CN109799212A - Method based on CdTe-ZnCdSe double quantum point paper chip substrate detection organophosphorus pesticide - Google Patents
Method based on CdTe-ZnCdSe double quantum point paper chip substrate detection organophosphorus pesticide Download PDFInfo
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Abstract
The present invention relates to paper chip sensory field more particularly to a kind of methods based on CdTe-ZnCdSe double quantum point paper chip substrate detection organophosphorus pesticide.Based on the method for CdTe-ZnCdSe double quantum point paper chip substrate detection organophosphorus pesticide, comprising steps of the synthesis of (1) CdTe quantum；(2) synthesis of the quantum dot of ZnCdSe；(3) preparation of CdTe-ZnCdSe double quantum point paper chip substrate；The synthesis of (4) four-(4- pyridyl group) zinc protoporphyrin self assembly solution；(5) organophosphorus pesticide standard color comparison card is made；(6) the organophosphorus pesticide concentration of sample is detected；The present invention have the characteristics that preparation it is simple, can rapid field detection, at low cost, fast response time, sensitivity and selectively high, and compared with single quantum, the mixed fluorescence color of double quantum point solution is easier to generate color differentiation in paper chip after being influenced by quencher, improves the sensitivity of detection.
Description
Technical field
The present invention relates to paper chip sensory fields, more particularly to one kind to be based on CdTe-ZnCdSe double quantum point core chip base
The method of bottom detection organophosphorus pesticide.
Background technique
Organophosphorus pesticide is one of most common pesticide in China, remain in organophosphorus pesticide on crops and fruits and vegetables into
After entering in human body, it will lead to acetylcholine and excessively generate the illnesss such as neurological disorders, or even human body can be caused irremediable
Damage.With extensive use of the organophosphorus insecticide in terms of China crops and fruits and vegetables cultivation, develop it is a kind of it is novel quickly,
Easy and highly sensitive organophosphorus pesticide minimal residue detection method seems especially urgent.
Gas chromatography mass spectrometry method (GC- of the detection means of organophosphorus insecticide from initial bioassay into chromatographic technique
MS), gas chromatography (GC), capillary electrophoresis, LC-MS (HPLC-MS), high performance liquid chromatography (HPLC) and existing
In more commonly used chemical sensor method and immuno analytical method, all there are some disadvantages in varying degrees and cannot obtain extensively
Using.
Summary of the invention
In order to solve the above problem, the object of the present invention is to provide one kind to be based on CdTe-ZnCdSe double quantum point core chip base
The method that organophosphorus pesticide is detected at bottom, can not only detect organophosphorus pesticide, and can be realized and exempt from instrument fast, in high sensitivity
Live detection immediately.
To achieve the above object, the CdTe-ZnCdSe double quantum point paper chip substrate designed by the present invention, feature exist
In including paper base material and the CdTe-ZnCdSe double quantum point being fixed on paper base material, the CdTe-ZnCdSe double quantum point
It is mixed with by CdTe quantum and ZnCdSe quantum dot.
Preferably, the CdTe quantum concentration is 143~146nmol/L, and ZnCdSe quantum dot concentration is 318
The volume ratio of~422nmol/L, CdTe quantum and the mixing of ZnCdSe quantum dot is 1~2:1~2.
It preferably, further include paper support, multiple CdTe-ZnCdSe double quantum point paper chip substrates pass through hydrophobic
Property viscosity immobilization with adhesive tape is in paper support.
4, a kind of preparation method of CdTe-ZnCdSe double quantum point paper chip substrate, which is characterized in that comprising steps of
(1) synthesis of CdTe quantum
By dichloride cadmium and N-acetyl-L-cysteine be dissolved in pure water be uniformly mixed, then sequentially add sodium tellurite,
Sodium borohydride, finally baking oven in react after the CdTe quantum that is fluoresced；
(2) synthesis of the quantum dot of ZnCdSe
By ZnCl2It is dissolved in pure water and being uniformly mixed with N-acetyl-L-cysteine, sequentially add CdCl2It is obtained with NaHSe
Mixed liquor is finally placed in reaction kettle reaction, the ZnCdSe quantum dot to be fluoresced by mixed liquor；
(3) preparation of CdTe-ZnCdSe double quantum point paper chip substrate
It is added dropwise on paper base material after CdTe quantum and ZnCdSe quantum dot are mixed, paper base material absorbs fixed CdTe quantum
Up to CdTe-ZnCdSe quantum dot paper chip substrate after point and ZnCdSe quantum dot.
Preferably, the CdTe quantum emits aubergine fluorescence and launch wavelength is 630~640nm.
Preferably, the ZnCdSe quantum dot emission yellow-greenish phosphorescent light and launch wavelength are 480~500nm.
7, a kind of method based on CdTe-ZnCdSe double quantum point paper chip substrate detection organophosphorus pesticide, feature exist
In, comprising steps of
(1) synthesis of CdTe quantum
By dichloride cadmium and N-acetyl-L-cysteine be dissolved in pure water be uniformly mixed, then sequentially add sodium tellurite,
Sodium borohydride, finally baking oven in react after the CdTe quantum that is fluoresced；
(2) synthesis of the quantum dot of ZnCdSe
By ZnCl2It is dissolved in pure water and being uniformly mixed with N-acetyl-L-cysteine, sequentially add CdCl2It is obtained with NaHSe
Mixed liquor is finally placed in reaction kettle reaction, the ZnCdSe quantum dot to be fluoresced by mixed liquor；
(3) preparation of CdTe-ZnCdSe double quantum point paper chip substrate
It is added dropwise on paper base material after CdTe quantum and ZnCdSe quantum dot are mixed, paper base material absorbs fixed CdTe quantum
Up to CdTe-ZnCdSe quantum dot paper chip substrate after point and ZnCdSe quantum dot；
The synthesis of (4) four-(4- pyridyl group) zinc protoporphyrin self assembly solution
Four-(4- pyridyl group) zinc protoporphyrins are dissolved in n,N-Dimethylformamide solution, obtain four-(4- pyridyl group) zinc protoporphyrins
Four-(4- pyridyl group) zinc protoporphyrin solution are added into dodecyl trimethyl ammonium bromide for solution, and reaction stops after mixing evenly,
Obtain four-(4- pyridyl group) zinc protoporphyrin self assembly solution；
(5) organophosphorus pesticide standard color comparison card is made
The organophosphorus pesticide of various concentration and the mixed solution of four-(4- pyridyl group) zinc protoporphyrin self assembly solution are prepared, it will
Mixed solution is successively added dropwise in CdTe-ZnCdSe double quantum point paper chip substrate, observes in ultraviolet camera bellows, various concentration has
The machine phosphorus insecticide color different from the reaction generation of CdTe-ZnCdSe double quantum point paper chip substrate, it is bis- to each CdTe-ZnCdSe
Quantum dot paper chip substrate is taken pictures, and arrangement obtains organophosphorus pesticide standard color comparison card；
(6) the organophosphorus pesticide concentration of sample is detected
Sample and four-(4- pyridyl group) zinc protoporphyrin self assembly solution are mixed, are added dropwise in double quantum point paper chip substrate,
There is color response to sample in double quantum point paper chip substrate, control organophosphorus pesticide standard color comparison card obtains organic phosphorus in sample
The concentration of pesticide.
Preferably, step (1) CdTe quantum transmitting aubergine fluorescence and launch wavelength are 630~640nm；Step
Suddenly (2) ZnCdSe quantum dot emission yellow-greenish phosphorescent light and launch wavelength are 480~500nm.
Preferably, the CdTe quantum concentration is 143~146nmol/L, and ZnCdSe quantum dot concentration is 318
The volume ratio of~422nmol/L, CdTe quantum and the mixing of ZnCdSe quantum dot is 1~2:1~2.
Preferably, in the step (5), the concentration of four-(4- pyridyl group) zinc protoporphyrin self assembly solution is 0.46
~0.48 μm of ol/L, the concentration of the organophosphorus pesticide are 0~50 μ g/L.
The present invention has the advantages that the present invention is based on CdTe-ZnCdSe compared with existing organophosphorus insecticide detection method
The method that double quantum point paper chip substrate detects organophosphorus pesticide have preparation it is simple, can rapid field detection, at low cost, response
The feature that speed is fast, sensitivity and selectivity are high, and compared with single quantum solid color, double quantum point solution is mixed glimmering
Light color is easier to generate color differentiation in paper chip after being influenced by quencher, improves the sensitivity of detection.
Detailed description of the invention
Fig. 1 is the machine that the method for organophosphorus pesticide is detected the present invention is based on CdTe-ZnCdSe double quantum point paper chip substrate
Manage schematic diagram；
Fig. 2 is four-(4- pyridyl group) zinc protoporphyrin self assembly solution transmission electron microscope figures of the invention；
Fig. 3 is four-(4- pyridyl group) zinc protoporphyrin self assembly solution and CdTe-ZnCdSe double quantum point transmission electricity of the invention
Sub- microscope figure；
Fig. 4 is that the present invention is based on the feasibility test figures that double quantum point paper chip substrate detects organophosphorus pesticide；4A is double
Quantum dot paper chip base color, 4B are that four-(4- pyridyl group) zinc protoporphyrin self assemblies are added into double quantum point paper chip substrate
Double quantum point fluorescent quenching forms dark violet chromatic graph after solution, and 4C is that four-(4- pyridines are added into double quantum point paper chip substrate
Base) zinc protoporphyrin self assembly solution (0.47 μM) and Rogor (50 μ g/L) mixed solution from mulberry become red；
Fig. 5 is the standard color comparison card of Rogor prepared by the present invention；Fig. 5 A~5F be corresponding in turn to 0 μ g/L, 1 μ g/L, 5 μ g/L,
The color that 10 μ g/L, 20 μ g/L, 50 μ g/L Rogor generate；
Fig. 6 is the comparative diagram that Rogor is detected based on CdTe single quantum dot or ZnCdSe single quantum dot paper chip, and Fig. 6 A is
The color change figure of CdTe quantum paper chip substrate, Fig. 6 B are the color change figure of ZnCdSe quantum dot paper chip substrate；
Fig. 7 is the spy that double quantum point of the present invention-nanometer porphyrin fluorescence paper chip sensor visualization detects organophosphorus pesticide
It is anisotropic.7A is the blank control figure of double quantum point paper chip substrate, and Fig. 7 B double quantum point paper chip substrate detects the color of Rogor
Variation diagram, 7C are the comparative diagram that four-(4- pyridyl group) zinc protoporphyrin self assembly solution (0.47 μM) fluorescent quenching afterwards is added dropwise, Fig. 7 D~
7G is followed successively by the color change figure of double quantum point paper chip substrate detection Deltamethrin, MTMC, cartap, Acetochlor；
Fig. 8 is the standard color comparison card of DDVP prepared by the present invention；Fig. 8 A~8E is corresponding in turn to 1 μ g/L, 5 μ g/L, 10 μ g/
L, the color that 20 μ g/L, 50 μ g/L DDVP generate；
Fig. 9 is the standard color comparison card of demeton prepared by the present invention；Fig. 9 A~9E is corresponding in turn to 1 μ g/L, 5 μ g/L, 10 μ g/
L, the color that 20 μ g/L, 50 μ g/L DDVP generate；
Figure 10 is that the present invention is based on the training sets and forecast set of three kinds of organophosphorus pesticides in PLSDA model inspection complex matrices
Analyze result.10A is Rogor training set analysis as a result, 10a is Rogor prediction set analysis as a result, 10B is DDVP training set point
Analysis is as a result, 10b is DDVP prediction set analysis as a result, 10C is demeton training set analysis as a result, 10c is demeton forecast set
Analyze result.
Specific embodiment
For a better understanding of the invention, invention is described in detail below with reference to drawings and concrete examples.
To solve in existing detection organophosphorus pesticide technology, there are instrumentation complexity, the problem of analysis time length, this hairs
It is bright that a kind of method based on CdTe-ZnCdSe double quantum point paper chip substrate detection organophosphorus pesticide is provided, specifically, this hair
The bright mixed solution using organophosphorus pesticide and four-(4- pyridyl group) zinc protoporphyrin self assembly solution can make the bis- amounts of CdTe-ZnCdSe
The son point changed principle of fluorescence color, prepares the standard color comparison card of organophosphorus pesticide, by carrying out pair with standard color comparison card
The concentration of organophosphorus pesticide to be measured is judged according to color.Below by by specific embodiment come to of the invention based on CdTe-
The preferred embodiment of the method for ZnCdSe double quantum point paper chip substrate detection organophosphorus pesticide is described in detail.
Embodiment 1
The method for preparing CdTe-ZnCdSe double quantum point paper chip substrate, comprising steps of
(1) synthesis of CdTe quantum
It is super that dichloride cadmium (0.1142g, 12.5mM) and N-acetyl-L-cysteine (0.0979g, 15mM) are dissolved in 40mL
In pure water, pH value of solution is adjusted to 8.00 with sodium hydroxide solution after stirring 15 minutes under room temperature, normal pressure, then inflated with nitrogen ice bath
Stirring 20 minutes, be added sodium tellurite (0.0216g, 2.5mM), stir 15 minutes, add hydroboration (0.0113g,
7.5mM), it stirs 15 minutes, finally this solution is put into reaction kettle, is reacted 50 minutes in 200 DEG C of baking oven, is cooled to room
Temperature obtains the CdTe quantum for the aubergine that launch wavelength is 635nm.
(2) synthesis of the quantum dot of ZnCdSe
By ZnCl2(6.4mM) and N-acetyl-L-cysteine (19.2mM) are dissolved in ultrapure water, in ice bath and normal pressure
Under the conditions of be stirred to react 20min, the pH of mixed liquor is then adjusted to 9.70 with sodium hydroxide solution, CdCl is added2(0.064mM)
And inflated with nitrogen continues ice bath stirring 5min.Then NaHSe (0.64mM) is added, continues to stir 5min, finally by reaction mixture
It is placed in reaction kettle, 65min is reacted at 200 DEG C, then launch wavelength can be prepared in the ZnCdSe of the pistac of 490nm
Quantum dot.
(3) preparation of CdTe-ZnCdSe double quantum point paper chip substrate
By CdTe quantum and ZnCdSe quantum dot to obtain CdTe-ZnCdSe double quantum point after identical volume mixture,
It draws 10 μ LCdTe-ZnCdSe double quantum points with liquid-transfering gun to be added dropwise on the circular filter paper that 3 diameters are 5mm, by 3 round filters
Paper places 37 DEG C of baking ovens and dries 4 minutes or so to doing slightly, obtains 3 CdTe-ZnCdSe double quantum point paper chip substrates,
It is red in the ultraviolet camera bellows of 365nm, takes pictures and save picture.
Embodiment 2
Based on the method for CdTe-ZnCdSe double quantum point paper chip substrate detection Rogor, comprising steps of
(1) synthesis of CdTe quantum
It is super that dichloride cadmium (0.1142g, 12.5mM) and N-acetyl-L-cysteine (0.0979g, 15mM) are dissolved in 40mL
In pure water, pH value of solution is adjusted to 8.00 with sodium hydroxide solution after stirring 15 minutes under room temperature, normal pressure, then inflated with nitrogen ice bath
Stirring 20 minutes, be added sodium tellurite (0.0216g, 2.5mM), stir 15 minutes, add hydroboration (0.0113g,
7.5mM), it stirs 15 minutes, finally this solution is put into reaction kettle, is reacted 50 minutes in 200 DEG C of baking oven, is cooled to room
Temperature obtains 145nM, the CdTe quantum for the aubergine that launch wavelength is 635nm.
(2) synthesis of the quantum dot of ZnCdSe
By ZnCl2(6.4mM) and N-acetyl-L-cysteine (19.2mM) are dissolved in ultrapure water, in ice bath and normal pressure
Under the conditions of be stirred to react 20min, the pH of mixed liquor is then adjusted to 9.70 with sodium hydroxide solution, CdCl is added2(0.064mM)
And inflated with nitrogen continues ice bath stirring 5min.Then NaHSe (0.64mM) is added, continues to stir 5min, finally by reaction mixture
Be placed in reaction kettle, react 65min at 200 DEG C, obtain 420nM, launch wavelength the pistac of about 490nm ZnCdSe
Quantum dot.
(3) preparation of CdTe-ZnCdSe double quantum point paper chip substrate
By CdTe quantum and ZnCdSe quantum dot to obtain CdTe-ZnCdSe double quantum point after identical volume mixture,
It draws 10 μ LCdTe-ZnCdSe double quantum points with liquid-transfering gun to be added dropwise on the circular filter paper that 3 diameters are 5mm, by 3 round filters
Paper places 37 DEG C of baking ovens and dries 4 minutes or so to doing slightly, obtains 3 CdTe-ZnCdSe double quantum point paper chip substrates,
It is red in the ultraviolet camera bellows of 365nm, takes pictures and save picture.
The synthesis of (4) four-(4- pyridyl group) zinc protoporphyrin self assembly solution
Four-(4- pyridyl group) zinc protoporphyrins are dissolved in n,N-Dimethylformamide (DMF) solution, obtain 8.5 × 10-5M's
Four-(4- pyridyl group) zinc protoporphyrin solution.500 μ L, tetra--(4- pyridyl group) zinc protoporphyrin solution is drawn in the centrifuge tube of 14mL, is added
After the 0.1M dodecyl trimethyl ammonium bromide (DTAB) of 9.5mL, ultrasonic 10min, subsequent 70 DEG C of hot bath 15min are obtained
17.85 μM of four-(4- pyridyl group) zinc protoporphyrin self assembly solution, is kept in dark place, as shown in Fig. 2, four-(4- pyridyl group) zinc protoporphyrins are certainly
The transmission electron microscope characterization of assembling solution is shown as the nanometer rods of 60~100nm of partial size.
(5) Rogor standard color comparison card is made
Prepare one: 0 μ g/L Rogor of solution and 0.47 μM of four-(4- pyridyl group) zinc protoporphyrin self assembly solution；
Two: 1 μ g/L Rogor of solution and 0.47 μM of four-(4- pyridyl group) zinc protoporphyrin self assembly solution；
Three: 5 μ g/L Rogor of solution and 0.47 μM of four-(4- pyridyl group) zinc protoporphyrin self assembly solution；
Four: 10 μ g/L Rogor of solution and 0.47 μM of four-(4- pyridyl group) zinc protoporphyrin self assembly solution；
Five: 20 μ g/L Rogor of solution and 0.47 μM of four-(4- pyridyl group) zinc protoporphyrin self assembly solution；
Six: 50 μ g/L Rogor of solution and 0.47 μM of four-(4- pyridyl group) zinc protoporphyrin self assembly solution；
The above-mentioned solution one to six of 10 μ L is drawn with liquid-transfering gun to be added dropwise respectively in CdTe-ZnCdSe double quantum point paper chip substrate
On, observation has different color changes in ultraviolet camera bellows, takes pictures in the ultraviolet camera bellows of 365nm and saves picture, picture is imported
PhotoShop software extracts the color data RGB on picture, and goes out colored dot with the numerical simulation and obtain Rogor standard colorimetric
Card.The standard color comparison card of Rogor as shown in connection with fig. 5, Fig. 5 A~5F are corresponding in turn to 0 μ g/L, 1 μ g/L, 5 μ g/L, 10 μ g/L, 20 μ g/
L, the color that 50 μ g/L Rogor generate.
In conjunction with shown in Fig. 1 and Fig. 3, four-(4- pyridyl group) zinc protoporphyrin self assembly solution are added dropwise as can be seen from Figure 1
In CdTe-ZnCdSe double quantum point paper chip substrate, acted on by fluorescence resonance energy transfer and Photo-induced electron transfer so that
Double quantum point fluorescent quenching, color becomes mulberry from red on paper, however, four-(4- pyridyl group) zinc quinolines are self-assembly of increasing
Quick type micelle volume can be formed efficiently in conjunction with the electron rich group in organophosphorus pesticide stable by electron adsorption effect
Structure, the spatial position between the nanometer porphyrin and double quantum point of organophosphorus pesticide molecule package change, double quantum point
Fluorescence property is restored.Such as Fig. 4, double quantum point paper chip base color such as Fig. 4 A is red, to double quantum point core chip base
Double quantum point fluorescent quenching forms mulberry (such as Fig. 4 B) after four-(4- pyridyl group) zinc protoporphyrin self assembly solution are added in bottom, to
Four-(4- pyridyl group) zinc protoporphyrin self assembly solution (0.47 μM) are added in double quantum point paper chip substrate and Rogor (50 μ g/L) is mixed
Closing solution becomes red (such as Fig. 4 C) from mulberry.As shown in connection with fig. 5, various concentration organophosphorus pesticide is mixed with nanometer porphyrin,
In double quantum point paper chip substrate different color changes occurs for dropwise addition, as organophosphorus pesticide concentration increases, color on paper
Lilac is become from mulberry, then becomes light red, eventually becomes red, reaches Visual retrieval organophosphorus pesticide on paper.
(6) the Rogor concentration of sample is detected
Sample and 0.47 μM of four-(4- pyridyl group) zinc protoporphyrin self assembly solution are mixed, are added dropwise in double quantum point paper chip
In substrate, there is color response to sample in double quantum point paper chip substrate, control Rogor standard color comparison card obtains Rogor in sample
Concentration.
Why the present invention uses double quantum point as paper chip substrate, is because of double quantum and single quantum solid color phase
Than double quantum point can be combined the characteristics of luminescence that two amounts is put, and can produce more color intervals for more smart
The organophosphorus pesticide for really analyzing various concentration improves the sensitivity of probe, the mixed fluorescence color of double quantum point solution
It is easier to generate color differentiation in paper chip after being influenced by quencher, it can be achieved that recognizing various concentration on fluorescence color
Sample carries out single quantum comparative experiments, specific mistake to verify the superiority that double quantum recognize on fluorescence color than single quantum
Cheng Wei, the CdTe quantum paper chip substrate and ZnCdSe quantum dot paper chip substrate of preparation, respectively to CdTe quantum core
The Rogor (1~50 μ g/L) and four-(4- pyridyl groups) of various concentration are added dropwise in piece substrate and ZnCdSe quantum dot paper chip substrate
The mixed solution of zinc protoporphyrin self assembly solution (0.47 μM) does not generate apparent color and distinguishes as a result such as Fig. 6.Fig. 6 A is
The color change figure of CdTe quantum paper chip substrate, Fig. 6 B are the color change figure of ZnCdSe quantum dot paper chip substrate.It can
To find out, Rogor (1~50 μ g/ of the mono- quantum paper chip substrate of CdTe or the mono- quantum paper chip substrate of ZnCdSe to various concentration
L apparent color) is not generated to distinguish.
In order to verify the specificity based on double quantum point paper chip substrate detection organophosphorus pesticide, organophosphorus pesticide is carried out
Specific selection test, detailed process are that drawing 10 μ L concentration with liquid-transfering gun is 20 μ g/L other class pesticide (Deltamethrins, speed
Go out prestige, cartap, Acetochlor) with four-(4- pyridyl group) zinc protoporphyrin self assembly solution (0.47 μM) mixed solutions in double quantum point
In paper chip substrate, as shown in Fig. 7 D~7G, restore without apparent fluorescence, be still mulberry, and 10 μ L concentration are added and are
10 μ g/L Rogor and four-(4- pyridyl group) zinc protoporphyrin self assembly solution (0.47 μM) mixed solutions are in double quantum point paper chip substrate
On, light red (such as Fig. 7 B) is become from mulberry, extracts the color data RGB on picture with photoshop software, wherein 7A is
The blank control figure of double quantum point paper chip substrate, 7C are that four-(4- pyridyl group) zinc protoporphyrin self assembly solution (0.47 μM) are added dropwise
The comparative diagram of fluorescent quenching afterwards.
In addition, the Rogor in the complex matrices (cider and cabbage juice) of various concentration is added dropwise in double quantum point core chip base
On bottom, still there is significantly different degree color to distinguish, it was demonstrated that the side based on double quantum point paper chip substrate detection organophosphorus pesticide
Method can accurately detect Rogor in complex matrices, and the interference by matrix is small.
Embodiment 3
Based on the method for CdTe-ZnCdSe double quantum point paper chip substrate detection DDVP, comprising steps of
(1) synthesis of CdTe quantum fluorescence probe
(2) synthesis of the quantum dot fluorescence probe of ZnCdSe
(3) preparation of double quantum point paper chip substrate
The synthesis of (4) four-(4- pyridyl group) zinc protoporphyrin self assembly solution
Above step (1)~(4) are identical as (1) the step of embodiment 2~(4), and details are not described herein.
(5) DDVP standard color comparison card is made
One: 1 μ g/L DDVP of solution and 0.47 μM of four-(4- pyridyl group) zinc protoporphyrin self assembly solution；
Two: 5 μ g/L DDVP of solution and 0.47 μM of four-(4- pyridyl group) zinc protoporphyrin self assembly solution；
Three: 10 μ g/L DDVP of solution and 0.47 μM of four-(4- pyridyl group) zinc protoporphyrin self assembly solution；
Four: 20 μ g/L DDVP of solution and 0.47 μM of four-(4- pyridyl group) zinc protoporphyrin self assembly solution；
Five: 50 μ g/L DDVP of solution and 0.47 μM of four-(4- pyridyl group) zinc protoporphyrin self assembly solution；
The above-mentioned solution one to six of 10 μ L is drawn with liquid-transfering gun to be added dropwise respectively in CdTe-ZnCdSe double quantum point paper chip substrate
On, observation has different color changes in ultraviolet camera bellows, takes pictures in the ultraviolet camera bellows of 365nm and saves picture, picture is imported
PhotoShop software extracts the color data RGB on picture, and goes out colored dot with the numerical simulation and obtain DDVP standard ratio
Colour atla.DDVP standard color comparison card as shown in connection with fig. 8, Fig. 8 A~8E are corresponding in turn to 1 μ g/L, 5 μ g/L, 10 μ g/L, 20 μ g/L, 50
The color that μ g/L DDVP generates.
(6) the DDVP concentration of sample is detected
Sample and 0.47 μM of four-(4- pyridyl group) zinc protoporphyrin self assembly solution are mixed, are added dropwise in double quantum point paper chip
In substrate, there is color response to sample in double quantum point paper chip substrate, control DDVP standard color comparison card obtains opposing in sample
The concentration of dichlorvos.
Embodiment 4
Based on the method for CdTe-ZnCdSe double quantum point paper chip substrate detection demeton, comprising steps of
(1) synthesis of CdTe quantum fluorescence probe
(2) synthesis of the quantum dot fluorescence probe of ZnCdSe
(3) preparation of double quantum point paper chip substrate
The synthesis of (4) four-(4- pyridyl group) zinc protoporphyrin self assembly solution
Above step (1)~(4) are identical as (1) the step of embodiment 2~(4), and details are not described herein.
(5) demeton standard color comparison card is made
Prepare one: 0 μ g/L demeton of solution and 0.47 μM of four-(4- pyridyl group) zinc protoporphyrin self assembly solution；
Two: 1 μ g/L demeton of solution and 0.47 μM of four-(4- pyridyl group) zinc protoporphyrin self assembly solution；
Three: 5 μ g/L demeton of solution and 0.47 μM of four-(4- pyridyl group) zinc protoporphyrin self assembly solution；
Four: 10 μ g/L demeton of solution and 0.47 μM of four-(4- pyridyl group) zinc protoporphyrin self assembly solution；
Five: 20 μ g/L demeton of solution and 0.47 μM of four-(4- pyridyl group) zinc protoporphyrin self assembly solution；
Six: 50 μ g/L demeton of solution and 0.47 μM of four-(4- pyridyl group) zinc protoporphyrin self assembly solution；
The above-mentioned solution one to six of 10 μ L is drawn with liquid-transfering gun to be added dropwise respectively in CdTe-ZnCdSe double quantum point paper chip substrate
On, observation has different color changes in ultraviolet camera bellows, takes pictures in the ultraviolet camera bellows of 365nm and saves picture, picture is imported
PhotoShop software extracts the color data RGB on picture, and goes out colored dot with the numerical simulation and obtain demeton standard ratio
Colour atla.Demeton standard color comparison card as shown in connection with fig. 9, Fig. 9 A~9E are corresponding in turn to 1 μ g/L, 5 μ g/L, 10 μ g/L, 20 μ g/L, 50
The color that μ g/L DDVP generates.
(6) the interior suction phosphorus concentration of sample is detected
Sample and 0.47 μM of four-(4- pyridyl group) zinc protoporphyrin self assembly solution are mixed, are added dropwise in double quantum point paper chip
In substrate, there is color response to sample in double quantum point paper chip substrate, control demeton standard color comparison card obtains in sample
Inhale the concentration of phosphorus.
Demeton in the complex matrices (cider and cabbage juice) of various concentration is added dropwise in double quantum point core chip base
On bottom, still there is significantly different degree color to distinguish, extract rgb value with PS software, will in complex matrices Rogor, DDVP and
The RGB of demeton detection establishes data array, and data modeling is sentenced in application mode identification partial least squares discriminant analysis (PLSDA)
It does not analyze, as a result, it has been found that having good differentiation for the different organophosphorus pesticides in different substrates as a result, such as Figure 10.
3 kinds of embodiments of the invention above described embodiment only expresses, the description thereof is more specific and detailed, but not
Limitations on the scope of the patent of the present invention therefore can be interpreted as.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of CdTe-ZnCdSe double quantum point paper chip substrate, which is characterized in that including paper base material and be fixed on paper base material
On CdTe-ZnCdSe double quantum point, the CdTe-ZnCdSe double quantum point mixes by CdTe quantum and ZnCdSe quantum dot
It is prepared.
2. CdTe-ZnCdSe double quantum point paper chip substrate according to claim 1, which is characterized in that the CdTe amount
Son point concentration is 143~146nmol/L, and ZnCdSe quantum dot concentration is 318~422nmol/L, CdTe quantum and ZnCdSe
The volume ratio of quantum dot mixing is 1~2:1~2.
3. CdTe-ZnCdSe double quantum point paper chip substrate according to claim 1, which is characterized in that it further include paper support,
Multiple CdTe-ZnCdSe double quantum point paper chip substrates are by hydrophobic viscous immobilization with adhesive tape in paper support.
4. a kind of preparation method of CdTe-ZnCdSe double quantum point paper chip substrate, which is characterized in that comprising steps of
(1) synthesis of CdTe quantum
Dichloride cadmium and N-acetyl-L-cysteine are dissolved in pure water and are uniformly mixed, sodium tellurite, boron hydrogen are then sequentially added
Change sodium, finally baking oven in react after the CdTe quantum that is fluoresced；
(2) synthesis of the quantum dot of ZnCdSe
By ZnCl2It is dissolved in pure water and being uniformly mixed with N-acetyl-L-cysteine, sequentially add CdCl2It is mixed with NaHSe
Mixed liquor is finally placed in reaction kettle reaction, the ZnCdSe quantum dot to be fluoresced by liquid；
(3) preparation of CdTe-ZnCdSe double quantum point paper chip substrate
Will CdTe quantum and ZnCdSe quantum dot mix after be added dropwise on paper base material, paper base material absorb fixed CdTe quantum and
Up to CdTe-ZnCdSe quantum dot paper chip substrate after ZnCdSe quantum dot.
5. the preparation method of CdTe-ZnCdSe double quantum point paper chip substrate according to claim 4, which is characterized in that
The CdTe quantum emits aubergine fluorescence and launch wavelength is 630~640nm.
6. the preparation method of CdTe-ZnCdSe double quantum point paper chip substrate according to claim 4, which is characterized in that
The ZnCdSe quantum dot emission yellow-greenish phosphorescent light and launch wavelength are 480~500nm.
7. a kind of method based on CdTe-ZnCdSe double quantum point paper chip substrate detection organophosphorus pesticide, which is characterized in that packet
Include step:
(1) synthesis of CdTe quantum
Dichloride cadmium and N-acetyl-L-cysteine are dissolved in pure water and are uniformly mixed, sodium tellurite, boron hydrogen are then sequentially added
Change sodium, finally baking oven in react after the CdTe quantum that is fluoresced；
(2) synthesis of the quantum dot of ZnCdSe
By ZnCl2It is dissolved in pure water and being uniformly mixed with N-acetyl-L-cysteine, sequentially add CdCl2It is mixed with NaHSe
Mixed liquor is finally placed in reaction kettle reaction, the ZnCdSe quantum dot to be fluoresced by liquid；
(3) preparation of CdTe-ZnCdSe double quantum point paper chip substrate
Will CdTe quantum and ZnCdSe quantum dot mix after be added dropwise on paper base material, paper base material absorb fixed CdTe quantum and
Up to CdTe-ZnCdSe quantum dot paper chip substrate after ZnCdSe quantum dot；
The synthesis of (4) four-(4- pyridyl group) zinc protoporphyrin self assembly solution
Four-(4- pyridyl group) zinc protoporphyrins are dissolved in n,N-Dimethylformamide solution, it is molten to obtain four-(4- pyridyl group) zinc protoporphyrins
Four-(4- pyridyl group) zinc protoporphyrin solution are added into dodecyl trimethyl ammonium bromide for liquid, and reaction stops after mixing evenly, obtain
To four-(4- pyridyl group) zinc protoporphyrin self assembly solution；
(5) organophosphorus pesticide standard color comparison card is made
The organophosphorus pesticide of various concentration and the mixed solution of four-(4- pyridyl group) zinc protoporphyrin self assembly solution are prepared, will be mixed
Solution is successively added dropwise in CdTe-ZnCdSe double quantum point paper chip substrate, observes in ultraviolet camera bellows, various concentration is organic phosphorus
The pesticide color different from the reaction generation of CdTe-ZnCdSe double quantum point paper chip substrate, to the bis- quantum of each CdTe-ZnCdSe
Point paper chip substrate is taken pictures, and arrangement obtains organophosphorus pesticide standard color comparison card；
(6) the organophosphorus pesticide concentration of sample is detected
Sample and four-(4- pyridyl group) zinc protoporphyrin self assembly solution are mixed, double amounts in double quantum point paper chip substrate are added dropwise
There is color response to sample in son point paper chip substrate, control organophosphorus pesticide standard color comparison card obtains organophosphorus pesticide in sample
Concentration.
8. the side according to claim 7 based on CdTe-ZnCdSe double quantum point paper chip substrate detection organophosphorus pesticide
Method, which is characterized in that step (1) CdTe quantum emits aubergine fluorescence and launch wavelength is 630~640nm；Step (2)
ZnCdSe quantum dot emission yellow-greenish phosphorescent light and launch wavelength are 480~500nm.
9. the side according to claim 7 based on CdTe-ZnCdSe double quantum point paper chip substrate detection organophosphorus pesticide
Method, which is characterized in that the CdTe quantum concentration be 143~146nmol/L, ZnCdSe quantum dot concentration be 318~
The volume ratio of 422nmol/L, CdTe quantum and the mixing of ZnCdSe quantum dot is 1~2:1~2.
10. the side according to claim 7 based on CdTe-ZnCdSe double quantum point paper chip substrate detection organophosphorus pesticide
Method, which is characterized in that in the step (5), the concentration of four-(4- pyridyl group) zinc protoporphyrin self assembly solution is 0.46~0.48 μ
Mol/L, the concentration of the organophosphorus pesticide are 0~50 μ g/L.
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