CN105733032A - Preparation method and application of silver nanocluster gel - Google Patents

Preparation method and application of silver nanocluster gel Download PDF

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CN105733032A
CN105733032A CN201610107128.7A CN201610107128A CN105733032A CN 105733032 A CN105733032 A CN 105733032A CN 201610107128 A CN201610107128 A CN 201610107128A CN 105733032 A CN105733032 A CN 105733032A
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silver nanoclusters
gel
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silver
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CN105733032B (en
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熊华玉
梁继超
王薇
王升富
文为
张修华
郑慧铃
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Hubei University
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L5/00Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
    • C08L5/12Agar or agar-agar, i.e. mixture of agarose and agaropectin; Derivatives thereof
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/02Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/075Macromolecular gels
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64Fluorescence; Phosphorescence
    • G01N21/6428Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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    • C08J2305/00Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
    • C08J2305/12Agar-agar; Derivatives thereof
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    • C08J2405/00Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
    • C08J2405/04Alginic acid; Derivatives thereof
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    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08L2205/00Polymer mixtures characterised by other features
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    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend

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Abstract

The invention provides a preparation method of silver nanocluster gel. The prepared gel is uniform and high in reproducibility; the preparation method is simple, easy and rapid, materials are extensive in resource and low in cost, and a preparation process is pollution-free, and can be used for large-scale production; the prepared silver nanocluster gel is sensitive to a pH value, the fluorescence intensity is enhanced along with increase of the pH, and the silver nanocluster gel is non-fluorescent in a buffer solution with pH of 4-5, so that the silver nanocluster gel can be used for indicating changes of the pH of a system as a fluorescent switch.

Description

The preparation method and applications of silver nanoclusters gel
Technical field
The present invention relates to hydrogel synthetic technology, particularly relate to the preparation method of a kind of silver nanoclusters gel and answer With.
Background technology
The change of pH value is the important mark weighing living organism physiological change, with modern medicine, biological engineering Closely bound up Deng field of scientific study.The method of the change measuring pH value is a lot, such as acidometer, fluorescent material Deng.Fluorimetry uses the change instruction pH value of fluorescence parameter, easy, quick, sensitivity is good, exploitation For detecting living things system H+The pH fluorescent probe of change has wide application in terms of biomedical research Prospect.
Gel is the three-dimensional net structure of crosslinking, typically swelling by the certain solvent of polymeric absorbent prepares, tool Have environment such as temperature, pH value, the characteristic of particular chemicals sensitivity.When by environmental stimuli, gel The conformation of network can have greatly changed.Hydrogel sensitive for pH typically has the acid such as carboxylic acid group, sulfonic group Property group, when pH value changes, gel is because of proton translocation, and changes in certain effect power lower volume Become, thus cause some characteristic changing of gel.Synthesis patent currently for silver nanoclusters gel has CN105193706A " a kind of pH responsive type carries doxorubicin hydrochloride silver nanoclusters hydrogel and application thereof ", this is special Profit is that doxorubicin hydrochloride powder joins silver nanoclusters dispersion liquid, synthesizes in autoclave and noble gas PH responsive type carry doxorubicin hydrochloride hydrogel.This patented technology mainly uses silver nanoclusters hydrogel as load Body, it is achieved medicine slowly discharges." a kind of pH is quick to have CN104893010A for the synthesis patent of hydrogel The preparation method of sense type hydrogel ", this patent is sodium alginate, gelatin, collagen protein of fish skin, agar to be mixed Conjunction is scattered in distilled water, adds calcium carbonate and prepares as gellant.This hydrogel may indicate that pH value Change, does not but have fluorescence display.
Summary of the invention
It is an object of the invention to provide a kind of to pH sensitive, increase along with pH fluorescence intensity strengthen silver The preparation method and applications of nano-cluster gel.
In order to achieve the above object, on the one hand, the invention provides the preparation method of a kind of silver nanoclusters gel, It comprises the following steps:
Step 1, with solvable silver salt, solvable BH4 -Salt, and bovine serum albumin, thioctic acid or gluathione Any one in peptide is raw material, prepares silver nanoclusters solution;
Step 2, joins in deionized water after agarose, sodium alginate and gelatin mix homogeneously, heating, It is made to be completely dissolved formation polysaccharide solution;
Step 3, after the polysaccharide solution obtained until step 2 is cooled to 50-80 DEG C, adds what step 1 obtained Silver nanoclusters solution, stirs, and prepares silver nanoclusters polysaccharide solution, stands, and washing obtains silver nanoclusters Gel.
On the other hand, the silver nanoclusters gel using method described in first aspect present invention to prepare, it is applied to Detection living things system H+The pH fluorescent probe of change.
The invention has the beneficial effects as follows: the preparation method of silver nanoclusters gel provided by the present invention, prepare Gel is more uniform, favorable reproducibility;Preparation method is simple, and quickly, material source is extensively cheap, preparation Process is pollution-free, can be used for large-scale industrial production;Silver nanoclusters gel prepared by the present invention, to pH Value increase fluorescence intensity sensitive, along with pH strengthens, and in the buffer that pH is 4-5, silver nanoclusters coagulates Glue does not has fluorescence, shows that silver nanoclusters gel can be as the change of pH in fluorescent switch directive system.
Accompanying drawing explanation
Fig. 1 is the fluorescence emission spectrogram of the silver nanoclusters gel that the embodiment of the present invention 1 prepares;
Fig. 2 is the silver nanoclusters gel for preparing of the embodiment of the present invention 2 fluorescence under different pH condition Image.
Detailed description of the invention
On the one hand, the invention provides the preparation method of a kind of silver nanoclusters gel, it comprises the following steps:
Step 1, with solvable silver salt, solvable BH4 -Salt, and bovine serum albumin, thioctic acid or glutathion In any one be raw material, prepare silver nanoclusters solution;
Step 2, joins in deionized water after agarose, sodium alginate and gelatin mix homogeneously, heating, It is made to be completely dissolved formation polysaccharide solution;
Step 3, after the polysaccharide solution obtained until step 2 is cooled to 50-80 DEG C, adds what step 1 obtained Silver nanoclusters solution, stirs, and prepares silver nanoclusters polysaccharide solution, stands, and washing obtains silver nanoclusters Gel.
Preferably, described step 1 comprises the following steps:
Step 1-1, any one in configuration BSA, thioctic acid or glutathion is water-soluble with the mixing of solvable silver salt Liquid, drips solvable BH under agitation4 -Saline solution, continues stirring and obtains silver nanoclusters stock solution;
Step 1-2, silver nanoclusters stock solution step 1-1 obtained is dialysed in bag filter, and to obtain silver nanoclusters molten Liquid.
It is further preferred that arbitrary in bovine serum albumin, thioctic acid or glutathion in described step 1-1 Plant and Ag+Mol ratio is 12-16:1.
It is further preferred that Ag in described step 1-1+With BH4 -Mol ratio is 1:4-6.
It is further preferred that continuing mixing time in described step 1-1 is 6-12 hour.
It is further preferred that dialysis time is two days two nights in described step 1-2, centre is changed ultrapure in every three hours Water.
Preferably, in described step 2, agarose, sodium alginate and gelatin weight ratio are 5-9:1-3:0.5-2, add Entering the polysaccharide solution mass concentration obtained in deionized water is 0.1%-1.3%.
Preferably, in described step 3, silver nanoclusters solution and polysaccharide solution volume ratio are 1:1-3.
Preferably, in described step 3, quiescent time is 10-60 minute, uses ultra-pure water cleaning 3-5 time, often Secondary consumption 3-10ml.
On the other hand, the silver nanoclusters gel using method described in first aspect present invention to prepare, it is applied to Detection living things system H+The pH fluorescent probe of change.
Below in conjunction with specific embodiment, the preparation method of silver nanoclusters gel of the present invention is made furtherly Bright.
Embodiment 1
(1) bovine serum albumin dissolving is formed in aqueous the solution of clear;
(2) by AgNO3According to bovine serum albumin: Ag+Mol ratio is that 14.75:1 adds in solution, mixed Close uniformly, form mixed material;
(3) under stirring, Ag in molar ratio+:NaBH4Ratio for 1:4.8 is slowly added dropwise hydroboration Sodium solution, in mixed material, continues 6 hours prepared silver nanoclusters stock solution of stirring;
(4) stock solution is dialysed two days two nights in the bag filter that molecular cut off is 500, middle every three little Time change ultra-pure water, prepare silver nanoclusters solution;
(5) it is 5:3:2 mix homogeneously by agarose, sodium alginate and gelatin according to weight ratio, then by 0.5% (w/v) mixed-powder joins in deionized water, heating so that it is be completely dissolved formation polysaccharide solution, Stop heating;
(6) after polysaccharide solution is cooled to 60 degree, it is that silver nanoclusters solution is added by 0.5:1 according to volume ratio Enter in polysaccharide solution, stir, prepare silver nanoclusters polysaccharide solution;
(7) while hot silver nanoclusters polysaccharide mixed solution is poured in mould, static placement 30 minutes, use Ultra-pure water cleans 4 times, and each consumption 5ml i.e. prepares silver nanoclusters gel.
Embodiment 2
(1) thioctic acid dissolving is formed in aqueous the solution of clear;
(2) by AgNO3According to thioctic acid: Ag+Mol ratio is that 15:1 adds in solution, mix homogeneously, Form mixed material;
(3) under stirring, Ag in molar ratio+:NaBH4Ratio for 1:5 is slowly added dropwise hydroboration Sodium solution, in mixed material, continues 7 hours prepared silver nanoclusters stock solution of stirring;
(4) stock solution is dialysed two days two nights in the bag filter that molecular cut off is 500, middle every three little Time change ultra-pure water, prepare silver nanoclusters solution;
(5) it is 6:3:1 mix homogeneously by agarose, sodium alginate and gelatin according to weight ratio, then by 1% (w/v) Mixed-powder join in deionized water, heating so that it is be completely dissolved formation polysaccharide solution, stop heating;
(6) after polysaccharide solution is cooled to 70 degree, it is that silver nanoclusters solution is added by 1:1 according to volume ratio In polysaccharide solution, stir, prepare silver nanoclusters polysaccharide solution;
(7) while hot silver nanoclusters polysaccharide mixed solution is poured in mould, static placement 20 minutes, use Ultra-pure water cleans 3 times, and each consumption 8ml i.e. prepares silver nanoclusters gel.
Embodiment 3
(1) glutathion dissolving is formed in aqueous the solution of clear;
(2) by AgNO3According to glutathion: Ag+Mol ratio is that 15.5:1 adds in solution, and mixing is all Even, form mixed material;
(3) under stirring, Ag in molar ratio+:NaBH4Ratio for 1:5.5 is slowly added dropwise hydroboration Sodium solution, in mixed material, continues 8 hours prepared silver nanoclusters stock solution of stirring;
(4) stock solution is dialysed two days two nights in the bag filter that molecular cut off is 500, middle every three little Time change ultra-pure water, prepare silver nanoclusters solution;
(5) it is 7:2:1 mix homogeneously by agarose, sodium alginate and gelatin according to weight ratio, then by 0.5% (w/v) mixed-powder joins in deionized water, heating so that it is be completely dissolved formation polysaccharide solution, Stop heating;
(6) after polysaccharide solution is cooled to 60 degree, it is that silver nanoclusters solution is added by 1:2 according to volume ratio In polysaccharide solution, stir, prepare silver nanoclusters polysaccharide solution;
(7) pouring in mould by silver nanoclusters polysaccharide mixed solution while hot, static placement 30 minutes, with super Pure water cleans 5 times, and each consumption 3ml i.e. prepares silver nanoclusters gel.
Embodiment 4
(1) thioctic acid dissolving is formed in aqueous the solution of clear;
(2) by AgNO3According to thioctic acid: Ag+Mol ratio is that 16:1 adds in solution, mix homogeneously, Form mixed material;
(3) under stirring, Ag in molar ratio+:NaBH4Ratio for 1:6 is slowly added dropwise hydroboration Sodium solution, in mixed material, continues 9 hours prepared silver nanoclusters stock solution of stirring;
(4) stock solution is dialysed two days two nights in the bag filter that molecular cut off is 500, middle every three little Time change ultra-pure water, prepare silver nanoclusters solution;
(5) it is 8:1:1 mix homogeneously by agarose, sodium alginate and gelatin according to weight ratio, then by 1% (w/v) Mixed-powder join in deionized water, heating so that it is be completely dissolved formation polysaccharide solution, stop heating;
(6) after polysaccharide solution is cooled to 65 degree, it is that silver nanoclusters solution is added by 1:2 according to volume ratio In polysaccharide solution, stir, prepare silver nanoclusters polysaccharide solution;
(7) pouring in mould by silver nanoclusters polysaccharide mixed solution while hot, static placement 60 minutes, with super Pure water cleans 5 times, and each consumption 5ml i.e. prepares silver nanoclusters gel.
Embodiment 5
(1) bovine serum albumin dissolving is formed in aqueous the solution of clear;
(2) by AgNO3According to bovine serum albumin: Ag+Mol ratio is that 14.5:1 adds in solution, mixed Close uniformly, form mixed material;
(3) under stirring, Ag in molar ratio+:NaBH4Ratio for 1:4.5 is slowly added dropwise hydroboration Sodium solution, in mixed material, continues 10 hours prepared silver nanoclusters stock solution of stirring;
(4) stock solution is dialysed two days two nights in the bag filter that molecular cut off is 500, middle every three little Time change ultra-pure water, prepare silver nanoclusters solution;
(5) it is 9:1:0.5 mix homogeneously by agarose, sodium alginate and gelatin according to weight ratio, then by 0.6% (w/v) mixed-powder joins in deionized water, heating so that it is be completely dissolved formation polysaccharide solution, Stop heating;
(6) after polysaccharide solution is cooled to 60 degree, it is that silver nanoclusters solution is added by 1:3 according to volume ratio In polysaccharide solution, stir, prepare silver nanoclusters polysaccharide solution;
(7) pouring in mould by silver nanoclusters polysaccharide mixed solution while hot, static placement 30 minutes, with super Pure water cleans 3 times, and each consumption 4ml i.e. prepares silver nanoclusters gel.
Embodiment 6
(1) glutathion dissolving is formed in aqueous the solution of clear;
(2) by AgNO3According to glutathion: Ag+Mol ratio is that 14:1 adds in solution, mix homogeneously, Form mixed material;
(3) under stirring, Ag in molar ratio+:NaBH4Ratio for 1:4 is slowly added dropwise hydroboration Sodium solution, in mixed material, continues 11 hours prepared silver nanoclusters stock solution of stirring;
(4) stock solution is dialysed two days two nights in the bag filter that molecular cut off is 500, middle every three little Time change ultra-pure water, prepare silver nanoclusters solution;
(5) it is 8:1.5:0.5 mix homogeneously by agarose, sodium alginate and gelatin according to weight ratio, then will The mixed-powder of 1.2% (w/v) joins in deionized water, heating so that it is be completely dissolved formation polysaccharide molten Liquid, stops heating;
(6) after polysaccharide solution is cooled to 75 degree, it is that silver nanoclusters solution is added by 1:3 according to volume ratio In polysaccharide solution, stir, prepare silver nanoclusters polysaccharide solution;
(7) pouring in mould by silver nanoclusters polysaccharide mixed solution while hot, static placement 30 minutes, with super Pure water cleans 4 times, and each consumption 5ml i.e. prepares silver nanoclusters gel.
Embodiment 7
(1) glutathion dissolving is formed in aqueous the solution of clear;
(2) by AgNO3According to glutathion: Ag+Mol ratio is that 13:1 adds in solution, mix homogeneously, Form mixed material;
(3) under stirring, Ag in molar ratio+:NaBH4Ratio for 1:4 is slowly added dropwise hydroboration Sodium solution, in mixed material, continues 12 hours prepared silver nanoclusters stock solution of stirring;
(4) stock solution is dialysed two days two nights in the bag filter that molecular cut off is 500, middle every three little Time change ultra-pure water, prepare silver nanoclusters solution;
(5) it is 8:0.5:1.5 mix homogeneously by agarose, sodium alginate and gelatin according to weight ratio, then will The mixed-powder of 0.9% (w/v) joins in deionized water, heating so that it is be completely dissolved formation polysaccharide molten Liquid, stops heating;
(6) after polysaccharide solution is cooled to 70 degree, it is that silver nanoclusters solution is added by 1:1 according to volume ratio In polysaccharide solution, stir, prepare silver nanoclusters polysaccharide solution;
(7) pouring in mould by silver nanoclusters polysaccharide mixed solution while hot, static placement 40 minutes, with super Pure water cleans 3 times, and each consumption 5ml i.e. prepares silver nanoclusters gel.
Embodiment 8
(1) glutathion dissolving is formed in aqueous the solution of clear;
(2) by AgNO3According to glutathion: Ag+Mol ratio is that 12:1 adds in solution, mix homogeneously, Form mixed material;
(3) under stirring, Ag in molar ratio+:NaBH4Ratio for 1:4 is slowly added dropwise hydroboration Sodium solution, in mixed material, continues 12 hours prepared silver nanoclusters stock solution of stirring;
(4) stock solution is dialysed two days two nights in the bag filter that molecular cut off is 500, middle every three little Time change ultra-pure water, prepare silver nanoclusters solution;
(5) it is 7:2:1 mix homogeneously by agarose, sodium alginate and gelatin according to weight ratio, then by 1.3% (w/v) mixed-powder joins in deionized water, heating so that it is be completely dissolved formation polysaccharide solution, Stop heating;
(6) after polysaccharide solution is cooled to 70 degree, it is that silver nanoclusters solution is added by 1:2 according to volume ratio In polysaccharide solution, stir, prepare silver nanoclusters polysaccharide solution;
(7) while hot silver nanoclusters polysaccharide mixed solution is poured in mould, static placement 40 minutes, use Ultra-pure water cleans 4 times, and each consumption 4ml i.e. prepares silver nanoclusters gel.
The fluorescence spectrum of the silver nanoclusters gel at room temperature test solution obtaining embodiment 1, obtains Fig. 1 Shown result, as shown in Figure 1, prepared bunch solution has good fluorescence emission spectrum.
After the silver nanoclusters gel obtaining embodiment 2 soaks 2 hours in different ph values buffer, with solidifying Glue imager is taken a picture, and obtains the result shown in Fig. 2, as shown in Figure 2, under the exciting of ultraviolet, different Gel under the conditions of ph value presents different fluorescence intensities.
The foregoing is only the better embodiment of the present invention, not in order to limit invention, all essences in the present invention Within god and principle, any modification, equivalent substitution and improvement etc. done, should be included in the protection of the present invention Within the scope of.

Claims (10)

1. the preparation method of a silver nanoclusters gel, it is characterised in that: it comprises the following steps:
Step 1, with solvable silver salt, solvable BH4 -Salt, and bovine serum albumin, thioctic acid or gluathione Any one in peptide is raw material, prepares silver nanoclusters solution;
Step 2, joins in deionized water after agarose, sodium alginate and gelatin mix homogeneously, heating, It is made to be completely dissolved formation polysaccharide solution;
Step 3, after the polysaccharide solution obtained until step 2 is cooled to 50-80 DEG C, adds what step 1 obtained Silver nanoclusters solution, stirs, and prepares silver nanoclusters polysaccharide solution, stands, and washing obtains silver nanoclusters Gel.
2. the preparation method of silver nanoclusters gel as claimed in claim 1, it is characterised in that: described step 1 is wrapped Include following steps:
Step 1-1, any one in configuration bovine serum albumin, thioctic acid or glutathion and solvable silver salt Mixed aqueous solution, drips solvable BH under agitation4 -Saline solution, continues stirring and obtains silver nanoclusters stock solution;
Step 1-2, silver nanoclusters stock solution step 1-1 obtained is dialysed in bag filter, and to obtain silver nanoclusters molten Liquid.
3. the preparation method of silver nanoclusters gel as claimed in claim 2, it is characterised in that: described step 1-1 Any one in middle bovine serum albumin, thioctic acid or glutathion and Ag+Mol ratio is 12-16:1.
4. the preparation method of silver nanoclusters gel as claimed in claim 2, it is characterised in that: described step 1-1 Middle Ag+With BH4 -Mol ratio is 1:4-6.
5. the preparation method of silver nanoclusters gel as claimed in claim 2, it is characterised in that: described step 1-1 Middle continuation mixing time is 6-12 hour.
6. the preparation method of silver nanoclusters gel as claimed in claim 2, it is characterised in that: described step 1-2 Middle dialysis time is two days two nights, and ultra-pure water is changed in every three hours in centre.
7. the preparation method of silver nanoclusters gel as claimed in claim 1, it is characterised in that: in described step 2 Agarose, sodium alginate and gelatin weight ratio are 5-9:1-3:0.5-2, join the poly obtained in deionized water Sugar juice mass concentration is 0.1%-1.3%.
8. the preparation method of silver nanoclusters gel as claimed in claim 1, it is characterised in that: in described step 3 Silver nanoclusters solution and polysaccharide solution volume ratio are 1:1-3.
9. the preparation method of silver nanoclusters gel as claimed in claim 1, it is characterised in that: in described step 3 Quiescent time is 10-60 minute, uses ultra-pure water to clean 3-5 time, each consumption 3-10ml.
10. the silver nanoclusters gel using method described in claim 1 to prepare, is applied to detect organism It is H+The pH fluorescent probe of change.
CN201610107128.7A 2016-02-26 2016-02-26 The preparation method and applications of silver nanoclusters gel Expired - Fee Related CN105733032B (en)

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Cited By (6)

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CN106891016A (en) * 2017-01-10 2017-06-27 青岛科技大学 A kind of preparation of fluorescence silver nanoclusters and its method for manifesting latent fingerprint
CN107596436A (en) * 2017-09-26 2018-01-19 天津大学 A kind of DNA fluorescence hydrogel and preparation method thereof
CN111035801A (en) * 2020-01-14 2020-04-21 青岛科技大学 Silver nanocluster based chitosan hydrogel dressing and preparation method and application thereof
CN111228302A (en) * 2020-02-27 2020-06-05 青岛科技大学 Antibacterial hydrogel and preparation method and application thereof
CN111739998A (en) * 2020-07-03 2020-10-02 青岛科技大学 High-color-rendering white light LED based on silver clusters and preparation method thereof
CN115216108A (en) * 2022-06-21 2022-10-21 清华-伯克利深圳学院筹备办公室 Hydrogel and preparation method and application thereof

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