CN105820814B - A kind of gold nano fluorescence probe and its preparation method and application - Google Patents
A kind of gold nano fluorescence probe and its preparation method and application Download PDFInfo
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- CN105820814B CN105820814B CN201610317154.2A CN201610317154A CN105820814B CN 105820814 B CN105820814 B CN 105820814B CN 201610317154 A CN201610317154 A CN 201610317154A CN 105820814 B CN105820814 B CN 105820814B
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Abstract
The present invention provides a kind of gold nano fluorescence probes and its preparation method and application.Preparation method：1 10 part of 3 5mmol/L aqueous solution of chloraurate is heated to 80 120 DEG C, then 15 part of 42 sulfydryls of 6mmol/L, 4 methyl, 5 thiazolyl acetic acid aqueous solution is added to above-mentioned aqueous solution of chloraurate and continuous heating stirs 5 30min to get to gold nano fluorescence probe.Reaction condition of the present invention is simple, rapidly, environmentally friendly.2 sulfydryl, 4 methyl, 5 thiazolyl acetic acid is reducing agent and protective agent, its own avoids the addition of common reducing agent sodium borohydride, surfactant etc. with reproducibility.Strong blue-fluorescence is presented near 430nm in the fluorescence emission peak of the gold nano-probe, and room temperature preservation has good stability, and can be used for Fe3+Highly sensitive, highly selective detection, and detection process is easy, quickly, and testing result is accurate.
Description
Technical field
The present invention relates to fluorescence probe, especially a kind of water-soluble blue gold nano fluorescence probe and preparation method thereof and answer
With.
Background technology
Iron is one of most important constituent of hemoglobin, participates in the transport of oxygen, such as sub- to maintaining other oxygen carrying albumen
Ferri-hemoglobin enzyme, myoglobins, the normal function of cytochromes are also essential, while it is also many participation energetic supersessions
The important composition of enzyme has serious influence, especially hematological system to health.Iron deficiency can cause red blood cell very little or even poor
Blood, on the contrary, Fe supply can also give rise to diseases, such as parkinsonism, Alzheimer's disease and cancer.Currently, traditional
Science detection iron there are many ways to, such as：Atomic absorption spectrography (AAS), inductive coupling Plasma Mass Spectrometry and gas-chromatography
Method etc., also document report use organic dyestuff or quantum dots characterization iron.But most methods are of high cost, time-consuming or it is multiple to need
Miscellaneous precision instrument, therefore develop a kind of side novel, easy to operate, sample is tractable, instrument is relatively inexpensive
Method becomes a hot spot of analytical chemistry field.Fluorescence analysis has high sensitivity, can detect in real time, is substantially lossless to sample
The advantages that hindering and have broad application prospects.
Gold nano is had received widespread attention due to its unique physicochemical property in recent years, also in analytical chemistry field
To being widely applied, the gold nano of functionalization as probe be widely used to Pharmaceutical Analysis, food security, environmental analysis,
The fields such as bioanalysis, biomarker.It is more likely to generate receiving for greater particle size in general, gold ion is reduced in the solution
Rice grain rather than small particle nano-cluster with fluorescence, this is because the large specific surface area of nano-cluster, apparent activation energy is high, more
It is easy aggregation.Based on this, the synthesis of nano-cluster needs the protection of special groups to prevent it to be further gathered into not no fluorescence
Nano particle.Blocking group plays a very important role to the photoluminescent property tool of gold nano-probe, therefore selects suitable protecting group
Group seems most important.The blocking group for being presently used for synthesis gold nano fluorescence probe generally comprises the biologies such as protein, polypeptide
Macromolecular and mercaptan micromolecular.When using protein and other as protective agent, because of the tyrosine institute in protein
The phenolic groups contained just have reproducibility in pH=12, can Au (III) be reduced into Au atoms, so generally to use NaOH will
Solution is adjusted to strong basicity.When using polypeptide as blocking group, NaBH is generally used using traditional chemical reduction method4By chlorine gold
Acid reduction obtains the weaker gold nano grain of photoluminescent property, recycles between cetyl trimethylammonium bromide and gold nano grain
Electrostatic interaction gold nano grain is transferred in organic phase toluene, in organic phase by etching obtain the gold with photoluminescent property
Nano-probe.When using mercaptan micromolecular as protective agent, many reports use NaBH4Gold chloride is passed through into power for reducing agent
Control method is learned to restore to obtain the weaker gold nano grain of photoluminescent property, it is then (as excessive in heated and being added under proper condition
Mercaptan etc.) further obtain gold nano fluorescence probe.The method reported needs to use strong reductant NaBH4, surface-active
Agent (cetyl trimethylammonium bromide) or strong basic reagent NaOH etc., and preparation process is cumbersome, required time is longer.
Invention content
The object of the present invention is to provide a kind of gold nano fluorescence probes and its preparation method and application.The gold nano is glimmering
Light probe preparation method is simple, has high selectivity to ferric ion, can be used for detecting ferric ion, and detection means
Simply.
In order to solve the above technical problems, the technical solution adopted by the present invention is：
A kind of preparation method of gold nano fluorescence probe, including step：In terms of volume parts, by 1-10 parts of 3-5mmol/L
Aqueous solution of chloraurate is heated to 80-120 DEG C, then by 1-5 parts of 4-6mmol/L 2- sulfydryl -4- methyl-5-thiazole acetic acid aqueous solutions
It is added to above-mentioned aqueous solution of chloraurate and continuous heating stirring 5-30min, you can obtain gold nano fluorescence probe.
The volume of aqueous solution of chloraurate and 2- sulfydryl -4- methyl-5-thiazole acetic acid aqueous solutions as a preferred technical solution,
Than for 7-9:2-4.
A concentration of 4mmol/L of aqueous solution of chloraurate as a preferred technical solution,.
A concentration of 5mmol/L of 2- sulfydryls -4- methyl-5-thiazole acetic acid aqueous solutions as a preferred technical solution,.
Aqueous solution of chloraurate is heated to 100 DEG C as a preferred technical solution,.
2- sulfydryl -4- methyl-5-thiazole acetic acid aqueous solutions are added to aqueous solution of chloraurate as a preferred technical solution,
And continuous heating stirs 20min.
Prepared gold nano fluorescence probe has high selectivity to ferric ion, can be in detecting ferric ion
Using.
A kind of detection method of ferric ion, includes the following steps：By gold nano fluorescence probe of the present invention
(200 μ L) and phosphate buffer solution (2.5mL, 10mmol/L) are added in fluorescence cuvette together, in above-mentioned fluorescence cuvette
In be separately added into the Fe of various concentration again3+Standard solution or solution to be measured measure its fluorescence spectrum using 350nm as excitation wavelength,
With Fe3+The fluorescence of the increase of concentration of standard solution, gold nano fluorescence probe is gradually quenched, and detection Fe is established based on this3+
Working curve.Fe3+Relative intensity of fluorescence (the I of concentration and gold nano fluorescence probe0/ I) it is in two sections of good linear relationships,
The range of linearity is respectively 9.9 × 10-9-3.0×10-6Mol/L (Y=1.06+0.171X, linear coefficient R2=0.998) and 3.2 ×
10-6-1.1×10-3Mol/L (Y=1.68+0.00309X, linear coefficient R2=0.987), wherein I0Fe is indicated respectively with I3+No
In the presence of the fluorescence intensity of the gold nano fluorescence probe in the presence of, detection is limited to 3.3 × 10-9mol/L.Above-mentioned working curve can be applied
The Fe in solution to be measured3+Detection.
Compared with prior art, the present invention is prepared for a kind of good blue-fluorescence nanometer material of water solubility using " one kettle way "
Expect probe, reaction condition is simple, is swift in response, environmentally friendly.Selected 2- sulfydryls -4- methyl-5-thiazole acetic acid is reduction
Agent and protective agent itself have reproducibility, avoid the addition of common reducing agent sodium borohydride, surfactant etc..
In the UV lamp, strong blue-fluorescence, fluorescence quantum yield is presented in gold nano fluorescence probe provided by the invention
Up to 4.5%；With good photostability, can save 12 months or more at room temperature；There is height to select ferric ion
Property, it can be applied in detecting ferric ion, and detection means is simple, it is only necessary to can be realized, detect by Fluorescence Spectrometer
As a result accurate.
Description of the drawings
The preparation of 1 gold nano fluorescence probe of Fig. 1 embodiments and the schematic diagram that ferric ion is measured.
The fluorescence excitation and launching light spectrogram of 1 gold nano fluorescence probe of Fig. 2 embodiments.
1 gold nano fluorescence probe of Fig. 3 embodiments and the fluorescence block diagram after various cation sites.
The working curve that 1 gold nano fluorescence probe of Fig. 4 embodiments responds ferric ion.
Specific implementation mode
The method of the present invention is illustrated below by specific embodiment.Method described in subordinate's embodiment, such as without spy
Different explanation, is conventional method；The reagent and material commercially obtain unless otherwise specified.In experimentation
All glasswares used were cleaned with chloroazotic acid rinsed again with distilled water after be dried for standby.Fluorescence Spectrometer is used in experiment
(F4500) fluorescence spectrum and fluorescence quantum yield of gold nano-probe are measured.
Embodiment 1
7mL 4mmol/L aqueous solution of chloraurate is heated to 100 DEG C, then by 2mL 5mmol/L 2- sulfydryl -4- methyl -5-
Thiazolyl acetic acid aqueous solution is added to above-mentioned aqueous solution of chloraurate and continuous heating stirring 20min, you can obtains the spy of gold nano fluorescence
Needle.Strong blue-fluorescence is presented near 430nm in the fluorescence emission peak of the gold nano fluorescence probe, and quantum yield is
4.5%.
Embodiment 2
10mL 4mmol/L aqueous solution of chloraurate is heated to 120 DEG C, then by 1mL 5mmol/L 2- sulfydryl -4- methyl -
5- thiazolyl acetic acid aqueous solutions are added to above-mentioned aqueous solution of chloraurate and continuous heating stirring 30min, you can obtain gold nano fluorescence
Probe.Strong blue-fluorescence is presented near 430nm in the fluorescence emission peak of the gold nano fluorescence probe, and quantum yield is
3.5%.
Embodiment 3
1mL 4mmol/L aqueous solution of chloraurate is heated to 110 DEG C, then by 5mL 5mmol/L 2- sulfydryl -4- methyl -5-
Thiazolyl acetic acid aqueous solution is added to above-mentioned aqueous solution of chloraurate and continuous heating stirring 20min, you can obtains the spy of gold nano fluorescence
Needle.Strong blue-fluorescence is presented near 430nm in the fluorescence emission peak of the gold nano fluorescence probe, and quantum yield is
2.7%.
Embodiment 4
3mL 4mmol/L aqueous solution of chloraurate is heated to 90 DEG C, then by 3mL 5mmol/L 2- sulfydryl -4- methyl -5-
Thiazolyl acetic acid aqueous solution is added to above-mentioned aqueous solution of chloraurate and continuous heating stirring 5min, you can obtains the spy of gold nano fluorescence
Needle.Strong blue-fluorescence is presented near 430nm in the fluorescence emission peak of the gold nano fluorescence probe, and quantum yield is
3.3%.
Embodiment 5
5mL 4mmol/L aqueous solution of chloraurate is heated to 80 DEG C, then by 4mL 5mmol/L 2- sulfydryl -4- methyl -5-
Thiazolyl acetic acid aqueous solution is added to above-mentioned aqueous solution of chloraurate and continuous heating stirring 10min, you can obtains the spy of gold nano fluorescence
Needle.Strong blue-fluorescence is presented near 430nm in the fluorescence emission peak of the gold nano fluorescence probe, and quantum yield is
3.0%.
Embodiment 6
9mL 4mmol/L aqueous solution of chloraurate is heated to 100 DEG C, then by 4mL 5mmol/L 2- sulfydryl -4- methyl -5-
Thiazolyl acetic acid aqueous solution is added to above-mentioned aqueous solution of chloraurate and continuous heating stirring 20min, you can obtains the spy of gold nano fluorescence
Needle.Strong blue-fluorescence is presented near 430nm in the fluorescence emission peak of the gold nano fluorescence probe, and quantum yield is
4.3%.
Embodiment 7
7mL 3mmol/L aqueous solution of chloraurate is heated to 100 DEG C, then by 3mL 6mmol/L 2- sulfydryl -4- methyl -5-
Thiazolyl acetic acid aqueous solution is added to above-mentioned aqueous solution of chloraurate and continuous heating stirring 30min, you can obtains the spy of gold nano fluorescence
Needle.Strong blue-fluorescence is presented near 430nm in the fluorescence emission peak of the gold nano fluorescence probe, and quantum yield is
3.6%.
Embodiment 8
7mL 5mmol/L aqueous solution of chloraurate is heated to 100 DEG C, then by 5mL 4mmol/L 2- sulfydryl -4- methyl -5-
Thiazolyl acetic acid aqueous solution is added to above-mentioned aqueous solution of chloraurate and continuous heating stirring 20min, you can obtains the spy of gold nano fluorescence
Needle.Strong blue-fluorescence is presented near 430nm in the fluorescence emission peak of the gold nano fluorescence probe, and quantum yield is
3.4%.
Embodiment 9
Phosphate buffer solution (the 10mmol/ of gold nano fluorescence probe solution (200 μ L) and 2.5mL prepared by embodiment 1
L it) is added in fluorescence cuvette, is separately added into the Fe of 10 μ L 0.5mmol/L again in above-mentioned fluorescence cuvette3+With 10 μ L
Other cation K of 1mol/L+,Na+,Li+,Ni+,Zn2+,Mn2+,Ba2+,Ca2+,Cd2+,Mg2+,Pb2+,Co2+,Hg2+,Cu2+,
Fe2+,Al3+,Cr3+Solution surveys its fluorescence spectrum respectively, draws the block diagram that different ions correspond to fluorescence intensity at 430nm, sees
Fig. 3.The experiment proved that other cation not detections of the interference system to ferric ion.
Embodiment 10
Gold nano fluorescence probe solution (200 μ L) and phosphate buffer solution (2.5mL, 10mmol/ prepared by embodiment 1
L it) is added in fluorescence cuvette together, is separately added into the Fe of various concentration again in above-mentioned fluorescence cuvette3+Standard solution or
Solution to be measured measures its fluorescence spectrum using 350nm as excitation wavelength.With Fe3+The increase of concentration of standard solution, gold nano are glimmering
The fluorescence of light probe is gradually quenched, as shown in figure 4, variation and the Fe of fluorescence intensity3+Concentration it is in a linear relationship, fluorescence in figure
The variation of intensity is with I0/ I expressions, wherein I0Indicate fluorescence of the iron ion the absence and presence of lower gold nano fluorescence probe respectively with I
Intensity obtains Fe by linear fit3+Relative intensity of fluorescence (the I of concentration and gold nano fluorescence probe0/ I) it is good in two sections
Linear relationship, the range of linearity are respectively 9.9 × 10-9-3.0×10-6Mol/L (Y=1.06+0.171X, linear coefficient R2=
And 3.2 × 10 0.998)-6-1.1×10-3Mol/L (Y=1.68+0.00309X, linear coefficient R2=0.987), Fe3+Detection
It is limited to 3.3 × 10-9mol/L.The gold nano fluorescence probe can be applied to the detection of ferric ion in serum.
Claims (2)
1. a kind of preparation method of gold nano fluorescence probe, which is characterized in that completed by following steps：It, will in terms of volume parts
7-9 parts of 4mmol/L aqueous solution of chloraurate are heated to 100 DEG C, then by 2-4 parts of 5mmol/L 2- sulfydryl -4- methyl-5-thiazole acetic acid
Aqueous solution is added to above-mentioned aqueous solution of chloraurate and continuous heating stirring 20min is to get to gold nano fluorescence probe.
2. gold nano fluorescence probe prepared by method as described in claim 1 is applied in detecting ferric ion.
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| CN104215594A (en) * | 2014-09-15 | 2014-12-17 | 天津师范大学 | Method for detecting hazardous substance-thiourea by utilizing gold nanoparticles |
| CN105067601A (en) * | 2015-07-16 | 2015-11-18 | 重庆大学 | Functional test paper film based on nanogold and method for detecting iron ions |
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| CN103439267A (en) * | 2013-08-28 | 2013-12-11 | 中国科学院宁波材料技术与工程研究所 | Detection reagent combination and detection method of bivalent mercury ions |
| CN104215594A (en) * | 2014-09-15 | 2014-12-17 | 天津师范大学 | Method for detecting hazardous substance-thiourea by utilizing gold nanoparticles |
| CN105067601A (en) * | 2015-07-16 | 2015-11-18 | 重庆大学 | Functional test paper film based on nanogold and method for detecting iron ions |
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