CN110006869A - The preparation method of gold nanoclusters fluorescence probe and test paper based on zeins - Google Patents

The preparation method of gold nanoclusters fluorescence probe and test paper based on zeins Download PDF

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CN110006869A
CN110006869A CN201910332105.XA CN201910332105A CN110006869A CN 110006869 A CN110006869 A CN 110006869A CN 201910332105 A CN201910332105 A CN 201910332105A CN 110006869 A CN110006869 A CN 110006869A
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gold nanoclusters
zeins
solution
gold
test paper
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CN110006869B (en
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黄臻臻
段博惠
李月
王敏
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Jilin University
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Jilin University
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    • 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"
    • G01N21/643Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
    • 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
    • G01N2021/6417Spectrofluorimetric devices
    • G01N2021/6421Measuring at two or more wavelengths
    • 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"
    • G01N2021/6432Quenching

Abstract

The preparation method of gold nanoclusters fluorescence probe and test paper based on zeins of the invention belongs to fluorescent probe technique field, there are following steps: with vigorous stirring, zein solution is mixed with chlorauric acid solution, heating reaction obtains gold nanoclusters crude product in solution;It is mixed with acidic buffer solution, after centrifugation, washs, obtain gold nanoclusters after purification;Again it disperses gold nanoclusters in deionized water, obtains the gold nanoclusters fluorescence probe based on zeins;Or be dispersed in gold nanoclusters in ethanol solution again, glycerol or polyethylene glycol is added, takes mixed solution drop on teflon gasket, obtains the gold nanoclusters fluorescent test paper based on zeins after dry.Raw material sources used in the present invention are abundant, cheap, and preparation method is easy to operate, and the product of synthesis has Two Colour Fluorescence property, it can be achieved that the ratio fluorescent method of silver ion and mercury ion detects.

Description

The preparation method of gold nanoclusters fluorescence probe and test paper based on zeins
Technical field
The invention belongs to fluorescent probe technique fields, relate generally to a kind of gold nanoclusters fluorescence based on zeins The synthesis of probe and purification process, the probe can be used for ratio fluorescent method detection silver ion and mercury ion.
Background technique
Gold nanoclusters are the novel nano-materials collectively constituted by ligand and several to dozens of gold atom/ions.Because of it With extra small size (2nm or so), excellent photoluminescent property and good biocompatibility, gold nanoclusters are in biochemical analysis, life Object imaging, illuminating material etc. present huge application potential.Currently, gold nanoclusters mostly use protein, small peptide, amino The biomolecule such as acid, nucleic acid are synthesized as ligand.However common biomolecule ligand, such as glutathione, the white egg of serum White, lysozyme, insulin etc. are expensive, so that the preparation cost of gold nanoclusters is higher, are unfavorable for large-scale production and application. In addition, the purifying of gold nanoclusters mainly uses dialysis to remove the impurity such as unreacted gold chloride, reducing agent, purification process at present It is cumbersome, time-consuming.Thus, Development of Novel, the synthesis of gold nanoclusters based on cheap ligand and purification process are to pushing gold nanoclusters Practical application have very important significance.
Silver ion and mercury ion are two kinds of common heavy metal pollution of water body objects, are easily enriched in vivo, are seriously endangered Human health.Currently, realized by fluorescence enhancement, fluorescent quenching or ratio fluorescent method to silver ion there are many gold nanoclusters and The concentration mensuration of mercury ion.Including seralbumin-gold nanoclusters, lysozyme-gold nanoclusters, trypsase-gold nanoclusters with And glutathione-cluster nano-cluster etc..Most of metal ion inspections based on gold nanoclusters are all to carry out in the solution, also There are a small number of reports gold nanoclusters to be fixed or are deposited on filter paper, high polymer fiber, electrostatic assembly film or glass matrix, To realize the real-time detection of metal ion.However, the immobilization or deposition process of gold nanoclusters are often to its photoluminescent property It has an impact.In addition, host material introducing increases testing cost, and gold nanoclusters are potentially interfered with to the fluorescence of metal ion Response.
Corn is one of world's Three major grain crops.2017, corn whole world total output was up to 10.3 hundred million tons.Corn alcohol is molten Albumen is the main protein in corn, is soluble in 70% ethyl alcohol and alkaline solution.Zeins can be from corn wet Production starch or prepare extracts in the by-product after bio-ethanol, cheap, has excellent biological degradability, bio-safety Property, inoxidizability and film forming, are widely used to the numerous areas such as medicament slow release, food fresh keeping and organizational project at present.Closely Nian Lai, zeins have been used for the preparation of CdS semiconductor quantum dot and synthesize 30-80nm under additional reducing agent effect Gold, silver nanoparticle, but there is not been reported for the gold nanoclusters synthetic method based on zeins and related application.
Summary of the invention
The present invention is used as ligand and reducing agent simultaneously using abundance, cheap zeins, develops A kind of purification process that easy, economic gold nanoclusters synthetic method and pH value of solution mediate.Prepared zeins-gold Nano-cluster has Two Colour Fluorescence property, i.e., under the excitation of 365nm wavelength, while showing the blue endogenous fluorescence of zeins And the red fluorescence of gold nanoclusters.The nano-cluster can be used as ratio fluorescent probe in detecting Ag+And Hg2+Ion, fast response time, High sensitivity.In addition, can also prepare zeins-gold nanoclusters test paper using the easy film-forming quality of zeins For Ag+And Hg2+The visualization real-time detection of ion.
The technical solution adopted by the invention is as follows:
A kind of preparation method of gold nanoclusters fluorescence probe and test paper based on zeins, there is following steps:
1) zeins solid powder is added in the sodium hydroxide solution of 0.1~1M and dissolve by heating obtain it is dense Degree is the zein solution of 1~50mg/mL, with vigorous stirring, by zein solution and concentration be 1~ The chlorauric acid solution of 25mM mixes, and zeins and gold chloride mole are to heat 40~100 DEG C of reactions 5 than 1:2~100 Obtain within~12 minutes the gold nanoclusters crude product in solution using zeins as ligand;
2) crude product in solution will be obtained in step 1) to mix with acidic buffer solution, after centrifugation, discard supernatant liquid, precipitating is used Acidic buffer solution washing, obtains gold nanoclusters after purification;
3) it disperses the gold nanoclusters obtained in step 2) in deionized water again, obtains based on zeins Gold nanoclusters fluorescence probe;Or be dispersed in the gold nanoclusters obtained in step 2) in ethanol solution again, to gold nanoclusters Glycerol or polyethylene glycol are added in ethanol solution, takes mixed solution drop on teflon gasket, is obtained after dry based on jade The gold nanoclusters fluorescent test paper of rice alcohol soluble protein.
In step 2), the preferred phosphoric acid of the acidic buffer solution, hac buffer;The centrifugation refer to It is centrifuged 10~30 minutes under the conditions of 8000~12000 revs/min.
In step 3), the ethanol solution refers to that volume fraction of ethanol is 60~95% ethanol water;Gold The preferred 0.1g/L of concentration of the nano-cluster in ethanol solution, mass fraction in total system is after glycerol or polyethylene glycol are added 1~10%;The drying refers to 1~24 hour dry in room temperature or baking oven.
The utility model has the advantages that
1, the present invention used in raw material zeins abundance, be easy to largely extract, it is cheap.
2, the present invention is separated gold nanoclusters and the complete gold chloride of unreacted etc. by regulation pH value of solution, realization gold nano The purifying of cluster, it is easy to operate.
3, the gold nanoclusters based on zeins synthesis that the present invention synthesizes have Two Colour Fluorescence property, it can be achieved that silver The detection of the ratio fluorescent method of ion and mercury ion.
4, the present invention is self-assembly of membrane structure by zeins-gold nanoclusters, can be used as test paper and is used for gold Belong to the visualization real-time detection of ion.
Detailed description of the invention
Fig. 1 is the gold nanoclusters fluorescence spectra synthesized using zeins as ligand in embodiment 1.
Fig. 2 is the high resolution scanning electron microscopic of the gold nanoclusters synthesized using zeins as ligand in embodiment 1 Mirror photo.
Fig. 3 is zeins in embodiment 7-gold nanoclusters 650nm and 450nm fluorescence intensity ratio (I650/I450) With Ag+The variation diagram of concentration.
Fig. 4 is zeins-gold nanoclusters 650nm and 450nm fluorescence intensity ratio (I in embodiment 8650/I450) With Hg2+The variation diagram of concentration.
Fig. 5 is zeins-gold nanoclusters in embodiment 9 for Ag+, Hg2+Detecting and selecting property figure.
Fig. 6 is zeins-gold nanoclusters test paper in embodiment 10 under fluorescent light and under 365nm ultraviolet lamp Photo.
Fig. 7 is in embodiment 11, and under 365nm ultraviolet light, zeins-gold nanoclusters test paper is to Ag+Into Row Visual retrieval photo.
Fig. 8 is in embodiment 11, and under 365nm ultraviolet light, zeins-gold nanoclusters test paper is to Hg2+Into Row Visual retrieval photo.
Specific embodiment
The present invention is specifically described below with reference to embodiment.
Embodiment 1: the preparation of zeins-gold nanoclusters and purifying
50mg zeins is added in the sodium hydroxide solution 5mL of 1M, is dissolved by heating, with isometric chlorine gold Aqueous acid (25mM) mixing, zeins and gold chloride mole are than 1:18, under intense agitation, instead in 80 DEG C 10min is answered, the gold nanoclusters solution using zeins as ligand is obtained, it is molten with 10mL 0.2mol/L phosphoric acid buffer Liquid mixing, zeins-gold nanoclusters form precipitating, and complete gold chloride of unreacted etc. remains in solution.It will mix It closes liquid to be centrifuged 20 minutes in 12000 revs/min, discards supernatant liquid, precipitating is washed with phosphate buffer solution again to be obtained after purification Zeins-gold nanoclusters.Again it disperses zeins-gold nanoclusters of acquisition in deionized water, obtains Gold nanoclusters fluorescence probe based on zeins.Its fluorescence spectrum is measured using Fluorescence Spectrometer, as a result such as Fig. 1 institute Show, zeins-gold nanoclusters have Two Colour Fluorescence property, i.e., under the excitation of 365nm wavelength, while it is molten to show corn alcohol The blue endogenous fluorescence of albumen and the red fluorescence of gold nanoclusters, maximum emission wavelength are located at 450nm and 650nm.It is beautiful Rice alcohol soluble protein-gold nanoclusters high resolution transmission electron microscopy photo is as shown in Fig. 2, zeins-gold nanoclusters Size be 2.5 ± 0.1nm.
Embodiment 2: zeins-gold nanoclusters preparation
25mg zeins is added in the sodium hydroxide solution 5mL of 0.7M, is dissolved by heating, with isometric chlorine Auric acid aqueous solution (14mM) mixing, zeins and gold chloride mole are than 1:20, under intense agitation, in 60 DEG C 5min is reacted, the gold nanoclusters solution using zeins as ligand is obtained.
Embodiment 3: zeins-gold nanoclusters preparation
17.5mg zeins is added in the sodium hydroxide solution 5mL of 0.5M, is dissolved by heating, and it is isometric Aqueous solution of chloraurate (1mM) mixing, zeins and gold chloride mole are than 1:2, under intense agitation, in 40 DEG C 12min is reacted, the gold nanoclusters solution using zeins as ligand is obtained.
Embodiment 4: zeins-gold nanoclusters preparation
10mg zeins is added in the sodium hydroxide solution 5mL of 0.3M, is dissolved by heating, with isometric chlorine Auric acid aqueous solution (11.2mM) mixing, zeins and gold chloride mole are than 1:40, under intense agitation, in 80 DEG C reaction 5min, obtain the gold nanoclusters solution using zeins as ligand.
Embodiment 5: zeins-gold nanoclusters preparation
5mg zeins is added in the sodium hydroxide solution 5mL of 0.2M, is dissolved by heating, with isometric chlorine Auric acid aqueous solution (7mM) mixing, zeins and gold chloride mole are than 1:50, under intense agitation, in 80 DEG C 5min is reacted, the gold nanoclusters solution using zeins as ligand is obtained.
Embodiment 6: zeins-gold nanoclusters preparation
1mg zeins is added in the sodium hydroxide solution 5mL of 0.1M, is dissolved by heating, with isometric chlorine Auric acid aqueous solution (2.8mM) mixing, zeins and gold chloride mole be than 1:100, under intense agitation, in 100 DEG C of reaction 12min, obtain the gold nanoclusters solution using zeins as ligand.
Embodiment 7: zeins-gold nanoclusters are as fluorescence enhancement probe in detecting concentration of silver ions
500 μ L of the zeins prepared in Example 1-gold nanoclusters solution is dense with (500 μ L) in equal volume respectively Degree is respectively 0,1.6,3.2,6.4 and 12.8 μM of silver nitrate solution mixing.Record zeins-gold nanoclusters exist Fluorescence intensity at 450nm and 650nm wavelength.As shown in Fig. 3, with Ag+The raising of concentration, zeins 650nm With 450nm fluorescence intensity ratio (I650/I450) to Ag+Concentration linearly responds.
Embodiment 8: zeins-gold nanoclusters are as fluorescent quenching probe in detecting ion concentration of mercury
500 μ L of the zeins prepared in Example 1-gold nanoclusters solution is dense with (500 μ L) in equal volume respectively Degree is respectively 0,1.6,3.2,6.4 and 12.8 μM of Hg2+Solution mixing.Record zeins-gold nanoclusters in 450nm and Fluorescence intensity at 650nm wavelength.As shown in Fig. 4, with Hg2+The raising of concentration, zeins 650nm and 450nm Fluorescence intensity ratio (I650/I450) to Ag+Concentration linearly responds.
Embodiment 9: zeins-gold nanoclusters are as fluorescence probe to the selective enumeration method of metal ion
500 μ L of the zeins prepared in Example 1-gold nanoclusters solution, respectively with (500 μ L) in equal volume The NH that concentration is 50 μM4 +, Li+, Na+, K+, Fe2+, Mg2+, Ca2+, Zn2+, Ba2+,Pb2+, Fe3, Al3+, Ag+, Hg2+Solion is mixed It closes.5min is reacted at room temperature, measurement 365nm wavelength excites the fluorescence emission spectrum of lower zeins-gold nanoclusters, Record the fluorescence intensity at 450nm and 650nm wavelength.As a result as shown in Fig. 5, Ag is removed+、Hg2+Except ion, other ions are all Zeins-gold nanoclusters fluorescent emission intensity is not caused to substantially change.Show zeins-gold nanoclusters pair Ag+And Hg2+Ion has the fluorescence response behavior of specificity.
Embodiment 10: zeins-gold nanoclusters test paper preparation
Zeins-the gold nanoclusters prepared in embodiment 1 are dispersed in again in 70% ethanol solution, are obtained The zeins of 0.1g/L-gold nanoclusters alcohol dispersion liquid.Dispersion liquid 1mL is taken, 45 μ L of glycerol is added, takes 50 μ L above-mentioned Solution drop is in teflon gasket, and dry 2h, obtains zeins-gold nanoclusters test paper in 40 DEG C of baking ovens.Respectively Test paper is irradiated with fluorescent lamp and 365nm ultraviolet lamp, comparison photo is as shown in Fig. 6, and in Fig. 6, left figure is under natural light Zeins-gold nanoclusters test paper, in faint yellow, right figure is zeins-gold nano under ultraviolet light irradiation Cluster test paper issues aubergine fluorescence.
Embodiment 11: zeins-application of the gold nanoclusters test paper in ion detection
The zeins prepared in Example 10-gold nanoclusters test paper, by 10 μ L concentration be 20,50,100, 200,300 and 400 μM of Ag+Or Hg2+Solution is dripped respectively on test paper.As shown in Fig. 7, under 365nm ultraviolet light, with Ag+Concentration improves, and test paper color gradually becomes bright red by aubergine.As shown in Fig. 8, in 365nm ultraviolet light Under, with Hg2+Concentration improves, and test paper color gradually becomes blue by aubergine.

Claims (3)

1. a kind of preparation method of gold nanoclusters fluorescence probe and test paper based on zeins, there is following steps:
1) zeins solid powder is added in the sodium hydroxide solution of 0.1~1 M and is dissolved by heating and obtain concentration It is with vigorous stirring 1~25mM by zein solution and concentration for the zein solution of 1~50mg/mL Chlorauric acid solution mixing, zeins and gold chloride mole are to heat 40~100 DEG C of reactions 5~12 than 1:2~100 Minute obtains the gold nanoclusters crude product in solution using zeins as ligand;
2) crude product in solution will be obtained in step 1) to mix with acidic buffer solution, after centrifugation, discard supernatant liquid, precipitating acidity Buffer solution washing, obtains gold nanoclusters after purification;
3) it disperses the gold nanoclusters obtained in step 2) in deionized water again, obtains the Jenner based on zeins Rice cluster fluorescence probe;Or be dispersed in the gold nanoclusters obtained in step 2) in ethanol solution again, to the ethyl alcohol of gold nanoclusters Glycerol or polyethylene glycol are added in solution, takes mixed solution drop on teflon gasket, is obtained after dry based on corn alcohol The gold nanoclusters fluorescent test paper of molten albumen.
2. a kind of preparation side of gold nanoclusters fluorescence probe and test paper based on zeins according to claim 1 Method, which is characterized in that in step 2), the acidic buffer solution is phosphoric acid, hac buffer;The centrifugation refers to Be centrifuged 10~30 minutes under the conditions of 8000~12000 revs/min.
3. a kind of system of gold nanoclusters fluorescence probe and test paper based on zeins according to claim 1 or 2 Preparation Method, which is characterized in that in step 3), the ethanol solution refers to that volume fraction of ethanol is 60%~95% second Alcohol solution;Concentration of the gold nanoclusters in ethanol solution is 0.1g/L, glycerol or polyethylene glycol be added after in total system Mass fraction is 1%~10%;The drying refers to 1~24 hour dry in room temperature or baking oven.
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CN114381257A (en) * 2022-01-21 2022-04-22 吉林大学 Ratio-type fluorescent probe of near-infrared luminescent gold nanocluster based on thiolactic acid protection and application of ratio-type fluorescent probe in silver ion detection

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