CN109813689A - Method based on CdTe quantum paper chip substrate detection carbamate chemicals for agriculture - Google Patents
Method based on CdTe quantum paper chip substrate detection carbamate chemicals for agriculture Download PDFInfo
- Publication number
- CN109813689A CN109813689A CN201811395821.4A CN201811395821A CN109813689A CN 109813689 A CN109813689 A CN 109813689A CN 201811395821 A CN201811395821 A CN 201811395821A CN 109813689 A CN109813689 A CN 109813689A
- Authority
- CN
- China
- Prior art keywords
- agriculture
- cdte quantum
- chip substrate
- paper chip
- pyridyl group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The present invention relates to paper chip sensory field more particularly to a kind of methods based on CdTe quantum paper chip substrate detection carbamate chemicals for agriculture.The present invention is based on the methods of CdTe quantum paper chip substrate detection carbamate chemicals for agriculture, comprising steps of the synthesis of (1) CdTe quantum；The synthesis of (2) four-(4- pyridyl group) zinc protoporphyrin self assembly solution；(3) preparation of CdTe quantum paper chip substrate；(4) carbamate chemicals for agriculture standard color comparison card is made；(5) the carbamate chemicals for agriculture concentration in sample to be tested is detected；Compared with existing carbamate chemicals for agriculture detection method, 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 CdTe quantum paper chip substrate has specific reaction to carbamate chemicals for agriculture, can be used for the detection of carbamate chemicals for agriculture in complex matrices water sample.
Description
Technical field
The present invention relates to paper chip sensory fields, more particularly to a kind of CdTe quantum paper chip substrate that is based on to detect amino
The method of formate ester pesticide.
Background technique
China is large agricultural country, while being also the country for producing and using pesticide most.Pesticide is in prevention and control agriculture, forestry
Disease, worm, play a very important role in terms of grass and other harmful organisms, but pesticide can remain in crops, ring again simultaneously
In border, the pollution of food and environment is caused.European Food Safety Authority provides that Pesticide maximum residue limit is 10 μ g/L.It eats by mistake
The food of pesticide residue be easy to cause the symptoms such as acute poisoning, so reinforce the research to Pesticide Residue Detection Technique in Foods,
It has very important significance.
Water-soluble quantum dot has stability high, fluorescence lifetime is long, good biology as excellent fluorescent nano material
The advantages that compatibility.Environmental monitoring, medical diagnosis, clinic are used for as efficient fluorescence probe using its fluorescent characteristic
Medicine etc..Nanometer porphyrin colour sensitivity and light sensitivity are good, are the ideal model compounds for studying sensor sensing element.Porphyrin
Class compound and nanometer porphyrin are a kind of excellent quantum dot fluorescence quenchers, and porphyrin is answered extensively with being used in combination for quantum dot
It is analyzed for food and medicine.The residual detection method of traditional agriculture includes liquid chromatography, gas chromatography and mass spectrometry, enzyme inhibition etc.
Deng, they are directed to the instrument of complex precise, cumbersome operating process etc., make its application be subject to certain restrictions, be not enough to
Meet the residual quickly needs that detect on the spot of agriculture, therefore, it is necessary to establish it is a kind of it is simple, economical, quickly, can carry out exempting from instrument reality
The residual detection method of agriculture of ground detection.
Summary of the invention
In order to solve the above problem, the object of the present invention is to provide one kind detects amino based on CdTe quantum paper chip substrate
The method of formate ester pesticide can not only detect carbamate chemicals for agriculture fast, in high sensitivity, and can be realized and exempt from instrument
The detection immediately of device scene.
To achieve the above object, carbamates is detected based on CdTe quantum paper chip substrate designed by the present invention
The method of pesticide, 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；
The synthesis of (2) four-(4- pyridyl group) zinc protoporphyrin self assembly solution
Four-(4- pyridyl group) zinc protoporphyrins are dissolved in tetrahydrofuran solution, obtain four-(4- pyridyl group) zinc protoporphyrin tetrahydrofurans
Solution, four-(4- pyridyl group) zinc protoporphyrin tetrahydrofuran solutions are added into cetyl trimethylammonium bromide aqueous solution, and stirring is equal
After even, solution becomes clarification by muddiness, and reaction stops, and obtains four-(4- pyridyl group) zinc protoporphyrin self assembly solution；
(3) preparation of CdTe quantum paper chip substrate
CdTe quantum is added dropwise in paper base material, paper base material, which absorbs, to be fixed after CdTe quantum up to CdTe quantum core
Piece substrate；
(4) carbamate chemicals for agriculture standard color comparison card is made
The mixing for preparing the carbamate chemicals for agriculture and four-(4- pyridyl group) zinc protoporphyrin self assembly solution of various concentration is molten
Mixed solution is successively added dropwise in CdTe quantum paper chip substrate, observes in ultraviolet camera bellows by liquid, various concentration amino first
The esters of gallic acid pesticide color different from the reaction generation of CdTe quantum paper chip substrate, to each CdTe quantum paper chip substrate
It takes pictures, arrangement obtains carbamate chemicals for agriculture standard color comparison card；
(5) the carbamate chemicals for agriculture concentration in sample to be tested is detected
Mixed solution is made in sample and four-(4- pyridyl group) zinc protoporphyrin self assembly solution to be added dropwise in paper chip substrate,
Paper chip substrate has color response to sample, and the carbamate chemicals for agriculture standard color comparison card that control step (4) obtains obtains examination
The concentration of carbamate chemicals for agriculture in sample.
Preferably, by the mixed solution pH tune of dichloride cadmium and N-acetyl-L-cysteine in the step (1)
It is 4.5~4.8, oven temperature control is 180~220 DEG C, obtains the CdTe quantum that launch wavelength is 540~560nm, green light
Point.
Preferably, in the step (4) and step (5) four-(4- pyridyl group) zinc protoporphyrin self assembly solution it is dense
Degree is 17.5~18.0 μM.
Preferably, mixed solution is respectively 0 μ g/L carbamate chemicals for agriculture and 17.85 μ in the step (4)
M tetra--(4- pyridyl group) zinc protoporphyrin self assembly solution, 1 μ g/L carbamate chemicals for agriculture and 17.85 μM of four-(4- pyridyl group) zinc
Porphyrin self assembly solution, 5 μ g/L carbamates chemicals for agriculture and 17.85 μM of four-(4- pyridyl group) zinc protoporphyrin self assembly solution, 10
μ g/L carbamate chemicals for agriculture and 17.85 μM of four-(4- pyridyl group) zinc protoporphyrin self assembly solution, 15 μ g/L carbamates
Pesticide and 17.85 μM of four-(4- pyridyl group) zinc protoporphyrin self assembly solution, 20 μ g/L carbamates chemicals for agriculture and 17.85 μM four-
(4- pyridyl group) zinc protoporphyrin self assembly solution.
Preferably, in the step (4), various concentration carbamate chemicals for agriculture is reacted with paper chip substrate
The color data in the photo importing PaintShop extraction picture of different colours is generated, simulates amino using color data
Formate ester pesticide standard colorimetric card.
Preferably, in the step (1), dichloride cadmium, N-acetyl-L-cysteine, sodium tellurite substance
Amount ratio are as follows: 2.0:3.8~4.2:1.0.
Preferably, in the step (2), four-(4- pyridyl group) zinc protoporphyrins and cetyl trimethylammonium bromide
The mass ratio of the material is 1:66.5~67.0.
Preferably, in the step (3), CdTe quantum concentration is 20~30 μm of ol/L.
Preferably, in the step (3), in the step (2), CdTe quantum dripping quantity is 8~10uL, paper
Substrate is the circular filter paper that diameter is 4~6mm, and the paper chip substrate that CdTe quantum has been added dropwise is placed in 36~39 DEG C of baking oven
In, it dries 5~7 minutes.
Preferably, in described four-(4- pyridyl group) zinc protoporphyrin self assembly solution nanometer porphyrin partial size be 70~
90nm。
The present invention has the advantages that the present invention is based on CdTe amounts compared with existing carbamate chemicals for agriculture detection method
The method that son select paper chip substrate detection carbamate chemicals for agriculture have preparation it is simple, can rapid field detect, be at low cost, loud
Fast speed, sensitivity and selective high feature are answered, and CdTe quantum paper chip substrate has carbamate chemicals for agriculture
There is specific reaction, can be used for the detection of carbamate chemicals for agriculture in complex matrices water sample.
Detailed description of the invention
Fig. 1 is that the present invention is based on the mechanism schematic diagrames that CdTe quantum paper chip substrate detects carbamate chemicals for agriculture；
Fig. 2 is the transmission electron microscope figure of four-(4- pyridyl group) zinc protoporphyrin self assembly solution；
Fig. 3 is the transmission electricity that four-(4- pyridyl group) zinc protoporphyrin self assembly solution are added to CdTe quantum paper chip substrate
Sub- microscope figure；
Fig. 4 is that the present invention is based on the feasibility tests that CdTe quantum paper chip substrate detects carbamate chemicals for agriculture
Figure；Fig. 4 A is the paper chip base color for being fixed with CdTe quantum；Fig. 4 B is that four-(4- pyridyl groups) are added to paper chip substrate
Color reaction figure after zinc protoporphyrin；Fig. 4 C is that carbamate chemicals for agriculture and four-(4- pyridyl group) zinc porphins is added to paper chip substrate
Color reaction figure after quinoline mixed solution；
Fig. 5 is that the present invention prepares the standard color comparison card of MTMC, 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, 15 μ g/L, 20 μ g/L MTMCs generate, Fig. 5 G are blank control (color of paper chip substrate)；Fig. 5 a~
5g is the standard color comparison card for the MTMC that the extraction color data of Fig. 5 A~5G obtains；
Fig. 6 is that the present invention prepares the standard color comparison card of carbofuran, Fig. 6 A~6F be corresponding in turn to 0 μ g/L, 1 μ g/L, 5 μ g/L,
The color that 10 μ g/L, 15 μ g/L, 20 μ g/L carbofurans generate, Fig. 6 G are blank control (color of paper chip substrate)；
Fig. 7 is that the present invention prepares the standard color comparison card of carbaryl, Fig. 6 A~6F be corresponding in turn to 0 μ g/L, 1 μ g/L, 5 μ g/L,
The color that 10 μ g/L, 15 μ g/L, 20 μ g/L carbaryls generate, Fig. 6 G are blank control (color of paper chip substrate)；
Fig. 8 is the specificity figure that carbamate chemicals for agriculture is detected the present invention is based on CdTe quantum paper chip substrate；Figure
8A~8I is followed successively by blank, Acetochlor, Deltamethrin, cartap, metrifonate, DDVP, demeton, Rogor, MTMC and four-
The color reaction figure in paper chip substrate is added dropwise after the mixing of (4- pyridyl group) zinc protoporphyrin；Fig. 8 a~8i is followed successively by Fig. 8 A~8I's
Extract the colorimetric card figure that color data obtains；
Fig. 9 is to detect MTMC figure in complex matrices based on CdTe quantum paper chip substrate, and Fig. 9 A is human plasma base
The colorimetric card figure of MTMC in matter；Fig. 9 B is the colorimetric card figure of MTMC in cow's serum matrix；Fig. 9 C is cider matrix middling speed
The colorimetric card figure for prestige of going out；Fig. 9 D is the colorimetric card figure of MTMC in cabbage juice matrix；Fig. 9 E is MTMC in Longjing tea matrix
Colorimetric card figure；
Figure 10 is accurately to detect carbofuran figure in complex matrices based on CdTe quantum paper chip substrate, and Figure 10 A is people
The colorimetric card figure of carbofuran in plasma matrix；Figure 10 B is the colorimetric card figure of carbofuran in cow's serum matrix；Figure 10 C is cider
The colorimetric card figure of carbofuran in matrix；Figure 10 D is the colorimetric card figure of carbofuran in cabbage juice matrix；Figure 10 E is Longjing tea matrix
The colorimetric card figure of middle carbofuran；
Figure 11 is accurately to detect carbaryl figure in complex matrices based on CdTe quantum paper chip substrate, and Figure 11 A is people
The colorimetric card figure of carbaryl in plasma matrix；Figure 10 B is the colorimetric card figure of carbaryl in cow's serum matrix；Figure 11 C is cider
The colorimetric card figure of carbaryl in matrix；Figure 11 D is the colorimetric card figure of carbaryl in cabbage juice matrix；Figure 11 E is Longjing tea matrix
The colorimetric card figure of middle carbaryl.
Specific embodiment
For a better understanding of the invention, invention is described in detail below with reference to drawings and concrete examples.
To solve there are instrumentation complexity in existing detection carbamate chemicals for agriculture technology, analysis time length is asked
Topic, the present invention provide a kind of method based on CdTe quantum paper chip substrate detection carbamate chemicals for agriculture, specifically,
The present invention can make CdTe amount using the mixed solution of carbamate chemicals for agriculture and four-(4- pyridyl group) zinc protoporphyrin self assembly solution
Son point the changed principle of fluorescence color, prepare the standard color comparison card of various concentration carbamate chemicals for agriculture, by with mark
Quasi- colorimetric card carries out the concentration that control color judges carbamate chemicals for agriculture to be measured.Below will by specific embodiment come pair
The preferred embodiment of method using self assembly porphyrin detection carbamate chemicals for agriculture of the invention is described in detail.
Embodiment 1
Based on the method for CdTe quantum paper chip substrate detection MTMC, comprising steps of
(1) synthesis of CdTe quantum
Dichloride cadmium (0.1096g) and N-acetyl-L-cysteine (0.1567g) are dissolved in 40mL ultrapure water, normal
PH value of solution is adjusted to 4.60 with sodium hydroxide solution after stirring 15 minutes under temperature, normal pressure, then inflated with nitrogen ice bath stirring 20 minutes,
It is added sodium tellurite (0.0532g, 2.5mM), stirs 15 minutes；It adds sodium borohydride (0.0109g), stirring 15 minutes, most
This solution is put into reaction kettle afterwards, is reacted 50 minutes in 200 DEG C of baking oven, obtaining launch wavelength after being cooled to room temperature is
550nm, glow green, concentration are 2.51 × 10-5The CdTe quantum of mol/L.
The synthesis of (2) four-(4- pyridyl group) zinc protoporphyrin self assembly solution
It weighs 0.0037g tetra--(4- pyridyl group) zinc protoporphyrin solid powder to be dissolved in 5mL tetrahydrofuran solution, obtains concentration
It is 1.14 × 10-3Mol/L tetra--(4- pyridyl group) zinc protoporphyrin tetrahydrofuran solution.By cetyl trimethyl bromination (0.0732g)
It being dissolved in 40mL aqueous solution, 2.8mL tetra--(4- pyridyl group) zinc protoporphyrin tetrahydrofuran solution is added, normal temperature and pressure stirs 10 minutes,
Solution becomes clarification by muddiness, and reaction stops.Obtain 7.5 × 10-5Mol/L tetra--(4- pyridyl group) zinc protoporphyrin self assembly solution is such as schemed
Shown in 2, transmission electron microscope characterizes the nanometer rods for being shown as 70~90nm of partial size.
(3) preparation of CdTe quantum paper chip substrate
10 μ L CdTe quantums (25.1 μM) are drawn with liquid-transfering gun to be added dropwise respectively on the circular filter paper that 3 diameters are 5mm
3 CdTe quantum paper chip substrates are made, 3 paper chip substrates are placed into 37 DEG C of baking ovens bakings and are done to pico- within 4 minutes or so,
Paper chip substrate is observed in the ultraviolet camera bellows of 365nm in green, is taken pictures.
(4) MTMC standard color comparison card is made
Prepare one: 0 μ g/L MTMC of solution and 17.85 μM of four-(4- pyridyl group) zinc protoporphyrin self assembly solution；
Two: 1 μ g/L MTMC of solution and 17.85 μM of four-(4- pyridyl group) zinc protoporphyrin self assembly solution；
Three: 5 μ g/L MTMC of solution and 17.85 μM of four-(4- pyridyl group) zinc protoporphyrin self assembly solution；
Four: 10 μ g/L MTMC of solution and 17.85 μM of four-(4- pyridyl group) zinc protoporphyrin self assembly solution；
Five: 15 μ g/L MTMC of solution and 17.85 μM of four-(4- pyridyl group) zinc protoporphyrin self assembly solution；
Six: 20 μ g/L MTMC of solution and 17.85 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 quantum paper chip substrate, it is ultraviolet dark
Observation has different color changes in case, 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 MTMC standard color comparison card.
MTMC standard color comparison card as shown in connection with fig. 5, Fig. 5 A~5F be corresponding in turn to 0 μ g/L, 1 μ g/L, 5 μ g/L, 10 μ g/L,
The color that 15 μ g/L, 20 μ g/L MTMCs generate, Fig. 5 G are blank control (color of paper chip substrate).
In conjunction with shown in Fig. 1 and Fig. 4, it is glimmering can to quench CdTe quantum for four-(4- pyridyl group) zinc protoporphyrins as can be seen from Figure 1
The mixed solution of light, carbamate chemicals for agriculture and four-(4- pyridyl group) zinc protoporphyrins can be such that CdTe quantum fluorescence color occurs
The principle of variation.If Fig. 4 A is the paper chip base color for being fixed with CdTe quantum；Such as Fig. 4 B, it is added to paper chip substrate
The fluorescent quenching of CdTe quantum becomes dirty-green from green after four-(4- pyridyl group) zinc protoporphyrins, and utilizes transmission electron microscopy
Sem observation paper chip substrate is as shown in Figure 3；Such as Fig. 4 C, carbamate chemicals for agriculture and four-(4- pyridines is added to paper chip substrate
Base) zinc protoporphyrin mixed solution, light green color is become from green, and not with the concentration of carbamate chemicals for agriculture in mixed solution
Together, the color of paper chip substrate also changes, as shown in figure 5, the concentration of MTMC increases to 20 by 0 μ g/L in mixed solution
The color of μ g/L, paper chip substrate become yellow green from dirty-green, then become light green, eventually become green, and reaching can on paper
Effect depending on changing detection MTMC.
(5) the MTMC concentration of sample is detected
Sample and 17.85 μM of four-(4- pyridyl group) zinc protoporphyrin self assembly solution are mixed, are added dropwise in paper chip substrate,
Paper chip substrate has a color response to sample, and control MTMC standard color comparison card obtains going out in sample the concentration of prestige concentration.
It can be in complex matrices (people in order to verify the method for detecting MTMC the present invention is based on CdTe quantum paper chip substrate
Blood plasma, cow's serum, cider, cabbage juice, Longjing tea) in accurately detect MTMC, carry out complex matrices verification test.Specific mistake
Human plasma matrix: Cheng Wei prepares 0 μ g/L MTMC and 17.85 μM of four-(4- pyridyl group) zinc protoporphyrin, 1 μ respectively in human plasma
G/L MTMC and 17.85 μM of four-(4- pyridyl group) zinc protoporphyrin, 5 μ g/L MTMCs and 17.85 μM of four-(4- pyridyl group) zinc porphin
Quinoline, 10 μ g/L MTMCs and 17.85 μM of four-(4- pyridyl group) zinc protoporphyrin, 15 μ g/L MTMCs and 17.85 μM of four-(4- pyridine
Base) zinc protoporphyrin, 20 μ g/L MTMCs and 17.85 μM of four-(4- pyridyl group) zinc protoporphyrin；
Cow's serum, cider, cabbage juice, Longjing tea matrix is identical as the process for preparation of human plasma matrix, no longer superfluous herein
It states.
As a result as shown in figure 9, Fig. 9 A is the colorimetric card figure of MTMC in people's plasma matrix；Fig. 9 B is cider matrix middling speed
The colorimetric card figure for prestige of going out；Fig. 9 C is the colorimetric card figure of MTMC in cabbage juice matrix；Fig. 9 D is MTMC in Longjing tea matrix
Colorimetric card figure.From fig. 9, it can be seen that the method based on CdTe quantum paper chip substrate detection MTMC can be in complex matrices
Accurate detection MTMC, the interference by matrix are small.
In order to verify the specificity using the method based on CdTe quantum paper chip substrate detection MTMC, amino is carried out
The specific selection of formate ester pesticide is tested, and detailed process is that drawing 10 μ L concentration with liquid-transfering gun is other class pesticides of 5 μ g/L
(Acetochlor, Deltamethrin, cartap, metrifonate, DDVP, demeton, Rogor) and four-(4- pyridyl group) zinc protoporphyrin self assemblies
Solution (17.85 μM) mixed solution restores without apparent fluorescence in paper chip substrate, is still dirty-green, and 10 μ are added
L concentration is 5 μ g/L MTMCs and four-(4- pyridyl group) zinc protoporphyrin self assembly solution (17.85 μM) mixed solutions in core chip base
On bottom, paper chip becomes yellow green from dirty-green, the color data RGB on picture is extracted with photoshop software, such as Fig. 8 institute
Show.
Embodiment 2
Detection carbofuran is detected based on CdTe quantum paper chip substrate, comprising steps of
(1) preparation of paper chip substrate and four-(4- pyridyl group) zinc protoporphyrin self assembly solution
Paper chip substrate and preparing for four-(4- pyridyl group) zinc protoporphyrin self assembly solution are same as Example 1.
(2) carbofuran standard color comparison card is made
By the MTMC (1~20 μ g/L) of various concentration and four-(4- pyridyl group) zinc protoporphyrin self assembly solution (17.85 μM)
Mixing is drawn 10 μ L mixed solutions with liquid-transfering gun and is added dropwise in paper chip substrate, and observation has different colors to become in ultraviolet camera bellows
Change, as shown in connection with fig. 6, as carbofuran concentration increases, color becomes yellow green from dirty-green in paper chip substrate, then becomes light
Green eventually becomes green, reaches Visual retrieval carbofuran on paper, takes pictures in the ultraviolet camera bellows of 365nm and saves picture, will
Picture imports PhotoShop software and extracts color data RGB on picture, and goes out colored dot with the numerical simulation and obtain grams hundred
Prestige standard color comparison card；
Carbofuran standard color comparison card as shown in connection with fig. 6, Fig. 6 A~6F be corresponding in turn to 0 μ g/L, 1 μ g/L, 5 μ g/L, 10 μ g/L,
The color that 15 μ g/L, 20 μ g/L carbofurans generate, Fig. 6 G are blank control (color of paper chip substrate).
(5) the carbofuran concentration of sample is detected
Sample and 17.85 μM of four-(4- pyridyl group) zinc protoporphyrin self assembly solution are mixed, are added dropwise in paper chip substrate,
Paper chip substrate has color response to sample, and control carbofuran standard color comparison card obtains the concentration of carbofuran concentration in sample.
It can be in complex matrices (people's blood in order to verify the method for detecting detection carbofuran based on CdTe quantum paper chip substrate
Slurry, cow's serum, cider, cabbage juice, Longjing tea) in accurately detect carbofuran, carry out complex matrices verification test.Detailed process
For human plasma matrix: preparing 0 μ g/L carbofuran and 17.85 μM of four-(4- pyridyl group) zinc protoporphyrin, 1 μ g/L respectively in human plasma
Carbofuran and 17.85 μM of four-(4- pyridyl group) zinc protoporphyrin, 5 μ g/L carbofurans and 17.85 μM of four-(4- pyridyl group) zinc protoporphyrin, 10
μ g/L carbofuran and 17.85 μM of four-(4- pyridyl group) zinc protoporphyrin, 15 μ g/L carbofurans and 17.85 μM of four-(4- pyridyl group) zinc porphin
Quinoline, 20 μ g/L carbofurans and 17.85 μM of four-(4- pyridyl group) zinc protoporphyrin.
Cow's serum, cider, cabbage juice, Longjing tea matrix is identical as the process for preparation of human plasma matrix, no longer superfluous herein
It states.
The results are shown in Figure 10, and Figure 10 A is the colorimetric card figure of carbofuran in people's plasma matrix；Figure 10 B is cider matrix
The colorimetric card figure of middle carbofuran；Figure 10 C is the colorimetric card figure of carbofuran in cabbage juice matrix；Figure 10 D is in Longjing tea matrix grams
The colorimetric card figure of Budweiser.From fig. 10 it can be seen that can be in complexity based on CdTe quantum paper chip substrate detection detection carbofuran
Carbofuran is accurately detected in matrix, the interference by matrix is small.
Embodiment 3
Based on the method that CdTe quantum paper chip substrate detects detection carbaryl, comprising steps of
(1) preparation of paper chip substrate and four-(4- pyridyl group) zinc protoporphyrin self assembly solution
Paper chip substrate and preparing for four-(4- pyridyl group) zinc protoporphyrin self assembly solution are same as Example 1.
(2) carbaryl standard color comparison card is made
By the carbaryl (1~20 μ g/L) of various concentration and four-(4- pyridyl group) zinc protoporphyrin self assembly solution (17.85 μM)
Mixing is drawn 10 μ L mixed solutions with liquid-transfering gun and is added dropwise in paper chip substrate, and observation has different colors to become in ultraviolet camera bellows
Change, as shown in connection with fig. 7, as carbaryl concentration increases, color becomes yellow green from dirty-green in paper chip substrate, then becomes light
Green eventually becomes green, reaches Visual retrieval carbaryl on paper, takes pictures in the ultraviolet camera bellows of 365nm and saves picture, will
Picture imports the color data RGB on PhotoShop software extraction picture, and goes out colored dot with the numerical simulation and obtain first naphthalene
The standard color comparison card of prestige；
The standard color comparison card of carbaryl as shown in connection with fig. 7, Fig. 7 A~7F are corresponding in turn to 0 μ g/L, 1 μ g/L, 5 μ g/L, 10 μ g/
L, the color that 15 μ g/L, 20 μ g/L carbofurans generate, Fig. 7 G are blank control (color of paper chip substrate).
(5) the carbofuran concentration of sample is detected
Sample and 17.85 μM of four-(4- pyridyl group) zinc protoporphyrin self assembly solution are mixed, are added dropwise in paper chip substrate,
Paper chip substrate has color response to sample, and the standard color comparison card for compareing carbaryl obtains the concentration of carbofuran concentration in sample.
In order to verify the present invention is based on CdTe quantum paper chip substrate detect detection carbaryl can be in complex matrices (people's blood
Slurry, cow's serum, cider, cabbage juice, Longjing tea) in accurately detect carbaryl, carry out complex matrices verification test.Detailed process
For human plasma matrix: preparing 0 μ g/L carbaryl and 17.85 μM of four-(4- pyridyl group) zinc protoporphyrin, 1 μ g/L respectively in human plasma
Carbaryl and 17.85 μM of four-(4- pyridyl group) zinc protoporphyrin, 5 μ g/L carbaryls and 17.85 μM of four-(4- pyridyl group) zinc protoporphyrin, 10
μ g/L carbaryl and 17.85 μM of four-(4- pyridyl group) zinc protoporphyrin, 15 μ g/L carbaryls and 17.85 μM of four-(4- pyridyl group) zinc porphin
Quinoline, 20 μ g/L carbaryls and 17.85 μM of four-(4- pyridyl group) zinc protoporphyrin.
Cow's serum, cider, cabbage juice, Longjing tea matrix is identical as the process for preparation of human plasma matrix, no longer superfluous herein
It states.
The results are shown in Figure 10, and Figure 10 A is the colorimetric card figure of carbaryl in people's plasma matrix；Figure 10 B is cider matrix
The colorimetric card figure of middle carbaryl；Figure 10 C is the colorimetric card figure of carbaryl in cabbage juice matrix；Figure 10 D is first in Longjing tea matrix
The colorimetric card figure of naphthalene prestige.From fig. 10 it can be seen that can based on the method that CdTe quantum paper chip substrate detects detection carbaryl
Carbaryl is accurately detected in complex matrices, the interference by matrix is small.
Examples 1 to 3 lists the side based on CdTe quantum paper chip substrate detection MTMC, carbofuran, carbaryl
Method, but be not limited to that detection MTMC, carbofuran, carbaryl.
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 method based on CdTe quantum paper chip substrate detection carbamate chemicals for agriculture, which is characterized in that including
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；
The synthesis of (2) four-(4- pyridyl group) zinc protoporphyrin self assembly solution
Four-(4- pyridyl group) zinc protoporphyrins are dissolved in tetrahydrofuran solution, it is molten to obtain four-(4- pyridyl group) zinc protoporphyrin tetrahydrofurans
Four-(4- pyridyl group) zinc protoporphyrin tetrahydrofuran solutions are added into cetyl trimethylammonium bromide aqueous solution, stir evenly for liquid
Afterwards, solution becomes clarification by muddiness, and reaction stops, and obtains four-(4- pyridyl group) zinc protoporphyrin self assembly solution；
(3) preparation of CdTe quantum paper chip substrate
CdTe quantum is added dropwise in paper base material, paper base material, which absorbs, to be fixed after CdTe quantum up to CdTe quantum core chip base
Bottom；
(4) carbamate chemicals for agriculture standard color comparison card is made
The carbamate chemicals for agriculture of various concentration and the mixed solution of four-(4- pyridyl group) zinc protoporphyrin self assembly solution are prepared,
Mixed solution is successively added dropwise in CdTe quantum paper chip substrate, is observed in ultraviolet camera bellows, various concentration carbamic acid
The different color of ester pesticides and CdTe quantum paper chip substrate reaction generation, to each CdTe quantum paper chip substrate into
Row is taken pictures, and arrangement obtains carbamate chemicals for agriculture standard color comparison card；
(5) the carbamate chemicals for agriculture concentration in sample to be tested is detected
Mixed solution is made in sample and four-(4- pyridyl group) zinc protoporphyrin self assembly solution, the core in paper chip substrate is added dropwise
Piece substrate has color response to sample, and the carbamate chemicals for agriculture standard color comparison card that control step (4) obtains obtains in sample
The concentration of carbamate chemicals for agriculture.
2. the method according to claim 1 based on CdTe quantum paper chip substrate detection carbamate chemicals for agriculture,
It is characterized in that, the mixed solution pH of dichloride cadmium and N-acetyl-L-cysteine is adjusted to 4.5 in the step (1)~
4.8, oven temperature control is 180~220 DEG C, obtains the CdTe quantum that launch wavelength is 540~560nm, green light.
3. the side according to claim 1 or 2 based on CdTe quantum paper chip substrate detection carbamate chemicals for agriculture
Method, which is characterized in that the concentration of four-(4- pyridyl group) zinc protoporphyrin self assembly solution is 17.5 in the step (4) and step (5)
~18.0 μM.
4. the method based on CdTe quantum paper chip substrate detection carbamate chemicals for agriculture according to right 3, special
Sign is that mixed solution is respectively 0 μ g/L carbamate chemicals for agriculture and 17.85 μM four-(4- pyridyl group) in the step (4)
Zinc protoporphyrin self assembly solution, 1 μ g/L carbamate chemicals for agriculture and 17.85 μM of four-(4- pyridyl group) zinc protoporphyrin self assembly solution,
5 μ g/L carbamates chemicals for agriculture and 17.85 μM of four-(4- pyridyl group) zinc protoporphyrin self assembly solution, 10 μ g/L carbamates
Class pesticide and 17.85 μM of four-(4- pyridyl group) zinc protoporphyrin self assembly solution, 15 μ g/L carbamates chemicals for agriculture and 17.85 μM
Four-(4- pyridyl group) zinc protoporphyrin self assembly solution, 20 μ g/L carbamates chemicals for agriculture and 17.85 μM of four-(4- pyridyl group) zinc
Porphyrin self assembly solution.
5. the method according to claim 1 based on CdTe quantum paper chip substrate detection carbamate chemicals for agriculture,
It is characterized in that, in the step (4), by various concentration carbamate chemicals for agriculture face different from the reaction generation of paper chip substrate
The photo of color imports the color data in PaintShop extraction picture, simulates carbamates agriculture using color data
Medicine standard color comparison card.
6. the method according to claim 2 based on CdTe quantum paper chip substrate detection carbamate chemicals for agriculture,
It is characterized in that, in the step (1), dichloride cadmium, N-acetyl-L-cysteine, sodium tellurite substance amount ratio are as follows:
2.0:3.8~4.2:1.0.
7. the method according to claim 1 based on CdTe quantum paper chip substrate detection carbamate chemicals for agriculture,
It is characterized in that, in the step (2), four-(4- pyridyl group) zinc protoporphyrins and cetyl trimethylammonium bromide the mass ratio of the material
For 1:66.5~67.0.
8. the method according to claim 1 based on CdTe quantum paper chip substrate detection carbamate chemicals for agriculture,
It is characterized in that, CdTe quantum concentration is 20~30 μm of ol/L in the step (3).
9. the method according to claim 1 based on CdTe quantum paper chip substrate detection carbamate chemicals for agriculture,
It is characterized in that, in the step (2), CdTe quantum dripping quantity is 8~10uL, and paper base material is diameter in the step (3)
For the circular filter paper of 4~6mm, the paper chip substrate that CdTe quantum has been added dropwise is placed in 36~39 DEG C of baking oven, dries 5~7
Minute.
10. the method according to claim 1 based on CdTe quantum paper chip substrate detection carbamate chemicals for agriculture,
It is characterized in that, nanometer porphyrin partial size is 70~90nm in described four-(4- pyridyl group) zinc protoporphyrin self assembly solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811395821.4A CN109813689B (en) | 2018-11-22 | 2018-11-22 | Method for detecting carbamate pesticide based on CdTe quantum dot paper chip substrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811395821.4A CN109813689B (en) | 2018-11-22 | 2018-11-22 | Method for detecting carbamate pesticide based on CdTe quantum dot paper chip substrate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109813689A true CN109813689A (en) | 2019-05-28 |
| CN109813689B CN109813689B (en) | 2020-04-03 |
Family
ID=66601888
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811395821.4A Active CN109813689B (en) | 2018-11-22 | 2018-11-22 | Method for detecting carbamate pesticide based on CdTe quantum dot paper chip substrate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109813689B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103364379A (en) * | 2013-05-08 | 2013-10-23 | 吉林大学 | Method for detecting carbamate pesticide in vegetables by utilizing fluorescence inner-filter effect of gold nanoparticles and cadmium telluride quantum dots |
| CN105067580A (en) * | 2015-07-28 | 2015-11-18 | 重庆大学 | Test paper for detecting fluazinam and detection method thereof |
| CN105785021A (en) * | 2016-04-08 | 2016-07-20 | 广州万联生物科技有限公司 | Quick detecting card for immunochromatography of organophosphorus and carbamate pesticide multiresidue cholinesterase |
| CN106916159A (en) * | 2017-02-27 | 2017-07-04 | 中南民族大学 | One kind switch nanometer porphyrin fluorescence sensor controllable method for preparing |
-
2018
- 2018-11-22 CN CN201811395821.4A patent/CN109813689B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103364379A (en) * | 2013-05-08 | 2013-10-23 | 吉林大学 | Method for detecting carbamate pesticide in vegetables by utilizing fluorescence inner-filter effect of gold nanoparticles and cadmium telluride quantum dots |
| CN105067580A (en) * | 2015-07-28 | 2015-11-18 | 重庆大学 | Test paper for detecting fluazinam and detection method thereof |
| CN105785021A (en) * | 2016-04-08 | 2016-07-20 | 广州万联生物科技有限公司 | Quick detecting card for immunochromatography of organophosphorus and carbamate pesticide multiresidue cholinesterase |
| CN106916159A (en) * | 2017-02-27 | 2017-07-04 | 中南民族大学 | One kind switch nanometer porphyrin fluorescence sensor controllable method for preparing |
Non-Patent Citations (3)
| Title |
|---|
| A. APILUX等: "Paper-based thioglycolic acid (TGA)-capped CdTe QD device for rapid screening of organophosphorus and carbamate insecticides", 《ANALYTICAL METHODS》 * |
| GAO XUE等: "Sensitive fluorescence assay of organophosphorus pesticides based on the fluorescence resonance energy transfer between CdTe quantum dots and porphyrin", 《ANALYST》 * |
| 吴宇: "基于二聚体卟啉传感器阵列的构件及检测应用研究", 《中国博士学位论文全文数据库》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109813689B (en) | 2020-04-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Kühl et al. | Functional and structural imaging of phototrophic microbial communities and symbioses | |
| US6989246B2 (en) | Sensor formulation for simultaneously monitoring at least two components of a gas composition | |
| CN106124475B (en) | A kind of trace pesticide residue Raman spectrum method for detecting surface reinforcement based on aptamer | |
| CN104198357B (en) | Flow Cytometry methods application in production of vaccine is monitored in real time | |
| CN106092983B (en) | A kind of Y of detection organo-chlorine pesticide2O3:Tb3+@SiO2-NH2Fluorescent sensor array preparation method | |
| CN106238112A (en) | A kind of micro-fluidic chip and the application in the qualification and drug sensitive experiment of pathogen thereof | |
| CN107677656A (en) | A kind of ratio fluorescent nano probe and its application | |
| CN110511751B (en) | Tunable dual-emission fluorescent carbon dot, and preparation method and application thereof | |
| US20040171094A1 (en) | Oxygen sensors disposed on a microtiter plate | |
| CN110423611A (en) | A kind of red fluorescence carbon dots and preparation method thereof, fluorescent optical sensor and its construction method and application | |
| CN107796681B (en) | A kind of fungi fluorescent staining liquid and preparation method thereof | |
| CN110044894B (en) | Colorimetric detection method of triadimenol | |
| Xiaowei et al. | Fabrication and characterization of colorimetric indicator for Salmon freshness monitoring using agar/polyvinyl alcohol gel and anthocyanin from different plant sources | |
| CN109813689A (en) | Method based on CdTe quantum paper chip substrate detection carbamate chemicals for agriculture | |
| CN104990876B (en) | A kind of method of fast imagingization detection pesticide residue | |
| CN109738400A (en) | A method of Visual retrieval caffeine is sensed based on nanometer porphyrin fluorescence paper | |
| CN106323723B (en) | Double indigo plant decoration methods | |
| CN109825298A (en) | The method of paper chip the detection silver ion and serine of CdTe quantum based on dimercaptosuccinic acid modification | |
| CN107478647A (en) | A kind of method based on noble metal nano particles rapid field detection decis | |
| CN109738405A (en) | A method of quantitative determination flavone compound | |
| CN109738399B (en) | Method for detecting dopamine by visual paper sensing | |
| CN101620188A (en) | Method for quickly measuring total number of live bacteria of luminous bacteria by using MTT method | |
| CN210465268U (en) | Pesticide on-site detection device | |
| CN110196249A (en) | A kind of paper chip of integration standard colour band | |
| CN111024689B (en) | White spirit alcoholic strength detection method based on color-changing nano material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |