CN114951683B - Synthesis method of gold nanocluster and detection method of hexavalent chromium ions thereof - Google Patents
Synthesis method of gold nanocluster and detection method of hexavalent chromium ions thereof Download PDFInfo
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- 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
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- 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
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- 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
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- B82Y40/00—Manufacture or treatment of nanostructures
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- 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"
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- 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"
- G01N2021/6432—Quenching
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Abstract
The invention provides a synthesis method of gold nanoclusters AuNCs, which comprises the following synthesis steps: adding histidine and polylysine into chloroauric acid solution to obtain a reaction mixed solution; the mixed solution obtained in the step (A) is stirred by a stirrer, the synthesized solution is filtered by a filter membrane, the obtained solution is transferred to an ultrafiltration tube, and then a weapon is centrifuged in a centrifuge to obtain supernatant; and thirdly, freeze-drying the supernatant obtained in the step II to obtain gold nanocluster AuNCs solid, and re-dissolving the gold nanocluster AuNCs by using phosphate buffer solution PBS to obtain gold nanocluster AuNCs solution. The method solves the problems of high cost and long time consumption of synthesizing gold nanoclusters AuNCs in the prior art; the gold nanocluster fluorescent probe constructed by the invention detects Cr 6+ The method has the advantages of simple and quick operation, low cost, no need of complex large-scale instrument, strong practicability and Cr 6+ Has wide application prospect in the field of rapid detection.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a synthesis method of gold nanoclusters and a detection method of hexavalent chromium ions.
Background
With the development of the modern industry, chromium and its compounds are used in many industrial processes, such as metal working, electroplating and leather tanning, where even some manufacturers produce edible capsule shells from leather waste. A large amount of chromium leaks into the environment where humans live through these industrial processes, seriously jeopardizing the life safety of humans. Generally, two main valence states of chromium in nature are Cr 3+ And Cr (V) 6+ Wherein Cr is 3+ Is an essential element in human nutrition, and Cr 6+ Is a highly toxic substance with non-biodegradability and carcinogenicity, even when exposed to low concentrations of Cr 6+ May cause hemolysis, renal failure, liver failure, etc., resulting in the occurrence of cancer. Therefore, the establishment of an accurate and feasible detection method for hexavalent chromium ions has important significance for environmental monitoring and human health maintenance.
Currently, conventional methods for detecting chromium ions mainly include inductively coupled plasma mass spectrometry (ICP-MS), ion Chromatography (IC), atomic Absorption Spectroscopy (AAS), and the like. These large-scale equipment-based methods, while having high sensitivity, superior accuracy and stability, suffer from the disadvantages of high detection costs, complicated and time-consuming pretreatment processes, and high requirements for the operation of technicians. Wherein, the ICP-MS and AAS methods can only detect the total amount of chromium, but can not detect Cr 6+ Quantification was performed. Therefore, there is still a need to develop a simple, fast, highly sensitive Cr 6+ A detection method.
With the rapid development of nanotechnology, novel nanomaterials have become hot spots in various research fields due to their special physicochemical properties, wherein gold nanoclusters (AuNCs) are attracting attention due to their advantages of adjustable fluorescence, good hydrophilicity, high biocompatibility, simple synthetic route, and the like. AuNCs is a special fluorescent nanoparticle, which generally consists of several to hundreds of gold atoms, has a size below 3nm, and is a relatively stable molecular-like aggregate. Scientific researchers have successfully used AuNCs as fluorescent probes for Cr by utilizing the physicochemical properties of AuNCs 6+ Is used in the analytical detection of (a). Grand et al (Sun, zhang)&Jin,Journal of Materials Chemistry C,2013,1(1)138-143.) preparation of 11-mercaptoundecanoic acid modified gold nanoclusters for Cr 3+ Specific response followed by ascorbic acid to Cr 6+ Reduction to Cr 3+ Can indirectly detect Cr 6+ . While glutathione-modified gold nanoclusters were prepared by Zhang et al (Zhang, liu, wang, yun, li, liu, et al 2013, analytica Chimica Acta,770, 140-146.) to directly detect hexavalent chromium. Although both studies sensitively detected Cr 6+ And Cr (V) 3+ However, EDTA is required to be added to mask Cr in the detection process 3+ EDTA and Cr 3+ The complexing time is long, and Cr cannot be treated 6+ And the rapid detection is realized. YIN et al (YIN, coonrod, heck, lejarza)&Wong,ACS Applied Materials&Interface, 2019,11 (19), 17491-17500.) microcapsules of glutathione modified AuNCs were synthesized, shelliah et al (Shelliah, simon, thirumalaivasan, sun, ko)&Wu, microchimica Acta,2019,186 (12), 788.) synthesized cysteamine-modified gold-copper nanoclusters, although both methods can directly detect Cr 6+ Without being affected by Cr 3+ However, these two fluorescent probes have the disadvantage of complicated and time-consuming synthetic routes, which is not beneficial for large-scale synthesis in practical applications. Referring to the related literature, a method for detecting hexavalent chromium ions by utilizing a gold nanocluster fluorescent probe modified by histidine and polylysine is not reported yet.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a method for modifying gold nanoclusters by utilizing histidine and polylysine, which is carried out at normal temperature, has a simple synthesis process, and can be used as a fluorescent probe for rapidly and quantitatively detecting hexavalent chromium ions directly.
The synthesis method of the gold nanoclusters is characterized by comprising the following steps of:
adding histidine and polylysine into chloroauric acid solution to obtain a reaction mixed solution;
the mixed solution obtained in the step (A) is stirred by a stirrer, the synthesized solution is filtered by a filter membrane, the obtained solution is transferred to an ultrafiltration tube and is centrifuged in a centrifuge, and supernatant is obtained;
and thirdly, freeze-drying the supernatant obtained in the step II to obtain gold nanocluster AuNCs solid, and re-dissolving the gold nanocluster AuNCs by using phosphate buffer solution PBS to obtain gold nanocluster AuNCs solution.
Preferably, the histidine is one of D-histidine, L-histidine and DL-histidine, the histidine content is 0.1-5 mmol, the polylysine content is 0.01-1 mmol, the polylysine molecular weight is 1000-300000, and the chloroauric acid content is 0.01-1 mmol.
Preferably, the stirring speed of the stirrer is 400-1200 rpm, the stirring time is 0.5-3 h, the specification of the filter membrane is 0.22 mu m, the molecular weight of the ultrafiltration tube is 3 KD-100 KD, the rotating speed of the centrifuge is 8000-15000 rpm, and the centrifuging time is 10-30 min;
preferably, in the step (c), the pH of the phosphate buffer solution PBS is 7-9, and the color of the gold nanocluster AuNCs solution is light yellow.
Preferably, the particle size of the gold nanocluster AuNCs is 1.4-2.5 nm, the excitation wavelength of the gold nanocluster AuNCs is 370nm, the emission wavelength is 480nm, and the emission wavelength increases with the increase of the excitation wavelength.
The invention also aims to provide an application of the gold nanocluster as a fluorescent probe for hexavalent chromium ion measurement, which is characterized by comprising the following specific steps:
preparation of Cr by phosphate buffer PBS solution 6+ A standard solution;
secondly, gold nanoclusters AuNCs and Cr 6+ Mixing standard solutions, and measuring a fluorescence emission spectrum intensity diagram of the solution at the excitation wavelength of 370nm after reaction;
with Cr 6+ Concentration values are on the abscissa, fluorescence quenching efficiency { qe= (FL) 0 -FL)/FL 0 And is the ordinate, in which: FL and FL 0 Respectively indicates the presence and absence of Cr 6+ Fluorescence intensity of AuNCs at time; to obtain Cr with different concentrations 6+ Fluorescence quenching efficiency of AuNCs fluorescent probe solution and Cr 6+ Establishing a standard curve by using a linear relation graph between concentrations；
Selecting different inorganic interferents, wherein the inorganic interferents comprise Cr 6+ Or does not contain Cr 6+ Obtaining fluorescence intensity according to the step II and the detection method in the step III;
after the actual sample is pretreated, cr is added in 6+ To be formulated into Cr 6+ Adding a sample to be measured with a standard concentration; according to the step (III) and the detection method in the step (III), fluorescence intensity is obtained, and Cr in the sample to be detected can be determined by comparing the fluorescence intensity with a standard curve 6+ And calculating the standard addition recovery rate and the relative standard deviation; to verify the reliability of the fluorescence method, cr in the actual sample was also detected by conventional ion chromatography 6+ Concentration, and comparing the results with fluorescence.
Preferably, in the step (a), the pH of the PBS solution is 7-9.
Preferably, in the step (a), the gold nanoclusters AuNCs and Cr 6+ The volume ratio of the standard solution is 1:1, and the reaction time is 1-5 min.
Preferably, in step (ii) and step (iii), the gold nanocluster fluorescence method detects Cr 6+ Further comprises: histidine and polylysine are coated around the gold core, which results in gold nanoclusters AuNCs having a number of oxygen-containing and nitrogen-containing groups that are compatible with Cr 6+ Binding gold nanoclusters AuNCs and Cr 6+ Generating energy resonance transfer and aggregating the gold nanoclusters AuNCs, thereby performing fluorescence quenching on the gold nanoclusters AuNCs; cr is realized through the change value of the gold nanocluster AuNCs fluorescence intensity signal 6+ Is a quantitative detection of (a).
Preferably, the step of pre-treating the object to be detected further comprises the steps of: agricultural products: grinding 1-10 g of agricultural products into slurry or powder, adding 100mL of phosphate buffer solution PBS (phosphate buffer solution), wherein the pH=7-9, and then carrying out ultrasonic treatment for 30min; capsule sample: dissolving 1g of capsule shell in 100mL of phosphate buffer solution PBS, heating to dissolve in pH=7-9, and then cooling to room temperature; leather sample: cutting 1g leather into small pieces, dissolving in 100mL phosphate buffer solution PBS, and then shaking for 3h under nitrogen atmosphere, wherein pH=7-9; soil sample: 1g of soil is taken and dissolved in 100mL of phosphate buffer solution PBS (pH=7-9), and then treated by ultrasonic waves for 30min; water sample: boiling a water sample, and then cooling to room temperature; all sample solutions were then centrifuged at 13000rpm for 30min and the resulting supernatant was filtered through a 0.45 μm filter to give the treated actual sample solution.
Compared with the prior art, the invention has the beneficial effects that:
the gold nanocluster AuNCs prepared by the method is used as a fluorescent probe for detecting Cr 6+ The method has simple and rapid operation, good selectivity and high sensitivity, and can reach Cr specified in national standard or pharmacopoeia 6+ Limited detection level. Hexavalent chromium limit value is regulated to be 0.05mg/L in sanitary standard GB5749-2022 of domestic drinking water; the food safety national standard GB2762-2017 prescribes that the limiting value of chromium in grains and products thereof is 1mg/kg, and the limiting value of chromium in vegetables and products thereof is 0.5mg/kg; the 2010 edition of Chinese pharmacopoeia prescribes that the chromium content in the medicinal capsules and the used gelatin raw materials is not more than 2mg/kg; EU regulated 5 month reach regulations in 2015, the limit value of hexavalent chromium in leather is 3mg/kg, and Cr in the method 6+ The detection limit of (C) was 7.2. Mu.g/L.
The reagents used by the gold nanocluster AuNCs fluorescent probe prepared by the method are histidine, polylysine and chloroauric acid, have no toxic or side effect, are environment-friendly, and the synthesis method of the probe has the characteristics of simplicity in synthesis, low cost, rapidness and convenience, and can only react at normal temperature, and no toxic pollutants are produced in the synthesis process.
The detection method is simple and quick to operate, low in cost, free of complex large-scale instruments, high in practicability and capable of detecting Cr 6+ Has wide application prospect in the field of rapid detection.
Drawings
FIG. 1A is a high resolution transmission electron microscope image of gold nanoclusters AuNCs of the present invention; FIG. 1B is a graph showing the particle size distribution of the high resolution transmission electron microscope of the AuNCs of the present invention;
FIG. 2 shows the addition of different Cr according to the present invention 6+ A fluorescence intensity diagram of the gold nanoclusters AuNCs with the content;
FIG. 3 is a gold nanoparticle of the present inventionFluorescence quenching efficiency of cluster AuNCs and Cr 6+ A linear relation graph of content;
FIG. 4A is a schematic diagram of the addition of Cr according to the present invention 6+ High resolution transmission electron microscopy images of the rear gold nanoclusters AuNCs;
FIG. 4B shows the addition of Cr according to the present invention 6+ Particle size distribution diagram of high-resolution transmission electron microscope of the gold nanoclusters AuNCs;
FIG. 5 is a graph showing the selectivity of the present invention for fluorescence by adding different metal ions.
Detailed Description
The invention will be further described in detail below with reference to the accompanying drawings:
[ example 1 ]:
the preparation method of the gold nanocluster AuNCs comprises the following specific steps:
1 mmole of D-histidine and 0.1 mmole of polylysine (molecular weight: about 5000) were added to a solution of 0.1 mmole of chloroauric acid, and after stirring on a stirrer at 800rpm for 1 hour, the resultant pale yellow solution was filtered with a 0.22 μm filter membrane, and the resulting solution was centrifuged at 10000rpm for 20 minutes in a 3KD ultrafilter tube. Finally, freeze-drying the obtained supernatant to obtain gold nanocluster AuNCs solid, and re-dissolving the gold nanocluster AuNCs by using phosphate buffer solution PBS (pH=7) through weighing to obtain the light yellow AuNCs fluorescent probe with the particle size of 1.4-2.5 nm and uniform dispersion, wherein a high-resolution transmission electron microscope image and a particle size distribution diagram thereof are shown in figure 1.
[ example 2 ]:
the preparation method of the gold nanocluster AuNCs comprises the following specific steps:
5 mmole of DL-histidine and 1 mmole of polylysine (molecular weight: about 5000) were added to 1 mmole of chloroauric acid solution, and after stirring on a stirrer at 1200rpm for 3 hours, the resultant pale yellow solution was filtered with a 0.22 μm filter membrane, and the resulting solution was centrifuged in a 3KD ultrafilter tube at 15000rpm for 10 minutes. And finally, freeze-drying the obtained supernatant to obtain gold nanocluster AuNCs solid, and re-dissolving the gold nanocluster AuNCs by PBS (pH=7.5) through weighing to obtain the light yellow gold nanocluster AuNCs fluorescent probe.
[ example 3 ]:
the preparation method of the gold nanocluster AuNCs comprises the following specific steps:
0.1 mmole of L-histidine and 0.01 mmole of polylysine (molecular weight: about 5000) were added to a 0.01 mmole of chloroauric acid solution, which was stirred on a stirrer at 400rpm for 0.5h, and the resulting pale yellow solution was filtered through a 0.22 μm filter membrane, and the resulting solution was centrifuged in a 3KD ultrafilter tube at 8000rpm for 30min. Finally, the obtained supernatant was freeze-dried to obtain gold nanocluster AuNCs solid, and the AuNCs was redissolved with PBS (ph=8) by weighing to obtain pale yellow AuNCs fluorescent probe.
[ example 4 ]:
the preparation method of AuNCs comprises the following specific steps:
1 mmole of D-histidine and 0.05 mmole of polylysine (molecular weight: about 30000) were added to a solution of 0.1 mmole of chloroauric acid, and after stirring on a stirrer at 1200rpm for 2 hours, the resulting pale yellow solution was filtered through a 0.22 μm filter membrane, and the resulting solution was centrifuged in a 10KD ultrafilter tube at 1200rpm for 15 minutes. Finally, the obtained supernatant was freeze-dried to obtain AuNCs solid, and the AuNCs was redissolved with PBS (ph=9) by weighing to obtain pale yellow AuNCs fluorescent probe.
[ example 5 ]:
AuNCs in the detection of Cr 6+ Application in (a)
Cr 6+ Is detected by (a)
Preparation of 1g/LCr with ultrapure water 6+ Mother liquor is diluted by PBS (pH=7) solution to obtain Cr with different concentrations 6+ Standard solutions (0.01, 0.04, 0.07, 0.1, 0.4, 0.7, 1, 4, 7, 10, 40, 70, 100 mg/L). Then 200. Mu.L of 1mg/mL AuNCs was directly combined with 200. Mu.L of Cr 6+ The standard solutions were mixed and after 2min of reaction, the fluorescence emission spectrum intensity of the solution at an excitation wavelength of 370nm was measured and shown in FIG. 2. By Cr 6+ Concentration values are on the abscissa, fluorescence quenching efficiency { qe= (FL) 0 -FL)/FL 0 Is ordinate (where FL and FL 0 Respectively indicates the presence and absence of Cr 6+ Fluorescence intensity of AuNCs at the time of addition) to obtain Cr with different concentrations 6+ Is a sudden fluorescence of AuNCs fluorescent probe solutionEfficiency of killing and Cr 6+ The linear relationship between concentrations is shown in fig. 3, and the linear relationship is qe= 0.0462C Cr 6+ +0.0002(R 2 =0.991), the linear range of detection is 10 to 10000 μg/L, and the detection limit is 7.2 μg/L.
Detection principle:
referring to FIG. 1, detection of Cr using AuNCs fluorescent probe synthesized from histidine and polylysine 6+ . As histidine and polylysine are coated around the gold core, auNCs have a number of oxygen-containing and nitrogen-containing groups that can be bound to Cr 6+ Binding AuNCs and Cr 6+ Generating energy resonance transfer and aggregating AuNCs, adding Cr 6+ The high resolution transmission electron micrograph of the AuNCs and the particle size distribution of the latter are shown in FIG. 4, thereby causing fluorescence quenching of the AuNCs. Cr is realized by the change value of AuNCs fluorescence intensity signal 6+ Is a quantitative detection of (a).
Selectivity experiment:
50mg/L of Cr-free formulations were prepared with PBS (pH=7), respectively 6+ Or 50mg/LCr 6+ Is different from inorganic substances (K) 2 Cr 2 O 7 、CrCl 3 、PbCl 2 、CoCl 2 、CdCl 2 、Hg(NO 3 ) 2 、AlCl 3 、FeCl 3 、MnCl 2 、Fe(NH 4 ) 2 (SO 4 ) 2 、BaCl 2 、CaCl 2 、NaCl、MgCl 2 、InCl 3 And GaCl 3 ) As interfering substances, 200. Mu.L of 1mg/mL AuNCs were then directly combined with 200. Mu.L of Cr-free 6+ Or Cr-containing 6+ After 2min of reaction, the fluorescence signal of the solution at an excitation wavelength of 370nm was measured. As shown in FIG. 5, the AuNCs fluorescence quenching efficiency is obtained by adding Cr alone 6+ The fluorescence quenching efficiency of AuNCs is far higher than that of AuNCs without Cr addition 6+ And only fluorescence quenching efficiency of other interferents is added. While Cr is added into the system at the same time 6+ And other single interferents, the fluorescence quenching efficiency of AuNCs is obviously improved, and the purposes of adding Cr independently are achieved 6+ A similar level. This indicates that other inorganic substances have little interference with the method, a tableFluorescent method based on AuNCs for Cr 6+ Has good selectivity.
Feasibility experiment:
to verify that the method detects Cr in an actual sample 6+ And (3) carrying out a labeling recovery rate experiment. Cabbage, rice, capsule shells, leather, soil and river water are selected as actual samples, and the samples are subjected to independent pretreatment. Pretreatment of each sample was as follows: cabbage: 10g of celery cabbage is ground into a paste, 100ml of pbs (ph=7) is added, and then sonicated for 30min; rice flour: 1g of rice flour was dissolved in 100ml of LPBS (pH=7) and then sonicated for 30min; capsule shell: 1g of the capsule shell was dissolved in 100ml of lpbs (ph=7), heated to dissolve, and then cooled to room temperature; leather: 1g of leather was cut into small pieces and dissolved in 100ml fbs (ph=7), and then shaken under nitrogen for 3h; river water: heating the collected river water to a boiling point, and then cooling to room temperature; soil: 1g of soil was dissolved in 100ml fbs (ph=7) and then sonicated for 30min. Then, all the sample solutions were centrifuged at 13000rpm for 30min, and the resulting supernatant was filtered with a 0.45 μm filter to obtain a treated actual sample solution. Then, cr with different content of 1.0g/L is added into the actual sample solution 6+ To prepare sample solutions with different standard adding concentrations (50, 300 and 3000 mug/L). 200. Mu.L of 1mg/mLAuNCs were then directly reacted with 200. Mu.L of different Cr 6+ Mixing the concentration of the solution of the actual sample with the standard, measuring a fluorescence emission spectrum intensity graph of the solution with the excitation wavelength of 370nm after 2min of reaction, and obtaining a standard curve linear equation QE= 0.0462C Cr 6+ +0.0002, cr calculated by AuNCs fluorescence method can be obtained 6+ Concentration, and calculate the normalized recovery and relative standard deviation. In addition, in order to verify the reliability of the fluorescence method, cr in the actual sample was also detected by a conventional method (ion chromatography) which is commonly used 6+ The concentrations were compared with the fluorescence method, and the results are shown in table 1:
TABLE 1
The recovery rate of the fluorescence method based on AuNCs is 84.9-102.9%, and the RSD value is 2.7-5.8%. As compared with ion chromatography, it was found that the fluorescence method also has good precision and accuracy, indicating that AuNCs-based fluorescence method can be used for detecting Cr 6+ Is an alternative to the above.
The foregoing description is only of the preferred embodiments of the invention, and all changes and modifications that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (7)
1. The synthesis method of the gold nanocluster of the fluorescent probe for hexavalent chromium ion measurement is characterized by comprising the following steps of:
adding histidine and polylysine into chloroauric acid solution to obtain a reaction mixed solution; the method comprises the following steps that histidine is one of D-histidine, L-histidine and DL-histidine, the histidine content is 0.1-5 mmol, the polylysine content is 0.01-1 mmol, the polylysine molecular weight is 1000-300000, and the chloroauric acid content is 0.01-1 mmol; the stirring speed of the stirrer is 400-1200 rpm, the stirring time is 0.5-3 h, the specification of a filter membrane is 0.22 mu m, the molecular weight of a ultrafiltration tube is 3 KD-100 KD, the rotating speed of a centrifuge is 8000-15000 rpm, and the centrifugation time is 10-30 min;
the mixed solution obtained in the step (A) is stirred by a stirrer, the synthesized solution is filtered by a filter membrane, the obtained solution is transferred to an ultrafiltration tube and is centrifuged in a centrifuge, and supernatant is obtained;
freeze-drying the supernatant obtained in the step (III) to obtain gold nanocluster AuNCs solid, weighing, and redissolving the gold nanocluster AuNCs by using phosphate buffer solution PBS to obtain gold nanocluster AuNCs solution; step III, the pH value of the phosphate buffer solution PBS is 7-9, and the color of the gold nanocluster AuNCs solution is light yellow.
2. The gold nanocluster prepared by the synthesis method of claim 1, wherein the particle size of the gold nanocluster AuNCs is 1.4-2.5 nm, the excitation wavelength of the gold nanocluster AuNCs is 370nm, the emission wavelength is 480nm, and the emission wavelength increases with the increase of the excitation wavelength.
3. Use of gold nanoclusters according to claim 1 as fluorescent probe in hexavalent chromium ion measurement, characterized by the specific steps of:
preparation of Cr by phosphate buffer PBS solution 6+ A standard solution;
secondly, gold nanoclusters AuNCs and Cr 6+ Mixing standard solutions, and measuring a fluorescence emission spectrum intensity diagram of the solution at the excitation wavelength of 370nm after reaction;
with Cr 6+ Concentration values are on the abscissa, fluorescence quenching efficiency { qe= (FL) 0 -FL)/FL 0 And is the ordinate, in which: FL and FL 0 Respectively indicates the presence and absence of Cr 6+ Fluorescence intensity of AuNCs at time; to obtain Cr with different concentrations 6+ Fluorescence quenching efficiency of AuNCs fluorescent probe solution and Cr 6+ A linear relation diagram between the concentrations is used for establishing a standard curve;
selecting different inorganic interferents, wherein the inorganic interferents comprise Cr 6+ Or does not contain Cr 6+ Obtaining fluorescence intensity according to the step II and the detection method in the step III;
after the actual sample is pretreated, cr is added in 6+ To be formulated into Cr 6+ Adding a sample to be measured with a standard concentration; according to the step (III) and the detection method in the step (III), fluorescence intensity is obtained, and Cr in the sample to be detected can be determined by comparing the fluorescence intensity with a standard curve 6+ And calculating the standard addition recovery rate and the relative standard deviation; to verify the reliability of the fluorescence method, cr in the actual sample was also detected by conventional ion chromatography 6+ Concentration, and comparing the results with fluorescence.
4. The use of gold nanoclusters according to claim 3 as fluorescent probes for hexavalent chromium ion measurement, characterized in that in the step, the pH of the PBS solution is 7-9.
5. Use of gold nanoclusters as fluorescent probes in hexavalent chromium ion assays according to claim 3, characterized in that the gold nanoclusters AuNCs and Cr are 6+ The volume ratio of the standard solution is 1:1, and the reaction time is 1-5 min.
6. The use of the gold nanoclusters as fluorescent probes for hexavalent chromium ion measurement according to claim 3, wherein in the steps and the step, the gold nanocluster fluorescence method detects Cr 6+ Further comprises: histidine and polylysine are coated around the gold core, which results in gold nanoclusters AuNCs having a number of oxygen-containing and nitrogen-containing groups that are compatible with Cr 6+ Binding gold nanoclusters AuNCs and Cr 6+ Generating energy resonance transfer and aggregating the gold nanoclusters AuNCs, thereby performing fluorescence quenching on the gold nanoclusters AuNCs; cr is realized through the change value of the gold nanocluster AuNCs fluorescence intensity signal 6+ Is a quantitative detection of (a).
7. The use of gold nanoclusters as fluorescent probes in hexavalent chromium ion measurement according to claim 3, characterized in that the step of performing a pretreatment of the object to be measured further comprises the step of performing a pretreatment of the object to be measured, specifically: agricultural products: grinding 1-10 g of agricultural products into slurry or powder, adding 100mL of phosphate buffer solution PBS (phosphate buffer solution), wherein the pH=7-9, and then carrying out ultrasonic treatment for 30min; capsule sample: dissolving 1g of capsule shell in 100mL of phosphate buffer solution PBS, heating to dissolve in pH=7-9, and then cooling to room temperature; leather sample: cutting 1g leather into small pieces, dissolving in 100mL phosphate buffer solution PBS, and then shaking for 3h under nitrogen atmosphere, wherein pH=7-9; soil sample: 1g of soil is taken and dissolved in 100mL of phosphate buffer solution PBS (pH=7-9), and then treated by ultrasonic waves for 30min; water sample: boiling a water sample, and then cooling to room temperature; all sample solutions were then centrifuged at 13000rpm for 30min and the resulting supernatant was filtered through a 0.45 μm filter to give the treated actual sample solution.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013144674A2 (en) * | 2012-03-30 | 2013-10-03 | Indian Institute Of Technology Madras | Visual detection of mercury ions |
| CN106370612A (en) * | 2016-10-31 | 2017-02-01 | 中国工程物理研究院材料研究所 | Preparation method of nano gold colorimetric sensor, and sensor prepared by method and application thereof |
| CN106908427A (en) * | 2017-03-01 | 2017-06-30 | 哈尔滨师范大学 | Gold nanoclusters and carbon quantum dot composite fluorescence probe and its application |
| CN106940308A (en) * | 2017-04-21 | 2017-07-11 | 吉林化工学院 | A kind of method that hexavalent chromium is detected based on luminous copper nano-cluster |
| CN109211861A (en) * | 2018-10-10 | 2019-01-15 | 吉林化工学院 | A kind of polymerization object point/gold nanoclusters ratio fluorescent probe synthesis and its application to the detection of melamine ratio fluorescent |
| CN110346356A (en) * | 2019-07-04 | 2019-10-18 | 云南大学 | Application of the nanogold GSH-AuNPs in detection trivalent chromic ion and/or hexavalent chromium |
| CN113502158A (en) * | 2021-07-14 | 2021-10-15 | 桂林电子科技大学 | Preparation method of gold nanocluster and application of gold nanocluster in bilirubin and zinc ion cascade detection |
| CN113916858A (en) * | 2021-10-13 | 2022-01-11 | 深圳技术大学 | Cr detection by using nitrogen-doped carbon quantum dot fluorescent probe6+Method (2) |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI530674B (en) * | 2014-11-06 | 2016-04-21 | 財團法人工業技術研究院 | Gold nanocluster composition and method for preparing the same and method for detecting thiol-containing compounds |
| KR101730801B1 (en) * | 2015-08-03 | 2017-04-28 | 한국과학기술연구원 | Selective colorimetric detection sensor and method for hexavalent chromium ions using size controlled label-free gold nanoparticles |
-
2022
- 2022-05-27 CN CN202210591413.6A patent/CN114951683B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013144674A2 (en) * | 2012-03-30 | 2013-10-03 | Indian Institute Of Technology Madras | Visual detection of mercury ions |
| CN106370612A (en) * | 2016-10-31 | 2017-02-01 | 中国工程物理研究院材料研究所 | Preparation method of nano gold colorimetric sensor, and sensor prepared by method and application thereof |
| CN106908427A (en) * | 2017-03-01 | 2017-06-30 | 哈尔滨师范大学 | Gold nanoclusters and carbon quantum dot composite fluorescence probe and its application |
| CN106940308A (en) * | 2017-04-21 | 2017-07-11 | 吉林化工学院 | A kind of method that hexavalent chromium is detected based on luminous copper nano-cluster |
| CN109211861A (en) * | 2018-10-10 | 2019-01-15 | 吉林化工学院 | A kind of polymerization object point/gold nanoclusters ratio fluorescent probe synthesis and its application to the detection of melamine ratio fluorescent |
| CN110346356A (en) * | 2019-07-04 | 2019-10-18 | 云南大学 | Application of the nanogold GSH-AuNPs in detection trivalent chromic ion and/or hexavalent chromium |
| CN113502158A (en) * | 2021-07-14 | 2021-10-15 | 桂林电子科技大学 | Preparation method of gold nanocluster and application of gold nanocluster in bilirubin and zinc ion cascade detection |
| CN113916858A (en) * | 2021-10-13 | 2022-01-11 | 深圳技术大学 | Cr detection by using nitrogen-doped carbon quantum dot fluorescent probe6+Method (2) |
Non-Patent Citations (4)
| Title |
|---|
| 六价铬测定方法研究进展;陈丽琼;《理化检验-化学分册》;1208-1212 * |
| 六价铬荧光探针的研究进展;陈元端;《四川化工》;12-14 * |
| 基于溴化氢诱导下纳米金氧化刻蚀比色法检测六价铬;贵莉莉;《化学试剂》;1315-1318 * |
| 金纳米材料光学传感快速检测方法研究要点初探;赵笙良;《材料导报》;19009-19115 * |
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