CN105717089B - Sensor and preparation and application for phosphorous Pesticides Testing - Google Patents
Sensor and preparation and application for phosphorous Pesticides Testing Download PDFInfo
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- CN105717089B CN105717089B CN201610271070.XA CN201610271070A CN105717089B CN 105717089 B CN105717089 B CN 105717089B CN 201610271070 A CN201610271070 A CN 201610271070A CN 105717089 B CN105717089 B CN 105717089B
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
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- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C309/41—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing singly-bound oxygen atoms bound to the carbon skeleton
- C07C309/43—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing singly-bound oxygen atoms bound to the carbon skeleton having at least one of the sulfo groups bound to a carbon atom of a six-membered aromatic ring being part of a condensed ring system
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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Abstract
The present invention discloses the carbon quantum dot nano-sensor and preparation and application method of a kind of Supramolecular Assembling that can detect phosphorous pesticide.Nano fluorescent sensor for phosphorous Pesticides Testing of the invention be assembled in nanoparticle surface using Sulfonated calixarenes alkylammonium carbon quantum dot as matrix, have terbium ion in nanoparticle surface complexed in situ.Detected using sensor of the invention, can according to testing result in terbium ion characteristic emission peak change determine it is whether phosphorous in tested pesticide.The invention has the advantages that sensor is low in cost, detect easy to operate；Sensor is the good hydrotrope, and does not have any toxicity；Detection sensitivity with higher.
Description
Technical field
The present invention relates to the preparation method and application method of a kind of nano-sensor and this sensor, exactly this hair
A kind of bright carbon quantum dot nano-sensor for being related to the Supramolecular Assembling that can detect phosphorous pesticide and preparation and application method.
Background technique
Pesticide refers to the chemical substance of the harmful organism for agriculture forest and husbandry yield of eliminating the effects of the act, pesticide also adjustable plant
The growth of object.The pesticide of some classifications is widely used in agricultural production, such as organic phosphates, carbamate
Class, organochlorine class and pyrethroid pesticide.But because health and food-safety problem caused by the residual of pesticide are that society is general
All over the major issue being concerned about.The management and use lack of standardization of pesticide, seriously threaten food and Agriculture Ecological Environment Security, to the mankind
Health there are potentially hazardous, Pesticide Residue increasingly causes the concern and attention of people's height.Pesticide variety multiplicity
So that the analysis of pesticide residue is more complicated, Detection task is very arduous.Therefore, quick, agriculture conveniently, efficient and practical is developed
Medicine residue analysis method, that especially detects phosphorous pesticide is detected as current research hot spot, this work is to preserving the ecological environment
There is important theoretical and practical significance with food safety strategy is implemented.
In industrial production and environmental monitoring, phosphorous pesticide is usually to pass through gas chromatography or liquid chromatography is examined
It surveys.These common methods generally require complicated treatment process and expensive instrument, therefore it is fast largely to limit it
The approach of speed detection.Therefore, inventing a kind of cheap quickly phosphorous Pesticides Testing method has great significance to environmental area.
Summary of the invention
The present invention provides a kind of nano fluorescent sensor that can be used for phosphorous Pesticides Testing, while providing this sensor
Preparation method and application method.
Nano fluorescent sensor for phosphorous Pesticides Testing of the invention is being assembled with Sulfonated calixarenes of showing such as formula 1
Nanoparticle surface alkylammonium carbon quantum dot be matrix, nanoparticle surface complexed in situ have terbium from
Son.
The matrix that the present invention is used to prepare the nano fluorescent sensor of the phosphorous Pesticides Testing is Sulfonated calixarenes group
Mounted in the alkylammonium carbon quantum dot of nanoparticle surface.
The preparation method that the present invention is used to prepare the matrix of the nano fluorescent sensor of phosphorous Pesticides Testing is: by alkylammonium
Change carbon quantum dot it is soluble in water, be preferably dissolved in 50 mL water with 20mg alkylammonium carbon quantum dot, under agitation plus
Enter Sulfonated calixarenes, sufficiently carries out ultrasonic reaction processing under inert gas protection, then reaction solution is sufficiently stirred, so
The supernatant extracted reaction solution afterwards 1000Da bag filter dialysis treatment, obtained solution are to be used to prepare phosphorous Pesticides Testing
Nano fluorescent sensor matrix.
The preparation method of the nano fluorescent sensor of phosphorous Pesticides Testing of the invention is: being added not in its matrix first
The buffer of phosphoric acid, is then added terbium ion wherein again.
Alkylammonium carbon quantum dot preparation method involved in the present invention is: 1.5g beet alkali hydrochlorate is dissolved in 5mL
In water, 1.2g trishydroxymethylaminomethane (Tris) is added in alkali solution of beet later, until solution becomes to clarify, then
Excessive isopropanol, which is wherein added, is precipitated the organic salt presoma generated, washs precipitate with isopropanol and removes excessive forerunner
Body, then obtained solid is heated to 250 DEG C after being dried, it is then kept the temperature, makes trishydroxymethylaminomethane carbon
Change temperature, while guaranteeing the integrality of external glycine betaine unit, handy water extracts solid after aforementioned heat treatment, then through going
Except large particle therein, a large amount of acetone is added in filtrate is precipitated carbon quantum dot from solution, the carbon being isolated to
Quantum dot.
The user of the nano fluorescent sensor of phosphorous Pesticides Testing of the invention is: phosphorous pesticide is added in determinand and is examined
In the nano fluorescent sensor of survey, with the fluorescence of 270-300 nm excitation wavelength measurement system, according to testing result in terbium ion
Characteristic emission peak change determine it is whether phosphorous in tested pesticide.Currently preferred excitation wavelength is 275 nm.
The present invention using the technology of Supramolecular Assembling be prepared surface modification cyclic compound calixarenes, with carbon quantum
Point is the nano-sensor of matrix.In recent years, diamond, fullerene, graphene, fluorescence carbon nanomaterial and carbon quantum dot etc.
Carbon nanomaterial shows a series of peculiar properties and has attracted the extensive concern of researcher.Wherein carbon quantum dot due to its solely
Special optics and fluorescent emission property and show one's talent in carbon nanomaterial family.A large number of studies show that conventional semiconductors quantum
Point has adjustable fluorescent emission property, and this characteristic applies it in bio-sensing and bio-imaging field.However,
Semiconductor-quantum-point have some limitations, such as due to semiconductor-quantum-point in the preparation mostly using heavy metal presoma from
And lead to its bio-toxicity with higher, therefore greatly limit application of the semiconductor-quantum-point in biological field.It is different
In traditional semiconductor-quantum-point, carbon quantum dot can in addition to, transmitting high with fluorescence intensity as a kind of novel nano material
The properties such as tune, while also there are the characteristics such as hypotoxicity, good biocompatibility, low cost and chemical inertness.These properties are more
The deficiency for having mended conventional semiconductors quantum dot applies carbon quantum dot all in various fields.Of the invention is this with carbon
Quantum dot is that the nano-sensor of matrix is not only low in cost, easy to operate, while can sensitively identify phosphorous pesticide, therefore
With biggish application prospect and industrial production potential.
Of the invention has the advantages that following several respects based on the sensor that carbon quantum dot is prepared: 1) low in cost, behaviour
Make simple；Sensor of the invention is prepared by common compound, while while detecting does not need the instrument of complex and expensive yet
Device only can realize the detection to pesticide by the change in fluorescence of tracking system.2) good water solubility, it is environmental-friendly；The present invention
Sensor there is good water solubility, therefore the Pesticides Testing in pure aquatic system may be implemented, meanwhile, the material itself does not have
There is any toxicity, therefore will not have any impact to environment.3) ratio sensor, sensitivity are good；More traditional sensor phase
Than ratio sensor can overcome in environment if pH, temperature, other substances and ionic strength factor are to system sensitivity
It influences, therefore sensitivity with higher.
Detailed description of the invention
Fig. 1 is the assembling process schematic diagram of nano-sensor of the invention.
Fig. 2 is the synthesis schematic diagram of surface modification molecule sulfonation calixarenes of the invention.
The nuclear-magnetism of Fig. 3 sulfonation cup [4] aromatic hydrocarbons characterizes map.
Fig. 4 is that carbon quantum dot of the invention prepares schematic diagram.
(a) in Fig. 5, (b) are respectively the transmission electron microscope phenogram of nano-sensor under different ruler diameters, and wherein b schemes
The illustration in the upper right corner is the lattice structure of nanoparticle under high power electron microscope, for illustrating the spacing of lattice of nano material.
Fig. 6,7,8 and 9 are the characterization of nano-sensor of the present invention respectively, in which: Fig. 6 is carbon quantum dot ,@glasss of carbon quantum dot
Aromatic hydrocarbons introduces the change in fluorescence after terbium ion；Fig. 7 is the system change in fluorescence for introducing the terbium ion of various concentration；Fig. 8 is nanometer
The photoelectron spectroscopy of fluorescent optical sensor characterizes；Fig. 9 is the photoelectron spectroscopy of terbium ion.
Figure 10 is not phosphorous pesticide structure formula used in choice experiment of the present invention.
Figure 11 is the selective fluorogram of not phosphorous pesticide used in choice experiment of the present invention.
Figure 12 is the ratio fluorescent histogram of different not phosphorous pesticides.
Figure 13 is phosphorous pesticide structure formula used in choice experiment of the present invention.
Figure 14 is the selective fluorogram of phosphorous pesticide used in choice experiment of the present invention；.
Figure 15 is the ratio fluorescent histogram of different phosphorous pesticides
Figure 16 is the fluorescence titration spectrogram of isocarbophos.
Figure 17 is the change in fluorescence trend after various concentration isocarbophos are added at 490 nm and 545 nm
Figure 18 and Figure 19 is respectively the Linear Fit Chart at 545 nm and 490 nm.
Specific embodiment
It is the embodiment of the present invention below.
One, hybridized nanometer biosensor matrix of the invention the preparation method is as follows:
(1) preparation of Sulfonated calixarenes
A. to the synthesis of tert-butyl p tertButylcalixarene
20 g p-tert-butylphenols, 0.24 g sodium hydroxide and 12.5 mL(37%) formaldehyde be added to 500 mL round bottoms burning
In bottle, bonus point hydrophone 110-120 DEG C of reaction temperature, with fraction water device water-dividing, reacts 2-3h, becomes thick to solution, stops adding
Heat is cooled to room temperature, and 200 mL diphenyl ether are added, and 40mL ethyl acetate is added thereto, and reaction temperature rises to 140 DEG C of left sides
Water 0.5-1h is divided on the right side, and reaction is then risen to 260 DEG C, and flow back 2-3h, stops reaction, is cooled to room temperature, and 150 mL acetic acid are added
Ethyl ester stirs 0.5h, there is solid precipitation, and twice with the elution of 20 mL ethyl acetate, 20 mL glacial acetic acid and 20 mL washing are dried
It is dry, with 180 DEG C of re crystallization from toluene, obtain to tert-butyl p tertButylcalixarene.Yield: 65%.
B. the synthesis of tert-butyl is taken off to tert-butyl p tertButylcalixarene
13.3 g previous step reaction products, 9.0 g (96 mmol) virtue phenol and 14.0 g are added in 250 mL there-necked flasks
(105 mmol) aluminum trichloride (anhydrous).125 mL dry toluenes are eventually adding, nitrogen protection is stirred to react 1h at room temperature, then falls
Enter in the flask equipped with 250 mL 0.2mol/L hydrochloric acid solutions, stirring, stratification.By mixture liquid separation, after obtaining organic phase
It is transferred into round-bottomed flask and rotates, filtered after methanol is added, recrystallized after dry with chloroform-methanol.Yield: 69%.
C. the synthesis of Sulfonated calixarenes
Product is walked on 5g adds 50 mL, 98% concentrated sulfuric acid in oil bath heating, and 4h is reacted in 80-90 DEG C of control reaction, water-soluble real
It can stop heating after testing no insoluble matter, be cooled to room temperature, added in 100mL saturated salt solution dropwise under ice salt bath, after dripping,
It is heated to reflux to be put into refrigerator after 5 min are cooled down and filter, suction filtration obtains white crude product.It is finally recrystallized to give with distilled water white
Color crystal.Yield: 78%.Its preparation process is referring to attached drawing 2.
Nucleus magnetic hydrogen spectrum characterization result (attached drawing 3):1H NMR (400 MHz, D2O, 25 °C) δ: 4.01 (s, 8H,
CH 2), 7.57 (s, 8H, ArH).Obtained result is consistent with the result of report, illustrates the sterling for having obtained the compound.
(2) preparation of alkylammonium carbon quantum dot
Alkylammonium carbon quantum dot passes through literature procedure (A. W. Zhu, Q. Qu, X. L. Shao, B.
Kong, Y. Tian, Angew. Chem. Int. EdIt 2012,51,7185.) prepares.Firstly, by 1.5g beet alkali salt
Hydrochlorate is dissolved in 5mL water, obtains a kind of acid solution.1.2g trishydroxymethylaminomethane (Tris) is added to glycine betaine later
In solution, until solution becomes to clarify, while pH value of solution gradually becomes neutral with the addition of Tris.It is this water-soluble organic
Salt can make its precipitation by the way that excessive isopropanol (100mL) is added.100 mL isopropanols of the syrupy substance of obtained class
Washing is three times.Whole process, which is repeated twice, above removes excessive presoma.Drying 1-3 days of 80 DEG C of obtained solid, then
250 DEG C are warming up in tube furnace 2 hours.The temperature reaches the carburizing temperature of Tris, while can guarantee external beet again
The integrality of alkali unit.The solid of brown has been obtained after heat treatment.Solid is extracted with 25 mL water, 13000 turns are centrifuged 15 points
Clock, remove large particle, filtrate take out after a large amount of acetone is added, if volume ratio be greater than 10:1 acetone, make carbon quantum dot from
It is precipitated in solution, the carbon quantum dot drying for standby obtained after centrifugation, acquired product is referring to Fig. 7.
(3) assembling of hybridized nanometer sensor (matrix i.e. of the invention)
The alkylammonium carbon quantum dot of 5 mg is dissolved in 20 mL ultrapure waters first, 2 mg/mL sulphurs are added under stirring condition
Change calixarenes aqueous solution, ultrasound 30 minutes under Ar gas shielded.Obtained reaction solution is stirred at room temperature 12 hours.Obtained palm fibre
10000 turns of color solution are centrifuged 30 minutes to remove biggish reaction particles, take supernatant 1000Da bag filter dialysis 72h, obtain
To solution be stand-by matrix, Spectroscopic Characterization is shown in attached drawing 8- Figure 11, and preparation process is referring to attached drawing 1.
Two, for the nano fluorescent transducer production method of phosphorous Pesticides Testing
It takes the above-mentioned resulting matrix solution of 100 μ L to be added in 2mL HEPES buffer solution, then 5mL is added wherein
10-2Terbium chloride (the TbCl of M3) aqueous solution, it reacts and obtains within five minutes the nano fluorescent biography for phosphorous Pesticides Testing of the invention
Sensor.Preparation process is referring to attached drawing 1.
Three, the nano fluorescent sensor application method for phosphorous Pesticides Testing of the invention
The non-phosphorous pesticide that the present invention surveys are as follows: Acetamiprid, carbendazim, carbofuran, Mobucin, Fipronil bromine and cyanogen chrysanthemum
Ester, structural formula are shown in attached drawing 10；The phosphorous pesticide that the present invention surveys are as follows: chlopyrifos, Profenofos, DDVP, parathion, methylamine
Phosphorus, fruit is happy, and isocarbophos and phosmet, structural formula are shown in attached drawing 13.It will be previously used for the nano fluorescent of phosphorous Pesticides Testing
Sensor solution is transferred in 1 centimetre of cuvette, is then separately added into determinand in different cuvettes, is sharp with 275 nm
Send out the fluorescence of the wavelength measurement system.The testing result of above-mentioned 6 kinds of non-phosphorous pesticides is shown in attached drawing 11 and Figure 12, by attached drawing 11 and figure
The 12 visible non-phosphorous pesticides of addition influence the fluorescence of system there is no apparent, still can show carbon quantum dot and terbium
The emission peak of ion.The testing result of aforementioned 8 kinds of phosphorous pesticides is shown in attached drawing 14 and Figure 15, visible with Figure 15 when addition by attached drawing 14
After phosphorous pesticide, the emission peak of rare earth terbium ion is decreased obviously in system, however there is no significantly change the fluorescence of carbon quantum dot
Become, therefore can realize the detection to phosphorous pesticide by rare earth ion and the ratio fluorescent of carbon quantum dot.
One actual detection example of the present invention is detection isocarbophos, is limited with the concentration linear fit of detection and detection
It calculates as follows:
It selects to carry out fluorescence titration test experience for isocarbophos, testing result is shown in Figure 16 and Figure 17, to acquired
Fluorescence intensity be fitted to obtain matched curve and see Figure 18 and Figure 19, utilize formula
Detection limit=3 × S.D./slope
In formula:I 0For the 275 obtained fluorescence intensities of nm excitation material；I 0For the 275 obtained fluorescence of nm excitation material
The average of intensity,nFor testing time, n=10 in the present invention；
It obtains first
S.D.(545 nm)=0.006129
S.D.(490 nm)=0.007477
Obtained detection limit, which is calculated, according to the above results is listed in table 1.
Claims (7)
1. being used for the nano fluorescent sensor of phosphorous Pesticides Testing, it is characterised in that the nano fluorescent sensor is with surface
It is assembled with
The alkylammonium carbon quantum dot of Sulfonated calixarenes as shown in Equation 1 is matrix, has terbium in the coordination of carbon quantum dot surface in situ
Ion.
2. being used to prepare the matrix of the nano fluorescent sensor described in claim 1 for phosphorous Pesticides Testing, feature exists
In the matrix be alkylammonium carbon quantum dot of the surface-assembled just like Sulfonated calixarenes shown in formula 1；
3. the preparation method of matrix as claimed in claim 2, it is characterised in that alkylammonium carbon quantum dot is soluble in water, it is stirring
Sulfonated calixarenes as shown in Equation 1 are added under the conditions of mixing, sufficiently carry out ultrasonic reaction processing under inert gas protection, then to anti-
Solution is answered to be sufficiently stirred, the supernatant then extracted reaction solution 1000Da bag filter dialysis treatment, obtained solution is
The matrix；
4. preparation method according to claim 3, it is characterised in that the alkylammonium carbon quantum dot of 5mg is dissolved in 20mL and is surpassed
In pure water, 2mg/mL Sulfonated calixarenes aqueous solution is added under stirring condition.
5. the preparation method of the nano fluorescent sensor described in claim 1 for phosphorous Pesticides Testing, it is characterised in that: first
Not phosphorous buffer is first added in matrix as claimed in claim 2, terbium ion is then added wherein again.
6. the application method of the nano fluorescent sensor described in claim 1 for phosphorous Pesticides Testing, it is characterized in that will be to
It surveys object to be added in the nano fluorescent sensor for phosphorous Pesticides Testing, with the glimmering of 270-300nm excitation wavelength measurement system
Light, whether the change at the characteristic emission peak of middle terbium ion determines phosphorous in tested pesticide according to testing result.
7. application method according to claim 6, it is characterized in that excitation wavelength used is 275nm.
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| CN109749738B (en) * | 2017-11-01 | 2021-08-17 | 浙江糖能科技有限公司 | Sulfonated carbon quantum dot, preparation method thereof and application of sulfonated carbon quantum dot as catalyst in preparation of 5-hydroxymethylfurfural |
| CN107941769B (en) * | 2017-11-29 | 2020-06-02 | 重庆大学 | Method for detecting methyl parathion |
| CN109374707A (en) * | 2018-11-16 | 2019-02-22 | 肇庆学院 | A method of with carboxylated carbon nanosheet@carboxylated graphene composite film electrochemical sensor trace fluoride worm nitrile |
| CN110132911B (en) * | 2019-04-15 | 2020-03-17 | 浙江大学 | Method for detecting total phosphorus in water sample based on compound ratiometric fluorescent probe |
| CN109991204A (en) * | 2019-04-24 | 2019-07-09 | 杭州嘉灏生态农业科技有限公司 | A kind of detection method of pesticide residue on agricultural product |
| CN110865061B (en) * | 2019-12-04 | 2020-09-01 | 浙江大学 | Simultaneous detection of nitrite ions and Hg2+Dual emission fluorescent probe and method thereof |
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