CN109211849A - Dopamine detection method based on copper-zinc-tin-sulfur alloy quantum dot - Google Patents
Dopamine detection method based on copper-zinc-tin-sulfur alloy quantum dot Download PDFInfo
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- CN109211849A CN109211849A CN201710552117.4A CN201710552117A CN109211849A CN 109211849 A CN109211849 A CN 109211849A CN 201710552117 A CN201710552117 A CN 201710552117A CN 109211849 A CN109211849 A CN 109211849A
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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"
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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
- G01N21/6486—Measuring fluorescence of biological material, e.g. DNA, RNA, cells
Abstract
The present invention discloses the dopamine detection method based on copper-zinc-tin-sulfur alloy quantum dot, copper-zinc-tin-sulfur alloy quantum dot uses the less toxic metal salt compound of mantoquita, zinc salt, tin salt, high molecular polymer is as cladding stabilizer, thiocarbamide is added dropwise and synthesizes copper-zinc-tin-sulfur alloy quantum dot under hydrothermal conditions, increase with the ratio of covering, launch wavelength gradually can shift to blue region and visible light region from ultraviolet region.When carrying out dopamine detection, using copper-zinc-tin-sulfur alloy quantum dot as fluorescent marker, dopamine and quantum dot are acted on, so that the fluorescence intensity of detection architecture is quenched, i.e. linear quenching relationship is presented in dopamine concentration and fluorescence intensity, and dopamine concentration can be obtained in contrast standard curve.
Description
Technical field
The invention belongs to technical field of biological, more particularly to one kind prepares copper zinc under hydrothermal conditions
The method of tin sulphur (CZTS) alloy quantum dot and dopamine detection method based on copper-zinc-tin-sulfur alloy quantum dot.
Background technique
Since 1970s, people have just fallen in focus on semiconductor nano, have been applied to crowd so far
It is multi-field.Quantum dot is provided with many special natures, such as unique optically and electrically property due to its nanoscale dimensional effect
Matter.Just because of these unique light, electrical properties, so that quantum dot becomes a kind of research tool in the ascendant.Originally people
Wish that quantum computer is made in the special nature that can use quantum dot, but never very big breakthrough.People again will later
Quantum dot is applied to biological field, but since quantum dot preparation at that time is difficult, synthesis condition is harsh, and quantum dot fluorescence yield
It is low, it is not easy in conjunction with biomolecule, so having no significant results.With continuously attempting to for researchers, the synthetic method of quantum dot
It continues to optimize, various bio-imaging marker research can be applied not only to by the quantum dot of synthesis in water, ground in life science
The future for studying carefully aspect is even more limitless.Alloy quantum dot can change its internal structure by adjusting each component content, reach
To the purpose for changing its fluorescence emission wavelengths, that is, launch the fluorescence of different colours.According to previous report, alloy quantum dot
Fluorescence intensity and efficiency and common quantum dot are similar, it might even be possible to be more than common quantum dot.
Dopamine belongs to one of biological source catecholamine, is that main endogenous neural is passed in central nervous system
Matter.The level of dopamine and the locomitivity of animal are closely related in brain, and also participation intraocular pressure and retinal information transmit
Regulation.The excess of dopamine usually causes happiness and excitement in mood in brain, and the shortage of dopamine may be led in brain
Cause Parkinson's disease and schizophrenia.So far, there are many methods that can carry out quantitative detection to dopamine, such as electrification
It learns, chemiluminescence, high performance liquid chromatography, Capillary Electrophoresis etc..However, the above method has a little drawback, set needed for having
Standby costly some operating process are complicated, and some is related to the use of high poison drug.Therefore, it needs to develop one urgently at present
Kind is quickly, easy, low cost, and high sensitivity detects Dopamine in biological fluids with selective strong method.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide the dopamines based on copper-zinc-tin-sulfur alloy quantum dot
Detection method, this method low toxicity, good water solubility, quantum efficiency is high, and good biocompatibility is low in cost, and step is simple, to operation
Personnel and instrument and equipment require low.
Technical purpose of the invention is achieved by following technical proposals:
Dopamine detection method based on copper-zinc-tin-sulfur alloy quantum dot, with H3PO4-HAc-H3BO3Buffered aqueous solution, copper
Zinc-tin sulphur alloy quantum dot solution and testing sample solution form dopamine detection architecture, detect its fluorescence using fluophotometer
The fluorescence intensity of intensity, detection architecture declines with the increase of dopamine concentration in detection architecture, i.e., outlet is presented in fluorescence intensity
Property quenching relationship；Contrast standard curve is determined to get the concentration of the dopamine into detection architecture using copper-zinc-tin-sulfur alloy quantum dot
Amount detection dopamine 0.2-300 it is micro- rub/liter in the range of fluorescence be linearly quenched, Fitting equations y=782.572-
3.821x+0.007x2,R2=0.985；Y is the fluorescence intensity of detection architecture, and x is dopamine concentration in detection architecture, minimum inspection
Rising limit is 92nmol/L.
In above-mentioned detection method, in obtaining detection architecture after dopamine concentration, it is according to the composition of detection architecture
The concentration of dopamine in testing sample solution can be conversed.
In above-mentioned detection method, 50-400 μ L copper-zinc-tin-sulfur alloy quantum dot solution, copper are sequentially added into centrifuge tube
The concentration of zinc-tin sulphur alloy quantum dot is 1-5mmol/L；The H that 100-1000 μ L 0.04mol/L pH is 123PO4-HAc-
H3BO3After mixing, 40 μ L testing sample solutions are added, then increase pure water and be settled to 4mL in buffer solution thereto, sufficiently mixed
It closes, stands 50-and detected after sixty minutes with sepectrophotofluorometer.
In above-mentioned detection method, preferably copper-zinc-tin-sulfur alloy quantum dot solution is 200 μ L, copper-zinc-tin-sulfur alloy quantum dot
Concentration be 1mmol/L, H3PO4-HAc-H3BO3Buffer solution is 200 μ L, 40 μ L testing sample solutions, then increase pure water constant volume
To 4mL.
In above-mentioned detection method, the excitation wavelength used is 300-500 nanometers；Preferably, excitation wavelength is 345-
355 nanometers；The wavelength of fluorescence emission peak is 400-600 nanometers；Preferably, the wavelength of fluorescence emission peak is 460-465 nanometers.
The copper-zinc-tin-sulfur alloy quantum dot is prepared as steps described below using hydrothermal preparing process:
Step 1, according to copper zinc-tin molar ratio (the mass ratio of the material) 2:1:1, mantoquita, zinc salt, tin salt are dispersed in
Dispersion is formed in solvent, the solvent is made of water and resolvability macromolecule, and resolvability macromolecule is steady as cladding
Determine agent；
In step 1, the concentration range of copper ion is 0.01-0.1mol/L.
In step 1, mantoquita is one of copper chloride, copper nitrate, copper sulphate or copper acetate.
In step 1, zinc salt is one of zinc chloride, zinc nitrate, zinc sulfate or zinc acetate.
In step 1, tin salt is one of stannous chloride, nitric acid stannous, stannous sulfate or stannous acetate.
In step 1, the high molecular dosage of resolvability is 0.0008-0.6 mass parts, and water is 8-10 parts by volume, often
One mass parts are 1g, and each parts by volume is 1mL.
In step 1, resolvability macromolecule is the macromolecule polyalcohol containing amino or carboxyl, such as polyethyleneimine
Amine, polyethylene glycol, one of polyacrylic acid, number-average molecular weight is 10000 hereinafter, such as number-average molecular weight is quantity up to a hundred
Grade, such as 200-800, preferably 400-600；Number-average molecular weight is thousands of order of magnitude, such as 1000-8000, preferably 1000-
2000。
Step 2, the aqueous solution of thiocarbamide is added into the dispersion of step 1 and is uniformly dispersed, forms Cu2+、Zn2+、Sn2+、
S and the high molecular dispersion of resolvability；The molar ratio of thiocarbamide and copper ion is at least 2:1；
In step 2, using the aqueous solution that thiocarbamide is added is added dropwise, speed is 1-5ml per minute.
In step 2, it is uniformly dispersed using mechanical stirring mode, mixing speed is 100-200 turns per minute.
In step 2, the molar ratio of thiocarbamide and copper ion is (2-5): 1.
Step 3, dispersion step 2 formed is passed through inert gas, to be transferred in reaction kettle after removing dissolved oxygen,
Water-soluble copper-zinc-tin-sulfur alloy quantum dot solution can be obtained in reaction under 160-200 degrees Celsius.
In step 3, inert gas is nitrogen, helium or argon gas, and being passed through the time is 15-30min.
In step 3, it is reacted 6-48 hours under 180-200 degrees Celsius.
After copper-zinc-tin-sulfur alloy quantum dot solution is prepared, yellow solution is presented in solution, can pass through drying mode
Obtain quantum dot (macroscopic observation is not powder, but is presented similar gluey), can again it is evenly dispersed in water.When being detected,
Water-soluble copper-zinc-tin-sulfur alloy quantum dot (water) solution that step 3 obtains can be used directly, calculating step is carried out according to ingredient proportion
The concentration of quantum dot in rapid 3 obtained solution calculates the quantum dot in final detection architecture further according to the composition of detection architecture
Concentration.
In the technical solution of the present invention, 160-200 DEG C of temperature provides in hydro-thermal reaction to generate copper zincium tin sulfur compound
Condition, the molar ratio of copper-zinc-tin-sulfur is 2:1:1:4 in feeding intake, and wherein elementary sulfur is kept slightly excessive, same after addition system
When embody reduction and chanza so that four kinds of elements keep stable molar ratio to generate Cu2Zn1Sn1S4, in nitrogen protection
In the state of, it eliminates dissolved oxygen and various metal salts is made to will not be oxidized and alloy cpd can be generated.The addition of PEI is appropriate
The growth size for controlling alloy cpd, on the one hand, PEI is as stabilizer, so that the alloy cpd nanoparticle generated
Retain between son must spacing, to realize its Quantum Properties with fluorescence property, on the other hand, PEI as covering,
So that quantum dot surface has amino as active function groups, it is able to achieve the good combination with other substances.
It is characterized using quantum dot of the TEM to preparation, the novel quantum dot synthesized as we know from the figure, size uniformity, shape
Shape is subsphaeroidal, and particle size is 2 ± 0.5nm；(instrument model: UV-2600 is characterized using ultraviolet specrophotometer；Production
Company: Japanese Shimadzu Corporation), it can illustrate that the novel quantum dot synthesized has UV absorption in 345-355nm by figure, this and its
Fluorescence exciting wavelength is consistent, and emits fluorescence at 460-465nm after being excited.It is characterized with FTIR, by right
Novel quantum dot surface than can be seen that synthesis is coated with polyethyleneimine, i.e. amino is its active group, illustrates solubility
Macromolecule, which successfully coats, stablizes quantum dot, and functional group (amino, hydroxyl or carboxyl) is active group.
Compared with prior art, the present invention provides a kind of hydrophily copper zinc-tins that can be directly synthesized in aqueous solution
The method of sulphur (CZTS) quantum dot.Copper-zinc-tin-sulfur is widely used in solar battery film material, but be rarely reported at present by
It regulates and controls synthesis and uses as quantum dot.Synthetic method provided by the invention is low in cost, and step is simple, to operator and instrument
Device equipment requirement is low, obtained copper-zinc-tin-sulfur quantum dot stable homogeneous, low toxicity, good water solubility, quantum efficiency height, biocompatibility
It well, is a kind of good fluorescent marker.
Water-soluble copper-zinc-tin-sulfur (CZTS) conjunction is made in the water-soluble inorganic salt of present invention copper, zinc and stannous in water phase
Golden quantum dot.The method of the present invention is low in cost, and step is simple, low to operator and instrument and equipment requirement, extensive for after
It is synthetically prepared and provides possibility.Synthesize obtained copper-zinc-tin-sulfur quantum dot stable homogeneous, low toxicity, good water solubility, quantum efficiency it is high,
Good biocompatibility is a kind of good fluorescent marker.A kind of label-free, the literalness alloy amount of utilization provided by the invention
Method of the son point as fluorescence probe detection dopamine, this method utilize showing for specificity quenching of the dopamine to the quantum dot
As, by preparing specific fluorescence probe, realize it is label-free can quantitative detection dopamine purpose, high sensitivity, accuracy
Height has good application prospect in the detection of various actual samples.
Detailed description of the invention
Fig. 1 is transmission electron microscope (TEM) photo of the water-soluble copper-zinc-tin-sulfur alloy quantum dot of technical solution of the present invention preparation.
Fig. 2 is the UV absorption figure of the water-soluble copper-zinc-tin-sulfur alloy quantum dot of technical solution of the present invention preparation.
Fig. 3 is the Fourier of water-soluble the copper-zinc-tin-sulfur alloy quantum dot and polyethyleneimine of technical solution of the present invention preparation
Transform infrared spectroscopy figure (FTIR).
Fig. 4 is the fluorescence Spectra that the water-soluble copper-zinc-tin-sulfur alloy quantum dot of the present invention optimizes heating duration in the synthesis process
Figure.
Fig. 5 be the water-soluble copper-zinc-tin-sulfur alloy quantum dot of the present invention in the synthesis process, it is glimmering with the difference of PEI additional amount
The spectrogram of light emitting wavelength change.
Fig. 6 is the fluorescent quenching schematic diagram that dopamine is detected using copper-zinc-tin-sulfur alloy quantum dot.
Fig. 7 is the linear graph (i.e. standard curve) using copper-zinc-tin-sulfur alloy quantum dot quantitative detection dopamine of the present invention,
Abscissa is the concentration of dopamine in detection architecture, and ordinate is the fluorescence intensity of detection architecture.
Fig. 8 is alloy quantum dot solution after the dopamine of various concentration is added in copper-zinc-tin-sulfur alloy quantum dot solution
The visible figure of the naked eye that color is gradually deepened.
Fig. 9 is after the different material of same concentrations is added in copper-zinc-tin-sulfur alloy quantum dot solution, and alloy quantum dot is molten
The result of variations schematic diagram of liquid fluorescence intensity.
Specific embodiment
By the description carried out with reference to the accompanying drawing to its exemplary embodiment, features described above and advantage of the present invention will become
It must be more clear and be readily appreciated that.Below with reference to specific example, invention is further described in detail.Height of the present invention
In water resources key lab of Tianjin Normal University (externally on sale), polyethyleneimine is bought in Beijing for pure water purchase
Mike's woods biological reagent Co., Ltd, other inorganic reagents are bought in Tianjin Ke Wei Co., Ltd.It is filled using mechanical stirring
It sets and is dispersed, mixing speed is 150 turns per minute.
The preparation of embodiment 1-water solubility copper-zinc-tin-sulfur (CZTS) quantum dot is divided into following steps:
A. the polyethyleneimine (PEI, number-average molecular weight 10000) that 0.0008g is weighed under 20 degrees celsius of room temperature is dissolved in
As the solvent of salting liquid in 9mL water；
B. the mass ratio of the material for taking copper zinc-tin is 2:1:1, and copper chloride, zinc chloride, stannous chloride are dissolved in above-mentioned solution, filled
Divide stirring, is allowed to be uniformly dispersed in solution, is prepared and contains Cu simultaneously2+、Zn2+、Sn2+Solution, wherein copper ion
Concentration range is 0.04mol/L；
C. the aqueous solution that thiocarbamide is slowly added in system, 5ml per minute are stated then up, and thiocarbamide rubs with what copper ion was added
You form Cu after being sufficiently stirred than being 2:12+、Zn2+、Sn2+With the complex of polymer P EI and good be dispersed in solution
In；
D. above-mentioned solution is led to nitrogen 15 minutes, is transferred in reaction kettle after removing dissolved oxygen, is heated under the conditions of 180 DEG C of temperature
48 hours, water-soluble copper-zinc-tin-sulfur alloy quantum dot solution can be obtained.
The preparation of embodiment 2-water solubility copper-zinc-tin-sulfur (CZTS) quantum dot is divided into following steps:
A. the polyethyleneimine (PEI, number-average molecular weight 10000) that 0.2058g is weighed under 20 degrees celsius of room temperature is dissolved in
As the solvent of salting liquid in 9mL water；
B. the mass ratio of the material for taking copper zinc-tin is 2:1:1, and copper nitrate, zinc nitrate, nitric acid stannous are dissolved in above-mentioned solution, filled
Divide stirring, is allowed to be uniformly dispersed in solution, is prepared and contains Cu simultaneously2+、Zn2+、Sn2+Solution, wherein copper ion
Concentration range is 0.04mol/L；
C. the aqueous solution that thiocarbamide is slowly added in system, 5ml per minute are stated then up, and thiocarbamide rubs with what copper ion was added
You form Cu after being sufficiently stirred than being 2:12+、Zn2+、Sn2+With the complex of polymer P EI and good be dispersed in solution
In；
D. above-mentioned solution is led to nitrogen 15 minutes, is transferred in reaction kettle after removing dissolved oxygen, is heated under the conditions of 180 DEG C of temperature
48 hours, water-soluble copper-zinc-tin-sulfur alloy quantum dot solution can be obtained.
The preparation of embodiment 3-water solubility copper-zinc-tin-sulfur (CZTS) quantum dot is divided into following steps:
A. the polyethyleneimine (PEI, number-average molecular weight 10000) that 0.3860g is weighed under 20 degrees celsius of room temperature is dissolved in
As the solvent of salting liquid in 9mL water；
B. the mass ratio of the material for taking copper zinc-tin is 2:1:1, and copper sulphate, zinc sulfate, stannous sulfate are dissolved in above-mentioned solution, filled
Divide stirring, is allowed to be uniformly dispersed in solution, is prepared and contains Cu simultaneously2+、Zn2+、Sn2+Solution, wherein copper ion
Concentration range is 0.04mol/L；
C. the aqueous solution that thiocarbamide is slowly added in system, 5ml per minute are stated then up, and thiocarbamide rubs with what copper ion was added
You form Cu after being sufficiently stirred than being 2:12+、Zn2+、Sn2+With the complex of polymer P EI and good be dispersed in solution
In；
D. above-mentioned solution is led to nitrogen 15 minutes, is transferred in reaction kettle after removing dissolved oxygen, is heated under the conditions of 180 DEG C of temperature
48 hours, water-soluble copper-zinc-tin-sulfur alloy quantum dot solution can be obtained.
The preparation of embodiment 4-water solubility copper-zinc-tin-sulfur (CZTS) quantum dot is divided into following steps:
A. the polyethyleneimine (PEI, number-average molecular weight 10000) that 0.4280g is weighed under 20 degrees celsius of room temperature is dissolved in
As the solvent of salting liquid in 9mL water；
B. the mass ratio of the material for taking copper zinc-tin is 2:1:1, and copper acetate, zinc acetate, stannous acetate are dissolved in above-mentioned solution, filled
Divide stirring, is allowed to be uniformly dispersed in solution, is prepared and contains Cu simultaneously2+、Zn2+、Sn2+Solution, wherein copper ion
Concentration range is 0.04mol/L；
C. the aqueous solution that thiocarbamide is slowly added in system, 5ml per minute are stated then up, and thiocarbamide rubs with what copper ion was added
You form Cu after being sufficiently stirred than being 2:12+、Zn2+、Sn2+With the complex of polymer P EI and good be dispersed in solution
In；
D. above-mentioned solution is led to nitrogen 15 minutes, is transferred in reaction kettle after removing dissolved oxygen, is heated under the conditions of 180 DEG C of temperature
48 hours, water-soluble copper-zinc-tin-sulfur alloy quantum dot solution can be obtained.
The preparation of embodiment 5-water solubility copper-zinc-tin-sulfur (CZTS) quantum dot is divided into following steps:
A. the polyethyleneimine (PEI, number-average molecular weight 10000) that 0.5640g is weighed under 20 degrees celsius of room temperature is dissolved in
As the solvent of salting liquid in 9mL water；
B. the mass ratio of the material for taking copper zinc-tin is 2:1:1, and copper acetate, zinc sulfate, nitric acid stannous are dissolved in above-mentioned solution, filled
Divide stirring, is allowed to be uniformly dispersed in solution, is prepared and contains Cu simultaneously2+、Zn2+、Sn2+Solution, wherein copper ion
Concentration range is 0.04mol/L；
C. the aqueous solution that thiocarbamide is slowly added in system, 5ml per minute are stated then up, and thiocarbamide rubs with what copper ion was added
You form Cu after being sufficiently stirred than being 2:12+、Zn2+、Sn2+With the complex of polymer P EI and good be dispersed in solution
In；
D. above-mentioned solution is led to nitrogen 15 minutes, is transferred in reaction kettle after removing dissolved oxygen, is heated under the conditions of 180 DEG C of temperature
48 hours, water-soluble copper-zinc-tin-sulfur alloy quantum dot solution can be obtained.
The preparation of embodiment 6-water solubility copper-zinc-tin-sulfur (CZTS) quantum dot is divided into following steps:
A. the polyethyleneimine (PEI, number-average molecular weight 10000) that 0.5640g is weighed under 25 degrees celsius of room temperature is dissolved in
As the solvent of salting liquid in 9mL water；
B. the mass ratio of the material for taking copper zinc-tin is 2:1:1, and copper chloride, zinc sulfate, nitric acid stannous are dissolved in above-mentioned solution, filled
Divide stirring, is allowed to be uniformly dispersed in solution, is prepared and contains Cu simultaneously2+、Zn2+、Sn2+Solution, wherein copper ion
Concentration range is 0.04mol/L；
C. the aqueous solution that thiocarbamide is slowly added in system, 3ml per minute are stated then up, and thiocarbamide rubs with what copper ion was added
You form Cu after being sufficiently stirred than being 2:12+、Zn2+、Sn2+With the complex of polymer P EI and good be dispersed in solution
In；
D. above-mentioned solution is led to nitrogen 30 minutes, is transferred in reaction kettle after removing dissolved oxygen, is heated under the conditions of 180 DEG C of temperature
48 hours, water-soluble copper-zinc-tin-sulfur alloy quantum dot solution can be obtained.
The preparation of embodiment 7-water solubility copper-zinc-tin-sulfur (CZTS) quantum dot is divided into following steps:
A. the polyethyleneimine (PEI, number-average molecular weight 10000) that 0.5640g is weighed under 25 degrees celsius of room temperature is dissolved in
As the solvent of salting liquid in 9mL water；
B. the mass ratio of the material for taking copper zinc-tin is 2:1:1, and copper chloride, zinc sulfate, nitric acid stannous are dissolved in above-mentioned solution, filled
Divide stirring, is allowed to be uniformly dispersed in solution, is prepared and contains Cu simultaneously2+、Zn2+、Sn2+Solution, wherein copper ion
Concentration range is 0.04mol/L；
C. the aqueous solution that thiocarbamide is slowly added in system, 3ml per minute are stated then up, and thiocarbamide rubs with what copper ion was added
You form Cu after being sufficiently stirred than being 2:12+、Zn2+、Sn2+With the complex of polymer P EI and good be dispersed in solution
In；
D. above-mentioned solution is led to nitrogen 30 minutes, is transferred in reaction kettle after removing dissolved oxygen, is heated under the conditions of 180 DEG C of temperature
7 hours, water-soluble copper-zinc-tin-sulfur alloy quantum dot solution can be obtained.
The preparation of embodiment 8-water solubility copper-zinc-tin-sulfur (CZTS) quantum dot is divided into following steps:
A. the polyethyleneimine (PEI, number-average molecular weight 10000) that 0.5640g is weighed under 25 degrees celsius of room temperature is dissolved in
As the solvent of salting liquid in 9mL water；
B. the mass ratio of the material for taking copper zinc-tin is 2:1:1, and copper chloride, zinc sulfate, nitric acid stannous are dissolved in above-mentioned solution, filled
Divide stirring, is allowed to be uniformly dispersed in solution, is prepared and contains Cu simultaneously2+、Zn2+、Sn2+Solution, wherein copper ion
Concentration range is 0.04mol/L；
C. the aqueous solution that thiocarbamide is slowly added in system, 3ml per minute are stated then up, and thiocarbamide rubs with what copper ion was added
You form Cu after being sufficiently stirred than being 2:12+、Zn2+、Sn2+With the complex of polymer P EI and good be dispersed in solution
In；
D. above-mentioned solution is led to nitrogen 30 minutes, is transferred in reaction kettle after removing dissolved oxygen, is heated under the conditions of 180 DEG C of temperature
15 hours, water-soluble copper-zinc-tin-sulfur alloy quantum dot solution can be obtained.
The preparation of embodiment 9-water solubility copper-zinc-tin-sulfur (CZTS) quantum dot is divided into following steps:
A. the polyethyleneimine (PEI, number-average molecular weight 10000) that 0.5640g is weighed under 25 degrees celsius of room temperature is dissolved in
As the solvent of salting liquid in 9mL water；
B. the mass ratio of the material for taking copper zinc-tin is 2:1:1, and copper chloride, zinc sulfate, nitric acid stannous are dissolved in above-mentioned solution, filled
Divide stirring, is allowed to be uniformly dispersed in solution, is prepared and contains Cu simultaneously2+、Zn2+、Sn2+Solution, wherein copper ion
Concentration range is 0.04mol/L；
C. the aqueous solution that thiocarbamide is slowly added in system, 3ml per minute are stated then up, and thiocarbamide rubs with what copper ion was added
You form Cu after being sufficiently stirred than being 2:12+、Zn2+、Sn2+With the complex of polymer P EI and good be dispersed in solution
In；
D. above-mentioned solution is led to nitrogen 30 minutes, is transferred in reaction kettle after removing dissolved oxygen, is heated under the conditions of 180 DEG C of temperature
30 hours, water-soluble copper-zinc-tin-sulfur alloy quantum dot solution can be obtained.
In the above-described embodiments, the mode for increasing cladding stabilizer additional amount and extending the hydro-thermal reaction time is respectively adopted,
Investigate variation-(1) in relation to luminescent properties and increase cladding stabilizer (i.e. resolvability macromolecule) additional amount, quantum dot it is glimmering
Light emitting wavelength location is added from ultraviolet region to blue visible light area (395nm-465nm) by adjusting cladding stabilizer
The mode of amount regulates and controls the luminous position of copper-zinc-tin-sulfur alloy quantum dot (from ultraviolet region to blue visible light area)；(2) extend water
Thermal response time, the luminous intensity enhancing of quantum dot can regulate and control copper-zinc-tin-sulfur conjunction by way of adjusting the hydro-thermal reaction time
The luminous intensity of golden quantum dot.
Selectivity of the examination copper-zinc-tin-sulfur alloy quantum dot to dopamine first
(1) 0.04mol/L, 25 DEG C, the H of pH=12.003PO4-HAc-H3BO3The configuration of buffer solution: 100mL is 1. made
The mixed liquor of phosphoric acid, three kinds of acid of boric acid and acetic acid (concentration is 0.04mol/L)；2. the hydroxide of different volumes is added thereto
Sodium solution (concentration 0.2mol/L)；3. being stored in after its pH is adjusted to 12.00 using acidometer in refrigerator stand-by.
(2) 200 μ L copper-zinc-tin-sulfur alloy quantum dot solution, 200 μ L 0.04mol/L are sequentially added into centrifuge tube
H3PO4-HAc-H3BO3After mixing, the dopamine of 40 μ L same concentrations, threonine, methionine, bright is added in solution thereto
Propylhomoserin, isoleucine, histidine, lysine, then increase pure water and be settled to 4mL.It is sufficiently mixed, stands after sixty minutes with fluorescence point
Light photometer is detected.As seen from Figure 9, fluorescence probe (copper-zinc-tin-sulfur alloy quantum dot) of the present invention has dopamine
There is specific recognition.
See that copper-zinc-tin-sulfur alloy quantum dot is directed to the fluorescence intensity of various concentration dopamine again
(1) 0.04mol/L, 25 DEG C, the H of pH=12.003PO4-HAc-H3BO3The configuration of buffer solution: 100mL is 1. made
The mixed liquor of phosphoric acid, three kinds of acid of boric acid and acetic acid (concentration is 0.04mol/L)；2. the hydroxide of different volumes is added thereto
Sodium solution (concentration 0.2mol/L)；3. being stored in after its pH is adjusted to 12.00 using acidometer in refrigerator stand-by.
(2) 200 μ L copper-zinc-tin-sulfur alloy quantum dot solution, 200 μ L 0.04mol/L are sequentially added into centrifuge tube
H3PO4-HAc-H3BO3After mixing, the dopamine of 40 μ L various concentrations is added in solution thereto, then increases pure water and be settled to
4mL.It is sufficiently mixed, standing is detected with sepectrophotofluorometer after sixty minutes.As shown in attached drawing 6 and 8, with dopamine concentration
Increase, quantum dot fluorescence intensity gradually decreases, and after the dopamine of various concentration is added, alloy quantum dot solution colour gradually adds
It is deep.
It is carried out respectively below by adjustment buffering (water) solution ph, quantum dot solution additional amount (preparation of embodiment 6)
Quantitative detection dopamine standard curve establishes the condition for carrying out optimizing detection dopamine:
Embodiment 1
(1) 0.04mol/L, 25 DEG C, the H of pH=6.003PO4-HAc-H3BO3The configuration of buffer solution: 100mL is 1. made
The mixed liquor of phosphoric acid, three kinds of acid of boric acid and acetic acid (concentration is 0.04mol/L)；2. the hydroxide of different volumes is added thereto
Sodium water solution (concentration 0.2mol/L)；3. being stored in after its pH is adjusted to 6.00 using acidometer in refrigerator stand-by.
(2) 200 μ L copper-zinc-tin-sulfur alloy quantum dot solution, 200 μ L0.04mol/L H are sequentially added into centrifuge tube3PO4-
HAc-H3BO3After mixing, 40 a series of gradient concentrations of μ L (100nM-50 μM) dopamine solutions are added in solution thereto, then
Increase pure water and is settled to 4mL.It is sufficiently mixed, standing is detected with sepectrophotofluorometer after sixty minutes.
(3) using aqueous dopamine solution concentration as abscissa, the fluorescence intensity of the mixed solution measured is ordinate, is established more
Standard curve bar between amine concentration and fluorescence intensity.
Embodiment 2
(1) 0.04mol/L, 25 DEG C, the H of pH=12.003PO4-HAc-H3BO3The configuration of buffer solution: 100mL is 1. made
The mixed liquor of phosphoric acid, three kinds of acid of boric acid and acetic acid (concentration is 0.04mol/L)；2. the hydroxide of different volumes is added thereto
Sodium solution (concentration 0.2mol/L)；3. being stored in after its pH is adjusted to 12.00 using acidometer in refrigerator stand-by.
(2) 50 μ L copper-zinc-tin-sulfur alloy quantum dot solution, 200 μ L 0.04mol/L H are sequentially added into centrifuge tube3PO4-
HAc-H3BO3After mixing, 40 a series of gradient concentrations of μ L (100nM-50 μM) dopamine solutions are added in solution thereto, then
Increase pure water and is settled to 4mL.It is sufficiently mixed, standing is detected with sepectrophotofluorometer after forty minutes.
(3) using aqueous dopamine solution concentration as abscissa, the fluorescence intensity of the mixed solution measured is ordinate, is established more
Standard curve bar between amine concentration and fluorescence intensity.
Embodiment 3
(1) 0.04mol/L, 25 DEG C, the H of pH=12.003PO4-HAc-H3BO3The configuration of buffer solution: 100mL is 1. made
The mixed liquor of phosphoric acid, three kinds of acid of boric acid and acetic acid (concentration is 0.04mol/L)；2. the hydroxide of different volumes is added thereto
Sodium solution (concentration 0.2mol/L)；3. being stored in after its pH is adjusted to 12.00 using acidometer in refrigerator stand-by.
(2) 200 μ L copper-zinc-tin-sulfur alloy quantum dot solution, 1000 μ L 0.04mol/L are sequentially added into centrifuge tube
H3PO4-HAc-H3BO3After mixing, it is molten that 40 a series of gradient concentrations of μ L (100nM-50 μM) dopamines are added in solution thereto
Liquid, then increase pure water and be settled to 4mL.It is sufficiently mixed, is detected after standing 50 minutes with sepectrophotofluorometer.
(3) using aqueous dopamine solution concentration as abscissa, the fluorescence intensity of the mixed solution measured is ordinate, is established more
Standard curve bar between amine concentration and fluorescence intensity.
Embodiment 4
(1) 0.04mol/L, 25 DEG C, the H of pH=12.003PO4-HAc-H3BO3The configuration of buffer solution: 100mL is 1. made
The mixed liquor of phosphoric acid, three kinds of acid of boric acid and acetic acid (concentration is 0.04mol/L)；2. the hydroxide of different volumes is added thereto
Sodium solution (concentration 0.2mol/L)；3. being stored in after its pH is adjusted to 12.00 using acidometer in refrigerator stand-by.
(2) 200 μ L copper-zinc-tin-sulfur alloy quantum dot solution, 200 μ L 0.04mol/L are sequentially added into centrifuge tube
H3PO4-HAc-H3BO3After mixing, it is molten that 40 a series of gradient concentrations of μ L (100nM-50 μM) dopamines are added in solution thereto
Liquid, then increase pure water and be settled to 4mL.It is sufficiently mixed, standing is detected with sepectrophotofluorometer after sixty minutes.
(3) using aqueous dopamine solution concentration as abscissa, the fluorescence intensity of the mixed solution measured is ordinate, is established more
Standard curve bar between amine concentration and fluorescence intensity.
Optimized, above-described embodiment 1-4 can be achieved to detect for the standard curve of dopamine, it is contemplated that fluorescence intensity
Detection need, it is contemplated that H3PO4-HAc-H3BO3The pH of buffer solution is 12, and copper-zinc-tin-sulfur alloy quantum dot solution is 200 μ
L, stand 50-60min, standard curve is as shown in Fig. 7, in detection architecture the concentration of dopamine 0.2-300 it is micro- rub/liter
(being quenched) linearly is quenched in range, Fitting equations y=782.572-3.821x+0.007x2,R2=0.985；Y is detection
The fluorescence intensity of system, x are dopamine concentration in detection architecture.By contrast standard curve, determine that fluorescence intensity is corresponding
After dopamine concentration, then pass through the dopamine concentration in the determining sample to be tested of detection architecture composition.
This patent is by state natural sciences fund general project 2137509, Tianjin " 131 " innovative talent cultivation work
The first hierarchical item of journey ZX110185, Tianjin Natural Science Fund In The Light youth's project 17JCQNJC05800 and Tianjin Normal University
The subsidy of doctor's fund project 52XB1510 and Tianjin Normal University transformation of scientific and technical result bonus items ZX0471601109.
The adjustment that preparation method is carried out according to the technological parameter that the content of present invention is recorded, can be achieved water-soluble copper zinc-tin
The preparation of sulphur alloy quantum dot and the detection of dopamine, and show almost the same performance.Example has been done to the present invention above
Property description, it should explanation, in the case where not departing from core of the invention, it is any it is simple deformation, modification or its
His those skilled in the art can not spend the equivalent replacement of creative work to each fall within protection scope of the present invention.
Claims (9)
1. the dopamine detection method based on copper-zinc-tin-sulfur alloy quantum dot, which is characterized in that with H3PO4-HAc-H3BO3Buffered water
Solution, copper-zinc-tin-sulfur alloy quantum dot solution and testing sample solution form dopamine detection architecture, are examined using fluophotometer
Its fluorescence intensity is surveyed, the fluorescence intensity of detection architecture declines with the increase of dopamine concentration in detection architecture, i.e. fluorescence intensity
Show linear quenching relationship；Contrast standard curve utilizes copper-zinc-tin-sulfur alloy to get the concentration of the dopamine into detection architecture
Quantum dot quantitative detection dopamine 0.2-300 it is micro- rub/liter in the range of fluorescence be linearly quenched, Fitting equations y=
782.572-3.821x+0.007x2,R2=0.985；Y is the fluorescence intensity of detection architecture, and x is that dopamine is dense in detection architecture
Degree, minimum detectability 92nmol/L；Copper-zinc-tin-sulfur alloy quantum dot size uniformity, shape is subsphaeroidal, particle size be 2 ±
0.5nm, zinc-tin sulphur alloy quantum dot solution are prepared as steps described below using hydrothermal preparing process:
Step 1, according to copper zinc-tin molar ratio (the mass ratio of the material) 2:1:1, mantoquita, zinc salt, tin salt are dispersed in solvent
Middle formation dispersion, the solvent are made of water and resolvability macromolecule, and resolvability macromolecule is as cladding stabilizer；
Step 2, the aqueous solution of thiocarbamide is added into the dispersion of step 1 and is uniformly dispersed, forms Cu2+、Zn2+、Sn2+, S with
The high molecular dispersion of resolvability；The molar ratio of thiocarbamide and copper ion is at least 2:1；
Step 3, dispersion step 2 formed is passed through inert gas, to be transferred in reaction kettle after removing dissolved oxygen,
Water-soluble copper-zinc-tin-sulfur alloy quantum dot solution can be obtained in reaction under 160-200 degrees Celsius.
2. the dopamine detection method according to claim 1 based on copper-zinc-tin-sulfur alloy quantum dot, which is characterized in that
50-400 μ L copper-zinc-tin-sulfur alloy quantum dot solution is sequentially added in centrifuge tube, the concentration of copper-zinc-tin-sulfur alloy quantum dot is 1-
5mmol/L；The H that 100-1000 μ L 0.04mol/L pH is 123PO4-HAc-H3BO3Buffer solution after mixing, thereto
40 μ L testing sample solutions are added, then increases pure water and is settled to 4mL, are sufficiently mixed, stands 50-and uses fluorescence spectrophotometer after sixty minutes
Photometer is detected.
3. the dopamine detection method according to claim 1 based on copper-zinc-tin-sulfur alloy quantum dot, which is characterized in that excellent
Selecting copper-zinc-tin-sulfur alloy quantum dot solution is 200 μ L, and the concentration of copper-zinc-tin-sulfur alloy quantum dot is 1mmol/L, H3PO4-HAc-
H3BO3Buffer solution is 200 μ L, 40 μ L testing sample solutions, then increase pure water and be settled to 4mL.
4. the dopamine detection method according to claim 1 based on copper-zinc-tin-sulfur alloy quantum dot, which is characterized in that make
Excitation wavelength is 300-500 nanometers；Preferably, excitation wavelength is 345-355 nanometers；The wavelength of fluorescence emission peak is
400-600 nanometers；Preferably, the wavelength of fluorescence emission peak is 460-465 nanometers.
5. the dopamine detection method according to claim 1 based on copper-zinc-tin-sulfur alloy quantum dot, which is characterized in that
In the step 1 of the preparation method of copper-zinc-tin-sulfur alloy quantum dot, the concentration range of copper ion is 0.01-0.1mol/L, and mantoquita is
One of copper chloride, copper nitrate, copper sulphate or copper acetate, zinc salt are one in zinc chloride, zinc nitrate, zinc sulfate or zinc acetate
Kind, tin salt is one of stannous chloride, nitric acid stannous, stannous sulfate or stannous acetate.
6. the dopamine detection method according to claim 1 based on copper-zinc-tin-sulfur alloy quantum dot, which is characterized in that
In the step 1 of the preparation method of copper-zinc-tin-sulfur alloy quantum dot, the high molecular dosage of resolvability is 0.0008-0.6 quality
Part, water is 8-10 parts by volume, and each mass parts are 1g, and each parts by volume is 1mL；Resolvability macromolecule be containing amino or
The macromolecule polyalcohol of carboxyl, such as polyethyleneimine, polyethylene glycol, one of polyacrylic acid, number-average molecular weight 10000
Hereinafter, such as number-average molecular weight is the order of magnitude up to a hundred, such as 200-800, preferably 400-600；Number-average molecular weight is thousands of
The order of magnitude, such as 1000-8000, preferably 1000-2000.
7. the dopamine detection method according to claim 1 based on copper-zinc-tin-sulfur alloy quantum dot, which is characterized in that
In the step 2 of the preparation method of copper-zinc-tin-sulfur alloy quantum dot, using the aqueous solution that thiocarbamide is added is added dropwise, speed is per minute
1—5ml；It is uniformly dispersed using mechanical stirring mode, mixing speed is 100-200 turns per minute；Thiocarbamide and copper ion
Molar ratio is (2-5): 1.
8. the dopamine detection method according to claim 1 based on copper-zinc-tin-sulfur alloy quantum dot, which is characterized in that
In the step 3 of the preparation method of copper-zinc-tin-sulfur alloy quantum dot, inert gas is nitrogen, helium or argon gas, and being passed through the time is
15—30min；It is reacted 6-48 hours under 180-200 degrees Celsius.
9. copper-zinc-tin-sulfur alloy quantum dot detection dopamine in application, which is characterized in that copper-zinc-tin-sulfur alloy quantum dot and
After testing sample solution effect, its fluorescence intensity is detected using fluophotometer, the fluorescence intensity of detection architecture is with detection architecture
The increase of middle dopamine concentration and decline, i.e., fluorescence intensity shows linear quenching relationship；Contrast standard curve to get arrive DOPA
The concentration of amine.
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