CN107552807B - Preparation method capable of preparing gold nanorods with controllable size and dispersibility on large scale - Google Patents
Preparation method capable of preparing gold nanorods with controllable size and dispersibility on large scale Download PDFInfo
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Abstract
The invention discloses a preparation method capable of preparing gold nanorods with controllable size and dispersibility on a large scale, belonging to the multidisciplinary cross fields of a high-molecular active polymerization method, functional polymer molecular design, inorganic crystal growth and the like. The method comprises the following steps: (1) adopting ionic liquid AMIMCl as a solvent, adopting anhydrous dimethylformamide and N-methylpyrrolidone as diluents and an acid absorbent, modifying hydroxyl on a cellulose chain by using 2-bromoisobutyryl bromide, and converting the hydroxyl into a macroinitiator for Atom Transfer Radical Polymerization (ATRP); (2) taking cellulose-Br as a macroinitiator, and preparing a series of brush-shaped diblock polymers by utilizing ATRP (atom transfer radical polymerization) and chemical linking technologies and the like of continuous polymerization: cellulose-g‑[PAA‑b‑PS]And cellulose-g‑[PAA‑b‑PEG](ii) a (3) Based on solution phase synthesis, a certain amount of brush-shaped diblock polymer is taken as a monomolecular template, and chloroauric acid (HAuCl) is taken4·3H2O) is used as a precursor compound and tert-butylamine boron (TBAB) is used as a reducing agent to prepare the oil-dispersible and water-dispersible golden rice stick.
Description
Technical Field
The invention relates to a preparation method capable of preparing gold nanorods with controllable size and dispersibility on a large scale, belonging to the multidisciplinary cross field of a high-molecular active polymerization method, functional polymer molecule design, inorganic crystal growth and the like. In particular to a method for preparing a series of gold nanorods with controllable size, length-diameter ratio and dispersibility by using a bottle brush-shaped functional polymer as a monomolecular template through in-situ crystal growth.
Background
Since the german scientist Gleiter prepares nano-crystal copper, iron and palladium for the first time in nine-eight-four years, the research of nano-materials gradually becomes a research hotspot field. Materials with more than one dimension of 1-100 nm are generally called nano materials. In general, a large number of free electrons on the back surface and the surface of a noble metal such as gold or silver form free electron gas clusters. Surface plasmon resonance can be formed when incident light and its surface free electrons resonate. Changes in the shape, size, dielectric constant of the surrounding environment, etc. of the nanoparticles cause changes in the frequency of oscillation of the surface free electrons. The gold nanorods have special optical properties due to the structural specificity, so that the gold nanorods have wide application prospects in the aspects of biomedicine, sewage treatment, information transmission technology, catalysts and the like.
The development of modern science and technology is revolutionized, relying to a great extent on the generation of new materials: energy requires new materials with excellent energy conversion characteristics, such as silicon plate materials capable of converting solar energy into electric energy in the photoelectric aspect; the information and data transmission and storage require a new material to meet higher transmission speed and higher storage density, and meanwhile, the new material also needs to have certain stability; aerospace requires that new materials have higher strength and lower density, and generally needs a series of materials which can still maintain the characteristics of the materials under severe conditions, such as good air tightness, high temperature resistance, high pressure resistance and the like.
Molecular level interconnect devices are key to implementing high-strength logic operation and memory circuits. Nanorods are the basic components for such interconnections. These nanorods are widely used in sensor, waveguide and photonics for building nanoelectronic device applications. The chemical inertness and lower resistivity of gold, these properties make gold nanorods an ideal material for connecting molecular devices. It can be formed by CTAB in aqueous solution and with small amounts of chloroauric acid, or in oleic acid/oleylamine organic solvent, small amounts of chloroauric acid and generated by nanoporous anodic alumina templates or other templates. After generation, these gold nanorods can be assembled to a substrate by hydration or in an electric field. However, the gold nanorods obtained by this method are polycrystalline phase, and the surface is very rough. Transmission studies indicate that the resistivity of polycrystalline gold nanorods is higher than gold. Therefore, the synthesis of the single crystal gold nanorods is of great significance.
Gold nanorods and other noble metal nanocrystals play an important role in diverse branch sciences such as chemical catalysis, nanomedicines, nanoelectronics, etc. For most applications, control of the particle size and particle size distribution of the nanomaterials is critical. Many aspects of the synthesis process can affect the particle size distribution and size of the nanomaterial, such as surfactant selection, pH, temperature, reducing agent concentration, and other metal salt concentrations.
The synthesized gold nanorods can be self-assembled by other methods. The self-assembly of the gold nanorods can be carried out on one dimension and two dimensions. Likewise, three-dimensional self-assembly is also possible. Research shows that the electric field enhancement strength of the nano material is related to the structure, size, polarization and excitation wavelength of the nano material. Therefore, the resonance characteristics of surface plasmon can be adjusted by designing the structure, size, shape and the like of the nano-particle, so that the sensitivity of detection of SERS single molecules can be improved.
In recent years, gold nanorods are increasingly widely used as an optical probe for SERS in biomacromolecules, cancer treatment and other aspects. The gold nanorods can be used for labeling biomacromolecules containing specific receptors, so that dynamic analysis and quantitative analysis of various active substances in living organisms are realized. Some organic dye molecules or polymers can be wrapped on the surface of the gold nanorod to form an SERS probe, and certain positions of the cell can be detected and imaged. In vivo imaging is an important application of gold nanorods. Photothermal therapy is another emerging application in recent years. Firstly, the SERS probe can be conveyed to a pathological cancer cell, then, in the laser irradiation of resonance wavelength, the gold nanorods in the probe can absorb a large amount of light energy, and then the light energy is converted into heat energy to generate high temperature to kill the pathological cell.
There are many methods for synthesizing gold nanorods, mainly four methods, including: photochemical, seeding, templating, and electrochemical methods, and the like. Although the existing preparation method has been successful in preparing the gold nanorods, the existing traditional synthesis method has a series of preparation limitations, mainly comprising the following aspects:
(1) precise control of nanoparticle size is difficult to achieve;
(2) the separation and purification process is complex, and large-scale preparation is difficult;
(3) the preparation conditions are harsh;
(4) the prepared nanostructure is not uniform;
(5) for the next application, further surface ligand modification and the like are needed to be carried out on the prepared one-dimensional nano material.
Aiming at the scientific and technical problems encountered in the design and synthesis of the gold nanorods, the invention provides a convenient method for preparing the gold nanorods with controllable size and dispersibility on a large scale.
Disclosure of Invention
The invention aims to provide a preparation method of gold nanorods, which is convenient, can be prepared in a large scale and has controllable size and dispersibility.
In order to realize the purpose of the invention, natural cellulose is used as an initial reaction raw material, a continuous ATRP technology and a technology combining ATRP and 'link' Chemistry are adopted to prepare a series of brush-shaped graft block copolymers with controllable molecular weight, structure and composition, and the brush-shaped polymers are used as single-molecule functional templates to prepare a series of gold nanorods with controllable length, length-diameter ratio and dispersibility.
The synthesis method specifically comprises the following steps: (1) preparation and fractionation of ATRP macroinitiator cellulose-bromoisobutyrate (cellulose-Br) based on cellulose molecules using ionic liquids (1-allyl-3-methylimidazole (amimccl, 1-allyl-3-methylimidazolium chloride) as solvent, anhydrous DMF and NMP as diluent and acid absorbent, 2-bromoisobutyryl bromide to modify the hydroxyl groups on the cellulose chain to convert them to macroinitiators useful for ATRP, since natural cellulose has a very broad molecular weight distribution, in order to obtain narrow distribution macroinitiators, the crude product of the synthesized macroinitiator is subjected to fractional precipitation by fractional precipitation, a series of macroinitiators with different molecular weights and narrow distributions are prepared by taking acetone as a solvent and deionized water as a precipitating agent, and the prepared macroinitiators are characterized by nuclear magnetism, infrared and GPC.
(2) Preparation of brush block Polymer: cellulose-bromoisobutyrate (cellulose-Br) is used as a macroinitiator, and an ATRP (atom transfer radical polymerization) technology of continuous polymerization is utilized to respectively initiate a tert-butyl acrylate monomer (tBA) and a styrene monomer (St) to prepare a series of brush-shaped two-block polymers with PS as outermost segments: cellulose-g- [ polyacrylic acid-b-polystyrene ] (cellulose-g- [ PAA-b-PS ]), cellulose-bromoisobutyrate as a macroinitiator, an experimental method combining an ATRP technology and a 'linking' chemistry is comprehensively utilized, and a series of brush-shaped two-block polymers with PEG at the outermost section are prepared by taking monofunctional polyethylene glycol mPEG with alkynyl as a precursor of the outermost-section block modified by an end group: cellulose-g- [ polyacrylic acid-b-polyethylene glycol ] (cellulose-g- [ PAA-b-PS ]).
(3) Preparing gold nanorods: based on solution phase synthesis method, a certain amount of cellulose-g- [ polyacrylic acid-b-polystyrene]Preparing an oil-soluble gold nanorod by using a monomolecular template: firstly, a certain amount of template molecule cellulose-g- [ polyacrylic acid-b-polystyrene]Dissolving in good solvent (such as DMF) to obtain monomolecular micelle template solution, and adding chloroauric acid (HAuCl) as precursor of target material into the reaction system4·3H2O) (molar ratio of acrylic acid repeating units to chloroauric acid in template 1:10) The precursor compound selectively diffuses and gathers on a PAA template phase due to coordination complexation with the template phase PAA, and then tert-butylamine boron (TBAB) is added as a reducing agent (the molar ratio of the reducing agent to chloroauric acid is 10: 1) and reacting for 2 hours at the temperature of 60 ℃, wherein the precursor compound generates corresponding gold nanorods in situ in the template phase, and the outermost PS phase is used as a ligand and covers the surface of the nanorods in situ, so that the generated nanorods can be dispersed in corresponding solvents (such as toluene, tetrahydrofuran, acetone and the like), and the nanorods are prevented from agglomerating in organic solvents. Under the same reaction conditions, with cellulose-g- [ poly [ ]Acrylic acid-b-polyethylene glycol]The water-soluble gold nanorod is a single-molecule template and is prepared by adopting the same synthesis method, experimental conditions and characterization means.
Compared with the prior art, the invention has the following advantages: (1) the innovative design idea is as follows: unlike the soft template of dynamically stable multi-molecular micelle formed by self-assembly and the hard template with extremely limited surface area, the functional brush-shaped graft copolymer with rigid straight-chain structure is precisely designed by means of active polymerization technology, and the single-molecular micelle of the brush-shaped copolymer is used as the template for growing inorganic nanometer crystal. The functional linear copolymer with definite structure is grafted on the rigid polymer main chain through a covalent bond, and a monomolecular micelle structure which is static and stable and has high grafting density can be formed in a benign solvent. When the statically stable micelle structure is used as a template for crystal growth, because the selected template phase Polymer (PAA) has coordination and complexation capacity on metal ions, a gold precursor compound is added after the structure and the shape of the template are determined, and a gold nanorod structure with the shape consistent with that of the template can be formed under the condition required by crystal generation.
(2) The innovative research content and research method are as follows: the applicant introduces natural macromolecular cellulose with a rigid linear structure into a polymer template preparation system, and the rigid chain characteristic of a cellulose molecule provides possibility for preparing a one-dimensional nano material with a linear structure. The cellulose is glucose as a constitutional unit, so that each repeating unit on the main chain of the biomacromolecule has 3 hydroxyl functional groups and is in spatial three-dimensional distribution, the prepared brush-shaped polymer has high grafting density, and the grafting chains are in spatial three-dimensional distribution, thus providing possibility for adsorbing a larger amount of precursor compounds by a template phase to form a continuous and regular one-dimensional crystal structure. In addition, the brush-shaped polymer template is prepared by using an ATRP active free radical polymerization means, so that the prepared polymer has a definite structure, and each component can realize the controllability of molecular weight, thereby realizing the multi-scale control of the template polymer.
Drawings
FIG. 1: schematic synthesis of gold nanorods covered with PS on the surface.
FIG. 2: TEM pictures of gold nanorods covered with PS on the surface (diameter about 10nm, length about 50 nm).
FIG. 3: TEM pictures of gold nanorods covered with PS on the surface (diameter about 10nm, length about 100 nm).
FIG. 4: gold nanorods EDS spectra (diameter about 10nm, length about 100nm) covered with PS on the surface.
FIG. 5: XRD analysis of gold nanorods coated with PS on the surface (diameter about 10nm, length about 100 nm).
FIG. 6: schematic synthesis of gold nanorods coated with water-soluble PEG on the surface.
FIG. 7: TEM pictures of gold nanorods covered with PEG on the surface (diameter about 10nm, length about 100 nm).
Detailed Description
Example 1 (fig. 1) the present invention is further described below with reference to examples, but the present invention is not limited thereto.
(1) Preparation and fractionation of ATRP macroinitiator cellulose-bromoisobutyrate based on cellulose molecules: adding 10g of natural cellulose into a 250mL single-neck flask, dissolving the natural cellulose in 100mL of ionic liquid chlorinated 1-allyl-3-methylimidazole (AMIMCl), after the natural cellulose is completely dissolved, respectively adding 10mL of anhydrous DMF and 10mL of NMP which are taken as a diluent and an acid absorbent, slowly dripping 50mL of 2-bromoisobutyryl bromide within 1 hour under the condition of cooling to zero temperature, and modifying hydroxyl on a modified cellulose chain to convert the hydroxyl into a macromolecular initiator for ATRP. Then, the temperature was naturally raised to room temperature (25 ℃ C.) and the reaction was carried out at room temperature for 24 hours. Finally, using 500mL of deionized water as a precipitating agent to precipitate the final product. Then, the mixture was purified again by using 50mL of acetone as a solvent and 500mL of deionized water as a precipitant, and finally placed in a vacuum oven at 50 ℃ for 24 hours, and the yield was 87%. Because natural cellulose has very wide molecular weight distribution, in order to obtain the narrow-distribution macroinitiator, the crude product of the synthesized macroinitiator is subjected to fractional precipitation by fractional precipitation, acetone is used as a solvent, deionized water is used as a precipitating agent, and a series of the narrow-distribution macroinitiators with different molecular weights are prepared.
(2) Preparation of brush block Polymer: cellulose-bromoisobutyrate is taken as a macroinitiator, and an ATRP (atom transfer radical polymerization) technology of continuous polymerization is utilized to respectively initiate a tert-butyl acrylate monomer (tBA) and a styrene monomer (St) to prepare a series of brush-shaped two-block polymers with PS at the outermost section: cellulose-g- [ polyacrylic acid-b-polystyrene ]. The details are as follows.
(a) Preparation of cellulose-g-PolyAcrylic acid Tert-butyl ester: the process for initiating t-butyl acrylate monomer (tBA) by ATRP polymerization mechanism with cellulose-bromoisobutyrate as macroinitiator is as follows: to a 50mL ampoule, CuBr (58.3mg,0.4mmol), PMDETA (N, N, N ', N, ' N ' -pentamethyldiethylenetriamine, 70.3mg,0.4mmol), cellulose-bromoisobutyrate (Mn. RTM. 11.2K g/mol,0.25g,0.021mmol), t-butyl acrylate tBA (3mL,21mmol), acetone (3.0mL) were added, and the reaction system was subjected to a freeze-vacuum-nitrogen-thawing cycle three times, sealed, and then placed in a 60 ℃ oil bath to react. Then, the ampoules were taken out at regular intervals and put into liquid nitrogen to terminate the reaction. The crude product was diluted in tetrahydrofuran and filtered in neutral alumina column packing to remove impurities such as colored divalent copper ions to give a pale yellow filtrate, which was concentrated and precipitated in n-heptane to give a pale yellow viscous product, which was vacuum dried at 40 ℃ for 12 hours after repeating the dissolution/precipitation operation twice.
(b) Preparation of cellulose-g- [ Tert-butyl polyacrylate-b-polystyrene ]: the process for initiating styrene polymerization by ATRP polymerization mechanism from polyfunctional cyclic macroinitiator cellulose-g-poly (tert-butyl acrylate) (cellulose-g-PtBA) is as follows: CuBr (54.6mg,0.38mmol), PMDETA (70.3mg,0.4mmol), cellulose-g-poly (tert-butyl acrylate) (molecular weight Mn per PtBA arm 8.6K g/mol; 0.2g,0.017mmol), St (8mL, 69.8mmol) were added to a 50mL ampoule and the reaction was placed in liquid nitrogen and degassed by freeze-pump-thaw cycles three times, sealed and placed in a 90 ℃ oil bath for reaction. Then taking out the ampoule bottles at certain time intervals, and putting the ampoule bottles into liquid nitrogen to terminate the reaction. The crude product was diluted with dichloromethane and passed through a neutral alumina column to remove impurities such as coloured cupric ions, which were then precipitated in cold methanol. After repeating the dissolution/precipitation operation twice, the resulting white powdery product was dried under vacuum at 35 ℃ for 12 hours.
(c) Preparation of cellulose-g- [ polyacrylic acid-b-polystyrene ]: polymer cellulose-g- [ tert-butyl polyacrylate-b-polystyrene ] (0.3g) was dissolved in 30mL of methylene chloride, and trifluoroacetic acid (5 times the amount of the substance as tBA units in the brush polymer) was added thereto with vigorous stirring at 0 ℃ and the mixture was held at 0 ℃ for 3 hours, followed by further stirring at room temperature for 21 hours. As the hydrolysis reaction proceeded, a white precipitate appeared, which was then filtered and washed with dichloromethane, and the precipitate was dissolved in dioxane containing a small amount of anhydrous methanol (anhydrous methanol: dioxane: 1:10) and lyophilized under vacuum to obtain white polymer cellulose-g- [ polyacrylic acid-b-polystyrene ].
(3) Preparation of oil-dispersible gold nanorods (fig. 2, fig. 3, fig. 4 and fig. 5): weighing 10mg of cellulose-g- [ polyacrylic acid-b-polystyrene with bottle brush-shaped structure]Template, dissolved in 10ml of DMF at room temperature, followed by addition of gold precursor compound (HAuCl)4·3H2O; 0.2548 g). In order to completely fill the PAA template, the precursor compound chloroauric acid (HAuCl) of the target material is added into the reaction system in excess4·3H2O) (molar ratio of acrylic acid repeating units to chloroauric acid in template 1:10) the precursor compound selectively diffuses and gathers to a PAA template plate due to the coordination complexation of PAA of the nuclear template plate, and then tert-butylamine boron (TBAB) is added as a reducing agent (the molar ratio of the reducing agent to chloroauric acid is 10: 1) and reacting for 2 hours at the temperature of 60 ℃, wherein the precursor compound generates corresponding gold nanorods in situ in the template phase, and the outermost PS phase is used as a ligand and covers the surface of the nanorods in situ, so that the generated nanorods can be dispersed in corresponding solvents (such as toluene, tetrahydrofuran, acetone and the like), and the nanorods are prevented from agglomerating in organic solvents. The by-product was removed by a low speed centrifuge (rotation speed: 1000rpm for 5 minutes), and the final purified gold nanorods were 0.0670g, with a yield of 52.6%.
Example 2 (fig. 6) preparation of water-dispersible gold nanorods.
(1) Preparation of brush block Polymer: cellulose-bromoisobutyrate is taken as a macroinitiator, an experimental method combining an ATRP technology and a 'linking' chemistry is comprehensively utilized, monofunctional polyethylene glycol mPEG with alkynyl modified end groups is taken as a precursor of an outermost block, and a series of brush-shaped two-block polymers with PEG at the outermost block are prepared: cellulose-g- [ polyacrylic acid-b-polyethylene glycol ].
(a) Preparation of alkynyl terminated mPEG: mPEG with an alkynyl end group (i.e., mPEG-propagyl, methoxypolyethylene glycol propynyl) was prepared by nucleophilic substitution, using mPEG of two molecular weights (respectively Mn ═ 5,000and Mn ═ 10,000). The method comprises the following specific steps: in a 250mL three-necked flask, 10g of hydroxyl terminated dry mPEG (10.0g,2.0mmol) was added followed by 150 mL of dry THF under argon. Then, benzhydryl sodium was slowly added to the solution until the color of the reaction system became reddish brown. Then, under the ice bath condition, 10mmol of bromopropyne reagent is slowly added into the reaction system, and then the reaction system is heated to room temperature (25 ℃) to continue the reaction for 24 hours. The crude product was diluted with 100mL of dichloromethane and then passed through a neutral alumina column to remove the by-product sodium salt. The entire reaction product solution was then concentrated and precipitated in cold ether. Drying in a vacuum oven at 50 ℃ to obtain white powder. Another modification of the mPEG sample with a molecular weight of 10,000g/mol was also performed in the same manner.
Synthesis of cellulose-g- (PtBA-N3) with terminal group of azide group: brush polymer cellulose-g- (tert-butyl polyacrylate-bromo) (cellulose-g- (PtBA-Br), BBCP), 1.0g) was dissolved in 20mL of dry DMF, and a quantitative amount of sodium azide solid powder cellulose-g- (tert-butyl polyacrylate-bromo) was added with a molar ratio of terminal bromine atoms to sodium azide of 1: 10). The reaction was carried out at room temperature for 24 hours. The reaction was then diluted with 50mL of dichloromethane and passed through a neutral alumina column to remove by-products. The resultant product was then washed three times with deionized water, then dried over anhydrous magnesium sulfate, and the solution was concentrated and precipitated in a mixed solution of methanol and water (volume ratio of 1 to 1). The final product was placed in a vacuum oven at 40 ℃ for 6 hours.
Synthesis of the Brush Polymer cellulose-g- [ Tert-butyl polyacrylate-b-polyethylene glycol: a series of brush polymer cellulose-g- [ poly (tert-butyl acrylate) -b-polyethylene glycol is synthesized by a linking chemical method. The specific reaction scheme is as follows: a50 mL dry ampoule was charged with cellulose-g- (tert-butyl polyacrylate-azido) (cellulose-g- (PtBA-N) as the desired reactant3) Methoxy polyethylene glycol alkynyl (mPEG-alkyne), CuBr, PMDETA and solvent DMF. Cellulose-g- (PolyAcrylic acid tert-butyl ester-Azide group) (Cellulose-g- (PtBA-N)3) The molar ratio of azide group, methoxy polyethylene glycol alkynyl (mPEG-alkyne), CuBr and PMDETA in the polymer is 1:2:10: 10. The reaction system is placed in liquid nitrogen for three times through freezing, vacuum degassing and unfreezing circulation, and the reaction system is sealed and placed in an oil bath at 90 ℃ for 24 hours. The crude product was diluted in tetrahydrofuran and filtered in neutral alumina column packing to remove impurities such as colored divalent copper ions to give a pale yellow filtrate, which was concentrated and precipitated in cold methanol to give a pale yellow viscous product after repeating the dissolution/precipitation operation twice, which was dried under vacuum at 60 ℃ for 12 hours.
(d) Preparation of cellulose-g- [ polyacrylic acid-b-polyethylene glycol ]: polymer cellulose-g- [ poly (tert-butyl acrylate) -b-polyethylene glycol (0.3g) was dissolved in 30mL of methylene chloride, trifluoroacetic acid (5 times the amount of the substance as the tBA unit in the brush polymer) was added thereto with vigorous stirring at 0 ℃ and the mixture was held at 0 ℃ for 3 hours, and then the reaction was continued with stirring at room temperature for 21 hours. As the hydrolysis reaction proceeded, a white precipitate appeared, which was then filtered and washed with dichloromethane, and the precipitate was dissolved in dioxane containing a small amount of anhydrous methanol (anhydrous methanol: dioxane: 1:10) and lyophilized under vacuum to obtain white polymer cellulose-g- [ polyacrylic acid-b-polyethylene glycol ].
(3) Preparation of water-dispersible gold nanorods (fig. 7): weighing 10mg of cellulose-g- [ polyacrylic acid-b-polyethylene glycol ] with bottle brush-shaped structure]Template, dissolved in 10mL DMF at room temperature, followed by addition of gold precursor compound (HAuCl)4·3H2O; 0.2548 g). In order to completely fill the PAA template, the precursor compound chloroauric acid (HAuCl) of the target material is added into the reaction system in excess4·3H2O) (molar ratio of acrylic acid repeating units to chloroauric acid in template 1:10) the precursor compound selectively diffuses and gathers to a PAA template plate due to coordination complexation of PAA of the core template plate, and then tert-butylamine boron (TBAB) is added as a reducing agent (0.1416g, the molar ratio of the reducing agent to chloroauric acid is 10: 1) and reacting for 2 hours at the temperature of 60 ℃, generating corresponding gold nanorods in situ by the precursor compound in the template phase, and covering the outermost PEG phase as a ligand on the surface of the nanorods in situ, so that the generated nanorods can be dispersed in a water solution, and simultaneously, the nanorods are prevented from agglomerating in an organic solvent. The by-product was removed by a low speed centrifuge (rotation speed: 1000rpm for 5 minutes), and the final purified gold nanorods were 0.0725g, and the yield was 56.9%.
Claims (4)
1. A method for preparing gold nanorods with controllable size and dispersibility on a large scale is characterized by comprising the following steps:
(1) adopting ionic liquid chlorinated 1-allyl-3-methylimidazole (AMIMCI) as a solvent, adopting anhydrous dimethylformamide and N-methylpyrrolidone (NMP) as a diluent and an acid absorbent, and modifying hydroxyl on a natural cellulose chain by using 2-bromoisobutyryl bromide to convert the hydroxyl into a macroinitiator for Atom Transfer Radical Polymerization (ATRP);
(2) cellulose-bromoisobutyrate is taken as a macroinitiator, and an ATRP (atom transfer radical polymerization) technology of continuous polymerization is utilized to respectively initiate a tert-butyl acrylate monomer (tBA) and a styrene monomer (St) to prepare a series of brush-shaped two-block polymers with PS at the outermost section: cellulose-g- [ polyacrylic acid-b-polystyrene ]; cellulose-bromoisobutyrate is taken as a macroinitiator, an experimental method combining an ATRP technology and a 'linking' chemistry is comprehensively utilized, monofunctional polyethylene glycol mPEG with alkynyl modified end groups is taken as a precursor of an outermost block, and a series of brush-shaped two-block polymers with PEG at the outermost block are prepared: cellulose-g- [ polyacrylic acid-b-polyethylene glycol ];
(3) based on a solution phase synthesis method, a certain amount of cellulose-g- [ polyacrylic acid-b-polystyrene ] monomolecular templates are used for preparing oil-soluble gold nanorods, and a certain amount of cellulose-g- [ polyacrylic acid-b-polyethylene glycol ] monomolecular templates are used for preparing water-soluble gold nanorods.
2. The method of claim 1, wherein the gold nanorods with controllable size and dispersibility are prepared by a solution phase synthesis method, and the gold nanorods with oil solubility and water solubility are prepared respectively by a certain amount of cellulose-g- [ polyacrylic acid-b-polystyrene ] monomolecular template or cellulose-g- [ polyacrylic acid-b-polyethylene glycol ] monomolecular template, a precursor compound chloroauric acid of a target material is added into a reaction system, and then tert-butylamine boron (TBAB) is added as a reducing agent to react for 2 hours at 60 ℃.
3. The method for preparing gold nanorods with controllable size and dispersibility according to claim 2, wherein the molar ratio of acrylic acid repeating units to chloroauric acid in the template is 1: 10; the molar ratio of the reducing agent to the chloroauric acid is 10: 1.
4. the method for preparing gold nanorods with controllable size and dispersibility according to claim 2, wherein the precursor compound chloroauric acid of the target material added into the reaction system is HAuCl4·3H2O。
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| CN111876757B (en) * | 2020-06-28 | 2021-09-21 | 华南理工大学 | Preparation method of inorganic two-dimensional nano material based on plane patterning polymer brush |
| CN112592431A (en) * | 2020-12-16 | 2021-04-02 | 陈凤春 | Degradable cellulose grafted acrylic acid-based high-water-absorptivity hydrogel and preparation method thereof |
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