CN106959289A - A kind of electrogenerated chemiluminescence material, its preparation method and application - Google Patents
A kind of electrogenerated chemiluminescence material, its preparation method and application Download PDFInfo
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- CN106959289A CN106959289A CN201710172187.7A CN201710172187A CN106959289A CN 106959289 A CN106959289 A CN 106959289A CN 201710172187 A CN201710172187 A CN 201710172187A CN 106959289 A CN106959289 A CN 106959289A
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Abstract
The invention provides a kind of electrogenerated chemiluminescence material, its preparation method and application, the electrogenerated chemiluminescence material isThe cadmium telluride nanocrystal of the compound cladding of expression, its preparation method includes：1) the cadmium telluride nanocrystal of 3 mercaptopropionic acids cladding is prepared；2) the cadmium telluride nanocrystal using the 3 mercaptopropionic acids cladding of preparation is prepared as template by ligand exchange reactionThe cadmium telluride nanocrystal of the compound cladding of expression.The electrogenerated chemiluminescence material of the present invention is self-reinforcing type anodic electrochemiluminescence material; in the case of being free of coreagent in the electrolytic solution; also strong electrochemical luminescence signals can be produced; it not only avoid and the problem of coreagent is brought is introduced in solution; the efficiency and performance of electrogenerated chemiluminescence can also effectively be strengthened; and the preparation method of the present invention is simple, efficient, convenient, with low cost, applied widely; easily realize scale application; 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, particularly a kind of electrogenerated chemiluminescence material, its preparation method
And application.
Background technology
The features such as electrogenerated chemiluminescence method has wide low cost, the range of linearity, simple equipment and high sensitivity, Ke Yiyong
In the chemiluminescence for exploring bioactivator and the rule of electro transfer in bioluminescence reaction, be conducive to chemiluminescence in
The understanding of bioluminescence reaction essence.Therefore, electrogenerated chemiluminescence such as clinical diagnosis, medicine, environment, immune, safety and
Application in terms of the measure of food quality and other materials, has become current light, electroanalysis worker very interested
Research field.
Due to illuminator, often electrogenerated chemiluminescence is low, it is necessary to introduce coreagent such as tripropyl amine (TPA), potassium peroxydisulfate in itself
When in system solution, to improve electrogenerated chemiluminescence intensity and analytical performance.Therefore, coreaction formulation 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 unnecessary coreagent
Plus complicated, analytical procedure is more cumbersome, and then limit utilization of the electrochemistry efficiency in some fields.At present, nanocrystal electricity
Chemistry with it is most of is cathodic electrochromic chemiluminescence, and the anodic electrochemiluminescence of nanocrystal is seldom, it is main because
There is problems with 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
Learn the coreagent that luminescent method is depended in solution.Therefore, regarding to the issue above, a kind of simple, efficient self-reinforcing is developed
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
Luminous new material, its preparation method is simply efficient, and with low cost, front and rear reactions change phenomenon is notable, it is easy to observe, while can
Produce very strong electrochemical signals.It not only avoid and introduced in system the shortcoming that coreagent is brought, while also effectively increasing
The electrogenerated chemiluminescence performance of nanocrystal, is that the anodic electrochemiluminescence of nanocrystal has established theoretical foundation；Be conducive to
Accomplish scale production and apply, bring good Social benefit and economic benefit：The directly electroluminescent chemistry of synthesis self-reinforcing type is sent out
Light nanocrystal such as quantum dot etc., without directly adding coreagent in system solution, had both made system become simple, had avoided again
Waste substantial amounts of coreagent, reduces cost.
The content of the invention
Goal of the invention：It is an object of the invention to provide a kind of electrogenerated chemiluminescence material, the material can be produced by force in itself
Electrochemiluminescence signal, without adding coreagent in the solution.
It is a further object to provide a kind of preparation method and application of electrogenerated chemiluminescence material.
Technical scheme：One aspect of the present invention provides a kind of electrogenerated chemiluminescence material, and the electrogenerated chemiluminescence material is change
The cadmium telluride nanocrystal of compound cladding shown in formula 1；
In chemical formula 1, R1The alkyl for being 0~5 for carbon number, R2The alkyl for being 1~5 for carbon number.
Specifically, the electrogenerated chemiluminescence material is the cadmium telluride nanocrystal or 2- bis- that 2- dimethylaminos ethyl mercaptan is coated
The cadmium telluride nanocrystal of ethylamino ethyl mercaptan cladding.
The particle diameter of above-mentioned nanocrystal is 1~8nm, further, and the particle diameter 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
Suddenly：
1) the cadmium telluride nanocrystal of 3- mercaptopropionic acids cladding is prepared；
2) using step 1) prepare 3- mercaptopropionic acids cladding cadmium telluride nanocrystal as template, pass through ligand exchange reaction
Prepare the cadmium telluride nanocrystal of the compound cladding shown in chemical formula 1.
Wherein, the method for preparing the cadmium telluride nanocrystal of 3- mercaptopropionic acids cladding comprises the following steps：
1) in inert atmosphere, Te and NaBH are made475 DEG C~85 DEG C are reacted 25~40 minutes in water, obtain NaHTe solution；
Wherein, the consumption of each reactant is：Every milliliter of water adds Te 4.5~5.18mg, NaBH43.5~4.0mg；
2) by CdCl2·2.5H2O is dissolved in water, and is added after 3- mercaptopropionic acids, regulation pH value of solution to 11.0~12.0, plus
Enter NaHTe solution, flow back 3~12h, uses ethanol centrifuge washing, isolated solid is dried, obtain 3- mercaptopropionic acids cladding
Cadmium telluride nanocrystal；The amount of each reactant wherein added is：Every milliliter of water adds CdCl2·2.5H2O 2.23~
0.01~the 0.04mL of μ L, NaHTe solution of 2.35mg, 3- mercaptopropionic acid 1.1~2.
Wherein, inert atmosphere is nitrogen atmosphere.
Ligand exchange reaction is specially：Using water or methanol as reaction dissolvent, by the salt of the compound shown in chemical formula 1
After reaction is stirred at room temperature 20~60 minutes in the cadmium telluride nanocrystal that hydrochlorate is coated with 3- mercaptopropionic acids, water is added, continues room temperature
Stirring reaction 6~20 hours, removes methanol, removes 3- mercaptopropionic acids and remaining hydrochloride in solution, is obtained after vacuum drying
The cadmium telluride nanocrystal of compound cladding shown in chemical formula 1；The amount of each reactant wherein added is：Every milliliter described anti-
Solvent is answered to add cadmium telluride 1~2mg of nanocrystal of 3- mercaptopropionic acids cladding, the hydrochloride 56 of the compound shown in chemical formula 1
~170mg.
The method that electrogenerated chemiluminescence performance to obtained electrogenerated chemiluminescence material is tested is：Respectively by 6 μ L-
The cadmium telluride nanocrystal of compound cladding shown in 12 μ L chemical formulas 1 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 is set：Initially
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 hydrochlorides
0.1M PBS (pH6.0-11.0) three-electrode system 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
In anodic electrochemiluminescence detection.
Another aspect of the invention provides a kind of application of above-mentioned electrogenerated chemiluminescence material, and electrogenerated chemiluminescence material is repaiied
Decorations set up three-electrode system and carry out being free of coreagent in electrochemiluminescdetection detection, electrolyte in working electrode surface.
Beneficial effect：Compared with prior art, the present invention has advantages below：
(1) electrogenerated chemiluminescence material of the invention is the electroluminescent chemical material of self-reinforcing type anode, i.e., be free of in the solution
In the case of coreagent, strong luminous signal can be also produced, therefore, the electroluminescent chemical material, which not only avoid in solution, to be drawn
Enter coreagent, can also effectively strengthen the efficiency and signal of electrogenerated chemiluminescence, make nanocrystal anodic electrochemiluminescence
With more preferable development and application prospect.
(2) the 3- mercaptopropionic acids of cadmium telluride nanocrystal surface are exchanged into 2- diethyls by the present invention using ligand exchange reaction
Aminoothyl mercaptan, solution colour is orange by red change under uviol lamp, and color change substantially, therefore can tentatively judge coreaction
The successful preparation of the cadmium telluride nanocrystal of agent 2- diethylamino ethanethiols cladding, the present invention prepares electrogenerated chemiluminescence material
The features such as method has simple, efficient, convenient, with low cost, applied widely, easily realizes scale application, it is easy to industry
Production, can apply to prepare in many nano materials.
Brief description of the drawings
Fig. 1 is the cadmium telluride nanocrystal schematic diagram that 2- diethylamino ethanethiols are coated；
Fig. 2 is the electrogenerated chemiluminescence mechanism figure for the cadmium telluride nanocrystal that 2- diethylamino ethanethiols are coated；
Fig. 3 is the cadmium telluride nanometer of the cadmium telluride nanocrystal that 3- mercaptopropionic acids are coated and 2- diethylamino ethanethiols cladding
The UV, visible light and change in fluorescence figure of crystal；Wherein, A is the UV absorption song for the cadmium telluride nanocrystal that 3- mercaptopropionic acids are coated
Line (a) and fluorescence emission curves (b)；B is the ultraviolet absorption curve for the cadmium telluride nanocrystal that 2- diethylamino ethanethiols are coated
(c) with fluorescence emission curves (d)；Illustration is the ultraviolet and fluorescence actual photographed figure of cadmium telluride nanocrystal, inserting wherein in A figures
It is respectively from left to right actual photographed figures of the CdTe of 3- mercaptopropionic acids cladding under visible ray and uviol lamp in figure；Scheme in B
It is respectively from left to right actual photographed figures of the CdTe of 2- diethylamino ethanethiols cladding under visible ray and uviol lamp in illustration.
Fig. 4 is the cadmium telluride nanometer of the cadmium telluride nanocrystal that 3- mercaptopropionic acids are coated and 2- diethylamino ethanethiols cladding
The transmission electron microscope and grain size distribution of crystal；Wherein, A is the Electronic Speculum for the cadmium telluride nanocrystal that 3- mercaptopropionic acids are coated
The high power electron microscope for the cadmium telluride nanocrystal that the illustration in the upper right corner coats for 3- mercaptopropionic acids in figure, figure A；B is 2- diethylaminos
The illustration in the upper right corner coats for 2- diethylamino ethanethiols in the electron microscope of the cadmium telluride nanocrystal of base ethyl mercaptan cladding, figure B
Cadmium telluride nanocrystal high power electron microscope；C is the grain size distribution for the cadmium telluride nanocrystal that 3- mercaptopropionic acids are coated；D
The grain size distribution of the cadmium telluride nanocrystal coated for 2- diethylamino ethanethiols；It can be seen that relative to 3- mercaptos
The cadmium telluride nanocrystal of base propionic acid cladding, the particle diameter of the cadmium telluride nanocrystal of 2- diethylamino ethanethiols cladding diminishes.
Fig. 5 is the cadmium telluride nanometer of the cadmium telluride nanocrystal that 3- mercaptopropionic acids are coated and 2- diethylamino ethanethiols cladding
The electrogenerated chemiluminescence variation diagram of crystal；Wherein, a curves are to modify in the cadmium telluride of the 3- mercaptopropionic acids cladding on glass-carbon electrode
The nanocrystal electrogenerated chemiluminescence that (0.1M, pH9.0) is measured in PBS cushioning liquid；B curves are to modify on glass-carbon electrode
2- diethylamino ethanethiols cladding cadmium telluride nanocrystal in PBS cushioning liquid (0.1M, pH9.0) measure electroluminescentization
Learn luminous；C curves are to modify the cadmium telluride nanocrystal in the 3- mercaptopropionic acids cladding on glass-carbon electrode containing 5mM 2- bis-
The electrogenerated chemiluminescence that (0.1M, pH9.0) is measured in the PBS cushioning liquid 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 is significantly enhanced.
Fig. 6 is the cadmium telluride nanometer of the cadmium telluride nanocrystal that 3- mercaptopropionic acids are coated and 2- dimethylaminos ethyl mercaptan cladding
The electrogenerated chemiluminescence variation diagram of crystal；Wherein, a curves are that the cadmium telluride nanocrystal that 3- mercaptopropionic acids are coated is modified in glass carbon
After electrode surface, the electrogenerated chemiluminescence that (0.1M, pH9.0) is measured in PBS cushioning liquid；B curves are 2- lignocaine second
The cadmium telluride nanocrystal of mercaptan cladding is modified in after glassy carbon electrode surface, and (0.1M, pH9.0) is measured in PBS cushioning liquid
Electrogenerated chemiluminescence；As can be seen from the figure the electroluminescent chemistry of the cadmium telluride nanocrystal of 2- dimethylaminos ethyl mercaptan cladding is sent out
Optical signal is significantly enhanced.
Embodiment
The reagent and instrument used in following examples：2- diethylamino ethanethiols hydrochloride (DEAET), 2- dimethylaminos
Ethyl mercaptan (DAET), 3- mercaptopropionic acids, tellurium powder, caddy, sodium borohydride, methanol, NaOH (NaOH), phosphate buffer solution
(PBS), electrochemical workstation (MPI-M, Xi'an Rui Mai Analytical Instrument Co., Ltd), ultraviolet-visual spectrometer (UV-2450,
Tokyo, Japan), XRF (Fluoromax-4, Horiba, USA), transmission electron microscope (JEM-2100, JEOL
Ltd.) it is and buys on the market.
Embodiment 1
The preparation method of the cadmium telluride nanocrystal of electrogenerated chemiluminescence material 2- diethylamino ethanethiols cladding, including with
Lower step：
(1) the cadmium telluride nanocrystal of 3- mercaptopropionic acids cladding is prepared：
(a) 50.8mg telluriums powder and 10mL H are taken2O is added in 25mL round-bottomed flasks, is passed through nitrogen 15min to exclude in solution
Oxygen, be placed in 80 DEG C of oil baths and system temperature be heated to after 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 are taken2·2.5H2O and 40mL H2O is added in 50mL round-bottomed flasks, and magnetic agitation makes its molten
Solution, then take 67 μ L 3- mercaptopropionic acids to be added thereto, with 0.1MNaOH regulation systems pH to 11.5；1mL steps are taken with syringe
(a) NaHTe solution is expelled to rapidly in above-mentioned system made from, and solution colour quickly becomes orange-yellow, places it in 100 DEG C of oil
Flow back 12h in bath, is dried finally centrifuge washing with ethanol repeatedly, produces the cadmium telluride nanocrystal of 3- mercaptopropionic acids cladding
(2) the cadmium telluride nanocrystal of 2- diethylamino ethanethiols cladding is prepared：
(a) the cadmium telluride nanocrystal for taking 3- mercaptopropionic acids made from 6mg steps (1) to coat is added to 3mL methanol solutions
Middle dissolving, obtains the cadmium telluride methanol solution of 3- mercaptopropionic acids cladding；
(b) methanol that 3mL 0.2M 2- diethylamino ethanethiol hydrochlorides are added into solution made from step (a) is molten
Liquid, is stirred at room temperature 30min；
(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 uviol lamp in course of reaction, color is turned to by red change
It is orange, show that diethylamino ethanethiol has exchanged to cadmium telluride surface.Illustration in such as Fig. 3, wherein from a left side in the illustration in A figures
To actual photographed figures of the CdTe that 3- mercaptopropionic acids are coated right respectively under visible ray and uviol lamp；Scheme B in illustration in from
Left-to-right is respectively actual photographed figures of the CdTe of 2- diethylamino ethanethiols cladding under visible ray and uviol lamp.By the illustration
It can be observed, the CdTe of ligand exchange reaction generation 2- diethylamino ethanethiol claddings occurs for the CdTe of 3- mercaptopropionic acids cladding,
Before and after the reaction, it is seen that solution is changed into faint yellow from orange under light, and solution is changed into orange from red under uviol lamp.Steamed by rotating
Hair removes methanol, and dialysis removes the 3- mercaptopropionic acids and unnecessary 2- diethylamino ethanethiol salt that ligand exchange comes out in solution
Hydrochlorate, vacuum drying obtains the cadmium telluride nanocrystal of 2- diethylamino ethanethiols cladding.
In Fig. 4, A is that the illustration in the upper right corner in the electron microscope for the cadmium telluride nanocrystal that 3- mercaptopropionic acids are coated, figure A is 3-
The high power electron microscope of the cadmium telluride nanocrystal of mercaptopropionic acid cladding；B is the cadmium telluride nanometer that 2- diethylamino ethanethiols are coated
The high power electricity for the cadmium telluride nanocrystal that the illustration in the upper right corner coats for 2- diethylamino ethanethiols in the electron microscope of crystal, figure B
Mirror figure；C is the grain size distribution for the cadmium telluride nanocrystal that 3- mercaptopropionic acids are coated；D is what 2- diethylamino ethanethiols were coated
The grain size distribution of cadmium telluride nanocrystal；It can be seen that nanocrystalline relative to the cadmium telluride that 3- mercaptopropionic acids are coated
Body, the particle diameter of the cadmium telluride nanocrystal of 2- diethylamino ethanethiols cladding diminishes.
The cadmium telluride of cadmium telluride nanocrystal and 2- the diethylamino ethanethiols cladding coated to 3- mercaptopropionic acids is nanocrystalline
The ultraviolet-visible absorption spectroscopy and fluorescence emission spectrum of body are detected：
The cadmium telluride nanocrystal and 2- diethylamino ethanethiol bags for the 3- mercaptopropionic acids cladding that the present embodiment is prepared
Then the cadmium telluride nanocrystal covered is diluted 5 times with distilled water, makes final solution concentration equal with 1mg/mL solution is prepared into
For 0.2mg/mL.
Detected using ultraviolet-uisible spectrophotometer to absorbing peak position：3mL 0.2mg/mL 3- sulfydryls are taken respectively
The cadmium telluride nanometer of the cadmium telluride nanocrystal solution of propionic acid cladding and 3mL 0.2mg/mL 2- diethylamino ethanethiols cladding
Crystalloid solution, is respectively placed in the UV, visible light quartz colorimetric utensil of two sides printing opacity, and quartz colorimetric utensil is placed in into UV, visible light light splitting
In photometric sample cell, start detection ultravioletvisible absorption intensity and wavelength, obtain ultraviolet-visible absorption spectroscopy.UV, visible light
Spectrophotometer parameter is set to：Ultravioletvisible absorption scope is 200nm-800nm, and slit width is 2nm.Detection is obtained after terminating
The c curves arrived in a curves and Fig. 3 B in Fig. 3 A, wherein a curves are the cadmium telluride nanocrystal that 3- mercaptopropionic acids are coated
Ultraviolet absorption curve, c curves are the ultraviolet absorption curve for the cadmium telluride nanocrystal that 2- diethylamino ethanethiols are coated.It is bent by a
Line and c curves understand that the UV absorption of the cadmium telluride nanocrystal of 2- diethylamino ethanethiols cladding there occurs blue shift, Qian Houbian
Change highly significant, it can be seen that there occurs ligand exchange reaction, successfully synthesize the cadmium telluride of 2- diethylamino ethanethiols cladding
Nanocrystal.
The fluorescence signal of generation is detected using XRF：0.8mL 0.2mg/mL 3- sulfydryls third are taken respectively
The cadmium telluride nanocrystal of the cadmium telluride nanocrystal of acid cladding and 0.8mL 0.2mg/mL 2- diethylamino ethanethiols cladding
Solution is placed in the fluorescence cuvette of four sides printing opacity, and fluorescence cuvette is placed in the sample cell of XRF, starts detection
Its fluorescence intensity and wavelength, obtain fluorescence emission spectrum.Fluorescence spectrum instrument parameter be respectively set to excitation wavelength 450nm and
350nm, launch wavelength is respectively 627nm and 590nm, and slit width is 5nm.Detection has obtained the b curves in Fig. 3 A after terminating
With the d curves in Fig. 3 B, wherein b curves are the fluorescence emission spectrum for the cadmium telluride nanocrystal that 3- mercaptopropionic acids are coated, d curves
The fluorescence emission spectrum of the cadmium telluride nanocrystal coated for 2- diethylamino ethanethiols.From the figure 3, it may be seen that 2- lignocaine second sulphur
The fluorescence emission spectrum of the cadmium telluride nanocrystal of alcohol cladding there occurs blue shift, front and rear change highly significant, it can be seen that occur
Ligand exchange reaction, successfully synthesizes the cadmium telluride nanocrystal of 2- diethylamino ethanethiols cladding.
Embodiment 2
The preparation method of the cadmium telluride nanocrystal of electrogenerated chemiluminescence material 2- diethylamino ethanethiols cladding, including with
Lower step：
(1) the cadmium telluride nanocrystal of 3- mercaptopropionic acids cladding is prepared：
(a) 51.8mg telluriums powder and 10mL H are taken2O is added in 25mL round-bottomed flasks, is passed through nitrogen 20min to exclude in solution
Oxygen, be placed in 80 DEG C of oil baths and system temperature be heated to after 80 DEG C, be rapidly added 40mg NaBH4, react 35min, solution
Color gradually becomes darkviolet, obtains NaHTe solution；
(b) 91.8mg CdCl are taken2·2.5H2O and 40mL H2O is added in 50mL round-bottomed flasks, and magnetic agitation makes its molten
Solution, then take 68 μ L 3- mercaptopropionic acids to be added thereto, with 0.2MNaOH regulation systems pH to 11.2；1mL steps are taken with syringe
(a) NaHTe solution is expelled to rapidly in above-mentioned system made from, and solution colour quickly becomes orange-yellow, places it in 100 DEG C of oil
Flow back 12h in bath, is dried finally centrifuge washing with ethanol repeatedly, produces the cadmium telluride nanocrystal of 3- mercaptopropionic acids cladding.
(2) the cadmium telluride nanocrystal of 2- diethylamino ethanethiols cladding is prepared：
(a) the cadmium telluride nanocrystal for taking 3- mercaptopropionic acids made from 6mg steps (1) to coat is added to 3mL methanol solutions
Middle dissolving, obtains the methanol solution of the cadmium telluride of 3- mercaptopropionic acids cladding；
(b) methanol that 3mL 0.2M 2- diethylamino ethanethiol hydrochlorides are added into solution made from step (a) is molten
Liquid, is stirred at room temperature 45min；
(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 uviol lamp in course of reaction, color turns to orange by red change
Color, shows that diethylamino ethanethiol has exchanged to cadmium telluride surface.Such as the illustration in Fig. 3, wherein in the illustration in A figures from a left side to
The right side is respectively actual photographed figures of the CdTe of 3- mercaptopropionic acids cladding under visible ray and uviol lamp；Scheme in the illustration in B from a left side
To actual photographed figures of the CdTe that 2- diethylamino ethanethiols are coated right respectively under visible ray and uviol lamp.Steamed by rotating
Hair removes methanol, and dialysis removes the 3- mercaptopropionic acids and unnecessary 2- diethylamino ethanethiol salt that ligand exchange comes out in solution
Hydrochlorate, vacuum drying obtains the cadmium telluride nanocrystal of 2- diethylamino ethanethiols cladding.
In Fig. 4, A is that the illustration in the upper right corner in the electron microscope for the cadmium telluride nanocrystal that 3- mercaptopropionic acids are coated, figure A is 3-
The high power electron microscope of the cadmium telluride nanocrystal of mercaptopropionic acid cladding；B is the cadmium telluride nanometer that 2- diethylamino ethanethiols are coated
The high power electricity for the cadmium telluride nanocrystal that the illustration in the upper right corner coats for 2- diethylamino ethanethiols in the electron microscope of crystal, figure B
Mirror figure；C is the grain size distribution for the cadmium telluride nanocrystal that 3- mercaptopropionic acids are coated；D is what 2- diethylamino ethanethiols were coated
The grain size distribution of cadmium telluride nanocrystal；It can be seen that nanocrystalline relative to the cadmium telluride that 3- mercaptopropionic acids are coated
Body, the particle diameter of the cadmium telluride nanocrystal of 2- diethylamino ethanethiols cladding diminishes.
Detect electrogenerated chemiluminescence situation：
Cadmium telluride nanocrystal and 2- the diethylamino ethanethiols cladding that 3- mercaptopropionic acids made from the present embodiment are coated
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
Being modified with the cadmium telluride nanocrystal that 6 μ L 2- diethylamino ethanethiols are coated 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 in electrochemical apparatus sample cell,
Proceed by cyclic voltammetry scan measurement.Electrochemical apparatus parameter is set to：Initial potential 0V, high potential 1.6V, low potential 0V,
Sweep speed 0.1V/S, sensitivity 10-4, RMT=900V.In addition, a cadmium telluride for being modified with 3- mercaptopropionic acids cladding is received
Meter Jing Ti glass-carbon electrode is placed on the 0.1M PBS (pH9.0) of the diethylamino ethanethiol hydrochlorides of 2- containing 5mM three-electrode system
In measure.
Fig. 2 is the electrogenerated chemiluminescence mechanism figure for the cadmium telluride nanocrystal that 2- diethylamino ethanethiols are coated, such as Fig. 2 institutes
Show, under certain potential, CdTe nanometer crystalline body and its surface coated coreagent molecule 2- diethylamino ethanethiol are same
Shi Fasheng is aoxidized, and forms radical cation；+ NR3 α-H generation deprotonations are anti-in subsequent molecule 2- diethylamino ethanethiols
Should, form strong reducing agent；Finally, the CdTe nanometer crystalline body of oxidation state is reduced into excited state molecule by reducing agent, final production
Raw electrogenerated chemiluminescence.
Cyclic voltammetry scan terminates to have obtained a, b and the c curve in Fig. 5, and wherein a curves are to modify on glass-carbon electrode
The cadmium telluride nanocrystal electrogenerated chemiluminescence feelings that (0.1M, pH9.0) is measured in PBS cushioning liquid of 3- mercaptopropionic acids cladding
Condition；B curves are to modify the cadmium telluride nanocrystal in the 2- diethylamino ethanethiols cladding on glass-carbon electrode in PBS cushioning liquid
In (0.1M, pH9.0) measure electrogenerated chemiluminescence situation；C curves are to modify in the 3- mercaptopropionic acids cladding on glass-carbon electrode
Cadmium telluride nanocrystal in the PBS cushioning liquid containing 5mM 2- diethylamino ethanethiol hydrochlorides (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 acids cladding is strong
Spend for 1005 that (such as curve a), the electrogenerated chemiluminescence intensity of the cadmium telluride nanocrystal of 2- diethylamino ethanethiols cladding is
17650 (such as curve b) and the luminous current potential of starting is 0.60 volt, the highest current potential that lights is 1.22 volts, 3- mercaptopropionic acids cladding
Cadmium telluride nanocrystal and add the electrogenerated chemiluminescence intensity of 5mM coreagent 2- diethylamino ethanethiols for 6200 (such as
Curve c) and the luminous current potential of starting is 0.75 volt, the highest current potential that lights is 1.30 volts；The telluride coated with 3- mercaptopropionic acids
The electrochemical luminescence intensity of cadmium nanocrystal compares, and the cadmium telluride nanocrystal electrochemistry of 2- diethylamino ethanethiols cladding is strong
Degree respectively may be about the cadmium telluride nanocrystal of 3- mercaptopropionic acids cladding and add the electricity of 5mM coreagent 2- diethylamino ethanethiols
Cause 17 times and 6 times of chemiluminescence intensity.2- diethylamino ethanethiols cladding cadmium telluride nanocrystal electrochemical strengths be about
The electroluminescent chemistry of the cadmium telluride nanocrystal of the 3- mercaptopropionic acids cladding of the 2- diethylamino ethanethiol hydrochlorides of coreagent containing 5mM
3 times of luminous intensity.Therefore, 2- diethylamino ethanethiols cladding cadmium telluride nanocrystal electrogenerated chemiluminescence intensity really
Than 3- mercaptopropionic acid coat cadmium telluride nanocrystal and add 5mM coreagent 2- diethylamino ethanethiol hydrochlorides it is electroluminescent
Chemiluminescence intensity significantly increases and originates that luminous current potential is low, and this illustrates to coat 2- diethylaminos in cadmium telluride nanocrystal surface
Base ethyl mercaptan can significantly increase the electrochemical signals of nanocrystal, with feasibility.
Embodiment 3
The preparation method of the cadmium telluride nanocrystal of electrogenerated chemiluminescence material 2- dimethylaminos ethyl mercaptan cladding, including with
Lower step：
(1) the cadmium telluride nanocrystal of 3- mercaptopropionic acids cladding is prepared：
(a) 25.4mg telluriums powder and 5mL H are taken2O is added in 25mL round-bottomed flasks, is passed through nitrogen 30min to exclude in solution
Oxygen, be placed in 80 DEG C of oil baths and system temperature be heated to after 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 are taken2·2.5H2O and 20mL H2O is added in 25mL round-bottomed flasks, and magnetic agitation dissolves it,
33.5 μ L 3- mercaptopropionic acids are taken to be added thereto again, with 0.1M NaOH regulation systems pH to 11.5；0.5mL steps are taken with syringe
(a) NaHTe solution is expelled to rapidly in above-mentioned system made from, and solution colour quickly becomes orange-yellow, places it in 100 DEG C of oil
Flow back 12h in bath, is dried finally centrifuge washing with ethanol repeatedly, produces the cadmium telluride nanocrystal of 3- mercaptopropionic acids cladding.
(2) the cadmium telluride nanocrystal of 2- dimethylaminos ethyl mercaptan cladding is prepared：
(a) it is molten that the cadmium telluride nanocrystal for taking 3- mercaptopropionic acids made from 3mg steps (1) to coat is added to 1.5mL methanol
Dissolved in liquid, obtain the methanol solution of the cadmium telluride of 3- mercaptopropionic acids cladding；
(b) methanol that 1.5mL 0.2M 2- dimethylamino ethanethiol hydrochlorides are added into solution made from step (a) is molten
Liquid, is stirred at room temperature 30min；
(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 uviol lamp in course of reaction, color is turned to by red change
It is orange, show that 2- dimethylamino ethyl mercaptans have exchanged to cadmium telluride surface.Methanol is removed by rotary evaporation, dialysis removes solution
3- mercaptopropionic acids and unnecessary 2- dimethylamino ethanethiol hydrochlorides that middle ligand exchange comes out, vacuum drying obtain 2- bis-
The cadmium telluride nanocrystal of methylamino ethyl mercaptan cladding.
Detect electrogenerated chemiluminescence situation：
Cadmium telluride nanocrystal and 2- dimethylaminos the ethyl mercaptan cladding that 3- mercaptopropionic acids made from the present embodiment are coated
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
Being modified with the cadmium telluride nanocrystal that 6 μ L 2- dimethylaminos ethyl mercaptans are coated 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 in electrochemical apparatus sample cell, is proceeded by
Cyclic voltammetry scan.Instrument parameter is set：Initial potential 0V, high potential 1.6V, low potential 0V, sweep speed 0.1V/S are sensitive
Degree 10-4, RMT=900V.
Detection has obtained a the and b curves in Fig. 6 after terminating.Wherein, a curves are that the cadmium telluride that 3- mercaptopropionic acids are coated is received
Meter Jing Ti is modified in after glassy carbon electrode surface, the electrogenerated chemiluminescence that (0.1M, pH9.0) is measured in PBS cushioning liquid；B is bent
Line is that the cadmium telluride nanocrystal that 2- diethylamino ethanethiols are coated is modified in after glassy carbon electrode surface, in PBS cushioning liquid
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 acids cladding
Chemiluminescence intensity is 1090 (such as curve a), the electroluminescent chemistry hair of the cadmium telluride nanocrystal of 2- dimethylaminos ethyl mercaptan cladding
Luminous intensity is 15600, and (such as curve b) and the luminous current potential of starting be 0.65 volt, the highest current potential that lights is 1.28 volts；With 3- mercaptos
The electrochemical luminescence intensity of the cadmium telluride nanocrystal of base propionic acid cladding compares, the cadmium telluride of 2- diethylamino ethanethiols cladding
Nanocrystal electrochemical strengths are about 14 times of its intensity.Therefore, the cadmium telluride nanocrystal of 2- dimethylaminos ethyl mercaptan cladding
The electrogenerated chemiluminescence intensity of cadmium telluride nanocrystal of electrogenerated chemiluminescence strength ratio 3- mercaptopropionic acids cladding significantly increase,
This illustrates that in cadmium telluride nanocrystal surface cladding 2- dimethylaminos ethyl mercaptan the electrochemistry of nanocrystal can be significantly increased
Signal, with feasibility and reliability.
Embodiment 4
The preparation method of the cadmium telluride nanocrystal of electrogenerated chemiluminescence material 2- dimethylaminos ethyl mercaptan cladding, including with
Lower step：
(1) the cadmium telluride nanocrystal of 3- mercaptopropionic acids cladding is prepared：
(a) 22.5mg telluriums powder and 5mL H are taken2O is added in 25mL round-bottomed flasks, is passed through nitrogen 30min to exclude in solution
Oxygen, be placed in 75 DEG C of oil baths and system temperature be heated to after 75 DEG C, be rapidly added 20mg NaBH4, react 40min, solution
Color gradually becomes darkviolet, obtains NaHTe solution；
(b) 47mg CdCl are taken2·2.5H2O and 20mL H2O is added in 25mL round-bottomed flasks, and magnetic agitation dissolves it,
40 μ L 3- mercaptopropionic acids are taken to be added thereto again, with 0.1M NaOH regulation systems pH to 11.0；0.8mL steps are taken with syringe
(a) NaHTe solution is expelled to rapidly in above-mentioned system made from, and solution colour quickly becomes orange-yellow, places it in 100 DEG C of oil
Flow back 3h in bath, is dried finally centrifuge washing with ethanol repeatedly, produces the cadmium telluride nanocrystal of 3- mercaptopropionic acids cladding.
(2) the cadmium telluride nanocrystal of 2- dimethylaminos ethyl mercaptan cladding is prepared：
(a) it is molten that the cadmium telluride nanocrystal for taking 3- mercaptopropionic acids made from 6mg steps (1) to coat is added to 1.5mL methanol
Dissolved in liquid, obtain the methanol solution of the cadmium telluride of 3- mercaptopropionic acids cladding；
(b) 1.5mL 112mg/mL 2- dimethylamino ethanethiol hydrochlorides are added into solution made from step (a)
Methanol solution, is stirred at room temperature 20min；
(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 uviol lamp in course of reaction, color turns to orange by red change
Color, shows that dimethylamino ethyl mercaptan has exchanged to cadmium telluride surface.Methanol is removed by rotary evaporation, dialysis is removed matches somebody with somebody in solution
3- mercaptopropionic acids and unnecessary 2- dimethylamino ethanethiol hydrochlorides that body is exchanged, vacuum drying obtain 2- diformazan ammonia
The cadmium telluride nanocrystal of base ethyl mercaptan cladding.
Detect electrogenerated chemiluminescence situation：
Cadmium telluride nanocrystal and 2- dimethylaminos the ethyl mercaptan cladding that 3- mercaptopropionic acids made from the present embodiment are coated
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
The cadmium telluride nanocrystal modification of body and 12 μ L 2- dimethylaminos ethyl mercaptans cladding dries it to the surface of glass-carbon electrode, will
Modified electrode is placed in three-electrode system solution (0.1M PBS, pH11.0), is placed in electrochemical apparatus sample cell, is started
It is circulated voltammetric scan.Instrument parameter is set：Initial potential 0V, high potential 1.6V, low potential 0V, sweep speed 0.1V/S,
Sensitivity 10-4, RMT=900V.Scanning result shows, electroluminescentization of the cadmium telluride nanocrystal of 2- dimethylaminos ethyl mercaptan cladding
The electrogenerated chemiluminescence intensity for learning the cadmium telluride nanocrystal of luminous strength ratio 3- mercaptopropionic acids cladding is significantly increased, and is illustrated in tellurium
Cadmium nanocrystal surface cladding 2- dimethylaminos ethyl mercaptan can significantly increase the electrochemical signals of nanocrystal, with feasible
Property and reliability.
Embodiment 5
The preparation method of the cadmium telluride nanocrystal of electrogenerated chemiluminescence material 2- dimethylaminos ethyl mercaptan cladding, including with
Lower step：
(1) the cadmium telluride nanocrystal of 3- mercaptopropionic acids cladding is prepared：
(a) 25mg telluriums powder and 5mL H are taken2O is added in 25mL round-bottomed flasks, is passed through nitrogen 30min to exclude in solution
Oxygen, is placed in 85 DEG C of oil baths and system temperature is heated to after 85 DEG C, be rapidly added 17.5mg NaBH4, react 25min, solution
Color gradually becomes darkviolet, obtains NaHTe solution；
(b) 44.6mg CdCl are taken2·2.5H2O and 20mL H2O is added in 25mL round-bottomed flasks, and magnetic agitation makes its molten
Solution, then take 22 μ L 3- mercaptopropionic acids to be added thereto, with 0.1M NaOH regulation systems pH to 12.0；0.2mL is taken to walk with syringe
Suddenly NaHTe solution is expelled to rapidly in above-mentioned system made from (a), and solution colour quickly becomes orange-yellow, places it in 100 DEG C
Flow back 8h in oil bath, is dried finally centrifuge washing with ethanol repeatedly, produces the cadmium telluride nanocrystal of 3- mercaptopropionic acids cladding.
(2) the cadmium telluride nanocrystal of 2- dimethylaminos ethyl mercaptan cladding is prepared：
(a) the cadmium telluride nanocrystal for taking 3- mercaptopropionic acids made from 6mg steps (1) to coat is added to the 1.5mL aqueous solution
Middle dissolving, obtains the methanol solution of the cadmium telluride of 3- mercaptopropionic acids cladding；
(b) 1.5mL 340mg/mL 2- dimethylamino ethanethiol hydrochlorides are added into solution made from step (a)
The aqueous solution, is stirred at room temperature 60min；
(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 uviol lamp in course of reaction, color turns to orange by red change
Color, shows that dimethylamino ethyl mercaptan has exchanged to cadmium telluride surface.Dialysis removes the 3- sulfydryls third that ligand exchange comes out in solution
Sour and unnecessary 2- dimethylamino ethanethiol hydrochlorides, vacuum drying obtains the cadmium telluride of 2- dimethylaminos ethyl mercaptan cladding
Nanocrystal.
Detect electrogenerated chemiluminescence situation：
Cadmium telluride nanocrystal and 2- dimethylaminos the ethyl mercaptan cladding that 3- mercaptopropionic acids made from the present embodiment are coated
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
Being modified with the cadmium telluride nanocrystal that 6 μ L 2- dimethylaminos ethyl mercaptans are coated 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 in electrochemical apparatus sample cell, is proceeded by
Cyclic voltammetry scan.Instrument parameter is set：Initial potential 0V, high potential 1.6V, low potential 0V, sweep speed 0.1V/S are sensitive
Degree 10-4, RMT=900V.From scanning result, the electroluminescent chemistry of the cadmium telluride nanocrystal of 2- dimethylaminos ethyl mercaptan cladding
The electrogenerated chemiluminescence intensity of the cadmium telluride nanocrystal of luminous strength ratio 3- mercaptopropionic acids cladding is significantly increased, and is illustrated in telluride
Cadmium nanocrystal surface cladding 2- dimethylaminos ethyl mercaptan can significantly increase the electrochemical signals of nanocrystal, with feasibility
And reliability.
Claims (10)
1. a kind of electrogenerated chemiluminescence material, it is characterised in that the electrogenerated chemiluminescence material is the chemical combination shown in chemical formula 1
The cadmium telluride nanocrystal of thing cladding；
In chemical formula 1, R1The alkyl for being 0~5 for carbon number, R2The alkyl for being 1~5 for carbon number.
2. electrogenerated chemiluminescence material according to claim 1, it is characterised in that the electrogenerated chemiluminescence material is 2-
The cadmium telluride nanocrystal of dimethylamino ethyl mercaptan cladding or the cadmium telluride nanocrystal of 2- diethylamino ethanethiols cladding.
3. electrogenerated chemiluminescence material according to claim 1 or 2, it is characterised in that the particle diameter of the nanocrystal is 1
~8nm.
4. electrogenerated chemiluminescence material according to claim 1 or 2, it is characterised in that the particle diameter of the nanocrystal is
1.7~2.7nm.
5. a kind of method for preparing the electrogenerated chemiluminescence material in Claims 1 to 4 described in any one, it is characterised in that
This method comprises the following steps：
1) the cadmium telluride nanocrystal of 3- mercaptopropionic acids cladding is prepared；
2) using step 1) prepare 3- mercaptopropionic acids cladding cadmium telluride nanocrystal as template, prepared by ligand exchange reaction
The cadmium telluride nanocrystal of compound cladding shown in chemical formula 1.
6. method according to claim 5, it is characterised in that the cadmium telluride for preparing 3- mercaptopropionic acids cladding is nanocrystalline
The method of body comprises the following steps：
1) in inert atmosphere, Te and NaBH are made475 DEG C~85 DEG C are reacted 25~40 minutes in water, obtain NaHTe solution；Wherein
The amount of each reactant added is：Every milliliter of water adds Te 4.5~5.18mg, NaBH43.5~4.0mg；
2) by CdCl2·2.5H2O is dissolved in water, and is added after 3- mercaptopropionic acids, regulation pH value of solution to 11.0~12.0, is added institute
State after NaHTe solution, 3~12h of backflow, use ethanol centrifuge washing, isolated solid is dried, obtain 3- mercaptopropionic acid bags
The cadmium telluride nanocrystal covered；The amount of each reactant wherein added is：Every milliliter of water adds CdCl2·2.5H2O 2.23~
0.01~the 0.04mL of μ L, NaHTe solution of 2.35mg, 3- mercaptopropionic acid 1.1~2.
7. method according to claim 5, it is characterised in that the step 2) be specially：Using water or methanol as anti-
Solvent is answered, by the hydrochloride of the compound shown in chemical formula 1 and step 1) prepare 3- mercaptopropionic acids cladding cadmium telluride nanometer
After reaction is stirred at room temperature 20~60 minutes in crystal, water is added, continues reaction to be stirred at room temperature 6~20 hours, remove methanol, removed molten
3- mercaptopropionic acids and remaining hydrochloride in liquid, the cadmium telluride that the cladding of the compound shown in chemical formula 1 is obtained after vacuum drying are received
Meter Jing Ti；The amount of each reactant wherein added is：Every milliliter of reaction dissolvent adds the cadmium telluride of 3- mercaptopropionic acids cladding
1~2mg of nanocrystal, 56~170mg of hydrochloride of the compound shown in chemical formula 1.
8. method according to claim 6, it is characterised in that the inert atmosphere is nitrogen atmosphere.
9. the application of the electrogenerated chemiluminescence material in a kind of Claims 1 to 4 described in any one, it is characterised in that by institute
Electrogenerated chemiluminescence material is stated to detect for anodic electrochemiluminescence.
10. the application of the electrogenerated chemiluminescence material in a kind of Claims 1 to 4 described in any one, it is characterised in that by institute
The modification of electrogenerated chemiluminescence material is stated in working electrode surface, three-electrode system is set up and carries out electrochemiluminescdetection detection, electrolysis
Coreagent is free of in liquid.
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