CN110006869B - Preparation method of gold nanocluster fluorescent probe and test paper based on zein - Google Patents
Preparation method of gold nanocluster fluorescent probe and test paper based on zein Download PDFInfo
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- CN110006869B CN110006869B CN201910332105.XA CN201910332105A CN110006869B CN 110006869 B CN110006869 B CN 110006869B CN 201910332105 A CN201910332105 A CN 201910332105A CN 110006869 B CN110006869 B CN 110006869B
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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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- 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
- G01N2021/6417—Spectrofluorimetric devices
- G01N2021/6421—Measuring at two or more wavelengths
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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"
- G01N2021/6432—Quenching
Abstract
The invention relates to a preparation method of a gold nanocluster fluorescent probe and test paper based on zein, belonging to the technical field of fluorescent probes and comprising the following steps: under the condition of violent stirring, mixing a zein solution and a chloroauric acid solution, and heating to react to obtain a gold nanocluster crude product solution; mixing with an acidic buffer solution, centrifuging, and washing to obtain purified gold nanoclusters; re-dispersing the gold nanoclusters in deionized water to obtain a zein-based gold nanocluster fluorescent probe; or dispersing the gold nanoclusters in an ethanol solution again, adding glycerol or polyethylene glycol, dripping the mixed solution on a polytetrafluoroethylene gasket, and drying to obtain the zein-based gold nanocluster fluorescent test paper. The raw materials used in the invention have rich sources and low price, the preparation method is simple to operate, and the synthesized product has bicolor fluorescence property and can realize the ratio fluorescence detection of silver ions and mercury ions.
Description
Technical Field
The invention belongs to the technical field of fluorescent probes, and mainly relates to a method for synthesizing and purifying a zein-based gold nanocluster fluorescent probe, which can be used for detecting silver ions and mercury ions by a fluorescence ratio method.
Background
The gold nanocluster is a novel nano material which is composed of a ligand and several to dozens of gold atoms/ions. Because the nano-gold nanoparticle has an ultra-small size (about 2 nm), excellent fluorescence property and good biocompatibility, the nano-gold nanoparticle shows huge application potential in the aspects of biochemical analysis, biological imaging, lighting materials and the like. Currently, gold nanoclusters are mostly synthesized by using biomolecules such as proteins, small peptides, amino acids, nucleic acids and the like as ligands. However, common biomolecule ligands such as glutathione, serum albumin, lysozyme and insulin are expensive, so that the preparation cost of the gold nanocluster is high, and the gold nanocluster is not favorable for large-scale production and application. In addition, the existing gold nanocluster is mainly purified by dialysis to remove unreacted chloroauric acid, reducing agent and other impurities, and the purification process is complicated and time-consuming. Therefore, the development of a novel gold nanocluster synthesis and purification method based on cheap ligands has very important significance for promoting the practical application of the gold nanoclusters.
Silver ions and mercury ions are two common water heavy metal pollutants, are easy to enrich in organisms and seriously harm human health. At present, the concentration of silver ions and mercury ions can be measured by a fluorescence enhancement method, a fluorescence quenching method or a ratio fluorescence method through various gold nanoclusters. Comprises serum albumin-gold nanoclusters, lysozyme-gold nanoclusters, trypsin-gold nanoclusters, glutathione-gold nanoclusters and the like. Most metal ion detection methods based on gold nanoclusters are carried out in solution, and few reports also show that the gold nanoclusters are fixed or deposited on filter paper, high-molecular polymer fibers, electrostatic assembly films or glass substrates, so that real-time detection of metal ions is realized. However, the process of immobilization or deposition of gold nanoclusters often has an effect on their fluorescent properties. In addition, the introduction of matrix materials increases the cost of detection and may interfere with the fluorescent response of the gold nanoclusters to metal ions.
Corn is one of the three major food crops in the world. In 2017, the global production of corn reaches 10.3 hundred million tons. Zein is the major protein in corn and is readily soluble in 70% ethanol and alkaline solutions. Zein can be extracted from a byproduct generated after starch is produced by a corn wet method or bioethanol is prepared, is low in price, has excellent biodegradability, biosafety, oxidation resistance and film forming property, and is widely applied to various fields such as drug slow release, food preservation, tissue engineering and the like at present. In recent years, zein has been used for preparing semiconductor CdS quantum dots and synthesizing 30-80nm gold and silver nano particles under the action of an external reducing agent, but a zein-based gold nano cluster synthesis method and related application have not been reported.
Disclosure of Invention
The invention adopts zein with rich sources and low price as a ligand and a reducing agent, develops a simple, convenient and economic gold nanocluster synthesis method and a solution pH-mediated pure gold nanoclusterA chemical method. The prepared zein-gold nanocluster has the bicolor fluorescence property, namely, under the excitation of 365nm wavelength, the blue endogenous fluorescence of the zein and the red fluorescence of the gold nanocluster are simultaneously displayed. The nanocluster can be used as a ratiometric fluorescent probe for detecting Ag+And Hg2+Ion, fast response speed and high sensitivity. In addition, by utilizing the easy film forming property of the zein, the zein-gold nanocluster test paper can be prepared for Ag+And Hg2+Visual real-time detection of ions.
The technical scheme adopted by the invention is as follows:
a preparation method of a gold nanocluster fluorescent probe and test paper based on zein comprises the following steps:
1) adding zein solid powder into 0.1-1M sodium hydroxide solution, heating and dissolving to obtain 1-50 mg/mL zein solution, mixing the zein solution with 1-25 mM chloroauric acid solution under vigorous stirring, heating at 40-100 ℃ for 5-12 minutes to obtain gold nanocluster crude product solution taking zein as ligand, wherein the molar ratio of zein to chloroauric acid is 1: 2-100;
2) mixing the crude product solution obtained in the step 1) with an acidic buffer solution, centrifuging, removing a supernatant, and washing a precipitate with the acidic buffer solution to obtain a purified gold nanocluster;
3) re-dispersing the gold nanoclusters obtained in the step 2) in deionized water to obtain a zein-based gold nanocluster fluorescent probe; or re-dispersing the gold nanoclusters obtained in the step 2) in an ethanol solution, adding glycerol or polyethylene glycol into the ethanol solution of the gold nanoclusters, dripping the mixed solution on a polytetrafluoroethylene gasket, and drying to obtain the zein-based gold nanocluster fluorescent test paper.
In the step 2), the acidic buffer solution is preferably phosphoric acid or acetic acid buffer solution; the centrifugation is performed for 10-30 minutes under the conditions of 8000-12000 r/min.
In the step 3), the ethanol solution refers to an ethanol water solution with the ethanol volume fraction of 60-95%; the concentration of the gold nanoclusters in the ethanol solution is preferably 0.1g/L, and the mass fraction of glycerol or polyethylene glycol added in the total system is 1-10%; the drying refers to drying for 1-24 hours at room temperature or in an oven.
Has the advantages that:
1. the raw material zein used by the invention has rich sources, is easy to extract in large quantity and has low price.
2. The method separates the gold nanocluster from unreacted chloroauric acid and the like by regulating and controlling the pH value of the solution, realizes the purification of the gold nanocluster, and is simple to operate.
3. The gold nanocluster synthesized based on zein has a bicolor fluorescent property, and can realize the ratio fluorescence detection of silver ions and mercury ions.
4. The zein-gold nanocluster self-assembly film structure can be used as test paper for visual real-time detection of metal ions.
Drawings
FIG. 1 is a fluorescence spectrum of gold nanoclusters synthesized using zein as a ligand in example 1.
Fig. 2 is a high-resolution scanning electron microscope photograph of gold nanoclusters synthesized using zein as a ligand in example 1.
FIG. 3 is the ratio of the fluorescence intensity of the zein-gold nanoclusters in example 7 at 650nm to 450nm (I)650/I450) With Ag+Graph of the change in concentration.
FIG. 4 shows the ratio of the fluorescence intensity of the zein-gold nanoclusters in example 8 at 650nm to 450nm (I)650/I450) With Hg2+Graph of the change in concentration.
FIG. 5 is a graph of zein-gold nanoclusters versus Ag in example 9+，Hg2+The detection selectivity map of (1).
FIG. 6 is a photograph of zein-gold nanocluster paper in example 10 under fluorescent light and under 365nm ultraviolet light.
FIG. 7 shows zein-gold in example 11 under 365nm UV irradiationNanocluster test paper pair Ag+And carrying out visual detection on the photo.
FIG. 8 shows zein-gold nanocluster test paper for Hg in example 11 under 365nm ultraviolet radiation2+And carrying out visual detection on the photo.
Detailed Description
The present invention will be described in detail with reference to examples.
Example 1: preparation and purification of zein-gold nanoclusters
Adding 50mg of zein into 5mL of 1M sodium hydroxide solution, heating for dissolving, mixing with an equal volume of chloroauric acid aqueous solution (25mM), wherein the molar ratio of the zein to the chloroauric acid is 1:18, reacting at 80 ℃ for 10min under the condition of vigorous stirring to obtain a gold nanocluster solution taking the zein as a ligand, mixing the gold nanocluster solution with 10mL of 0.2mol/L phosphoric acid buffer solution, forming a precipitate from the zein-gold nanoclusters, and remaining unreacted chloroauric acid and the like in the solution. Centrifuging the mixed solution at 12000 r/m for 20 min, discarding the supernatant, washing the precipitate with phosphoric acid buffer solution to obtain purified zein-gold nanoclusters. And re-dispersing the obtained zein-gold nanoclusters in deionized water to obtain the zein-based gold nanocluster fluorescent probe. The fluorescence spectrum of the zein-gold nanocluster is measured by a fluorescence spectrometer, the result is shown in fig. 1, the zein-gold nanocluster has a bicolor fluorescence property, namely, under the excitation of 365nm wavelength, the blue endogenous fluorescence of the zein and the red fluorescence of the gold nanocluster are simultaneously displayed, and the maximum emission wavelength is respectively 450nm and 650 nm. Fig. 2 shows a high-resolution transmission electron microscope photograph of the zein-gold nanoclusters, wherein the zein-gold nanoclusters have a size of 2.5 ± 0.1 nm.
Example 2: preparation of zein-gold nanoclusters
Adding 25mg of zein into 5mL of 0.7M sodium hydroxide solution, heating for dissolving, mixing with equal volume of chloroauric acid aqueous solution (14mM), wherein the molar ratio of the zein to the chloroauric acid is 1:20, and reacting at 60 ℃ for 5min under the condition of vigorous stirring to obtain the gold nanocluster solution taking the zein as a ligand.
Example 3: preparation of zein-gold nanoclusters
Adding 17.5mg of zein into 5mL of 0.5M sodium hydroxide solution, heating for dissolving, mixing with an equal volume of chloroauric acid aqueous solution (1mM), wherein the molar ratio of the zein to the chloroauric acid is 1:2, and reacting at 40 ℃ for 12min under the condition of vigorous stirring to obtain a gold nanocluster solution taking the zein as a ligand.
Example 4: preparation of zein-gold nanoclusters
Adding 10mg of zein into 5mL of 0.3M sodium hydroxide solution, heating for dissolving, mixing with equal volume of chloroauric acid aqueous solution (11.2mM), wherein the molar ratio of the zein to the chloroauric acid is 1:40, and reacting at 80 ℃ for 5min under the condition of vigorous stirring to obtain the gold nanocluster solution taking the zein as a ligand.
Example 5: preparation of zein-gold nanoclusters
Adding 5mg of zein into 5mL of 0.2M sodium hydroxide solution, heating for dissolving, mixing with equal volume of chloroauric acid aqueous solution (7mM), wherein the molar ratio of the zein to the chloroauric acid is 1:50, and reacting at 80 ℃ for 5min under the condition of vigorous stirring to obtain gold nanocluster solution taking the zein as ligand.
Example 6: preparation of zein-gold nanoclusters
Adding 1mg of zein into 5mL of 0.1M sodium hydroxide solution, heating for dissolving, mixing with equal volume of chloroauric acid aqueous solution (2.8mM), wherein the molar ratio of the zein to the chloroauric acid is 1:100, and reacting at 100 ℃ for 12min under the condition of vigorous stirring to obtain a gold nanocluster solution taking the zein as a ligand.
Example 7: zein-gold nanocluster as fluorescence enhancement probe for detecting silver ion concentration
500. mu.L of the zein-gold nanocluster solution prepared in example 1 was taken and mixed with equal volumes (500. mu.L) of silver nitrate solutions with concentrations of 0, 1.6, 3.2, 6.4 and 12.8. mu.M, respectively. Recording zein-gold nanoparticlesFluorescence intensities of the clusters at wavelengths of 450nm and 650 nm. As shown in FIG. 3, with Ag+The concentration is increased, and the fluorescence intensity ratio (I) of the zein at 650nm and 450nm650/I450) For Ag+The concentration is linearly responsive.
Example 8: method for detecting concentration of mercury ions by using zein-gold nanocluster as fluorescence quenching probe
500 μ L of the zein-gold nanocluster solution prepared in example 1 was mixed with equal volume (500 μ L) of Hg at concentrations of 0, 1.6, 3.2, 6.4 and 12.8 μ M, respectively2+The solutions were mixed. The fluorescence intensity of the zein-gold nanoclusters at the wavelengths of 450nm and 650nm was recorded. As shown in FIG. 4, with Hg2+The concentration is increased, and the fluorescence intensity ratio (I) of the zein at 650nm and 450nm650/I450) For Ag+The concentration is linearly responsive.
Example 9: selective detection of metal ions by using zein-gold nanocluster as fluorescent probe
500. mu.L of the zein-gold nanocluster solution prepared in example 1 was taken and mixed with an equal volume (500. mu.L) of NH with a concentration of 50. mu.M4 +，Li+，Na+，K+，Fe2+，Mg2+，Ca2+，Zn2+，Ba2+,Pb2+，Fe3，Al3+，Ag+，Hg2+And mixing the ionic solutions. Reacting for 5min at room temperature, measuring fluorescence emission spectrum of zein-gold nanocluster under 365nm wavelength excitation, and recording fluorescence intensity at 450nm and 650nm wavelength. The results are shown in FIG. 5, except for Ag+、Hg2+Besides the ions, other ions do not cause obvious change of the fluorescence emission intensity of the zein-gold nanoclusters. Shows that the zein-gold nanocluster is paired with Ag+And Hg2+The ions have a specific fluorescent response behavior.
Example 10: preparation of zein-gold nanocluster test paper
The zein-gold nanoclusters prepared in example 1 were redispersed in a 70% ethanol solution to obtain a 0.1g/L zein-gold nanocluster ethanol dispersion. And (3) taking 1mL of the dispersion, adding 45 mu L of glycerol, dropping 50 mu L of the solution on a polytetrafluoroethylene gasket, and drying in a 40 ℃ oven for 2h to obtain the zein-gold nanocluster test paper. The test paper is irradiated by a fluorescent lamp and a 365nm ultraviolet lamp respectively, the comparative picture is as shown in figure 6, the left picture is the zein-gold nanocluster test paper under natural light and is in light yellow, and the right picture is the zein-gold nanocluster test paper under the irradiation of the ultraviolet lamp and emits purple red fluorescence.
Example 11: application of zein-gold nanocluster test paper in ion detection
10 μ L of Ag at concentrations of 20, 50, 100, 200, 300 and 400 μ M were applied to the zein-gold nanocluster test paper prepared in example 10+Or Hg2+The solutions were dropped onto test paper. As shown in figure 7, under 365nm ultraviolet irradiation, the Ag is followed+The concentration is increased, and the color of the test paper is gradually changed from purple red to bright red. As shown in figure 8, under 365nm ultraviolet irradiation, with Hg2+The concentration is increased, and the color of the test paper is gradually changed from purple red to blue.
Claims (3)
1. A preparation method of a gold nanocluster fluorescent probe and test paper based on zein comprises the following steps:
1) adding zein solid powder into 0.1-1M sodium hydroxide solution, heating and dissolving to obtain 1-50 mg/mL zein solution, mixing the zein solution with 1-25 mM chloroauric acid solution under vigorous stirring, heating at 40-100 ℃ for 5-12 minutes to obtain gold nanocluster crude product solution taking zein as ligand, wherein the molar ratio of zein to chloroauric acid is 1: 2-100;
2) mixing the crude product solution obtained in the step 1) with an acidic buffer solution, centrifuging, removing a supernatant, and washing a precipitate with the acidic buffer solution to obtain a purified gold nanocluster; the acidic buffer solution is phosphoric acid or acetic acid buffer solution;
3) re-dispersing the gold nanoclusters obtained in the step 2) in deionized water to obtain a zein-based gold nanocluster fluorescent probe; or re-dispersing the gold nanoclusters obtained in the step 2) in an ethanol solution, adding glycerol or polyethylene glycol into the ethanol solution of the gold nanoclusters, dripping the mixed solution on a polytetrafluoroethylene gasket, and drying to obtain the zein-based gold nanocluster fluorescent test paper.
2. The method for preparing a zein-based gold nanocluster fluorescent probe and test paper as claimed in claim 1, wherein in step 2), the centrifugation is performed at 8000-12000 rpm for 10-30 minutes.
3. The method for preparing a gold nanocluster fluorescent probe and test paper based on zein as claimed in claim 1 or 2, wherein in step 3), the ethanol solution refers to an ethanol water solution with an ethanol volume fraction of 60% -95%; the concentration of the gold nanoclusters in the ethanol solution is 0.1g/L, and the mass fraction of glycerol or polyethylene glycol added in the total system is 1-10%; the drying refers to drying for 1-24 hours at room temperature or in an oven.
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| CN101898126A (en) * | 2010-07-20 | 2010-12-01 | 东华大学 | Heavy metal ion adsorption carrier and preparation method thereof |
| CN102072894A (en) * | 2009-11-25 | 2011-05-25 | 欧普图斯(苏州)光学纳米科技有限公司 | Nano-structure-based spectrum detecting method for detecting chemical and biochemical impurities |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102072894A (en) * | 2009-11-25 | 2011-05-25 | 欧普图斯(苏州)光学纳米科技有限公司 | Nano-structure-based spectrum detecting method for detecting chemical and biochemical impurities |
| CN101898126A (en) * | 2010-07-20 | 2010-12-01 | 东华大学 | Heavy metal ion adsorption carrier and preparation method thereof |
Non-Patent Citations (2)
| Title |
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| Dual-emitting zein-protected gold nanoclusters for ratiometric fluorescence detection of Hg Ag ions in both aqueous solution and self-assembled protein film;Bohui Duan等;《The Royal Society of Chemistry and the Centre National de la Recherche Scientifique》;20191031;第14655–15032页 * |
| 银纳米簇用于食品包装污染物的检测及其抗菌性能的应用;银娜 等;《包装工程》;20191130;第44-50页 * |
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