniformly mixed to obtain a chloroperoxidase catalytic system (aqueous phase). Covering liquid paraffin with the thickness of 5mm on the surface of a chloroperoxidase catalytic system by using a suction pipe, standing and reacting for 6 hours in an oven (Zhicheng, ZFD-5090, china) at the temperature of 40 ℃, and supplementing 5 percent of hydrogen peroxide into the reaction system for multiple times in the period of 16 mu L each time. The interface of the liquid paraffin and the water phase forms a 'sciadopitysin-spermine copolymer film'.
(17) The narcissus-2, 4-diaminoanisole copolymer membrane is prepared by catalysis of chloroperoxidase:
0.075g of narcissus and 0.125g of 2, 4-diaminoanisole are dissolved in 200mL of a mixed solvent of 0.05mol/L sodium malonate-malonic acid buffer solution (pH 4.0) and 50mL of ethanol, 0.75U of chloroperoxidase and 40 mu L of 5% hydrogen peroxide are added and mixed uniformly to obtain a chloroperoxidase catalytic system (aqueous phase). Covering liquid paraffin with the thickness of 5mm on the surface of a chloroperoxidase catalytic system by using a suction pipe, standing and reacting for 5 hours in an incubator (Zhicheng, ZSD-1090, china) at the temperature of 10 ℃, and supplementing 5 percent of hydrogen peroxide into the reaction system for multiple times during the reaction, wherein each time is 40 mu L. The interface between the liquid paraffin and the aqueous phase forms a "narcissus-2, 4-diaminoanisole copolymer film".
(18) Preparing a tyrosine-o-tolidine copolymer film by catalyzing monophenol monooxygenase:
0.075g of tyrosine and 0.050g of o-tolidine are dissolved in 250mL of 0.05mol/L disodium hydrogen phosphate-monopotassium phosphate buffer solution (pH 6.5), 150U of monophenol monooxygenase is added, and the mixture is uniformly mixed to obtain a monophenol monooxygenase catalytic system (water phase). Covering liquid paraffin with the thickness of 5mm on the surface of a monophenol monooxygenase catalytic system by using a suction pipe, and standing and reacting for 36 hours in an incubator (Zhicheng, ZSD-1090, china) at the temperature of 20 ℃. A "tyrosine-o-tolidine copolymer film" is formed at the interface between the liquid paraffin and the aqueous phase.
(19) Catechol-urea copolymer membrane preparation catalyzed by catechol oxidase:
dissolving 7.500g catechol and 5.000g urea in 250mL 0.05mol/L sodium succinate-succinic acid buffer solution (pH 4.0), adding 0.75U catechol oxidase, and mixing to obtain catechol oxidase catalytic system (water phase). Covering the surface of the catechol oxidase catalytic system with liquid paraffin with the thickness of 5mm by using a pipette, and standing and reacting for 8 hours in a 50 ℃ oven (Zhicheng, ZFD-5090, china). A "catechol-urea copolymer film" was formed at the interface between the liquid paraffin and the aqueous phase.
(20) Preparing a hesperetin-6-hydroxy-2, 4, 5-triaminopyrimidine copolymer film under catalysis of bilirubin oxidase:
0.020g of hesperetin and 0.020g of 6-hydroxy-2, 4, 5-triaminopyrimidine are dissolved in 140mL of a mixed solvent of 0.05mol/L trisodium phosphate-phosphate buffer solution (pH 5.0) and 60mL of ethanol, 100U of bilirubin oxidase is added and mixed evenly to obtain a bilirubin oxidase catalytic system (aqueous phase). Covering liquid paraffin with the thickness of 5mm on the surface of a bilirubin oxidase catalysis system by using a suction pipe, and standing and reacting for 8 hours in an oven (Zhicheng, ZFD-5090, china) at the temperature of 55 ℃. At the interface of the liquid paraffin and the aqueous phase, a "hesperetin-6-hydroxy-2, 4, 5-triaminopyrimidine copolymer film" is formed.
Example 3: preparation of copolymer membrane by enzymatic polymerization at aqueous solution-carbon tetrachloride interface
(1) 1, 3-dihydroxynaphthalene-kanamycin copolymer film preparation with laccase catalysis:
0.25g of 1, 3-dihydroxynaphthalene and 0.25g of kanamycin are dissolved in 50mL of 0.05mol/L sodium acetate-acetic acid buffer solution (pH 4.0), 0.6U of laccase is added, and the mixture is mixed uniformly to obtain a laccase catalytic system (aqueous phase). First, 55mm thick CCl was added to the vessel 4 (a liquid phase immiscible with the aqueous phase) and then slowly adding the aqueous phase to the vessel, the aqueous phase floating in the CCl 4 As above, a liquid-liquid interface is formed between the two phases. Standing and reacting for 12h in a 35 ℃ incubator (Zhicheng, ZSD-1090, china). A "1, 3-dihydroxynaphthalene-kanamycin copolymer film" (gas-liquid interfacial film) was formed on the upper surface of the aqueous phase (gas-liquid interface of the aqueous phase with air), while the aqueous phase and CCl were simultaneously present 4 The "1, 3-dihydroxynaphthalene-kanamycin copolymer film" (liquid-liquid interface film) is formed at the liquid-liquid interface of (a). Procedure for transfer of two interfacial films onto coverslips: (1) firstly, a cover glass is inserted into a water phase, and carefully moved to the position below the 1, 3-dihydroxynaphthalene-kanamycin at the gas-liquid interface to be gently fished up, so that the transfer of the gas-liquid interface film is completed. (2) Sucking out the solution from the upper side of the "1, 3-dihydroxynaphthalene-kanamycin copolymer membrane" at the liquid-liquid interface by using a syringe, injecting distilled water again into the upper side of the membrane, repeating the operations of imbibing-injecting-imbibing a plurality of times, and inserting another cover glass into the CCl 4 Carefully moving to the lower part of the liquid-liquid interface film, gently scooping up the liquid-liquid interface film, flatly spreading the liquid-liquid interface film on a cover glass, and sucking out the residual CCl on the lower side of the film by using filter paper 4 And drying at room temperature.
(2) Preparing ferulic acid-2, 3-dimethyl-p-phenylenediamine copolymer film by laccase catalysis:
0.125g of ferulic acid and 0.125g of 2, 3-dimethyl-p-phenylenediamine are dissolved in 250mL of 0.05mol/L phthalic acid-hydrochloric acid buffer solution (pH 3.0), 0.5U of laccase is added, and the mixture is mixed evenly to obtain a laccase catalytic system (aqueous phase). CCl with a thickness of 5mm was initially introduced into the vessel 4 (a liquid phase immiscible with the aqueous phase) and then slowly adding the aqueous phase to the vessel, the aqueous phase floating in the CCl 4 Upper, aqueous phase and CCl 4 A liquid-liquid interface is formed therebetween. Standing at room temperatureThe reaction is carried out for 2h. On the upper surface of the aqueous phase (gas-liquid interface between the aqueous phase and air) a "ferulic acid-2, 3-dimethyl-p-phenylenediamine copolymer film" is formed, while in water, CCl 4 The liquid-liquid interface of the two phases forms a "ferulic acid-2, 3-dimethyl-p-phenylenediamine copolymer film".
(3) Preparing p-coumaric acid-p-phenylenediamine copolymer film by manganese peroxidase catalysis:
dissolving 0.125g p-coumaric acid and 0.25g p-phenylenediamine in 250mL 0.05mol/L tartaric acid-sodium tartrate buffer solution (pH 5.0), adding manganese peroxidase 0.125U, 5% hydrogen peroxide 40 μ L and 0.1mol/LMnSO 4 3.5mL, and mixing to obtain a manganese peroxidase catalytic system (water phase). CCl with a thickness of 35mm was initially introduced into a vessel 4 (a liquid phase immiscible with the aqueous phase) and then slowly adding the aqueous phase to the vessel, the aqueous phase floating on the CCl 4 Upper, aqueous phase and CCl 4 A liquid-liquid interface is formed therebetween. The mixture was allowed to stand in a 10 ℃ incubator (Zhicheng, ZSD-1090, china) for 36 hours, during which the aqueous phase was supplemented with 5% hydrogen peroxide 40. Mu.L each time. The upper surface of the aqueous phase (gas-liquid interface of the aqueous phase and air) forms a 'p-coumaric acid-p-phenylenediamine film', and the water and the CCl are simultaneously coated with water 4 The liquid-liquid interface of (A) forms a p-coumaric acid-p-phenylenediamine copolymer film.
(4) Preparation of 3-methoxysalicylic acid-2, 3-diethyl-p-phenylenediamine copolymer film catalyzed by horseradish peroxidase:
dissolving 0.125g of 3-methoxysalicylic acid and 0.125g of 2, 3-diethyl-p-phenylenediamine in 250mL of 0.05mol/L dipotassium hydrogen phosphate-sodium hydroxide buffer solution (pH 6.5), adding 1.5U of horseradish peroxidase and 40 μ L of 5% hydrogen peroxide, and mixing to obtain a horseradish peroxidase catalytic system (aqueous phase). CCl with a thickness of 25mm was initially introduced into the vessel 4 (a liquid phase immiscible with the aqueous phase) and then slowly adding the aqueous phase to the vessel, the aqueous phase floating on the CCl 4 Upper, aqueous phase and CCl 4 A liquid-liquid interface is formed therebetween. Standing in a 55 deg.C oven (Zhicheng, ZFD-5090, china) for 8h, and adding 5% hydrogen peroxide into the water phase several times, 40 μ L each time. The upper surface of the aqueous phase (gas-liquid interface of the aqueous phase and air) forms "3-methoxysalicylic acid-2, 3-diethyl-p-benzeneDiamine "in water, CCl simultaneously 4 The liquid-liquid interface of (A) forms "3-methoxysalicylic acid-2, 3-diethyl-p-phenylenediamine".
(5) Preparing a 3, 5-diiodosalicylic acid-2-hydroxymethyl-p-phenylenediamine copolymer film by catalysis of lignin peroxidase:
0.050g of 3, 5-diiodosalicylic acid and 0.100g of 2-hydroxymethyl-p-phenylenediamine were dissolved in 250mL of 0.05mol/L tartaric acid-sodium tartrate buffer solution (pH 3.0), and 0.25U of lignin peroxidase and 40. Mu.L of 5% hydrogen peroxide were added thereto and mixed well to obtain a lignin peroxide catalytic system (aqueous phase). CCl with a thickness of 25mm was initially introduced into the vessel 4 (liquid phase immiscible with the aqueous phase) and then slowly adding the aqueous phase to the vessel, the aqueous phase floating in the CCl 4 In the aqueous phase and CCl 4 A liquid-liquid interface is formed therebetween. The reaction was allowed to stand in a 37 ℃ incubator (Zhicheng, ZSD-1090, china) for 3 hours, during which 5% hydrogen peroxide was added to the aqueous phase several times, 40. Mu.L each time. The upper surface of the aqueous phase (gas-liquid interface of the aqueous phase and air) forms a 3, 5-diiodosalicylic acid-2-hydroxymethyl-p-phenylenediamine copolymer film in water and CCl simultaneously 4 The liquid-liquid interface of (A) forms a 3, 5-diiodosalicylic acid-2-hydroxymethyl-p-phenylenediamine copolymer film.
(6) Preparing a gentisic acid-2-hydroxyethoxy-p-phenylenediamine copolymer membrane under catalysis of lignin peroxidase:
0.250g of gentisic acid and 0.250g of 2-hydroxyethoxy-p-phenylenediamine are dissolved in 250mL of 0.2mol/L disodium hydrogen phosphate-sodium dihydrogen phosphate buffer solution (pH 6.5), and lignin peroxidase 0.5U and 5% hydrogen peroxide 40 μ L are added and mixed uniformly to obtain a lignin peroxide catalytic system (aqueous phase). CCl with a thickness of 25mm was initially introduced into the vessel 4 (a liquid phase immiscible with the aqueous phase) and then slowly adding the aqueous phase to the vessel, the aqueous phase floating on the CCl 4 In the aqueous phase and CCl 4 A liquid-liquid interface is formed between the liquid phases. Standing in 40 deg.C oven (Zhicheng, ZFD-5090, china) for 36h, and adding 5% hydrogen peroxide into the water phase several times, 40 μ L each time. The upper surface of the aqueous phase (gas-liquid interface of the aqueous phase and air) formed a "Gentianoic acid-2-hydroxyethoxy-p-phenylenediamine copolymer film" with water, CCl 4 Liquid ofThe liquid interface formed a "gentisic acid-2-hydroxyethoxy-p-phenylenediamine copolymer film".
(7) Preparing a p-aminosalicylic acid-m-phenylenediamine copolymer film under catalysis of soybean peroxidase:
0.250g of para-aminosalicylic acid and 0.250g of m-phenylenediamine are dissolved in 250mL of 0.05mol/L disodium hydrogen phosphate-citric acid buffer solution (pH 7.0), 0.25U of soybean peroxidase and 40 mu L of 5% hydrogen peroxide are added, and the mixture is uniformly mixed to obtain a soybean peroxidase catalytic system (water phase). First, CCl with a thickness of 25mm was added to the vessel 4 (a liquid phase immiscible with the aqueous phase) and then slowly adding the aqueous phase to the vessel, the aqueous phase floating on the CCl 4 In the aqueous phase and CCl 4 A liquid-liquid interface is formed therebetween. The reaction was allowed to stand in a 10 ℃ incubator (Zhicheng, ZSD-1090, china) for 24 hours, during which the aqueous phase was supplemented with 5% hydrogen peroxide, 40. Mu.L each time. The upper surface of the aqueous phase (gas-liquid interface between the aqueous phase and the air) forms a 'p-aminosalicylic acid-m-phenylenediamine copolymer film' in the presence of water and CCl 4 The liquid-liquid interface of (1) forms a "p-aminosalicylic acid-m-phenylenediamine copolymer film".
(8) Preparing catechol-caffeic acid-3, 4-diaminotoluene copolymer membrane under catalysis of soybean peroxidase:
0.025g of catechol, 0.025g of caffeic acid and 0.050g of 3, 4-diaminotoluene were dissolved in 50mL of 0.05mol/L tartaric acid-sodium tartrate buffer solution (pH 4.0), and 0.15U of soybean peroxidase and 8. Mu.L of 5% hydrogen peroxide were added thereto and mixed well to obtain a soybean peroxidase catalytic system (aqueous phase). CCl with a thickness of 25mm was initially introduced into the vessel 4 (a liquid phase immiscible with the aqueous phase) and then slowly adding the aqueous phase to the vessel, the aqueous phase floating on the CCl 4 In the aqueous phase and CCl 4 A liquid-liquid interface is formed therebetween. The reaction was allowed to stand in an incubator (Zhicheng, ZSD-1090, china) at 20 ℃ for 6 hours, during which 5% hydrogen peroxide was added to the aqueous phase several times, 8. Mu.L each time. The upper surface of the aqueous phase (gas-liquid interface of the aqueous phase and air) forms a "catechol-caffeic acid-3, 4-diaminotoluene copolymer film" in water, CCl simultaneously 4 The liquid-liquid interface of (1) forms a "catechol-caffeic acid-3, 4-diaminotoluene copolymer film".
(9) Preparation of syringic acid-3, 4-diaminobenzoic acid copolymer film catalyzed by chloroperoxidase:
0.375g syringic acid and 0.200g 3, 4-diaminobenzoic acid are dissolved in 250mL of 0.05mol/L sodium acetate-acetic acid buffer solution (pH 3.5), 1.25U of chloroperoxidase and 40 mu L of 5% hydrogen peroxide are added, and the mixture is uniformly mixed to obtain a chloroperoxidase catalytic system (aqueous phase). CCl with a thickness of 25mm was initially introduced into the vessel 4 (a liquid phase immiscible with the aqueous phase) and then slowly adding the aqueous phase to the vessel, the aqueous phase floating on the CCl 4 In the aqueous phase and CCl 4 A liquid-liquid interface is formed therebetween. The reaction was allowed to stand in an incubator (Zhicheng, ZSD-1090, china) at 20 ℃ for 7 hours, during which 5% hydrogen peroxide was added to the aqueous phase several times, 40. Mu.L each time. The upper surface of the aqueous phase (gas-liquid interface of the aqueous phase and air) forms a film of syringic acid-3, 4-diaminobenzoic acid copolymer, in water, CCl 4 The liquid-liquid interface of (A) forms a "syringic acid-3, 4-diaminobenzoic acid copolymer film".
(10) Preparing an anthocyanin-4, 4' -diaminobibenzyl copolymer membrane under catalysis of chloroperoxidase:
0.020g of anthocyanin and 0.010g of 4,4' -diaminobibenzyl are dissolved in 100mL of 0.05mol/L sodium citrate-citric acid buffer solution (pH 4.0), 1U of chloroperoxidase and 16 mu L of 5% hydrogen peroxide are added, and the mixture is mixed uniformly to obtain a chloroperoxidase catalytic system (aqueous phase). CCl with a thickness of 25mm was initially introduced into the vessel 4 (a liquid phase immiscible with the aqueous phase) and then slowly adding the aqueous phase to the vessel, the aqueous phase floating on the CCl 4 In the aqueous phase and CCl 4 A liquid-liquid interface is formed therebetween. The reaction was allowed to stand in an incubator (Zhicheng, ZSD-1090, china) at 25 ℃ for 8 hours, during which time the aqueous phase was supplemented with 5% hydrogen peroxide, 16. Mu.L each time. The upper surface of the aqueous phase (gas-liquid interface of the aqueous phase and air) forms a "membrane of anthocyanin-4, 4' -diaminobibenzyl copolymer" in water, CCl simultaneously 4 The liquid-liquid interface of the two phases forms a ' membrane of anthocyanin-4, 4' -diaminobibenzyl copolymer '.
(11) Preparing a2, 6-dihydroxytoluene-4, 4' -dinaphthylamine copolymer film by catalyzing with monophenol monooxygenase:
0.050g of 2, 6-dihydroxytoluene and 0.025g ofDissolving 4,4' -dinaphthylamine in 250mL of 0.05mol/L potassium hydrogen phthalate-sodium hydroxide buffer solution (pH 5.5), adding 2.5U of monophenol monooxygenase, and mixing to obtain a monophenol monooxygenase catalytic system (aqueous phase). First, CCl with a thickness of 25mm was added to the vessel 4 (a liquid phase immiscible with the aqueous phase) and then slowly adding the aqueous phase to the vessel, the aqueous phase floating on the CCl 4 In the aqueous phase and CCl 4 A liquid-liquid interface is formed therebetween. Standing and reacting for 10h in a 30 ℃ incubator (Zhicheng, ZSD-1090, china). The upper surface of the aqueous phase (gas-liquid interface of the aqueous phase and air) formed a "2, 6-dihydroxytoluene-4, 4' -dinaphthylamine copolymer film", along with water, CCl 4 The liquid-liquid interface of the two phases forms a "2, 6-dihydroxytoluene-4, 4' -dinaphthylamine copolymer film".
(12) Preparation of hydroxytyrosol-guanidine copolymer membranes catalyzed by catechol oxidase:
dissolving 1.000g hydroxytyrosol and 1.250g guanidine in 250mL 0.05mol/L disodium hydrogen phosphate-citric acid buffer solution (pH 5.0), adding 0.005U catechol oxidase, and mixing to obtain catechol oxidase catalytic system (water phase). First, CCl with a thickness of 25mm was added to the vessel 4 (a liquid phase immiscible with the aqueous phase) and then slowly adding the aqueous phase to the vessel, the aqueous phase floating on the CCl 4 In the aqueous phase and CCl 4 A liquid-liquid interface is formed therebetween. Standing and reacting for 30h in an incubator (Zhicheng, ZSD-1090, china) at 30 ℃. The upper surface of the aqueous phase (gas-liquid interface between the aqueous phase and air) forms a "hydroxytyrosol-guanidine copolymer film", while water, CCl 4 The liquid-liquid interface of the two phases forms a "hydroxytyrosol-guanidine copolymer membrane".
(13) Preparing a2, 4, 6-trihydroxybenzaldehyde-1, 2-diaminocyclohexane copolymer film under catalysis of bilirubin oxidase:
0.400g of 2,4, 6-trihydroxybenzaldehyde and 0.400g of 1, 2-diaminocyclohexane are dissolved in 200mL of 0.05mol/L boric acid-borax buffer solution (pH 8.0), and bilirubin oxidase 120U is added and mixed uniformly to obtain a bilirubin oxidase catalytic system (water phase). CCl with a thickness of 25mm was initially introduced into the vessel 4 (a liquid phase immiscible with the aqueous phase) and then slowly adding the aqueous phase to the vessel, the aqueous phase floating on the CCl 4 In the aqueous phase and CCl 4 A liquid-liquid interface is formed therebetween. Standing and reacting for 14h in a 60 ℃ oven (Zhicheng, ZFD-5090, china). The upper surface of the aqueous phase (gas-liquid interface of the aqueous phase with air) formed a "2,4, 6-trihydroxybenzaldehyde-1, 2-diaminocyclohexane copolymer film" while in water, CCl 4 The liquid-liquid interface of the two phases forms a "film of 2,4, 6-trihydroxybenzaldehyde-1, 2-diaminocyclohexane copolymer".
Example 4: preparation of copolymer film by enzymatic polymerization at upper-layer water phase-lower-layer liquid gallium interface
Dissolving 0.125g of p-hydroxybenzoic acid and 0.250g of 2-fluoro-p-phenylenediamine in 125mL of distilled water, adjusting the pH to 6.0 by phosphoric acid, adding 0.125U of laccase, and uniformly mixing to obtain a laccase catalytic system (aqueous phase). Putting a layer of liquid gallium into a plastic container, then slowly adding a laccase catalytic system (aqueous phase) into the container, wherein the aqueous phase floats on the liquid gallium, and an upper aqueous phase-lower liquid gallium interface is formed between the aqueous phase and the liquid gallium. Standing in an oven (Zhicheng, ZFD-5090, china) at 40 ℃ for 48h. A "p-hydroxybenzoic acid-2-fluoro-p-phenylenediamine copolymer film" was formed at the aqueous solution-liquid gallium interface.
Example 5: preparation of copolymer film by enzymatic polymerization at upper-layer water phase-lower-layer paraffin interface
Dissolving 0.250g of chlorogenic acid and 0.125g of 2, 3-diaminopyridine in 125mL of 0.05mol/L disodium hydrogen phosphate-potassium dihydrogen phosphate buffer solution (pH 7.0), adding 0.125U of horseradish peroxidase and 20 μ L of 5% hydrogen peroxide, and mixing to obtain horseradish peroxidase catalytic system (water phase). And (3) placing the paraffin into a container, heating to melt and level the paraffin, and standing at room temperature to cool and solidify the paraffin into a solid. The horseradish peroxidase catalytic system (aqueous phase) was added to the solid paraffin in the vessel above the solidified paraffin. The reaction was carried out at 100rpm in a 25 ℃ constant temperature oscillator (Crystal, IS-RDV3, qi Ltd., USA) for 12h while supplementing the aqueous phase with 5% hydrogen peroxide for 20. Mu.L each time. A chlorogenic acid-2, 3-diaminopyridine copolymer film is formed on the upper surface of the solid paraffin. Meanwhile, granular chlorogenic acid-2, 3-diaminopyridine copolymer is generated in the aqueous phase, and suspended in the aqueous phase. The aqueous phase above the membrane was decanted and the copolymer membrane was washed with distilled water. The container was placed at 70 ℃ and paraffin was melted to a liquid, the PE plate was inserted into the liquid paraffin, carefully moved to below the "chlorogenic acid-2, 3-diaminopyridine copolymer film" to gently scoop up the film, and the film was spread flat on the PE plate.
Example 6: preparation of copolymer membrane by enzymatic polymerization of upper aqueous phase-lower tallow interface
0.300g of tannic acid and 0.300g of ethidium bromide are dissolved in 100mL of 0.05mol/L sodium malonate-malonic acid buffer solution (pH 6.0), 0.05U of lignin peroxidase and 15. Mu.L of 5% hydrogen peroxide are added, and the mixture is mixed uniformly to obtain a lignin peroxide catalytic system (aqueous phase). Placing the beef tallow in a container, heating to melt and level the beef tallow, and standing at room temperature to cool and solidify the beef tallow into solid. To this vessel was added the lignin peroxide catalytic system (aqueous phase) which was located above the solidified tallow. The reaction was carried out at 100rpm in a constant temperature oscillator (Crystal, IS-RDV3, qi Ltd., USA) at 25 ℃ for 20h while supplementing 5% hydrogen peroxide to the aqueous phase several times, 15. Mu.L each time. A 'tannin-ethidium bromide copolymer film' is formed on the upper surface of the solid butter. At the same time, a granular "tannic acid-ethidium bromide copolymer" is produced in the aqueous phase, suspended in the latter. The aqueous phase above the membrane was decanted and the copolymer membrane was washed with distilled water. The vessel was placed at 65 ℃ and the tallow melted to a liquid, the PE plate was inserted into the liquid tallow, carefully moved under the "tannic acid-ethidium bromide copolymer film" to gently scoop up the film, and the film was spread flat on the PE plate.
Example 7: preparation of copolymer membrane by enzymatic polymerization at water phase-oil phase interface
0.02g of lysine is dissolved in 50mL of 0.05mol/L trisodium phosphate-phosphate buffer solution (pH 5.0), laccase 2U is added, and the mixture is uniformly mixed to obtain the water phase part of the laccase catalytic system. Dissolving 0.02g of tert-butylhydroquinone in 50mL of soybean oil, uniformly mixing to obtain an oil phase part of the laccase catalytic system, covering the oil phase part on a water phase, and standing and reacting for 5 hours in a 30 ℃ incubator (Zhicheng, ZSD-1090, china). A 'tert-butylhydroquinone-lysine copolymer film' is formed at the interface of the water phase and the oil phase.
Example 8: preparation of copolymer membrane by enzymatic polymerization at water phase-oil phase interface
Dissolving 0.05g of diethylenetriamine in 50mL of 0.05mol/L trisodium phosphate-phosphoric acid buffer solution (pH 6.0), adding 5U of soybean peroxidase and 8 mu L of 5% hydrogen peroxide, and uniformly mixing to obtain the water phase part of the soybean peroxidase catalytic system. Slowly covering the water phase with a layer of urushiol with the thickness of more than 1mm, standing in an oven (Zhicheng, ZFD-5090, china) at 40 ℃ for 5h, and supplementing 8 mu L of 5% hydrogen peroxide into the water phase every 1 h. A "film of urushiol-diethylenetriamine copolymer" is formed at the interface of urushiol and the aqueous phase.
Example 9: preparation of multilayer films
0.040g of guaiacol and 0.025g of 4,4' -diaminodicyclohexylmethane were dissolved in 50mL of 0.05mol/L tartaric acid-sodium tartrate buffer solution (pH 7.0), and 20U of monophenol monooxygenase was added thereto and mixed well to obtain a monophenol monooxygenase catalytic system (aqueous phase). First, 55mm thick CCl was added to the vessel 4 (a liquid phase immiscible with the aqueous phase) and then slowly adding the aqueous phase to the vessel, the aqueous phase floating in the CCl 4 The above. Standing in 25 deg.C incubator (Zhicheng, ZSD-1090, china) for 48 hr to form "guaiacol-4, 4' -diaminodicyclohexylmethane copolymer film" (gas-liquid interface film) on the upper surface of the water phase (gas-liquid interface between the water phase and air), and simultaneously in the water phase and CCl 4 The liquid-liquid interface of (a) forms a "guaiacol-4, 4' -diaminodicyclohexylmethane copolymer film" (liquid-liquid interface film). The gas-liquid interface membrane was removed, the solution on the upper side of the liquid-liquid interface "guaiacol-4, 4' -diaminodicyclohexylmethane copolymer membrane" was aspirated by a syringe, and another aqueous phase (0.125 g of gallic acid, 0.125g of 2, 4-diaminobenzenesulfonic acid, dissolved in 250mL of 0.2mol/L disodium hydrogenphosphate-sodium dihydrogenphosphate buffer solution (pH 7.0), 0.5U of horseradish peroxidase and 40 μ L of 5% hydrogen peroxide were added thereto, and mixed well) was poured again on the upper side of the membrane, and thus the liquid-suction-liquid-suction operation was repeated several times. Standing in 40 deg.C oven (Zhicheng, ZFD-5090, china) for 20 hr while adding 5% hydrogen peroxide to the water phase for 40 μ L each time to form gallic acid-2, 4-diaminobenzenesulfonic acid copolymer film (gas-liquid interface film) on the upper surface of the water phase (gas-liquid interface of the water phase and air), and simultaneously adding guaiacol-4, 4' -diaminodicyclohexylmethaneThe upper side of the polymer membrane liquid-liquid interface membrane generates a gallic acid-2, 4-diaminobenzene sulfonic acid copolymer layer, and the gallic acid-2, 4 '-diaminodicyclohexyl methane copolymer layer is combined with the original guaiacol-4, 4' -diaminodicyclohexyl methane copolymer membrane to form a double-layer membrane.
Example 10: enzyme-catalyzed secondary reaction (introduction of sorbitol)
0.1g of bisphenol A, 0.1g of PEI and 10mg of ABTS are dissolved in a mixed solvent of 70mL of 0.05mol/L trisodium phosphate-phosphoric acid buffer solution (pH 4.0) and 30mL of ethanol, 0.6U of laccase is added, and the mixture is mixed uniformly to obtain a laccase catalytic system (aqueous phase). First, 55mm thick CCl was added to the vessel 4 (oil phase) then slowly adding the aqueous phase to the vessel, the aqueous phase floating on CCl 4 As above, a liquid-liquid interface is formed between the two phases. Standing in 40 deg.C oven (Zhicheng, ZFD-5090, china) for 10h to form a bisphenol A-PEI copolymer film (gas-liquid interface film) on the upper surface of the water phase (gas-liquid interface between the water phase and air), and simultaneously in water and CCl 4 The liquid-liquid interface of (a) forms a "bisphenol A-PEI copolymer film" (liquid-liquid interface film). The gas-liquid interfacial film is removed. The solution on the upper side of the liquid-liquid interface "bisphenol A-PEI copolymer membrane" was aspirated by a syringe, and another solution (0.3 g sorbitol was dissolved in 150mL of 0.05mol/L trisodium phosphate-phosphoric acid buffer solution (pH 5.0), 175mg of laccase 10U, 2, 6-tetramethylpiperidine oxide (2, 6-tetramethylyl-1-piperidinyloxy, TEMPO for short) was added thereto, and mixed well) was injected again on the upper side of the membrane, and thus the operation of imbibing-injecting-imbibing was repeated several times. And placing the mixture in an oven (Zhicheng, ZFD-5090, china) at 40 ℃ again for standing reaction for 24 hours. Injecting the liquid-liquid (CCl) with a syringe 4 ) The solution on the upper side of the interfacial film is sucked out and then is re-in liquid-liquid (CCl) 4 ) Injecting distilled water into the upper side of the interface membrane, and repeating the operations of liquid suction, liquid injection and liquid suction for multiple times. Insert coverslip into CCl 4 In the middle, carefully move to liquid-liquid (CCl) 4 ) Gently scoop the membrane under the interphase membrane, lay the membrane flat on a cover glass, and suck the residual CCl under the membrane with filter paper 4 And drying at room temperature.
The elemental composition of the film surface was measured using an X-ray Photoelectron Spectroscopy (XPS, thermo Fisher Scientific, escalab 250xi, USA) and the N/O ratio of the film surface was reduced from 0.695 to 0.527 after reaction with sorbitol. The bisphenol A-PEI copolymer membrane surface which is not combined with sorbitol contains four elements of C, H, O and N; the structure of the sorbitol contains three elements of C, H and O, and no N element; thus, the reduction in the N/O ratio at the membrane surface demonstrates that the membrane is bound to sorbitol, i.e., that the liquid-liquid interfacial membrane surface is available for enzymatic secondary reactions.
Example 11: vesicle and enzymatic polymerization preparation method thereof
Adding 100 μ L of oleic acid and 1mL of a 2mg/mL solution of cetyltrimethylammonium bromide (CTAB) into a centrifuge tube in sequence, performing vortex oscillation for 5min, and performing ultrasonic treatment for 15min to obtain an oil-in-water emulsion. And (2) centrifuging the emulsion at 6000 Xg for 5min, removing the supernatant by using an injector, adding 1mL of 0.05mol/L trisodium phosphate-phosphoric acid buffer solution (pH 5.0) dissolved with 0.05U of laccase, 2mg of hydroquinone and 2mg of PEI, oscillating and reacting for 24h at room temperature in a dark place, coating a hydroquinone-PEI copolymer membrane on the outer surface of oil drops to obtain the hydroquinone-PEI copolymer vesicle internally coated with oleic acid, wherein the stability of the emulsion is greatly improved.
Soaking the vesicle in ethanol, dissolving oleic acid and CTAB in the vesicle with ethanol, centrifuging at 10000 Xg for 10min, collecting vesicle, dissolving residual oleic acid and CTAB in ethanol, centrifuging, and collecting vesicle. Evaporating the solvent from the vesicle in a negative pressure environment to obtain the hollow vesicle.
The outer wall of the hydrophilic and hydrophobic vesicle can be prepared according to the requirement, and target molecules/atoms can be bonded/deposited on the outer wall of the vesicle.
The copolymer vesicle can be used for wrapping cells, organelles, antigens, antibodies, functional macromolecules, proteins, enzymes, DNA, RNA, polysaccharide, medicaments, nutrients, essence, pesticides, fertilizers, chemicals, fuels, explosives and the like.
The copolymer vesicles may also provide a suitable microenvironment for some chemical and biochemical reactions.
Example 12: copolymer film reduced metal
Hydroquinone-PEI vesicles were prepared according to the method in example 11, and the vesicles were immersed in 0.05mol/L AgNO 3 Placing in solution in dark for 30min 3 Ag in solution + The Ag nano particles reduced to be Ag are deposited on the outer surface of the vesicle wall. Centrifuging at 5000rpm for 5min, washing with ultrapure water twice to obtain vesicles with Ag nanoparticles deposited on the outer surface.
Those skilled in the art will appreciate that not only Ag + Higher oxidizing property than Ag for other materials + The metal ions can also be reduced and deposited on the surface of the film, for example, noble metal ions such as gold ions, foil ions, palladium ions and the like are reduced to generate corresponding simple substances, and the surface metallization of the electroless plating material is realized. The material covered with the silver particles has excellent antibacterial performance. Palladium, platinum, silver, etc. are important chemical catalysts, and thus, the copolymer film on which the metal is deposited can be used for chemical catalysis. The method can also be used to remove, enrich, recover these metals from water.
Example 13: preparation of films with conductive Properties
Dissolving 0.25g of ferulic acid and 0.25g of p-phenylenediamine in 125mL of 0.05mol/L trisodium phosphate-phosphoric acid buffer solution (pH 5.0), adding laccase 7.5U, and mixing to obtain a laccase catalytic system (aqueous phase). First, a CCl 15mm thick is added to the vessel 4 (oil phase) then slowly adding the aqueous phase to the vessel, the aqueous phase floating on CCl 4 Upper, water, CCl 4 A liquid-liquid interface is formed between the two phases. Standing and reacting for 13h in a 50 ℃ oven (Zhicheng, ZFD-5090, china). Forming a 'ferulic acid-p-phenylenediamine copolymer film' on the upper surface of the water phase (the gas-liquid interface of the water phase and the air) and simultaneously adding water and CCl 4 The liquid-liquid interface of the two phases forms a 'ferulic acid-p-phenylenediamine copolymer film'. The gas-liquid interfacial film is removed. Sucking out the solution from the upper side of the liquid-liquid interface membrane by using a syringe, and re-placing the solution in liquid-liquid (CCl) 4 ) Injecting distilled water into the upper side of the interface membrane, repeating the operations of liquid suction, liquid injection and liquid suction for multiple times, and inserting a cover glass into the CCl 4 In the middle, carefully move to liquid-liquid (CCl) 4 ) The membrane was gently scooped up under the interface membrane, laid flat on a cover glass, and the residual CCl on the lower side of the membrane was aspirated off with filter paper 4 And drying at room temperature. Determination of the position by means of a four-probe method using a resistance tester (lattice, ST2722, china)Liquid-liquid on coverslip (CCl) 4 ) The conductivity of the interface film surface was 1.67S/m.
The copolymer conducting film can be used in the fields of electroluminescence, electrochromism, photoconduction, electronic switches, all-solid-state batteries, nonlinear optical devices, high-density memory materials, flat panel displays, organic semiconductor devices, molecular leads, light-emitting diodes, antistatic materials, electromagnetic shielding materials, photovoltaic cell materials and the like.
By selecting different film-forming monomers, copolymer films with different conductivities in a certain range can be prepared.
The conductivity of the conductive copolymer film can be improved by doping and compositely depositing metal particle simple substances.
The metal ions can be reduced on the surface of the conductive copolymer film, so that the metal simple substance is deposited on the surface of the film, and the conductivity is improved.
Comparative example 1:
(1) 0.250g of bisphenol A and 0.250g of proflavine were dissolved in a mixed solvent of 175mL of 0.1mol/L Tris-hydrochloric acid buffer solution (pH 8.5) and 75mL of ethanol, and mixed well. The surface of the above solution (aqueous phase) was covered with liquid paraffin of 5mm thickness by a pipette and allowed to stand in an oven (Zhicheng, ZFD-5090, china) at 45 ℃ for 48 hours. No film was formed at the interface between the liquid paraffin and the aqueous phase, and no particles were formed in the aqueous phase.
(2) 0.250g of bisphenol A and 0.250g of proflavine were dissolved in a mixed solvent of 175mL of a 0.1mol/L10 g/L NaOH solution (pH 13.4) and 75mL of ethanol, and mixed well. The surface of the above solution (aqueous phase) was covered with liquid paraffin of 5mm thickness by a pipette and allowed to stand in an oven (Zhicheng, ZFD-5090, china) at 45 ℃ for 24 hours. No film was formed at the interface between the liquid paraffin and the aqueous phase, and no particles were formed in the aqueous phase.
Comparative example 2:
(1) 0.125g of 4,4' -dihydroxybiphenyl and 0.125g of 2, 3-diaminonaphthalene were dissolved in 215mL of a mixed solvent of 0.05mol/L glycine-sodium hydroxide buffer solution (pH 8.5) and 35mL of acetone, and mixed well. The surface of the above solution (aqueous phase) was covered with 10mm thick liquid paraffin by a pipette and allowed to stand in an oven (Zhicheng, ZFD-5090, china) at 40 ℃ for 48 hours. No film was formed at the interface between the liquid paraffin and the aqueous phase, and no particles were formed in the aqueous phase.
(2) 0.125g of 4,4' -dihydroxybiphenyl and 0.125g of 2, 3-diaminonaphthalene were dissolved in a mixed solvent of 215mL of 10g/L NaOH solution (pH 13.4) and 35mL of acetone, and mixed well. The surface of the above solution (aqueous phase) was covered with 10mm thick liquid paraffin by a pipette and allowed to stand in an oven (Zhicheng, ZFD-5090, china) at 40 ℃ for 24 hours. No film was formed at the interface between the liquid paraffin and the aqueous phase, and no particles were formed in the aqueous phase.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made without departing from the spirit and principle of the present invention shall fall within the protection scope of the present invention.

Claims (17)

1. A method of synthesizing a copolymer film, comprising the steps of:
dissolving a film-forming monomer containing phenolic hydroxyl, a film-forming monomer containing at least two amino groups and a catalyst in a water phase and/or a liquid phase which is not mutually soluble with the water phase, and polymerizing at the interface of the two phases to form a film so as to obtain the copolymer film;
the catalyst is at least one of peroxidase and/or oxidoreductase with laccase activity and/or artificial enzyme with catalytic activity;
the structure of the film-forming monomer containing phenolic hydroxyl is shown as formula I:
Figure FDA0003163387990000011
wherein each R is 1 Identical or different, independently of one another, from H, halogen, CN, NO 2 OH, SH, COOH, unsubstituted or substituted by one, two or more R a1 Substituted of the following groups: c 1-40 Alkyl radical, C 2-40 Alkenyl radical, C 2-40 Alkynyl, C 3-40 Cycloalkyl, C 3-40 Cycloalkenyl radical, C 3-40 A cycloalkynyl group,C 6-20 Aryl, 5-20 membered heteroaryl, 3-20 membered heterocyclyl, -OR 1-2 、-SR 1-3 、-NR 1-4 R 1-5 、-C(O)R 1-6 、-OC(O)R 1-7 、-S(O) 2 R 1-8 、-OS(O) 2 R 1-9 、-P(O)R 1-10 R 1-11 、-N＝NR 1-12 ；
A 1 Presence or absence; when A is 1 When present, is selected from unsubstituted or substituted by one, two or more R b1 Substituted C attached to a benzo ring 6-20 Aryl, 5-20 membered heteroaryl, 5-20 membered heterocyclyl; or A 1 Selected from a chemical bond, unsubstituted or optionally substituted by one, two or more R c1 Substituted O, C (O) O, S (O) 2 、N、C 1-6 Alkylene, CH = N, N = N, CH = N-N = CH, CH = CH-CO-CH 2 -CO-CH＝CH；
m is an integer of 0 to 5.
Each R a1 、R b1 、R c1 Identical or different, independently of one another, from H, halogen, CN, OH, SH, oxo (= O), NO 2 、COOH、-OR 1-2 、-SR 1-3 、-NR 1-4 R 1-5 、-C(O)R 1-6 、-OC(O)R 1-7 、-S(O) 2 R 1-8 、-OS(O) 2 R 1-9 、P(O)R 1-10 R 1-11 Unsubstituted or optionally substituted by one, two or more R 1-12 Substituted C 1-40 Alkyl radical, C 2-40 Alkenyl radical, C 2-40 Alkynyl, C 3-40 Cycloalkyl radical, C 3-40 Cycloalkenyl radical, C 3-40 Cycloalkynyl, C 6-20 Aryl, 5-20 membered heteroaryl, 3-20 membered heterocyclyl;
each R 1-2 、R 1-3 、R 1-4 、R 1-5 、R 1-6 、R 1-7 、R 1-8 、R 1-9 、R 1-10 、R 1-11 、R 1-12 Identical or different, independently of one another, from H, halogen, CN, OH, SH, oxo (= O), NO 2 、COOH、C 1-40 Alkyl radical, C 2-40 Alkenyl radical, C 2-40 Alkynyl, C 3-40 Cycloalkyl radical, C 3-40 Cycloalkenyl radical, C 3-40 Cycloalkynyl, C 6-20 Aryl, 5-20 membered heteroaryl, 3-20 membered heterocyclyl;
the film-forming monomer containing at least two amino groups has a structure shown in formula II:
Figure FDA0003163387990000021
each R 2 Identical or different, independently of one another, from H, halogen, CN, NO 2 NO, OH, SH, COOH, unsubstituted or substituted by one, two or more R a2 Substituted of the following groups: c 1-40 Alkyl radical, C 2-40 Alkenyl radical, C 2-40 Alkynyl, C 3-40 Cycloalkyl, C 3-40 Cycloalkenyl radical, C 3-40 Cycloalkynyl group, C 6-20 Aryl, 5-20 membered heteroaryl, 3-20 membered heterocyclyl, -OR 2-2 、-SR 2-3 、-NR 2-4 R 2-5 、-C(O)R 2-6 、-OC(O)R 2-7 、-S(O) 2 R 2-8 、-OS(O) 2 R 2-9 、P(O)R 2-10 R 2-11 ；
A 2 Selected from unsubstituted or substituted by one, two or more R b2 Substituted C attached to a benzo ring 1-40 Alkyl radical, C 2-40 Alkenyl radical, C 2-40 Alkynyl, C 3-40 Cycloalkyl radical, C 3-40 Cycloalkenyl radical, C 3-40 Cycloalkynyl group, C 6-20 Aryl, 5-20 membered heteroaryl, 3-20 membered heterocyclyl; or A 2 Selected from a chemical bond, unsubstituted or optionally substituted by one, two or more R c2 Substituted O, C (O) O, S (O) 2 、N、C 1-6 Alkylene, CH = N, N = N, CH = N-N = CH, CH = CH-CO-CH 2 -CO-CH＝CH；
p is an integer of 0 to 12;
each R a2 、R b2 、R c2 Identical or different, independently of one another, from H, halogen, CN, OH, SH, oxo (= O), = NH, NO 2 、COOH、C 1-40 Alkyl radical, C 2-40 Alkenyl radical, C 2-40 Alkynyl, C 3-40 Cycloalkyl radical, C 3-40 Cycloalkenyl radical, C 3-40 Cycloalkynyl group, C 6-20 Aryl, 5-20 membered heteroaryl, 3-20 membered heterocyclyl, -OR 2-2 、-SR 2-3 、-NR 2-4 R 2-5 、-C(O)R 2-6 、-OC(O)R 2-7 、-S(O) 2 R 2-8 、-OS(O) 2 R 2-9 、P(O)R 2-10 R 2-11 ；
Each R 2-2 、R 2-3 、R 2-4 、R 2-5 、R 2-6 、R 2-7 、R 2-8 、R 2-9 、R 2-10 、R 2-11 Identical or different, independently of one another, from H, halogen, NH 2 CN, OH, SH, oxo (= O), NO 2 、COOH、C 1-40 Alkyl radical, C 2-40 Alkenyl radical, C 2-40 Alkynyl, C 3-40 Cycloalkyl radical, C 3-40 Cycloalkenyl radical, C 3-40 Cycloalkynyl, C 6-20 Aryl, 5-20 membered heteroaryl, 3-20 membered heterocyclyl.
2. The method according to claim 1, wherein the copolymer film is obtained by dissolving a film-forming monomer having a phenolic hydroxyl group and a film-forming monomer having at least two amino groups in a solvent, adding a catalyst, mixing the resulting solution with the solvent to obtain an aqueous phase, and bringing the aqueous phase into contact with a liquid phase immiscible with the aqueous phase to polymerize and form a film at the interface between the two phases.
3. The method according to claim 1 or 2, wherein the copolymer film is obtained by dissolving a film-forming monomer having a phenolic hydroxyl group in a solvent, adding a catalyst, mixing to obtain an aqueous phase, dissolving a film-forming monomer having at least two amino groups in a liquid phase immiscible with the aqueous phase, contacting the aqueous phase with the liquid phase immiscible with the aqueous phase, and polymerizing the film at the interface between the two phases.
4. The method according to any one of claims 1 to 3, wherein the copolymer film is obtained by dissolving a film-forming monomer having at least two amino groups in a solvent, adding a catalyst, mixing to obtain an aqueous phase, dissolving a film-forming monomer having a phenolic hydroxyl group in a liquid phase immiscible with the aqueous phase, contacting the aqueous phase with the liquid phase immiscible with the aqueous phase, and polymerizing the film at the interface between the two phases.
5. The method according to any one of claims 1 to 4, wherein the copolymer film is obtained by dissolving a catalyst in an aqueous phase, dissolving the film-forming monomer having a phenolic hydroxyl group and the film-forming monomer having at least two amino groups in a liquid phase immiscible with the aqueous phase, bringing the aqueous phase and the liquid phase immiscible with the aqueous phase into contact to cause an enzymatic reaction, and polymerizing the aqueous phase and the liquid phase at the interface between the two phases to form a film.
6. The method according to any one of claims 1 to 5, wherein the peroxidase is at least one selected from the group consisting of manganese peroxidase, lignin peroxidase and chloroperoxidase, plant peroxidase; the plant peroxidase is at least one of horseradish peroxidase, soybean peroxidase, rice peroxidase, cotton peroxidase, red bean peroxidase, chickpea peroxidase, guar bean peroxidase and pea peroxidase;
the oxidoreductase having laccase activity is at least one selected from the group consisting of catechol oxidase, monophenol monooxygenase, and bilirubin oxidase;
the artificial enzyme is an enzyme simulant which simulates the biological catalysis function of natural enzyme according to the catalysis mechanism of the enzyme and is synthesized by organic chemistry and biological methods and has a specific catalysis function.
7. The method of claim 6, wherein the laccase is a fungal laccase, preferably a Polyporus pinsitus laccase.
8. The method of any one of claims 1-7, wherein the compound of formula I has a structure represented by formula I-1 to I-13:
Figure FDA0003163387990000041
wherein R is 1 M and R c1 Having the definition set forth in claim 1; b is selected from O or by R 1 Substituted N; D. d 1 、D 2 And D 3 Identical or different, independently of one another, from the group consisting of a bond, unsubstituted or optionally substituted by one, two or more R c1 Substituted O, CH 2 C (O) or N-CO-CH 3 (ii) a E and E 1 Identical or different, independently of one another, from the group consisting of a bond, unsubstituted or optionally substituted by one, two or more R c1 Substituted O, C (O) O, S (O) 2 、N、Se、P、C 1-6 Alkylene, CH = CH, CH = N, N = N, CH = N-N = CH, CH = CH-CO-CH 2 -CO-CH = CH; n is an integer of 0 to 5; f 1 And F 2 Identical or different, independently of one another, from N, CH or O + ；R 1 ’、R 1 And R 1 The same definition is applied.
9. The method according to any one of claims 1 to 8, wherein the film-forming monomer having a phenolic hydroxyl group is at least one selected from 1, 3-dihydroxynaphthalene, p-hydroxybenzoic acid, ferulic acid, 1, 6-dihydroxynaphthalene, shikonin, 3-methylsalicylic acid, p-coumaric acid, 4 '-dihydroxybiphenyl, bisphenol A, chlorogenic acid, 3-methoxysalicylic acid, gallic acid, 4',6, 7-trihydroxyisoflavone, diosmetin, tannic acid, 3, 5-diiodosalicylic acid, gentisic acid, resveratrol, esculetin, p-aminosalicylic acid, caffeic acid, ellagic acid, sciadonidin, anthocyanidin, syringic acid, tyrosine, guaiacol, 2, 6-dihydroxytoluene, catechol, hydroxytyrosol, hesperetin, 2,4, 6-trihydroxybenzaldehyde, chrysin, narcissus, rhein, gallic acid, 1,8, 9-trihydroxy, anthracene, terebyl hydroquinone.
10. The method of any one of claims 1-9, wherein the compound of formula II has a structure represented by formulae II-1 to II-10:
Figure FDA0003163387990000051
Figure FDA0003163387990000061
wherein R is 2 P and R c2 Having the definition set forth in claim 1; q is an integer of 0 to 12; r 2 ’、R 2 And R 2 The definitions of (A) are the same; and R is 2 、R 2 ’、R 2 "there are at least two amino groups;
each D 2 、D 3 、D 4 Identical or different, independently of one another, from N, unsubstituted or substituted by R 2 Substituted CH, N + ；
Each E 2 、E 3 、E 4 Identical or different, independently of one another, from a bond, unsubstituted or optionally substituted by one, two or more R c2 Substituted O, C (O), C (S), C (O) O, S (O) 2 、N、C 1-6 Alkylene, CH = N, N = N, CH = N-N = CH, C 0-6 alkylene/alkenyl-CO-C 1-6 alkylene-CO-C 0-6 Alkylene/alkenyl, C 0-6 alkylene/alkenyl-CO-NH-C 0-6 alkylene-CO-C 0-6 Alkylene/alkenyl, C 0-6 alkylene/alkenyl-NH-C 0-6 alkylene-NH-C 0-6 Alkylene/alkenyl, C 0-6 alkylene/alkenyl-C (O) O-C 0-6 alkylene-C (O) O-C 0-6 Alkylene/alkenyl;
each F 2 Identical or different, independently of one another, from O, S.
11. The method according to any one of claims 1 to 10, the film-forming monomer containing at least two amino groups is selected from the group consisting of arginine, polyethyleneimine (PEI), kanamycin, 2-fluoro-p-phenylenediamine, 2, 3-dimethyl-p-phenylenediamine, diethylenetriamine, lysine, 3-nitro-1, 2-phenylenediamine, p-phenylenediamine, 2, 3-diaminonaphthalene, proflavine, 2, 3-diaminopyridine, 2, 3-diethyl-p-phenylenediamine, 2, 4-diaminobenzenesulfonic acid, fuchsin, 1, 6-hexanediamine, ethidium bromide, 2-hydroxymethyl-p-phenylenediamine, 2-hydroxyethoxy-p-phenylenediamine, and mixtures thereof 5, 6-diamino-1, 3-dimethyluracil, melamine, m-phenylenediamine, 3, 4-diaminotoluene, spermine, 4 '-diaminobibenzyl, 3, 4-diaminobenzoic acid, 2, 4-diaminoanisole, o-tolidine, 4' -diaminodicyclohexylmethane, 4 '-binaphthylamine, urea, guanidine, 6-hydroxy-2, 4, 5-triaminopyrimidine, 1, 2-diaminocyclohexane, 2, 4-diamino-6-methyl-1, 3, 5-triazine, 4' -diaminodiphenyl sulfone, 1, 4-diaminoanthraquinone, 2,4, 6-triaminopyrimidine.
12. The method of any one of claims 1 to 11, wherein when the catalyst is at least one of laccase, bilirubin oxidase, and peroxidase, the combination of the film-forming monomer comprising a phenolic hydroxyl group and the film-forming monomer comprising at least two amino groups may be: the combination is as follows: r 1 And/or A 1 A combination of a compound of formula I and a compound of formula II wherein there is at least one phenolic hydroxyl group in the structure; or a combination of two: a compound of formula I-13 and 2 is as a quilt R 2 Substituted CH, and R 2 、R 2 ’、R 2 "a combination of compounds of formula II-1 wherein there are at least two amino groups;
when the catalyst is a monophenol monooxygenase, the combination of the film-forming monomer having a phenolic hydroxyl group and the film-forming monomer having two amino groups may be: a combination of a compound of formula I and a compound of formula II;
when the catalyst is a catechol oxidase, the combination of the film-forming monomer containing a phenolic hydroxyl group and the film-forming monomer containing at least two amino groups may be: r 1 A combination of a compound of formula I and a compound of formula II at the ortho position of the phenolic hydroxyl group;
the film-forming monomer containing phenolic hydroxyl and the film-forming monomer containing at least two amino groups are respectively one, two or more than two in a reaction system.
13. The method according to any one of claims 1 to 12, wherein the aqueous phase is an aqueous solution containing water in an amount of not less than 50% by mass; the film forming monomer can be dissolved, and the film forming monomer contains an organic solvent dissolved in water, wherein the organic solvent is at least one of methanol, ethanol, isopropanol, acetone, methyl formate, ethyl acetate, acetonitrile, tetrahydrofuran, N-dimethylformamide, 1, 4-dioxane, dimethyl sulfoxide, diethylene glycol butyl ether and diethylene glycol;
preferably, the enzymatic reaction further comprises at least one of an enhancer of an enzyme, hydrogen peroxide, a metal ion, a pair of buffer ions;
preferably, the liquid phase immiscible with the aqueous phase may be selected from the group consisting of an oil that is liquid at normal temperature, an oil that is solid at a set temperature, and a liquid metal.
14. The method according to any one of claims 1 to 13, wherein the solvent is selected from water or a buffer solution, preferably a sodium acetate-acetic acid buffer solution, a disodium hydrogen phosphate-citric acid buffer solution, a potassium hydrogen phthalate-sodium hydroxide buffer solution, a tartaric acid-sodium tartrate buffer solution, a sodium citrate-citric acid buffer solution, a trisodium phosphate-phosphoric acid buffer solution, a sodium malonate-malonic acid buffer solution, a sodium succinate-succinic acid buffer solution, a phthalic acid-hydrochloric acid buffer solution, a disodium hydrogen phosphate-sodium dihydrogen phosphate buffer solution, a disodium hydrogen phosphate-potassium dihydrogen phosphate buffer solution, a dipotassium hydrogen phosphate-sodium hydroxide buffer solution, a Tris-hydrochloric acid buffer solution, a boric acid-borax buffer solution, a glycine-sodium hydroxide buffer solution;
preferably, the dosage of the catalyst in the reaction system is 0.01U/L-600U/L, for example 0.5U/L-200U/L, based on enzyme activity;
preferably, the mass concentration of the film-forming monomer in the reaction system can be 0.002-380 g/L, such as 0.1-20 g/L;
preferably, the temperature of the film forming reaction is 4 to 90 ℃, for example 10 to 60 ℃;
preferably, the time of the film forming reaction is 0.01 to 72 hours, for example 2 to 48 hours;
preferably, the pH of the aqueous phase is between 2 and 10.
15. Copolymer particles or copolymer membranes prepared by the process of any one of claims 1 to 14, for example vesicles formed around the copolymer membranes.
16. A multilayer film comprising at least one layer of the copolymer film of claim 15.
17. Use of the copolymer particles or copolymer membranes according to claim 15, for example in the preparation of multilayer membranes, in the preparation of vesicles, in the preparation of conductive membranes, in the construction of supramolecular functional materials, in the preparation of organic-inorganic derived membranes, in antibacterials; and the application in reducing metal and coating; use in secondary reactions, for example, further modification of copolymer films;
preferably, the modification introduces sorbitol, quaternary ammonium salt and dye molecules on the surface of the copolymer film.
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