CN112970745A - Metal nano particle based on branched chitosan microreactor and preparation method thereof - Google Patents

Metal nano particle based on branched chitosan microreactor and preparation method thereof Download PDF

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Publication number
CN112970745A
CN112970745A CN202011618112.5A CN202011618112A CN112970745A CN 112970745 A CN112970745 A CN 112970745A CN 202011618112 A CN202011618112 A CN 202011618112A CN 112970745 A CN112970745 A CN 112970745A
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chitosan
metal
microreactor
metal nanoparticles
dendronized
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张阿方
姚欥
彭磊
曹世杰
张柯
张夏聪
李文
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University of Shanghai for Science and Technology
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University of Shanghai for Science and Technology
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/32—Ingredients for reducing the noxious effect of the active substances to organisms other than pests, e.g. toxicity reducing compositions, self-destructing compositions
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
    • A01N25/10—Macromolecular compounds
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/30—Making metallic powder or suspensions thereof using chemical processes with decomposition of metal compounds, e.g. by pyrolysis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures

Abstract

The invention relates to a metal nanoparticle of a microreactor constructed based on branched chitosan and a preparation method thereof. The metal nanoparticles take dendronized chitosan as a main body, at least one metal nanoparticle is dispersed, and the structural formula of the dendronized chitosan is as follows: wherein x + y + z is 1, x is 0-1, y is 0-1, and z is 0-1; q is 1-4, and X is methoxy Me or ethoxyAny one of Et, MNP is a metal nanoparticle which is: ag. At least one metal selected from Au and Cu; the molar ratio of the dendritic chitosan to the metal particles is as follows: mMetal ion：MChitosan0.1 to 100. The metal nano particles have excellent stability, have no toxicity to human bodies, and can be widely applied to various fields. The metal nano-particles and the bacteriostatic spray can be prepared, have the advantages of simple process, quick preparation, low price and environmental protection, and are expected to be used for emergency sterilization and disinfection operation in places with sudden bacterial or viral pollution.

Description

Metal nano particle based on branched chitosan microreactor and preparation method thereof
Technical Field
The invention relates to a metal nano particle of a microreactor constructed based on dendronized chitosan and a preparation method thereof.
Technical Field
Due to the outbreaks of infectious diseases caused by different pathogenic bacteria and the development of antibiotic resistance, the increase in the number of resistant pathogens has led to increased patient morbidity, higher mortality and greater burden on healthcare systems. This has therefore forced researchers to continually search for new antimicrobial agents, and to develop a new class of antimicrobial agents that do not develop resistance, are in principle not susceptible to the build-up of resistance, and can be produced simply and inexpensively. In the present situation, nanomaterials, especially metal nanoparticles, have gradually become novel antibacterial agents due to their high surface area to volume ratio and unique chemical and physical properties. Antibacterial metal nanoparticles, particularly silver nanoparticles (AgNPs), have found widespread use in the biomedical field.
Metal nanoparticles (particularly, silver nanoparticles) have been widely used in the fields of biomedicine and the like due to their unique physical properties and excellent antibacterial activity. The manner of preparing metal nanoparticles can be divided into physical and chemical methods, and these conventional production methods generally involve a costly and environmentally unfriendly process. In addition, silver nanoparticle disinfectants used as medicaments present some uncontrolled risks, since silver particles are toxic to mammalian cells and long term exposure to them can cause some conditions.
In recent years, attempts have been made to develop an environmentally friendly reducing agent as a substitute. The chitosan is a polysaccharide which is harmless to the environment, is easy to obtain and has easily modified active amino and hydroxyl functional groups, and the natural polysaccharide molecules widely existing in the biological carapace have excellent chelating/adsorbing capacity on metal ions, so that the chitosan has the unique advantage of being used as a metal nanoparticle synthetic reagent. In addition, the easy film-forming property of the chitosan aqueous solution provides convenience for preparing water-soluble spray. However, the existing methods for preparing metal nanoparticles by using chitosan as a microreactor still have many challenges, such as the need to be accomplished under harsh reaction conditions (ultraviolet light or high temperature, etc.) and/or in the presence of reducing agents (borohydrides, citrates, etc.). Therefore, there is a need to impart desirable properties to chitosan by graft modification for creating a green, fast synthetic stable and monodisperse method of metal nanoparticles and bacteriostatic spray. The dendritic macromolecule is an attractive potential candidate material, has a three-dimensional crowded microenvironment formed by densely arranged dendritic units, and can provide a nanoscale reaction space for chemical reactions in a system. Meanwhile, the dendritic macromolecules can play a synergistic role in the chemical reaction process, so that the energy required by the initiation of the chemical reaction from the outside is reduced, and the chemical reaction in the system can be quickly completed under the initiation condition with lower energy. It is worth noting that the dendritic structures can provide proper support for the metal nanoparticles in the preparation process and play a role in encapsulation, which not only plays a role in protecting or passivating the surfaces of the nanoparticles, but also can obviously reduce the cytotoxicity of the nanoparticles to mammals without obviously influencing the bacteriostatic effect of the nanoparticles. The unique method for preparing the antibacterial agent by the metal nano-particles can greatly reduce the potential risk brought by directly using metal ions as antibacterial components in the traditional method; on the other hand, the system can obtain the water-soluble metal nano-particles which can be stably dispersed for a long time and have the slow release effect on effective bacteriostatic components. It is these excellent properties that ultimately may help to make the process of making metal nanoparticles and their bacteriostatic sprays more controllable and operable.
Disclosure of Invention
The invention aims to provide metal nanoparticles for constructing a microreactor based on dendronized chitosan.
The second purpose of the invention is to provide a preparation method of the metal nano-particles and the bacteriostatic spray for constructing the micro-reactor based on the branched chitosan.
To achieve the above object, referring to fig. 6, the present invention adopts the following mechanism:
wherein x + y + z is 1, x is 0-1, y is 0-1, and z is 0-1; q is 1-4, and X is methoxy or ethoxy.
According to the mechanism, the invention adopts the following technical scheme:
a metal nanoparticle for constructing a microreactor based on branched chitosan is characterized in that the metal nanoparticle for constructing the microreactor based on branched chitosan takes branched chitosan as a main body, at least one metal nanoparticle is dispersed in the metal nanoparticle, and referring to figure 5, the branched chitosan has a structural formula as follows:
wherein x + y + z is 1, x is 0-1, y is 0-1, and z is 0-1; q is 1-4, X is any one of methoxyl Me or ethoxyl Et, MNP is metal nanoparticles, and the metal nanoparticles are: ag. At least one metal selected from Au and Cu; the molar ratio of the dendritic chitosan to the metal particles is as follows: mMetal ion：MChitosan＝0.1～100。
A method for preparing the metal nanoparticles for constructing the microreactor based on the branched chitosan is characterized by comprising the following specific steps: dissolving the branched chitosan D-CS in water at room temperature, adding a soluble aqueous solution of metal ions according to the molar ratio of the metal ions to the D-CS of 1: 1-10: 1, fully mixing, and irradiating for 2-10 minutes at the wavelength of 10 nm-1050 nm to obtain the metal nanoparticles for constructing the microreactor based on the branched chitosan, wherein the metal nanoparticles can be directly used without post-treatment.
The metal nano particles for constructing the microreactor based on the dendronized chitosan can be used for quickly preparing bacteriostatic spray based on single/multiple metal nano particles, and the inhibition on bacterial growth is realized through the slow release function of the system without toxicity on mammalian cells. The specific method comprises the following steps: adding 1-50 times of water or buffer solution into metal nanoparticles of a microreactor constructed based on branched chitosan to obtain the required antibacterial working solution.
The microreactor constructed by the branched chitosan has the characteristics of biodegradability, wide sources, low human body cytotoxicity and the like, so that the use cost of the microreactor can be reduced, and the microreactor has wide application prospects.
The invention constructs a microreactor based on dendronized chitosan. The micro-reactor can be used for green and rapid preparation of single/multi-metal nano-particles and bacteriostatic spray, and the inhibition on bacterial growth is realized through the slow release function of the system, and the micro-reactor has no toxicity on mammalian cells.
Compared with the prior art, the invention has the following obvious substantive characteristics and advantages:
1. the invention adopts the simply synthesized dendrized chitosan as the main body to construct a novel micro-reactor for preparing single/multi-metal nano particles, and has novel structure and low preparation cost;
2. the invention prepares the system which can prepare the single/multi-metal nano particles without adding other auxiliary reagents by reasonably designing the chemical structure of the system;
3. compared with other systems, the system can be used for preparing the water-soluble bacteriostatic spray which is based on the single/multi-metal nano particles and can be stably dispersed for a long time under mild conditions (room temperature) through green (illumination) for less than or equal to 2 minutes by a simple one-step method, has the slow release effect on effective bacteriostatic components, and is favorable for applying the bacteriostatic spray to emergency sterilization and disinfection operation of sudden bacteria or virus pollution places.
Drawings
FIG. 1 hydraulic radius of branched chitosan (silver) microreactors.
FIG. 2 electronic spectra of silver nanoparticles in a branched chitosan microreactor.
FIG. 3 cytotoxicity of silver nanoparticles in branched chitosan microreactors.
FIG. 4 is a diagram of bacteriostatic spray effect of branched chitosan-silver nanoparticles.
FIG. 5 is a schematic structural diagram of a microreactor constructed by branched chitosan.
FIG. 6 is a schematic diagram of a preparation mechanism of a microreactor constructed by branched chitosan.
Detailed Description
The following preferred embodiments of the present invention are further illustrated, but not intended to limit the scope of the claims of the present invention:
example one
Preparation of branched chitosan (silver) microreactor
The preparation method of the branched chitosan D-CS is disclosed in the document Afang Zhang, et al.Polym.chem.,2019,10,2305-2315 at the room temperature of less than or equal to 25 ℃; dissolving in water according to Ag+Adding a silver nitrate aqueous solution into the mixture according to the concentration ratio of the silver nitrate to the D-CS of 1: 1-10: 1, and fully mixing. Subsequently, it is diluted with a desired solvent in proportion to prepare a desired microreactor. Finally, successful fabrication of the microreactor was confirmed by testing its hydraulic radius. The solvent adopts deionized water or buffer solution.
Wherein the hydraulic radius diagram of the branched chitosan (silver) microreactor is shown in figure 1.
And (3) preparing the silver nanoparticles by irradiating the prepared dendritic chitosan (silver) microreactor for 2-10 minutes. The wavelength range is 10nm to 1050 nm. Subsequently, the formation of silver nanoparticles in the microreactors was determined by electron spectroscopy and proved to be non-toxic to mammals by cytotoxicity tests.
Wherein the electron energy spectrogram of the silver nanoparticles in the branched chitosan microreactor is shown in figure 2;
the cytotoxicity of the silver nanoparticles in the dendronized chitosan microreactor is shown in fig. 3.
Example two
Preparation of branched chitosan-silver nanoparticle antibacterial spray
Adding water into the silver nanoparticle solution prepared by the branched chitosan microreactor by 1-50 times for dilution to prepare the required antibacterial working solution.
EXAMPLE III
Bacteriostatic ability of branched chitosan-silver nanoparticle bacteriostatic spray
And respectively spraying the prepared dendritic chitosan-silver nanoparticle bacteriostatic working solution on the surface of a plate culture medium inoculated with bacteria, and observing the growth effect of colonies after culturing for 12 hours to determine the bacteriostatic ability.
Wherein the bacteriostatic spray bacteriostatic effect of the branched chitosan-silver nanoparticles is shown in figure 4.
The embodiments of the present invention have been described above with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes and modifications can be made according to the purpose of the invention, and all changes, modifications, substitutions, combinations and simplifications made according to the spirit and principle of the technical solution of the present invention shall be equivalent substitution ways, so long as the invention meets the purpose of the present invention, and the technical principle and inventive concept of the present invention based on the preparation method of the dendronized chitosan microreactor and the application thereof shall not depart from the protection scope of the present invention.

Claims (4)

1. The metal nanoparticles for constructing the microreactor based on the dendronized chitosan are characterized in that the metal nanoparticles for constructing the microreactor based on the dendronized chitosan take dendronized chitosan as a main body and are dispersed with at least one kind of metal nanoparticles, and the structural formula of the dendronized chitosan is as follows:
wherein x + y + z is 1, x is 0-1, y is 0-1, and z is 0-1; q is 1-4, X is any one of methoxyl Me or ethoxyl Et, and MNP is metal nanoparticles; the molar ratio of the dendritic chitosan to the metal particles is as follows: mMetal ion：MChitosan＝0.1～100。
2. The metal nanoparticle for constructing the microreactor based on the branched chitosan according to claim 1, wherein the metal nanoparticle is: ag. At least one of Au and Cu metals.
3. A method for preparing metal nanoparticles for constructing a microreactor based on dendronized chitosan according to claim 1 or 2, which comprises the following steps: dissolving the branched chitosan D-CS in water at room temperature, adding a soluble aqueous solution of metal ions according to the molar ratio of the metal ions to the D-CS of 1: 1-10: 1, fully mixing, and irradiating for 2-10 minutes at the wavelength of 10 nm-1050 nm to obtain the metal nanoparticles for constructing the microreactor based on the branched chitosan, wherein the metal nanoparticles can be directly used without post-treatment.
4. A method for preparing the bacteriostatic spray from the metal nanoparticles of the microreactor constructed based on the branched chitosan according to claims 2 and 3, which is characterized by comprising the following specific preparation steps: the metal nanoparticles of the microreactor constructed based on the branched chitosan are diluted by a required solvent according to the proportion of 1: 2-1: 20 to prepare a required antibacterial working solution, and the obtained antibacterial working solution can be stored for a long time and has a slow release function on effective antibacterial ingredients.
CN202011618112.5A 2020-12-31 2020-12-31 Metal nano particle based on branched chitosan microreactor and preparation method thereof Pending CN112970745A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101223887A (en) * 2008-01-31 2008-07-23 吴继贤 Nano silver antimicrobial solution and preparing method thereof
CN101618047A (en) * 2009-08-11 2010-01-06 聊城大学 Preparation method and application of nanocomposite of silver, chitosan and/or derivative thereof
CN102144817A (en) * 2011-04-02 2011-08-10 中国人民解放军军事医学科学院基础医学研究所 Protective facial mask containing nano silver and chitosan and production method of protective facial mask
CN107661504A (en) * 2017-10-25 2018-02-06 暨南大学 A kind of golden nanometer particle of dendritic macromole modification and its preparation method and application

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101223887A (en) * 2008-01-31 2008-07-23 吴继贤 Nano silver antimicrobial solution and preparing method thereof
CN101618047A (en) * 2009-08-11 2010-01-06 聊城大学 Preparation method and application of nanocomposite of silver, chitosan and/or derivative thereof
CN102144817A (en) * 2011-04-02 2011-08-10 中国人民解放军军事医学科学院基础医学研究所 Protective facial mask containing nano silver and chitosan and production method of protective facial mask
CN107661504A (en) * 2017-10-25 2018-02-06 暨南大学 A kind of golden nanometer particle of dendritic macromole modification and its preparation method and application

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
张阿方等: ""Thermoresponsive dendronized chitosan-based hydrogels as injectable stem cell carriers"", 《POLYMER CHEMISTRY》 *

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