CN105675556A - Method for detecting silver ions with glutathione-protected aggregation-induced emission type gold nanoclusters as fluorescent probe - Google Patents
Method for detecting silver ions with glutathione-protected aggregation-induced emission type gold nanoclusters as fluorescent probe Download PDFInfo
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/58—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing copper, silver or gold
Abstract
The invention discloses a method for detecting silver ions with glutathione-protected aggregation-induced emission type gold nanoclusters as a fluorescent probe, wherein the method comprises the steps of preparation of a pH regulation solution, drawing of a standard curve and fluorescence detection of the silver ions. With use of the interaction between the silver ions and the glutathione-protected gold nanoclusters, the fluorescence of the gold nanoclusters is enhanced, and the silver ions can be detected. The method for detecting the silver ions has the advantages of high selectivity, simple operation, rapid response, small quantity of required samples and high sensitivity, and can realize efficient, sensitive and real-time detection of the silver ions in complex substances.
Description
Technical field
The invention belongs to technical field of analysis and detection, specifically relate to using the gold nanoclusters of glutathione protection and examine as fluorescence probeSurvey the analytical method of silver ion.
Background technology
Owing to thering are good physicochemical properties, silver be widely used in jewelry, coin, medical supplies, image articles for use,In electronic electric equipment. There are some researches show that the silver that the mankind take in every day from daily life tools can reach 7 μ g-27 μ g, andDue to the pollution of environment, have higher cannot controlledly taking in. Excessively take in silver and can cause argyria of skin, also can be to machineBody produces many-sided harm, comprises nervous system, immune system etc. Environmental Protection Agency regulation silver in drinking water ionMaximum acceptable concentration be 0.46 μ mol/L, meanwhile the expert of this mechanism point out when in water the concentration of silver ion reach 1.6When nmol/L, will produce toxicity to microorganism and fish, and then affect the ecological balance. Therefore, find oneThe method of quantitative Trace Silver ion has very important realistic meaning accurately and fast.
Gold nanoclusters is a kind of novel fluorescent nano material, its particle diameter generally below 2nm, have ten a few to tens ofGold atom forms under the parcel of part. It has good water solubility, toxicity is low, Stokes shift is large, preparation condition is gentle,The advantages such as easily modification of surface, good stability are study hotspots in recent years. Except the field such as sensing, imaging, it is also used inThe field such as radio sensitization, catalysis photodissociation water, there is boundless application prospect.
Summary of the invention
The object of the present invention is to provide a kind of aggregation inducing light emitting-type gold nanoclusters taking glutathione protection as fluorescence probe,Provide a kind of quick, sensitive and there is the new method of the Silver detection of high selectivity, thickly overcome existing Silver detectionMethod insufficient sensitivity is high, detects the shortcoming of length consuming time and complex steps.
Object of the present invention can reach by following measures:
The aggregation inducing light emitting-type gold nanoclusters of protecting taking glutathione is a method for fluorescence probe detection silver ion, its bagDraw together following steps:
A) preparation of pH regulator solution: salpeter solution and sodium hydroxide solution are mixed to the pH that secure ph is 4.4～5.5Regulator solution;
B) drafting of calibration curve: get aggregation inducing light emitting-type gold nanoclusters solution and pH regulator solution with glutathione protectionAfter mixing, add the silver ion solution of different concentration known, measure fluorescence intensity level I separately630, make fluorescence intensity withThe calibration curve that concentration of silver ions is corresponding;
C) fluoroscopic examination silver ion: get aggregation inducing light emitting-type gold nanoclusters solution and pH regulator solution with glutathione protectionAfter mixing, add silver ion solution to be measured, measure its fluorescence intensity level I630, obtain to be measured containing according to described calibration curveThe concentration of silver ion in silver ion solution.
The present invention also provide a kind of aggregation inducing light emitting-type gold nanoclusters with glutathione protection detect in solution silver fromThe application of sub-concentration aspect. A kind of concrete application process also comprises above-mentioned a), b) and c) step.
Step a) in, in a kind of preferred version, the concentration of salpeter solution is 0.05～0.2mol/L, more preferably 0.1mol/L,The concentration of sodium hydroxide solution is 0.05～0.2mol/L, more preferably 0.1mol/L; The pH value of pH regulator solution is 5.
Step b) in, in a kind of preferred version, silver ion solution, with the aggregation inducing light emitting-type gold of glutathione protectionThe volume ratio of nano-cluster solution and pH regulator solution is 1.5～2.5:1:8～10, preferably 2:1:9; Reaction cumulative volume is0.5-1.5mL. In the silver ion solution of different concentration known, the concentration of each silver ion is 0 μ mol/L-150 μ mol/L.
Step c) in, in a kind of preferred version, in silver ion solution to be measured, the scope of application of concentration of silver ions is 0.5nmol/L-20μmol/L。
In step b) or c), with the aggregation inducing light emitting-type gold nanoclusters solution of glutathione protection and silver ion solutionReaction time is 20-120s, and reaction temperature is 20～30 DEG C (or room temperatures).
The preparation method of the aggregation inducing light emitting-type gold nanoclusters solution with glutathione protection in the present invention can be with reference to existingDocument (JAMCHEMSOC, 134 (2012) 16662.), specifically can make: get chlorauric acid solution and add by the following methodIn glutathione solution, then add ultra-pure water dilution, vigorous stirring reaction at 20～30 DEG C is until solution clarification, thenThe reaction of 60～80 DEG C of heating gentle agitation, obtains the jonquilleous gold nanoclusters aqueous solution; Gained solution is dialysed with bag filter,Finally obtain the aggregation inducing light emitting-type gold nanoclusters solution with glutathione protection of purifying.
In the preparation of gold nanoclusters solution, the concentration of chlorauric acid solution is 10～40mmol/L, glutathione solution denseDegree is 10～40mmol/L, chlorauric acid solution and glutathione solution and dilution with the volume ratio of ultra-pure water be 1:1～2:8～12; Reaction temperature is 70 DEG C, and the reaction time is 10～30h; Described bag filter is that molecular cut off is 3000 bag filter,Dialysis time is 10～30h; The aggregation inducing light emitting-type gold nanoclusters solution with glutathione protection obtaining is in 4 DEG C of preservationsFor subsequent use.
A kind of preparation method of the concrete aggregation inducing light emitting-type gold nanoclusters solution with glutathione protection is as follows: get 0.4ML25mmol/L chlorauric acid solution joins in 0.6mL25mmol/L glutathione solution, then adds 4mL ultra-pure waterDilution, vigorous stirring reaction under room temperature condition is until solution is clarified, and then 70 DEG C of heating gentle agitation reaction 24h, obtainThe jonquilleous gold nanoclusters aqueous solution. The bag filter that is 3000 with molecular cut off by gained solution dialysis 24h, every 4Hour change water one time, finally obtain the gold nanoclusters aqueous solution of purifying, save backup in 4 DEG C.
Fluorescence detection method in the present invention and condition: by measuring the aggregation inducing light emitting-type gold nanoclusters of glutathione protectionAt the emitted luminescence intensity I at 630nm place630Realize the assay of silver ion. I630Larger, show gold nanoclusters combinationSilver ion is more, and the efficiency that fluorescence strengthens is higher. Excitation wavelength is 400nm, and sweep speed is 1200nmmin-1, lightElectricity multiplier tube voltage is 700V, and exciting slit and transmitting slit width is 5nm.
Sample determination: as example, select lake water and two kinds of water samples of running water to measure silver ion in water sample. Before sample determination, needCarry out simple pretreatment, with solid impurity in 0.22 μ m filter membrane suction filtration removal water. Sample is used after salpeter solution acidifying,Adding sodium hydroxide solution to regulate pH value is 5.0, then gets the sample solution of 100 μ L and the pH that 450 μ LpH are 5.0Regulator solution mixes, then adds the gold nanoclusters solution of 50 μ L purifying, leaves standstill after 1min, taking 400nm as swashing under room temperatureSend out wavelength, be determined at the fluorescence intensity level at 630nm place, carry out the mensuration of silver ion by calibration curve method. We's legal systemThe aggregation inducing light emitting-type gold nanoclusters of standby glutathione protection is for fluoroscopic examination silver ion, and its detectability (LOD) can reachTo 0.2nmol/L, have highly sensitive, selectively good, response fast, the feature such as have good stability, can realize complicated baseEfficient, the sensitive and detection in real time of Trace Silver ion in matter.
The sign of the gold nanoclusters of glutathione protection
1.UV-VIS
From ultraviolet-visible absorption spectroscopy figure, can see the aggregation inducing light emitting-type gold nanoclusters absorption band of glutathione protectionFrom 500nm, and have acromion at 400nm wavelength place, this absorption characteristic is different from traditional gold-mercaptides nanometerBunch, most gold-mercaptides nano-cluster absworption peak is greater than 500nm.
2. fluorescence spectrum
The fluorescence emission spectrogram of the aggregation inducing light emitting-type gold nanoclusters of being protected from glutathione, excites at 400nmUnder wavelength, gained emission peak is at 610nm place.
3.XPS spectrum
Utilize XPS spectrum to confirm the valence distribution of gold in the aggregation inducing light emitting-type gold nanoclusters of glutathione protection. Au4F7 /2Corresponding A u (I) and the Au (0) respectively of 84.3eV and 83.7eV peak value place in spectrum, the ratio that wherein Au (I) accounts for is about 73%,Close with the result (～75%) of bibliographical information.
Above collection of illustrative plates result all can prove the successful preparation of the gold nanoclusters of glutathione protection.
The selective assessment of fluoroscopic examination silver ion:
Taking the pH regulator solution of pH=5.0 as solvent, prepare respectively 100 μ mol/LCa2+,K+,Mg2+,Na+,Zn2+,Cu2+,Fe2+,Fe3+,Cd2+,Ag+Solution, under optimum experimental condition, investigate other metal ions on silver ion measure impact.Measure and add the gold nanoclusters solution of metal ion and the fluorescence intensity I of blank solution respectively630, calculating both ratios is I/I0。Result shows to only have Ag+Can produce significant fluorescence and strengthen, other metal ions all can not produce this experiment significantly dryDisturb, illustrated that the gold nanoclusters of glutathione protection prepared by the present invention has selective preferably to the detection of silver ion.
Sample determination methodology:
1. calibration curve and detectability
Preparation concentration of silver ions is the serial solution of 0 μ mol/L-150 μ mol/L, under optimum experiment condition, carries out fluorescenceMeasure. Result shows, the gold nanoclusters of glutathione protection is at the emitted luminescence intensity I at 630nm place630With concentration of silver ionsWithin the scope of 0.5nmol/L-20 μ mol/L, be good linear relationship.
2. actual sample analysis
The aggregation inducing light emitting-type gold nanoclusters that makes glutathione protection with the present embodiment 1 is measured the silver ion in water sample. SampleProduct are measured need carry out simple pretreatment, with solid impurity in 0.22 μ m filter membrane suction filtration removal water. By sample salpeter solutionAfter acidifying, adding sodium hydroxide solution to regulate pH value is 5.0, and the sample solution and the 450 μ LpH that then get 100 μ L are5.0 pH regulator solution mixes, then adds the gold nanoclusters solution of 50 μ L purifying, under room temperature, leaves standstill after 1min, with 400Nm is excitation wavelength, is determined at the fluorescence intensity level at 630nm place. Result shows that in two kinds of water samples, silver ion does not all detectGo out. In two kinds of water samples, add respectively the silver ion standard liquid of 1,200,500,1000nmol/L to carry out application of sample recoveryRate test (n=6), concrete outcome is in table 1.
The assay of silver ion in table 1 water sample
Beneficial effect of the present invention:
1. the present invention utilizes the interaction between silver ion and the aggregation inducing light emitting-type gold nanoclusters of glutathione protection,The Enhancement of Fluorescence that produces gold nanoclusters, this Enhancement of Fluorescence can be for the detection of silver ion.
2. the present invention uses the aggregation inducing light emitting-type gold nanoclusters material of glutathione protection, and its preparation process is simple and quick,The gold nanoclusters stable in properties fluorescence obtaining is strong, and does not need to carry out any modification step for material.
3. it is selectively good, highly sensitive that the method that the present invention builds is measured, and detection limit is low to moderate 0.2nmol/L.
Brief description of the drawings
Fig. 1 is ultraviolet spectrogram and the fluorescence emission spectrogram of the aggregation inducing light emitting-type gold nanoclusters of glutathione protection;
Fig. 2 is the XPS spectrum figure of the aggregation inducing light emitting-type gold nanoclusters of glutathione protection;
Fig. 3 is the fluorescent emission that adds the aggregation inducing light emitting-type gold nanoclusters of glutathione protection after variable concentrations silver ionSpectrogram;
Fig. 4 is the I that adds the gold nanoclusters of glutathione protection after variable concentrations silver ion630With concentration of silver ions linear relationshipCurve;
Fig. 5 is selective experimental result picture.
Detailed description of the invention
Medicine and reagent: gold chloride (HAuCl4), glutathione (GSH) (West Asia reagent Co., Ltd), nitric acid (HNO3)、Silver nitrate (AgNO3), sodium nitrate (NaNO3), NaOH (NaOH) (Chemical Reagent Co., Ltd., Sinopharm Group), dialysisFilm (MWCO:3000) (Co., Ltd in Aladdin reagent), experimental water is redistilled water.
By specific embodiment, the present invention is described below, but the present invention is not merely defined in these embodiment.
Embodiment 1
A) preparation of the aggregation inducing light emitting-type gold nanoclusters of glutathione protection: get 0.4mL25mmol/L chlorauric acid solution and addEnter in 0.6mL25mmol/L glutathione solution, then add the dilution of 4mL ultra-pure water, under room temperature condition, acutely stirMix reaction until solution is clarified, then 70 DEG C of heating gentle agitation reaction 24h, obtain jonquilleous gold nanoclusters waterSolution. The bag filter that is 3000 with molecular cut off by gained solution dialysis 24h, changes one time water for every 4 hours,Finally obtain the gold nanoclusters aqueous solution of purifying.
B) fluorescence sense detects silver ion: get 0.1 of gold nanoclusters solution that 50 μ L steps a) obtain and 450 μ L preformulationmol/LHNO3Mix with 0.1mol/LNaOH mixed solution (pH=5), add the silver ion of 100 μ L variable concentrationsSolution, room temperature leaves standstill reaction 1min, measures fluorescence intensity level I630, and bring respective standard curve into and calculate recoveryRate (n=6), the results are shown in Table 2.
Table 2 embodiment 1 silver ion addition and measured value
Embodiment 2
A) preparation of the aggregation inducing light emitting-type gold nanoclusters of glutathione protection: get 0.4mL25mmol/L chlorauric acid solution and addEnter in 0.6mL25mmol/L glutathione solution, then add the dilution of 4mL ultra-pure water, under room temperature condition, acutely stirMix reaction until solution is clarified, then 70 DEG C of heating gentle agitation reaction 24h, obtain jonquilleous gold nanoclusters waterSolution. The bag filter that is 3000 with molecular cut off by gained solution dialysis 24h, changes one time water for every 4 hours,Finally obtain the gold nanoclusters aqueous solution of purifying.
B) fluorescence sense detects silver ion: get 0.1 of gold nanoclusters solution that 80 μ L steps a) obtain and 720 μ L preformulationmol/LHNO3Mix with 0.1mol/LNaOH mixed solution (pH=5), add the silver ion of 160 μ L variable concentrationsSolution, room temperature leaves standstill reaction 1.5min, measures fluorescence intensity level I630, and bring respective standard curve into and calculate backYield (n=6), the results are shown in Table 3.
Table 3 embodiment 2 silver ion addition and measured values
Embodiment 3
A) preparation of the aggregation inducing light emitting-type gold nanoclusters of glutathione protection: get 0.4mL25mmol/L chlorauric acid solution and addEnter in 0.6mL25mmol/L glutathione solution, then add the dilution of 4mL ultra-pure water, under room temperature condition, acutely stirMix reaction until solution is clarified, then 70 DEG C of heating gentle agitation reaction 24h, obtain jonquilleous gold nanoclusters waterSolution. The bag filter that is 3000 with molecular cut off by gained solution dialysis 24h, changes one time water for every 4 hours,Finally obtain the gold nanoclusters aqueous solution of purifying.
B) fluorescence sense detects silver ion: get 0.1 of gold nanoclusters solution that 50 μ L steps a) obtain and 450 μ L preformulationmol/LHNO3Mix with 0.1mol/LNaOH mixed solution (pH=5), add the silver ion of 100 μ L variable concentrationsSolution, room temperature leaves standstill reaction 1.5min, measures fluorescence intensity level I630, and bring respective standard curve into and calculate backYield (n=6), the results are shown in Table 4.
Table 4 embodiment 3 silver ion addition and measured values
Embodiment 4
A) preparation of the aggregation inducing light emitting-type gold nanoclusters of glutathione protection: get 0.4mL25mmol/L chlorauric acid solution and addEnter in 0.6mL25mmol/L glutathione solution, then add the dilution of 4mL ultra-pure water, under room temperature condition, acutely stirMix reaction until solution is clarified, then 70 DEG C of heating gentle agitation reaction 24h, obtain jonquilleous gold nanoclusters waterSolution. The bag filter that is 3000 with molecular cut off by gained solution dialysis 24h, changes one time water for every 4 hours,Finally obtain the gold nanoclusters aqueous solution of purifying.
B) fluorescence sense detects silver ion: get 0.1 of gold nanoclusters solution that 100 μ L steps a) obtain and 900 μ L preformulationmol/LHNO3Mix with 0.1mol/LNaOH mixed solution (pH=5), add the silver ion of 200 μ L variable concentrationsSolution, room temperature leaves standstill reaction 2min, measures fluorescence intensity level I630, and bring respective standard curve into and calculate recoveryRate (n=6), the results are shown in Table 5.
Table 5 embodiment 4 silver ion addition and measured values
Claims (10)
1. the aggregation inducing light emitting-type gold nanoclusters of protecting taking glutathione is a method for fluorescence probe detection silver ion, its spyLevy and be to comprise the steps:
A) preparation of pH regulator solution: salpeter solution and sodium hydroxide solution are mixed to the pH that secure ph is 4.4～5.5Regulator solution;
B) drafting of calibration curve: get aggregation inducing light emitting-type gold nanoclusters solution and pH regulator solution with glutathione protectionAfter mixing, add the silver ion solution of different concentration known, measure fluorescence intensity level I separately630, make fluorescence intensity withThe calibration curve that concentration of silver ions is corresponding;
C) fluoroscopic examination silver ion: get aggregation inducing light emitting-type gold nanoclusters solution and pH regulator solution with glutathione protectionAfter mixing, add silver ion solution to be measured, measure its fluorescence intensity level I630, obtain to be measured containing according to described calibration curveThe concentration of silver ion in silver ion solution.
2. method according to claim 1, is characterized in that step a), and the concentration of salpeter solution is 0.05～0.2Mol/L, preferably 0.1mol/L, the concentration of sodium hydroxide solution is 0.05～0.2mol/L, preferably 0.1mol/L; PHThe pH value of regulator solution is 5.
3. method according to claim 1, is characterized in that step b), silver ion solution, with glutathione protectionThe volume ratio of aggregation inducing light emitting-type gold nanoclusters solution and pH regulator solution is 1.5～2.5:1:8～10, preferably 2:1：9。
4. method according to claim 1, is characterized in that each silver in the silver ion solution of different concentration known during step b)The concentration of ion is 0 μ mol/L-150 μ mol/L; Step c) in, in silver ion solution to be measured, concentration of silver ions is suitableWith scope be 0.5nmol/L-20 μ mol/L.
5. method according to claim 1, is characterized in that step b) or c), with the aggregation inducing of glutathione protectionThe reaction time of light emitting-type gold nanoclusters solution and silver ion solution is 20-120s, and reaction temperature is 20～30 DEG C.
6. method according to claim 1, is characterized in that step b) or c), fluoroscopic examination condition is: gold nanoclustersAt the emitted luminescence intensity I at 630nm place630Realize the assay of silver ion, excitation wavelength is 400nm, scanningSpeed is 1200nmmin-1, photomultiplier transit tube voltage is 700V, exciting slit and transmitting slit width is 5nm.
7. method according to claim 1, is characterized in that step b) or c), the described gathering with glutathione protectionInduced luminescence type gold nanoclusters solution makes by the following method: gets chlorauric acid solution and joins in glutathione solution, thenAdd ultra-pure water dilution, vigorous stirring reaction at 20～30 DEG C is until solution clarification, and then 60～80 DEG C of heating gentlenesses are stirredMix reaction, obtain the jonquilleous gold nanoclusters aqueous solution; Gained solution is dialysed with bag filter, finally obtain purifyingWith the aggregation inducing light emitting-type gold nanoclusters solution of glutathione protection.
8. method according to claim 7, the concentration that it is characterized in that chlorauric acid solution is 10～40mmol/L, paddy GuangThe concentration of sweet peptide solution is 10～40mmol/L, the volume of ultra-pure water for chlorauric acid solution and glutathione solution and dilutionThan being 1:1～2:8～12; Reaction temperature is 70 DEG C, and the reaction time is 10～30h; Described bag filter is for holding back pointSon amount is 3000 bag filter, and dialysis time is 10～30h; The aggregation inducing with glutathione protection obtaining is luminousType gold nanoclusters solution saves backup in 4 DEG C.
9. the aggregation inducing light emitting-type gold nanoclusters with glutathione protection answering aspect concentration of silver ions in detection solutionWith.
10. application according to claim 9, is characterized in that its detection method comprises the steps:
A) preparation of pH regulator solution: salpeter solution and sodium hydroxide solution are mixed to the pH that secure ph is 4.4～5.5Regulator solution;
B) drafting of calibration curve: get aggregation inducing light emitting-type gold nanoclusters solution and pH regulator solution with glutathione protectionAfter mixing, add the silver ion solution of different concentration known, measure fluorescence intensity level I separately630, make fluorescence intensity withThe calibration curve that concentration of silver ions is corresponding;
C) fluoroscopic examination silver ion: get aggregation inducing light emitting-type gold nanoclusters solution and pH regulator solution with glutathione protectionAfter mixing, add silver ion solution to be measured, measure its fluorescence intensity level I630, obtain to be measured containing according to described calibration curveThe concentration of silver ion in silver ion solution.
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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 |
| CN107121421A (en) * | 2017-06-20 | 2017-09-01 | 内江师范学院 | Portable range estimation luminoscope and method for heavy metal ion in Site Detection water sample |
| CN107462536A (en) * | 2017-05-16 | 2017-12-12 | 首都师范大学 | A kind of method of silver ion in detection water sample |
| CN109324029A (en) * | 2018-12-14 | 2019-02-12 | 盐城工学院 | The method of gold nano cluster probe in detecting melamine concentration based on glutathione functionalization |
| CN109810694A (en) * | 2019-01-23 | 2019-05-28 | 山西大学 | A kind of water-soluble copper namo fluorescence probe and the preparation method and application thereof |
| CN109975266A (en) * | 2019-04-24 | 2019-07-05 | 吉林大学 | Pesticide thiuram concentration Test paper and preparation method thereof based on glutathione gold cluster and silver ion sensor-based system |
| CN110862820A (en) * | 2019-10-23 | 2020-03-06 | 云南大学 | Preparation method and application of cysteine-gold nanocluster |
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| CN112059204A (en) * | 2020-09-15 | 2020-12-11 | 北京师范大学 | Preparation method of gold nanoclusters |
| CN113199035A (en) * | 2021-04-21 | 2021-08-03 | 武汉理工大学 | Gold nanoparticle-gold nanocluster composite material and preparation method and application thereof |
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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 |
| CN107462536A (en) * | 2017-05-16 | 2017-12-12 | 首都师范大学 | A kind of method of silver ion in detection water sample |
| CN107121421A (en) * | 2017-06-20 | 2017-09-01 | 内江师范学院 | Portable range estimation luminoscope and method for heavy metal ion in Site Detection water sample |
| CN109324029A (en) * | 2018-12-14 | 2019-02-12 | 盐城工学院 | The method of gold nano cluster probe in detecting melamine concentration based on glutathione functionalization |
| CN109324029B (en) * | 2018-12-14 | 2021-08-06 | 盐城工学院 | Method for detecting melamine concentration by gold nanocluster probe based on glutathione functionalization |
| CN109810694A (en) * | 2019-01-23 | 2019-05-28 | 山西大学 | A kind of water-soluble copper namo fluorescence probe and the preparation method and application thereof |
| CN109810694B (en) * | 2019-01-23 | 2021-09-28 | 山西大学 | Water-soluble copper nano fluorescent probe and preparation method and application thereof |
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