CN106959289B - A kind of electrogenerated chemiluminescence material, preparation method and application - Google Patents
A kind of electrogenerated chemiluminescence material, preparation method and application Download PDFInfo
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- CN106959289B CN106959289B CN201710172187.7A CN201710172187A CN106959289B CN 106959289 B CN106959289 B CN 106959289B CN 201710172187 A CN201710172187 A CN 201710172187A CN 106959289 B CN106959289 B CN 106959289B
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Abstract
The present invention provides a kind of electrogenerated chemiluminescence material, preparation method and application, which isThe cadmium telluride nanocrystal of the compound cladding of expression, preparation method include: the cadmium telluride nanocrystal for 1) preparing 3- mercaptopropionic acid cladding；2) the cadmium telluride nanocrystal coated using the 3- mercaptopropionic acid of preparation is prepared as template by ligand exchange reactionThe cadmium telluride nanocrystal of the compound cladding of expression.Electrogenerated chemiluminescence material of the invention is self-reinforcing type anodic electrochemiluminescence material; in the electrolytic solution without in the case where coreagent; also strong electrochemical luminescence signals can be generated; it not only avoids and introduces problem brought by coreagent in solution; the efficiency and performance of electrogenerated chemiluminescence can also effectively be enhanced; and preparation method of the invention is simple, efficient, convenient, low in cost, applied widely; scale application easy to accomplish; it is easy to industrial production, can applies to prepare in many nano materials.
Description
Technical field
The present invention relates to Electrochemiluminescprocess process field, especially a kind of electrogenerated chemiluminescence material, preparation method
And application.
Background technique
Electrogenerated chemiluminescence method has the characteristics that at low cost, the range of linearity is wide, equipment is simple and high sensitivity, Ke Yiyong
In the rule for the chemiluminescence and electronics transfer in bioluminescence reaction for exploring bioactive substance, be conducive to chemiluminescence in
The understanding of bioluminescence reaction essence.Therefore, electrogenerated chemiluminescence such as clinical diagnosis, drug, environment, immune, safety and
It is very interested to have become current light, electroanalysis worker for the application of the measurement of food quality and other substances etc.
Research field.
Since often electrogenerated chemiluminescence is low for illuminator itself, need to introduce coreagent such as tripropyl amine (TPA), potassium peroxydisulfate
Until in system solution, to improve electrogenerated chemiluminescence intensity and analysis performance.Therefore, coreaction dosage form electrogenerated chemiluminescence point
Analysis method is the most widely used at present.However, electrochemical system may be made more into system by being introduced into extra coreagent
Add complexity, analytical procedure more cumbersome, and then limits electrochemistry efficiency in the utilization in some fields.Currently, nanocrystal is electric
The utilization of chemistry is largely cathodic electrochromic chemiluminescence, and the anodic electrochemiluminescence of nanocrystal is seldom, it is main because
Have the following problems for nanocrystal anodic electrochemiluminescence: 1) nanocrystal anodic electrochemiluminescence is sent out at low concentrations
Light is very low；2) the initial potential corrigendum of nanocrystal anodic electrochemiluminescence；3) most nanocrystal anode electroluminescentization
Luminescent method is learned dependent on the coreagent in solution.Therefore, in view of the above-mentioned problems, developing a kind of simple, efficient self-reinforcing
Electrogenerated chemiluminescence material and method are vital.
The present invention prepares the electroluminescent chemistry of self-reinforcing without introducing coreagent in the solution by ligand exchange reaction
Shine new material, and preparation method is simple and efficient, and low in cost, front and back reactions change phenomenon is significant, is easy to observe, while can
Generate very strong electrochemical signals.It not only avoids and introduces the shortcomings that coreagent is brought in system, while also effectively increasing
The electrogenerated chemiluminescence performance of nanocrystal has established theoretical basis for the anodic electrochemiluminescence of nanocrystal；Be conducive to
It accomplishes scale production and applies, bring good Social benefit and economic benefit: the directly electroluminescent chemistry hair of synthesis self-reinforcing type
Light nanocrystal such as quantum dot etc. became system simply, but also avoid it is not necessary that coreagent is directly added in system solution
Waste a large amount of coreagent, reduces costs.
Summary of the invention
Goal of the invention: the object of the present invention is to provide a kind of electrogenerated chemiluminescence material, the material itself can be generated by force
Electrochemiluminescence signal, it is not necessary that coreagent is added in the solution.
It is a further object to provide a kind of preparation method and applications of electrogenerated chemiluminescence material.
Technical solution: one aspect of the present invention provides a kind of electrogenerated chemiluminescence material, which is to change
The cadmium telluride nanocrystal of 1 compound represented of formula cladding；
In chemical formula 1, R1The alkyl for being 0~5 for carbon atom number, R2The alkyl for being 1~5 for carbon atom number.
Specifically, which is the cadmium telluride nanocrystal or 2- bis- of 2- dimethylamino ethyl mercaptan cladding
The cadmium telluride nanocrystal of ethylamino ethyl mercaptan cladding.
The partial size of above-mentioned nanocrystal is 1~8nm, and further, the partial size of the nanocrystal is 1.7~2.7nm.
Another aspect of the present invention provides a kind of method for preparing above-mentioned electrogenerated chemiluminescence material, and this method includes following step
It is rapid:
1) the cadmium telluride nanocrystal of 3- mercaptopropionic acid cladding is prepared；
2) using the cadmium telluride nanocrystal of the 3- mercaptopropionic acid cladding of step 1) preparation as template, pass through ligand exchange reaction
Prepare the cadmium telluride nanocrystal of 1 compound represented of chemical formula cladding.
Wherein, prepare 3- mercaptopropionic acid cladding cadmium telluride nanocrystal method the following steps are included:
1) in inert atmosphere, make Te and NaBH475 DEG C in water~85 DEG C are reacted 25~40 minutes, and NaHTe solution is obtained；
Wherein, the dosage of each reactant are as follows: 4.5~5.18mg of Te, NaBH is added in every milliliter of water43.5~4.0mg；
2) by CdCl2·2.5H2O is dissolved in water, addition 3- mercaptopropionic acid, after adjusting pH value of solution to 11.0~12.0, is added
Enter NaHTe solution, 3~12h of reflux is dried isolated solid with ethyl alcohol centrifuge washing, obtains 3- mercaptopropionic acid cladding
Cadmium telluride nanocrystal；The amount for each reactant being wherein added are as follows: CdCl is added in every milliliter of water2·2.5H2O 2.23~
1.1~2 0.01~0.04mL of μ L, NaHTe solution of 2.35mg, 3- mercaptopropionic acid.
Wherein, inert atmosphere is nitrogen atmosphere.
Ligand exchange reaction specifically: use water or methanol as reaction dissolvent, by the salt of 1 compound represented of chemical formula
Hydrochlorate be stirred at room temperature with the cadmium telluride nanocrystal that 3- mercaptopropionic acid coats react 20~after sixty minutes, water is added, continues room temperature
It is stirred to react 6~20 hours, removes methanol, remove 3- mercaptopropionic acid and remaining hydrochloride in solution, obtained after vacuum drying
The cadmium telluride nanocrystal of 1 compound represented of chemical formula cladding；The amount for each reactant being wherein added are as follows: every milliliter described anti-
Answer solvent that cadmium telluride 1~2mg of nanocrystal of 3- mercaptopropionic acid cladding, the hydrochloride 56 of 1 compound represented of chemical formula is added
~170mg.
The method that the electrogenerated chemiluminescence performance of electrogenerated chemiluminescence material obtained is tested are as follows: respectively by 6 μ L-
The cadmium telluride nanocrystal of 12 μ L chemical formula, 1 compound represented cladding and the cadmium telluride of 6 μ L-12 μ L 3- mercaptopropionic acids cladding
Nanocrystal modification dries it to the surface of glass-carbon electrode, and modified electrode is immersed to three-electrode system solution (0.1M respectively
PBS, pH6.0-11.0), it is placed in electrochemical apparatus sample cell, carries out electrogenerated chemiluminescence measurement, instrument parameter setting: initial
Current potential 0V, high potential 1.6V, low potential 0V, surface sweeping speed 0.1V/S, sensitivity 10-4, RMT=900V.In addition, 3- will be modified with
The glass-carbon electrode immersion of the cadmium telluride nanocrystal of mercaptopropionic acid cladding contains 5mM 2- diethylamino ethanethiol hydrochloride
The three-electrode system of 0.1M PBS (pH6.0-11.0) carries out electrogenerated chemiluminescence test.
Another aspect of the present invention provides a kind of application of above-mentioned electrogenerated chemiluminescence material, and electrogenerated chemiluminescence material is used
It is detected in anodic electrochemiluminescence.
Another aspect of the invention provides a kind of application of above-mentioned electrogenerated chemiluminescence material, and electrogenerated chemiluminescence material is repaired
Decorations establish three-electrode system and carry out electrochemiluminescdetection detection, be free of coreagent in electrolyte in working electrode surface.
The utility model has the advantages that compared with prior art, the invention has the following advantages that
(1) electrogenerated chemiluminescence material of the invention is the electroluminescent chemical material of self-reinforcing type anode, i.e., is free of in the solution
In the case where coreagent, strong luminous signal can be also generated, therefore, which, which not only avoids in solution, draws
Enter coreagent, can also effectively enhance the efficiency and signal of electrogenerated chemiluminescence, make nanocrystal anodic electrochemiluminescence
With better development and application prospect.
(2) the 3- mercaptopropionic acid of cadmium telluride nanocrystal surface is exchanged into 2- diethyl using ligand exchange reaction by the present invention
Aminoothyl mercaptan, solution colour becomes orange from red in the UV lamp, and color change is obvious, therefore can tentatively judge coreaction
The successful preparation of the cadmium telluride nanocrystal of agent 2- diethylamino ethanethiol cladding, the present invention prepare electrogenerated chemiluminescence material
Method has the characteristics that simple, efficient, convenient, low in cost, applied widely, scale application easy to accomplish, is easy to industry
Production, can apply to prepare in many nano materials.
Detailed description of the invention
Fig. 1 is the cadmium telluride nanocrystal schematic diagram of 2- diethylamino ethanethiol cladding；
Fig. 2 is the electrogenerated chemiluminescence mechanism figure of the cadmium telluride nanocrystal of 2- diethylamino ethanethiol cladding；
Fig. 3 is the cadmium telluride nanocrystal of 3- mercaptopropionic acid cladding and the cadmium telluride nanometer of 2- diethylamino ethanethiol cladding
The UV, visible light and change in fluorescence figure of crystal；Wherein, A is that the UV absorption of the cadmium telluride nanocrystal of 3- mercaptopropionic acid cladding is bent
Line (a) and fluorescence emission curves (b)；B is the ultraviolet absorption curve of the cadmium telluride nanocrystal of 2- diethylamino ethanethiol cladding
(c) and fluorescence emission curves (d)；Illustration is the ultraviolet and fluorescence actual photographed figure of cadmium telluride nanocrystal, wherein inserting in A figure
It is from left to right respectively actual photographed figure of the CdTe of 3- mercaptopropionic acid cladding under visible light and ultraviolet lamp in figure；Scheme in B
It is from left to right respectively actual photographed figure of the CdTe of 2- diethylamino ethanethiol cladding under visible light and ultraviolet lamp in illustration.
Fig. 4 is the cadmium telluride nanocrystal of 3- mercaptopropionic acid cladding and the cadmium telluride nanometer of 2- diethylamino ethanethiol cladding
The transmission electron microscope and grain size distribution of crystal；Wherein, A is the Electronic Speculum of the cadmium telluride nanocrystal of 3- mercaptopropionic acid cladding
Figure, the illustration for scheming the upper right corner in A is the high power electron microscope for the cadmium telluride nanocrystal that 3- mercaptopropionic acid coats；B is 2- diethylamino
The electron microscope of the cadmium telluride nanocrystal of base ethyl mercaptan cladding schemes the illustration in the upper right corner in B for 2- diethylamino ethanethiol cladding
Cadmium telluride nanocrystal high power electron microscope；C is the grain size distribution of the cadmium telluride nanocrystal of 3- mercaptopropionic acid cladding；D
For the grain size distribution of the cadmium telluride nanocrystal of 2- diethylamino ethanethiol cladding；It can be seen from the figure that relative to 3- mercapto
The partial size of the cadmium telluride nanocrystal of base propionic acid cladding, the cadmium telluride nanocrystal of 2- diethylamino ethanethiol cladding becomes smaller.
Fig. 5 is the cadmium telluride nanocrystal of 3- mercaptopropionic acid cladding and the cadmium telluride nanometer of 2- diethylamino ethanethiol cladding
The electrogenerated chemiluminescence variation diagram of crystal；Wherein, a curve is modification in the cadmium telluride of the 3- mercaptopropionic acid cladding on glass-carbon electrode
The nanocrystal electrogenerated chemiluminescence that (0.1M, pH9.0) is measured in PBS buffer solution；B curve is modification on glass-carbon electrode
2- diethylamino ethanethiol cladding cadmium telluride nanocrystal in PBS buffer solution (0.1M, pH9.0) measure electroluminescentization
It learns and shines；C curve is to modify the cadmium telluride nanocrystal coated in the 3- mercaptopropionic acid on glass-carbon electrode to contain 5mM 2- bis-
The electrogenerated chemiluminescence that (0.1M, pH9.0) is measured in the PBS buffer solution of ethylamino ethyl mercaptan；As can be seen from the figure 2- bis-
The electrochemiluminescence signal of the cadmium telluride nanocrystal of ethylamino ethyl mercaptan cladding significantly enhances.
Fig. 6 is the cadmium telluride nanocrystal of 3- mercaptopropionic acid cladding and the cadmium telluride nanometer of 2- dimethylamino ethyl mercaptan cladding
The electrogenerated chemiluminescence variation diagram of crystal；Wherein, a curve is that the cadmium telluride nanocrystal of 3- mercaptopropionic acid cladding is modified in glass carbon
After electrode surface, the electrogenerated chemiluminescence of (0.1M, pH9.0) measurement in PBS buffer solution；B curve is 2- lignocaine second
The cadmium telluride nanocrystal of mercaptan cladding is modified after glassy carbon electrode surface, and (0.1M, pH9.0) is measured in PBS buffer solution
Electrogenerated chemiluminescence；As can be seen from the figure the electroluminescent chemistry hair of the cadmium telluride nanocrystal of 2- dimethylamino ethyl mercaptan cladding
Optical signal significantly enhances.
Specific embodiment
The reagent and instrument used in following embodiment: 2- diethylamino ethanethiol hydrochloride (DEAET), 2- dimethylamino
Ethyl mercaptan (DAET), 3- mercaptopropionic acid, tellurium powder, caddy, sodium borohydride, methanol, sodium hydroxide (NaOH), phosphate buffer solution
(PBS), electrochemical workstation (MPI-M, Xi'an Rui Mai Analytical Instrument Co., Ltd), ultraviolet-visual spectrometer (UV-2450,
Tokyo, Japan), Fluorescence Spectrometer (Fluoromax-4, Horiba, USA), transmission electron microscope (JEM-2100, JEOL
It Ltd.) is to buy on the market.
Embodiment 1
The preparation method of the cadmium telluride nanocrystal of electrogenerated chemiluminescence material 2- diethylamino ethanethiol cladding, including with
Lower step:
(1) the cadmium telluride nanocrystal of 3- mercaptopropionic acid cladding is prepared:
(a) 50.8mg tellurium powder and 10mL H are taken2O is added in 25mL round-bottomed flask, is passed through nitrogen 15min to exclude in solution
Oxygen, be placed in 80 DEG C of oil baths after system temperature is heated to 80 DEG C, be rapidly added 37.8mg NaBH4, 30min is reacted, it is molten
Liquid color gradually becomes darkviolet, obtains NaHTe solution；
(b) 91.3mg CdCl is taken2·2.5H2O and 40mL H2O is added in 50mL round-bottomed flask, and magnetic agitation keeps its molten
Solution, then 67 μ L 3- mercaptopropionic acids is taken to be added thereto, with 0.1MNaOH regulation system pH to 11.5；1mL step is taken with syringe
(a) NaHTe solution made from is injected into rapidly in above-mentioned system, and solution colour quickly becomes orange-yellow, places it in 100 DEG C of oil
Flow back 12h in bath, finally multiple with ethyl alcohol centrifuge washing, dries to get the cadmium telluride nanocrystal of 3- mercaptopropionic acid cladding
(2) the cadmium telluride nanocrystal of 2- diethylamino ethanethiol cladding is prepared:
(a) the cadmium telluride nanocrystal for taking 3- mercaptopropionic acid made from 6mg step (1) to coat is added to 3mL methanol solution
Middle dissolution obtains the cadmium telluride methanol solution of 3- mercaptopropionic acid cladding；
(b) methanol that 3mL 0.2M 2- diethylamino ethanethiol hydrochloride is added into solution made from step (a) is molten
30min is stirred at room temperature in liquid；
(c) 3mL distilled water is added into solution made from step (b), is stirred at room temperature 12 hours, by 2- lignocaine second sulphur
The nanocrystal of alcohol cladding is transferred in water.Color change is observed using ultraviolet lamp in reaction process, color is by red variation
It is orange, show that diethylamino ethanethiol has exchanged to cadmium telluride surface.Such as the illustration in Fig. 3, wherein from a left side in the illustration in A figure
Actual photographed figure of the CdTe coated to right respectively 3- mercaptopropionic acid under visible light and ultraviolet lamp；Scheme B in illustration in from
Left-to-right is respectively actual photographed figure of the CdTe of 2- diethylamino ethanethiol cladding under visible light and ultraviolet lamp.By the illustration
Can be observed, the CdTe that ligand exchange reaction generates 2- diethylamino ethanethiol cladding occurs for the CdTe of 3- mercaptopropionic acid cladding,
Before and after the reaction, it is seen that solution becomes faint yellow from orange under light, and solution becomes orange from red under ultraviolet lamp.It is steamed by rotation
Hair removes methanol, and dialysis removes the 3- mercaptopropionic acid and extra 2- diethylamino ethanethiol salt that ligand exchange comes out in solution
Hydrochlorate, vacuum drying obtain the cadmium telluride nanocrystal of 2- diethylamino ethanethiol cladding.
In Fig. 4, A is the electron microscope of the cadmium telluride nanocrystal of 3- mercaptopropionic acid cladding, and the illustration for scheming the upper right corner in A is 3-
The high power electron microscope of the cadmium telluride nanocrystal of mercaptopropionic acid cladding；B is the cadmium telluride nanometer of 2- diethylamino ethanethiol cladding
The electron microscope of crystal, the illustration for scheming the upper right corner in B is the high power electricity for the cadmium telluride nanocrystal that 2- diethylamino ethanethiol coats
Mirror figure；C is the grain size distribution of the cadmium telluride nanocrystal of 3- mercaptopropionic acid cladding；D is 2- diethylamino ethanethiol cladding
The grain size distribution of cadmium telluride nanocrystal；It can be seen from the figure that the cadmium telluride relative to 3- mercaptopropionic acid cladding is nanocrystalline
The partial size of body, the cadmium telluride nanocrystal of 2- diethylamino ethanethiol cladding becomes smaller.
The cadmium telluride of cadmium telluride nanocrystal and 2- diethylamino ethanethiol cladding to 3- mercaptopropionic acid cladding is nanocrystalline
The ultraviolet-visible absorption spectroscopy and fluorescence emission spectrum of body are detected:
The cadmium telluride nanocrystal and 2- diethylamino ethanethiol packet for the 3- mercaptopropionic acid cladding that the present embodiment is prepared
Then the cadmium telluride nanocrystal covered is diluted 5 times with distilled water, keeps final solution concentration equal with 1mg/mL solution is prepared into
For 0.2mg/mL.
It is detected using ultraviolet-uisible spectrophotometer to peak position is absorbed: taking the 3- sulfydryl of 3mL 0.2mg/mL respectively
The cadmium telluride nanometer of the 2- diethylamino ethanethiol cladding of the cadmium telluride nanocrystal solution and 3mL 0.2mg/mL of propionic acid cladding
Crystalloid solution is respectively placed in the UV, visible light quartz colorimetric utensil of two sides light transmission, and quartz colorimetric utensil is placed in UV, visible light light splitting
In photometric sample cell, starts to detect ultravioletvisible absorption intensity and wavelength, obtain ultraviolet-visible absorption spectroscopy.UV, visible light
Spectrophotometer parameter setting are as follows: ultravioletvisible absorption range is 200nm-800nm, slit width 2nm.After detection
The c curve in a curve and Fig. 3 B in Fig. 3 A is arrived, wherein a curve is the cadmium telluride nanocrystal of 3- mercaptopropionic acid cladding
Ultraviolet absorption curve, c curve are the ultraviolet absorption curve of the cadmium telluride nanocrystal of 2- diethylamino ethanethiol cladding.By a song
It is found that blue shift has occurred in the UV absorption of the cadmium telluride nanocrystal of 2- diethylamino ethanethiol cladding, front and back becomes for line and c curve
Change highly significant, it can be seen that ligand exchange reaction has occurred, successfully synthesizes the cadmium telluride of 2- diethylamino ethanethiol cladding
Nanocrystal.
It is detected using fluorescence signal of the Fluorescence Spectrometer to generation: taking the 3- sulfydryl third of 0.8mL 0.2mg/mL respectively
The cadmium telluride nanocrystal of the 2- diethylamino ethanethiol cladding of the cadmium telluride nanocrystal and 0.8mL 0.2mg/mL of acid cladding
Solution is placed in the fluorescence cuvette of four sides light transmission, and fluorescence cuvette is placed in the sample cell of Fluorescence Spectrometer, starts to detect
Its fluorescence intensity and wavelength, obtain fluorescence emission spectrum.Fluorescence Spectrometer parameter be respectively set to excitation wavelength 450nm and
350nm, launch wavelength are respectively 627nm and 590nm, slit width 5nm.The b curve in Fig. 3 A has been obtained after detection
With the d curve in Fig. 3 B, wherein b curve is the fluorescence emission spectrum of the cadmium telluride nanocrystal of 3- mercaptopropionic acid cladding, d curve
For the fluorescence emission spectrum of the cadmium telluride nanocrystal of 2- diethylamino ethanethiol cladding.From the figure 3, it may be seen that 2- lignocaine second sulphur
Blue shift has occurred in the fluorescence emission spectrum of the cadmium telluride nanocrystal of alcohol cladding, and front and back changes highly significant, it can be seen that occurs
Ligand exchange reaction successfully synthesizes the cadmium telluride nanocrystal of 2- diethylamino ethanethiol cladding.
Embodiment 2
The preparation method of the cadmium telluride nanocrystal of electrogenerated chemiluminescence material 2- diethylamino ethanethiol cladding, including with
Lower step:
(1) the cadmium telluride nanocrystal of 3- mercaptopropionic acid cladding is prepared:
(a) 51.8mg tellurium powder and 10mL H are taken2O is added in 25mL round-bottomed flask, is passed through nitrogen 20min to exclude in solution
Oxygen, be placed in 80 DEG C of oil baths after system temperature is heated to 80 DEG C, be rapidly added 40mg NaBH4, react 35min, solution
Color gradually becomes darkviolet, obtains NaHTe solution；
(b) 91.8mg CdCl is taken2·2.5H2O and 40mL H2O is added in 50mL round-bottomed flask, and magnetic agitation keeps its molten
Solution, then 68 μ L 3- mercaptopropionic acids is taken to be added thereto, with 0.2MNaOH regulation system pH to 11.2；1mL step is taken with syringe
(a) NaHTe solution made from is injected into rapidly in above-mentioned system, and solution colour quickly becomes orange-yellow, places it in 100 DEG C of oil
Flow back 12h in bath, finally multiple with ethyl alcohol centrifuge washing, dries to get the cadmium telluride nanocrystal of 3- mercaptopropionic acid cladding.
(2) the cadmium telluride nanocrystal of 2- diethylamino ethanethiol cladding is prepared:
(a) the cadmium telluride nanocrystal for taking 3- mercaptopropionic acid made from 6mg step (1) to coat is added to 3mL methanol solution
Middle dissolution obtains the methanol solution of the cadmium telluride of 3- mercaptopropionic acid cladding；
(b) methanol that 3mL 0.2M 2- diethylamino ethanethiol hydrochloride is added into solution made from step (a) is molten
45min is stirred at room temperature in liquid；
(c) 3mL distilled water is added into solution made from step (b), is stirred at room temperature 12 hours, by 2- lignocaine second sulphur
The quantum dot of alcohol cladding is transformed into water.Color change is observed using ultraviolet lamp in reaction process, color is orange by red variation
Color shows that diethylamino ethanethiol has exchanged to cadmium telluride surface.Such as the illustration in Fig. 3, wherein in the illustration in A figure from a left side to
The right side is respectively actual photographed figure of the CdTe of 3- mercaptopropionic acid cladding under visible light and ultraviolet lamp；Scheme in the illustration in B from a left side
Actual photographed figure of the CdTe coated to right respectively 2- diethylamino ethanethiol under visible light and ultraviolet lamp.It is steamed by rotation
Hair removes methanol, and dialysis removes the 3- mercaptopropionic acid and extra 2- diethylamino ethanethiol salt that ligand exchange comes out in solution
Hydrochlorate, vacuum drying obtain the cadmium telluride nanocrystal of 2- diethylamino ethanethiol cladding.
In Fig. 4, A is the electron microscope of the cadmium telluride nanocrystal of 3- mercaptopropionic acid cladding, and the illustration for scheming the upper right corner in A is 3-
The high power electron microscope of the cadmium telluride nanocrystal of mercaptopropionic acid cladding；B is the cadmium telluride nanometer of 2- diethylamino ethanethiol cladding
The electron microscope of crystal, the illustration for scheming the upper right corner in B is the high power electricity for the cadmium telluride nanocrystal that 2- diethylamino ethanethiol coats
Mirror figure；C is the grain size distribution of the cadmium telluride nanocrystal of 3- mercaptopropionic acid cladding；D is 2- diethylamino ethanethiol cladding
The grain size distribution of cadmium telluride nanocrystal；It can be seen from the figure that the cadmium telluride relative to 3- mercaptopropionic acid cladding is nanocrystalline
The partial size of body, the cadmium telluride nanocrystal of 2- diethylamino ethanethiol cladding becomes smaller.
Detect electrogenerated chemiluminescence situation:
By the cadmium telluride nanocrystal of the cladding of 3- mercaptopropionic acid made from the present embodiment and 2- diethylamino ethanethiol cladding
Cadmium telluride nanocrystal be prepared into 1mg/mL solution respectively.The cadmium telluride nanocrystal for taking 6 μ L 3- mercaptopropionic acids to coat respectively
Modifying with the cadmium telluride nanocrystal of 6 μ L 2- diethylamino ethanethiols cladding to the surface of glass-carbon electrode dries it, will modify
Glass-carbon electrode afterwards is placed in three-electrode system solution (0.1M PBS, pH9.0), is placed it in electrochemical apparatus sample cell,
Start to carry out cyclic voltammetry scan measurement.Electrochemical apparatus parameter setting are as follows: initial potential 0V, high potential 1.6V, low potential 0V,
Scanning speed 0.1V/S, sensitivity 10-4, RMT=900V.In addition, the cadmium telluride that one is modified with 3- mercaptopropionic acid cladding is received
The glass-carbon electrode of meter Jing Ti is placed on the three-electrode system of the 0.1M PBS (pH9.0) of the diethylamino ethanethiol hydrochloride of 2- containing 5mM
In measure.
Fig. 2 is the electrogenerated chemiluminescence mechanism figure of the cadmium telluride nanocrystal of 2- diethylamino ethanethiol cladding, such as Fig. 2 institute
Show, under certain potential, CdTe nanometer crystalline body and its surface coated coreagent molecule 2- diethylamino ethanethiol are same
Shi Fasheng oxidation, forms radical cation；Deprotonation occurs for the α-H of+NR3 anti-in subsequent molecule 2- diethylamino ethanethiol
It answers, forms strong reducing agent；Finally, the CdTe nanometer crystalline body of oxidation state is reduced into excited state molecule by reducing agent, it is final to produce
Raw electrogenerated chemiluminescence.
Cyclic voltammetry scan terminates to have obtained a, b and the c curve in Fig. 5, and wherein a curve is modification on glass-carbon electrode
The cadmium telluride nanocrystal electrogenerated chemiluminescence feelings that (0.1M, pH9.0) is measured in PBS buffer solution of 3- mercaptopropionic acid cladding
Condition；B curve is to modify the cadmium telluride nanocrystal in the 2- diethylamino ethanethiol cladding on glass-carbon electrode in PBS buffer solution
In (0.1M, pH9.0) measurement electrogenerated chemiluminescence situation；C curve is modification in the 3- mercaptopropionic acid cladding on glass-carbon electrode
Cadmium telluride nanocrystal in the PBS buffer solution containing 5mM 2- diethylamino ethanethiol hydrochloride (0.1M, pH9.0) survey
The electrogenerated chemiluminescence situation of amount.As can be known from Fig. 5, the electrochemical luminescence of the cadmium telluride nanocrystal of 3- mercaptopropionic acid cladding is strong
(the electrogenerated chemiluminescence intensity of the cadmium telluride nanocrystal of such as curve a), 2- diethylamino ethanethiol cladding is degree for 1005
17650 (such as curve b) and originate shine current potential be 0.60 volt, highest shine current potential be 1.22 volts, 3- mercaptopropionic acid cladding
Cadmium telluride nanocrystal and the electrogenerated chemiluminescence intensity of 5mM coreagent 2- diethylamino ethanethiol is added is 6200 (such as
Curve c) and originate shine current potential be 0.75 volt, highest shine current potential be 1.30 volts；With the telluride of 3- mercaptopropionic acid cladding
The electrochemical luminescence intensity of cadmium nanocrystal compares, and the cadmium telluride nanocrystal electrochemistry of 2- diethylamino ethanethiol cladding is strong
Degree respectively may be about the cadmium telluride nanocrystal of 3- mercaptopropionic acid cladding and the electricity of 5mM coreagent 2- diethylamino ethanethiol be added
Cause 17 times and 6 times of chemiluminescence intensity.2- diethylamino ethanethiol cladding cadmium telluride nanocrystal electrochemical strengths be about
The electroluminescent chemistry of the cadmium telluride nanocrystal of the 3- mercaptopropionic acid cladding of the 2- diethylamino ethanethiol hydrochloride of coreagent containing 5mM
3 times of luminous intensity.Therefore, the electrogenerated chemiluminescence intensity for the cadmium telluride nanocrystal that 2- diethylamino ethanethiol coats is really
Than 3- mercaptopropionic acid cladding cadmium telluride nanocrystal and be added 5mM coreagent 2- diethylamino ethanethiol hydrochloride it is electroluminescent
Chemiluminescence intensity significantly increase and originate shine current potential it is low, this illustrate cadmium telluride nanocrystal surface coat 2- diethylamino
Base ethyl mercaptan can significantly increase the electrochemical signals of nanocrystal, have feasibility.
Embodiment 3
The preparation method of the cadmium telluride nanocrystal of electrogenerated chemiluminescence material 2- dimethylamino ethyl mercaptan cladding, including with
Lower step:
(1) the cadmium telluride nanocrystal of 3- mercaptopropionic acid cladding is prepared:
(a) 25.4mg tellurium powder and 5mL H are taken2O is added in 25mL round-bottomed flask, is passed through nitrogen 30min to exclude in solution
Oxygen, be placed in 80 DEG C of oil baths after system temperature is heated to 80 DEG C, be rapidly added 18.9mg NaBH4, 30min is reacted, it is molten
Liquid color gradually becomes darkviolet, obtains NaHTe solution；
(b) 46mg CdCl is taken2·2.5H2O and 20mL H2O is added in 25mL round-bottomed flask, and magnetic agitation makes it dissolve,
33.5 μ L 3- mercaptopropionic acids are taken to be added thereto again, with 0.1M NaOH regulation system pH to 11.5；0.5mL step is taken with syringe
(a) NaHTe solution made from is injected into rapidly in above-mentioned system, and solution colour quickly becomes orange-yellow, places it in 100 DEG C of oil
Flow back 12h in bath, finally multiple with ethyl alcohol centrifuge washing, dries to get the cadmium telluride nanocrystal of 3- mercaptopropionic acid cladding.
(2) the cadmium telluride nanocrystal of 2- dimethylamino ethyl mercaptan cladding is prepared:
(a) it is molten that the cadmium telluride nanocrystal for taking 3- mercaptopropionic acid made from 3mg step (1) to coat is added to 1.5mL methanol
It is dissolved in liquid, obtains the methanol solution of the cadmium telluride of 3- mercaptopropionic acid cladding；
(b) methanol that 1.5mL 0.2M 2- dimethylamino ethanethiol hydrochloride is added into solution made from step (a) is molten
30min is stirred at room temperature in liquid；
(c) 1.5mL distilled water is added into solution made from step (b), is stirred at room temperature 12 hours, by 2- dimethylamino second
The quantum dot of mercaptan cladding is transformed into water.Color change is observed using ultraviolet lamp in reaction process, color is by red variation
It is orange, show that 2- dimethylamino ethyl mercaptan has exchanged to cadmium telluride surface.Methanol is removed by rotary evaporation, dialysis removes solution
The 3- mercaptopropionic acid and extra 2- dimethylamino ethanethiol hydrochloride that middle ligand exchange comes out, vacuum drying obtain 2- bis-
The cadmium telluride nanocrystal of methylamino ethyl mercaptan cladding.
Detect electrogenerated chemiluminescence situation:
By the cadmium telluride nanocrystal of the cladding of 3- mercaptopropionic acid made from the present embodiment and 2- dimethylamino ethyl mercaptan cladding
Cadmium telluride nanocrystal be prepared into 1mg/mL solution respectively.The cadmium telluride nanocrystal for taking 6 μ L 3- mercaptopropionic acids to coat respectively
Modifying with the cadmium telluride nanocrystal of 6 μ L 2- dimethylamino ethyl mercaptans cladding to the surface of glass-carbon electrode dries it, will modify
Electrode is placed in three-electrode system solution (0.1M PBS, pH9.0), is placed it in electrochemical apparatus sample cell, is started to carry out
Cyclic voltammetry scan.Instrument parameter setting: initial potential 0V, high potential 1.6V, low potential 0V, scanning speed 0.1V/S are sensitive
Degree 10-4, RMT=900V.
A the and b curve in Fig. 6 has been obtained after detection.Wherein, a curve is that the cadmium telluride of 3- mercaptopropionic acid cladding is received
Meter Jing Ti is modified after glassy carbon electrode surface, the electrogenerated chemiluminescence that (0.1M, pH9.0) is measured in PBS buffer solution；B is bent
Line is that the cadmium telluride nanocrystal of 2- diethylamino ethanethiol cladding is modified after glassy carbon electrode surface, in PBS buffer solution
The electrogenerated chemiluminescence of (0.1M, pH9.0) measurement.As can be known from Fig. 6, the electricity of the cadmium telluride nanocrystal of 3- mercaptopropionic acid cladding
Chemiluminescence intensity is 1090 (the electroluminescent chemistry hairs of the cadmium telluride nanocrystal of such as curve a), 2- dimethylamino ethyl mercaptan cladding
Luminous intensity is 15600, and (such as curve b) and to originate the current potential that shines be 0.65 volt, the highest current potential that shines is 1.28 volts；With 3- mercapto
The electrochemical luminescence intensity of the cadmium telluride nanocrystal of base propionic acid cladding compares, the cadmium telluride of 2- diethylamino ethanethiol cladding
Nanocrystal electrochemical strengths are about 14 times of its intensity.Therefore, the cadmium telluride nanocrystal of 2- dimethylamino ethyl mercaptan cladding
The electrogenerated chemiluminescence intensity of cadmium telluride nanocrystal of electrogenerated chemiluminescence intensity ratio 3- mercaptopropionic acid cladding significantly increase,
This illustrates that the electrochemistry of nanocrystal can be significantly increased by coating 2- dimethylamino ethyl mercaptan in cadmium telluride nanocrystal surface
Signal has feasibility and reliability.
Embodiment 4
The preparation method of the cadmium telluride nanocrystal of electrogenerated chemiluminescence material 2- dimethylamino ethyl mercaptan cladding, including with
Lower step:
(1) the cadmium telluride nanocrystal of 3- mercaptopropionic acid cladding is prepared:
(a) 22.5mg tellurium powder and 5mL H are taken2O is added in 25mL round-bottomed flask, is passed through nitrogen 30min to exclude in solution
Oxygen, be placed in 75 DEG C of oil baths after system temperature is heated to 75 DEG C, be rapidly added 20mg NaBH4, react 40min, solution
Color gradually becomes darkviolet, obtains NaHTe solution；
(b) 47mg CdCl is taken2·2.5H2O and 20mL H2O is added in 25mL round-bottomed flask, and magnetic agitation makes it dissolve,
40 μ L 3- mercaptopropionic acids are taken to be added thereto again, with 0.1M NaOH regulation system pH to 11.0；0.8mL step is taken with syringe
(a) NaHTe solution made from is injected into rapidly in above-mentioned system, and solution colour quickly becomes orange-yellow, places it in 100 DEG C of oil
Flow back 3h in bath, finally multiple with ethyl alcohol centrifuge washing, dries to get the cadmium telluride nanocrystal of 3- mercaptopropionic acid cladding.
(2) the cadmium telluride nanocrystal of 2- dimethylamino ethyl mercaptan cladding is prepared:
(a) it is molten that the cadmium telluride nanocrystal for taking 3- mercaptopropionic acid made from 6mg step (1) to coat is added to 1.5mL methanol
It is dissolved in liquid, obtains the methanol solution of the cadmium telluride of 3- mercaptopropionic acid cladding；
(b) the 2- dimethylamino ethanethiol hydrochloride of 1.5mL 112mg/mL is added into solution made from step (a)
20min is stirred at room temperature in methanol solution；
(c) 4mL distilled water is added into solution made from step (b), is stirred at room temperature 6 hours, by 2- dimethylamino second sulphur
The quantum dot of alcohol cladding is transformed into water.Color change is observed using ultraviolet lamp in reaction process, color is orange by red variation
Color shows that dimethylamino ethyl mercaptan has exchanged to cadmium telluride surface.Methanol is removed by rotary evaporation, dialysis removes matches in solution
The 3- mercaptopropionic acid and extra 2- dimethylamino ethanethiol hydrochloride that body exchanges, vacuum drying obtain 2- diformazan ammonia
The cadmium telluride nanocrystal of base ethyl mercaptan cladding.
Detect electrogenerated chemiluminescence situation:
By the cadmium telluride nanocrystal of the cladding of 3- mercaptopropionic acid made from the present embodiment and 2- dimethylamino ethyl mercaptan cladding
Cadmium telluride nanocrystal be prepared into 1mg/mL solution respectively.The cadmium telluride for taking 12 μ L 3- mercaptopropionic acids to coat respectively is nanocrystalline
Body and the cadmium telluride nanocrystal of 12 μ L 2- dimethylamino ethyl mercaptans cladding, which are modified to the surface of glass-carbon electrode, dries it, will
Modified electrode is placed in three-electrode system solution (0.1M PBS, pH11.0), is placed it in electrochemical apparatus sample cell, is started
Carry out cyclic voltammetry scan.Instrument parameter setting: initial potential 0V, high potential 1.6V, low potential 0V, scanning speed 0.1V/S,
Sensitivity 10-4, RMT=900V.Scanning result shows, electroluminescentization of the cadmium telluride nanocrystal of 2- dimethylamino ethyl mercaptan cladding
The electrogenerated chemiluminescence intensity for learning the cadmium telluride nanocrystal of luminous strength ratio 3- mercaptopropionic acid cladding significantly increases, and illustrates in tellurium
Cadmium nanocrystal surface cladding 2- dimethylamino ethyl mercaptan can significantly increase the electrochemical signals of nanocrystal, have feasible
Property and reliability.
Embodiment 5
The preparation method of the cadmium telluride nanocrystal of electrogenerated chemiluminescence material 2- dimethylamino ethyl mercaptan cladding, including with
Lower step:
(1) the cadmium telluride nanocrystal of 3- mercaptopropionic acid cladding is prepared:
(a) 25mg tellurium powder and 5mL H are taken2O is added in 25mL round-bottomed flask, is passed through nitrogen 30min to exclude in solution
Oxygen is placed in 85 DEG C of oil baths after system temperature is heated to 85 DEG C, is rapidly added 17.5mg NaBH4, react 25min, solution
Color gradually becomes darkviolet, obtains NaHTe solution；
(b) 44.6mg CdCl is taken2·2.5H2O and 20mL H2O is added in 25mL round-bottomed flask, and magnetic agitation keeps its molten
Solution, then 22 μ L 3- mercaptopropionic acids is taken to be added thereto, with 0.1M NaOH regulation system pH to 12.0；0.2mL is taken to walk with syringe
Suddenly NaHTe solution made from (a) is injected into rapidly in above-mentioned system, and solution colour quickly becomes orange-yellow, places it in 100 DEG C
Flow back 8h in oil bath, finally multiple with ethyl alcohol centrifuge washing, dries to get the cadmium telluride nanocrystal of 3- mercaptopropionic acid cladding.
(2) the cadmium telluride nanocrystal of 2- dimethylamino ethyl mercaptan cladding is prepared:
(a) the cadmium telluride nanocrystal for taking 3- mercaptopropionic acid made from 6mg step (1) to coat is added to 1.5mL aqueous solution
Middle dissolution obtains the methanol solution of the cadmium telluride of 3- mercaptopropionic acid cladding；
(b) the 2- dimethylamino ethanethiol hydrochloride of 1.5mL 340mg/mL is added into solution made from step (a)
60min is stirred at room temperature in aqueous solution；
(c) 4mL distilled water is added into solution made from step (b), is stirred at room temperature 20 hours, by 2- dimethylamino second sulphur
The quantum dot of alcohol cladding is transformed into water.Color change is observed using ultraviolet lamp in reaction process, color is orange by red variation
Color shows that dimethylamino ethyl mercaptan has exchanged to cadmium telluride surface.Dialysis removes the 3- sulfydryl third that ligand exchange comes out in solution
Sour and extra 2- dimethylamino ethanethiol hydrochloride, vacuum drying obtain the cadmium telluride of 2- dimethylamino ethyl mercaptan cladding
Nanocrystal.
Detect electrogenerated chemiluminescence situation:
By the cadmium telluride nanocrystal of the cladding of 3- mercaptopropionic acid made from the present embodiment and 2- dimethylamino ethyl mercaptan cladding
Cadmium telluride nanocrystal be prepared into 1mg/mL solution respectively.The cadmium telluride nanocrystal for taking 6 μ L 3- mercaptopropionic acids to coat respectively
Modifying with the cadmium telluride nanocrystal of 6 μ L 2- dimethylamino ethyl mercaptans cladding to the surface of glass-carbon electrode dries it, will modify
Electrode is placed in three-electrode system solution (0.1M PBS, pH6.0), is placed it in electrochemical apparatus sample cell, is started to carry out
Cyclic voltammetry scan.Instrument parameter setting: initial potential 0V, high potential 1.6V, low potential 0V, scanning speed 0.1V/S are sensitive
Degree 10-4, RMT=900V.By scanning result it is found that the electroluminescent chemistry of the cadmium telluride nanocrystal of 2- dimethylamino ethyl mercaptan cladding
The electrogenerated chemiluminescence intensity of the cadmium telluride nanocrystal of luminous strength ratio 3- mercaptopropionic acid cladding significantly increases, and illustrates in telluride
Cadmium nanocrystal surface cladding 2- dimethylamino ethyl mercaptan can significantly increase the electrochemical signals of nanocrystal, have feasibility
And reliability.
Claims (6)
1. a kind of method for preparing electrogenerated chemiluminescence material, which is characterized in that method includes the following steps:
1) the cadmium telluride nanocrystal of 3- mercaptopropionic acid cladding is prepared；
2) it using the cadmium telluride nanocrystal of the 3- mercaptopropionic acid cladding of step 1) preparation as template, is prepared by ligand exchange reaction
The cadmium telluride nanocrystal of 1 compound represented of chemical formula cladding；
The electrogenerated chemiluminescence material is the cadmium telluride nanocrystal of 1 compound represented of chemical formula cladding；
In chemical formula 1, R1The alkyl for being 0~5 for carbon atom number, R2The alkyl for being 1~5 for carbon atom number；
It is described prepare 3- mercaptopropionic acid cladding cadmium telluride nanocrystal method the following steps are included:
A) in inert atmosphere, make Te and NaBH475 DEG C in water~85 DEG C are reacted 25~40 minutes, and NaHTe solution is obtained；Wherein
The amount for each reactant being added are as follows: Te4.5~5.18mg, NaBH is added in every milliliter of water43.5~4.0mg；
B) by CdCl2·2.5H2O is dissolved in water, addition 3- mercaptopropionic acid, and after adjusting pH value of solution to 11.0~12.0, institute is added
NaHTe solution is stated, flows back after 3~12h, with ethyl alcohol centrifuge washing, isolated solid is dried, obtains 3- mercaptopropionic acid packet
The cadmium telluride nanocrystal covered；The amount for each reactant being wherein added are as follows: CdCl is added in every milliliter of water2·2.5H2O2.23~
1.1~2 0.01~0.04mL of μ L, NaHTe solution of 2.35mg, 3- mercaptopropionic acid.
2. the method according to claim 1 for preparing electrogenerated chemiluminescence material, which is characterized in that the electroluminescent chemistry hair
Luminescent material is that the cadmium telluride nanocrystal of 2- dimethylamino ethyl mercaptan cladding or the cadmium telluride of 2- diethylamino ethanethiol cladding are received
Meter Jing Ti.
3. the method according to claim 1 or 2 for preparing electrogenerated chemiluminescence material, which is characterized in that described nanocrystalline
The partial size of body is 1~8nm.
4. the method according to claim 1 or 2 for preparing electrogenerated chemiluminescence material, which is characterized in that described nanocrystalline
The partial size of body is 1.7~2.7nm.
5. the method according to claim 1 for preparing electrogenerated chemiluminescence material, which is characterized in that the step 2) is specific
Are as follows: use water or methanol as reaction dissolvent, by the 3- sulfydryl of the hydrochloride of 1 compound represented of chemical formula and step 1) preparation
Reaction 20~after sixty minutes is stirred at room temperature in the cadmium telluride nanocrystal of propionic acid cladding, and water is added, continues that reaction 6~20 is stirred at room temperature
Hour, methanol is removed, 3- mercaptopropionic acid and remaining hydrochloride in solution is removed, is obtained after vacuum drying shown in chemical formula 1
The cadmium telluride nanocrystal of compound cladding；The amount for each reactant being wherein added are as follows: 3- is added in every milliliter of reaction dissolvent
Cadmium telluride 1~the 2mg of nanocrystal, 56~170mg of hydrochloride of 1 compound represented of chemical formula of mercaptopropionic acid cladding.
6. the method according to claim 1 for preparing electrogenerated chemiluminescence material, which is characterized in that the inert atmosphere is
Nitrogen atmosphere.
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