CN110484239A - The preparation method that composite material is converted on graphene-rare earth and its application in combined toxicity of pesticides evaluation - Google Patents
The preparation method that composite material is converted on graphene-rare earth and its application in combined toxicity of pesticides evaluation Download PDFInfo
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- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
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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
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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- G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
- G01N33/50—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing
- G01N33/5005—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing involving human or animal cells
- G01N33/5008—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing involving human or animal cells for testing or evaluating the effect of chemical or biological compounds, e.g. drugs, cosmetics
- G01N33/5014—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing involving human or animal cells for testing or evaluating the effect of chemical or biological compounds, e.g. drugs, cosmetics for testing toxicity
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- G—PHYSICS
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- 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
- G01N2021/6417—Spectrofluorimetric devices
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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
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6432—Quenching
Abstract
The invention belongs to chemical technology fields, more particularly to the preparation method for converting composite material on graphene-rare earth and its application in combined toxicity of pesticides evaluation, the following steps are included: the preparation of graphene quantum dot, the preparation of composite material is converted in the preparation of up-conversion nano material dispersion liquid and graphene-rare earth.The introducing of functionalization graphene quantum dot of the present invention assigns the more functional groups of up-conversion；Modified up-conversion good hydrophilic property；Rear-earth-doped upper conversion nano particle toxicity is low, is not easy light degradation, and inorganic matrix material rigid structure will not emit photobleaching effect, and shining highly stable is very suitable to the analysis of external or living imaging.
Description
Technical field
The invention belongs to chemical technology fields, and in particular on graphene-rare earth convert composite material preparation method and
Its application in combined toxicity of pesticides evaluation.
Background technique
Current environment quality standard formulate or ecological risk assessment mostly be using the poisonous effect of single compound as foundation, but
In the actual environment, often joint exists compound as a mixture, may will generate various joint toxic effects, than
As uncertain constitute to ecological safety and environmental quality assessment of synergistic effect, antagonistic effect, this joint toxic effect is dived
It is threatening.Its joint risk generated to human health needs to be assessed.Such as 1996, US Congress passed through " food quality protection
Regulations ", it is desirable that Environmental Protection Agency (EPA) carries out accumulative risk assessment to the allogenic material for having identical toxic mechanism, organic
Phosphorus pesticide is chosen to be the exogenous chemical substances for carrying out the assessment of joint exposure in the first batch.China carries out during the ninth five-year plan
The toxic effect of mixed insecticide (organophosphorus pesticide and plan worm chrysanthemum ester pesticide) and the research of mechanism, current common pesticide (have
Machine phosphorus insecticide and carbamate) joint toxicity, synergy mode (be added, cooperate with, antagonism) be considered as food safety
Property evaluation important research content.
Joint toxicity test model mainly includes living Animal Models and isolated cells model.In past pesticide toxicology
In research, living animal is most common test model.Wherein, the mammals such as rat, mouse change with morphological indexes
It is intuitive it is visible, be convenient for the evaluation of physiology allomeric function, pathology pharmacology metabolism (such as gene and human body approach) similar to human body,
Test result can be extrapolated to the advantages that people, therefore be one of the method generallyd use in combined toxicity of pesticides evaluation.With research
Deepen continuously, it has been found that and not all animal experiment can accurately reflect harm of the pesticide to human body, especially join
Close toxicity assessment in, the accumulation of a large amount of test sample and data, animal experiment exist time-consuming, effort, it is at high cost, uncontrollable because
The drawbacks such as more than plain, a kind of new method --- isolated cells are tested gradually by the favor of researcher.Cell culture invitro technology
Have many advantages, such as quick, easy, at low cost, animal test results are replaced and confirmed with test cell line, becomes and carries out agriculture in recent years
The common method of medicine safety evaluatio, it is dry in the neurotoxicity of pesticide combination, genetoxic, immunotoxicity and endocrine at present
It disturbs in effect study and has been widely used.
It is long that rare earth up-conversion luminescent material is that one kind can absorb near-infrared, and emits ultraviolet or visible light, short wavelength's
Novel fluorescent material.Compared with other conventional luminescent materials, up-conversion luminescent material has the advantage that (1) because of photoionization
The decaying of caused host material is effectively reduced；(2) to the of less demanding of phase matched and excitation wavelength stability；
(3) launch wavelength tunable.Presently relevant research work is primarily with regard to 3D display, upconversion laser, anti-counterfeiting technology mark
Know and Photobiology probe etc. progress.Especially in biomedical aspect, since up-conversion nano material uses near infrared light
Excitation, the advantage low with radiation injury, penetration power energy is strong, autofluorescence is weak, application prospect is more wide, becomes and processs in recent years
Hand can heat material " star ".But rare earth up-conversion luminescent material itself has certain limitation, for example, up-conversion luminescence
Low efficiency, poorly water-soluble and functionalization group are few etc..In order to overcome these disadvantages of up-conversion, we use Performances of Novel Nano-Porous
Rice graphene functionalized up-conversion nano material improves the water-soluble of material to improve the luminous efficiency of up-conversion luminescent material
Property, functional groups abundant are provided.
Summary of the invention
The purpose of the invention is to synthesize with good hydrophilic property, functional groups up-conversion luminescent material abundant,
The preparation method that composite material is converted on graphene-rare earth is provided, by the introducing of histidine in graphene quantum dot, so that
It is connected between graphene quantum dot and rare earth upconversion nano crystal body by the chelation of histidine, so as to improve rare earth
The water dispersible of upper conversion nano crystal, increases the functional groups of plane of crystal.
Technical solution according to the invention converts the preparation method of composite material on the graphene-rare earth, including following
Step:
(1) monohydrate potassium, histidine (His) and dimethylbiguanide hydrochloride (M) are weighed in beaker, 5-50ml is added
Water is put into 150-250 DEG C of constant temperature blast drying oven 0.5-10h and prepares histidine-dimethylbiguanide hydrochloride functionalization graphene
Quantum dot (His-M-GQD)；
Monohydrate potassium and histidine are weighed, 5-50ml water is added, is put into 150-250 DEG C of constant temperature blast drying oven 0.5-
10h prepares histidine functionalization graphene quantum dot (His-GQD)；
It weighs monohydrate potassium to be added in 5-50ml water, is put into 150-250 DEG C of constant temperature blast drying oven 0.5-10h preparation
Graphene quantum dot (GQD)；
Respectively by histidine-dimethylbiguanide hydrochloride functionalization graphene quantum dot, histidine functionalization graphene amount
Son point and graphene quantum dot are made into the aqueous solution of 25-100mg/ml, adjust pH to neutrality；
(2) up-conversion nano material (UCNP) of Coated with Oleic Acid is prepared by high temperature pyrolytic cracking (HTP), it will be prepared
In the hexamethylene that UCNP ultrasound is dispersed in, take 1-10mL dispersion liquid in centrifuge tube, ethyl alcohol, which is added, precipitates nanoparticle,
Centrifuge separation juxtaposition is dried in a vacuum drying oven, and HCl solution, vortex oscillation dispersion are added into dry obtained solid；
(3) polyvinylpyrrolidone (PVP) of 1-10mg is added into step (2) acquired solution, at room temperature magnetic agitation
4-10h；Then system pH is adjusted to neutrality with alkalinity PBS buffer solution, then is arrived system constant volume with neutrality PBS buffer solution
The up-conversion of PVP cladding is made in 15ml；0.1-10ml step is added in the UCNP for taking 3 parts of 1-5ml PVP to coat thereto respectively
Suddenly His-M-GQD, His-GQD and GQD aqueous solution is prepared in (1), and oscillation respectively obtains histidine-dimethylbiguanide after mixing
Composite material is converted on the rare earth of hydrochloride function fossil alkene quantum dot modification, histidine functionalization graphene quantum dot is modified
It is converted on rare earth and converts composite material on the rare earth of composite material and modified by graphene quantum dot；In use, being with excitation wavelength
The laser of 980nm does light source, carries out the scanning of the fluorescence spectrum of material.
Further, the molar ratio of monohydrate potassium and histidine is 1:0.1-10, a hydration in the step (1)
The mass ratio of citric acid and dimethylbiguanide hydrochloride is 1:0.05-0.5.
Further, the pH of His-M-GQD solution is adjusted in the step (1) using PBS buffer solution.
Further, the up-conversion nano material of Coated with Oleic Acid is prepared in the step (2) by high temperature pyrolytic cracking (HTP)
The concrete operations of preparation are as follows:
(1) 0.78:0.2:0.02:0.005 weighs YCl in molar ratio3·6H2O、YbCl3·6H2O、ErCl3·6H2O and
Tm(CH3COO)3In flask, then oleic acid (OA) and 1- octadecylene (1-ODE) are added thereto；Flask is closed, it vacuumizes, leads to
Nitrogen 30min, when system temperature rises to 70-80 DEG C, starts to vacuumize water removal deoxygenation, to system temperature by 110 DEG C of set temperature
After reaching 110 DEG C, continue to take out 20min；Logical nitrogen, is warming up to 160 DEG C, constant temperature 1h；Close heating, naturally cool to 50 DEG C with
Under；
(2) NaOH methanol solution is prepared, NH is added after dissolution4F, ultrasonic dissolution obtained solution A；
(3) solution A is added dropwise in step (1) in reaction flask, setting jacket temperature is 47 DEG C of constant temperature 45min；
It is 110 DEG C that temperature, which is arranged, starts to vacuumize except methanol, after temperature rises to 110 DEG C, vacuumizes 30min, leads to nitrogen 30min；Finally
320 DEG C of set temperature, after constant temperature 1h, removing heating mantle makes product up-conversion nano material quickly be down to room temperature；With excessive nothing
Water-ethanol precipitated product, and product is repeatedly washed with the mixed solution of dehydrated alcohol and hexamethylene, finally reaction is produced
Object is dried in vacuo 12h at 60 DEG C.
The present invention also provides application of the composite material in combined toxicity of pesticides evaluation, institute are converted on graphene-rare earth
It states and converts composite material on graphene-rare earth as the preparation side for converting composite material on graphene-rare earth as described in claim 1
Composite material is converted on the rare earth of the modification of histidine functionalization graphene quantum dot made from method.
The beneficial effects of the present invention are:
1) introducing of functionalization graphene quantum dot assigns the more functional groups of up-conversion: histidine functionalization
Graphene quantum dot in, histidine can chelate rare earth ion, so that between graphene quantum dot and up-conversion
It is connected by covalent effect, and up-conversion fluorescence can be enhanced to a certain extent；
2) modified up-conversion good hydrophilic property: the up-conversion of PVP cladding has preferable water stability, and
And the water dispersible of up-conversion can be enhanced in the introducing of graphene quantum dot；
3) rear-earth-doped upper conversion nano particle toxicity is low, is not easy light degradation, inorganic matrix material rigid structure, so
Photobleaching effect will not be emitted, shone highly stable, even if exciting for a long time, spectrochemical property is still highly stable；Wavelength is
The laser of 980/808nm is located near infrared region, and energy is lower, damages very little to bio-tissue；And general object tissue pair
The near infrared light of 980/808nm does not absorb, therefore 980/808nm exciting light has very deep penetration power in biological tissue,
It is very suitable to the analysis of external or living imaging.
4) improve the water dispersible of up-conversion nano material by PVP, then graphene quantum dot is simply mixed with it logical
The chelation between the imidazole radicals of histidine and the rare earth ion of up-conversion is crossed, function is carried out to up-conversion nano material
Change.The introducing of graphene quantum dot can enhance the water dispersible of up-conversion to a certain extent.Conversion nano material on this
The method of modifying process of material is simple, and can obtain water dispersible well and convert on functional graphene-rare earth abundant compound
Material.
Detailed description of the invention
Fig. 1 is the TEM figure (A) of the graphene quantum dot (His-GQD) of histidine functionalization, (B, illustration are HRTEM figure
FFT figure), AFM figure (C, illustration are thickness distribution curve) and FTIR scheme (D).
Fig. 2 is that the TEM of up-conversion nano material schemes (A) and XRD diagram (B).
Fig. 3 is the fluorescence at the fluorescence spectrum (A) and 541nm of the up-conversion luminescent material of different function with respect to blank sample
Intensity compares figure (B)；U=RE-UCNPs, C=GQD, CH=His-GQD, CHM=His-M-GQD.
Fig. 4 is the up-conversion fluorescence that histidine functionalization graphene quantum dot modifies that up-conversion nano material responds Cu2+
Fluorescence intensity at spectrum (A) and 541nm with respect to blank sample compares figure (B)；U=RE-UCNPs, CH=His-GQD.
Fig. 5 be after a series of different amounts of GQD are added the up-conversion fluorescence emission spectrum (A) of upper conversion nano crystal and
Fluorescence intensity at 541nm with respect to blank sample compares figure (B)；U=RE-UCNPs, C=GQD.
Fig. 6 is a series of up-conversion fluorescence emission spectrum (A) of upper conversion nano crystal after different amounts of His-GQD are added
Compare figure (B) with the fluorescence intensity at 541nm with respect to blank sample；U=RE-UCNPs, CH=His-GQD.
Fig. 7 is a series of up-conversion fluorescence emission spectrum (A) of upper conversion nano crystal after different amounts of His-M-G are added
Compare figure (B) with the fluorescence intensity at 541nm with respect to blank sample；U=RE-UCNPs, CHM=His-M-GQD.
Specific embodiment
Below in conjunction with attached drawing, the invention will be further described.
The title, model, manufacturer of key instrument used are tested in following table:
Experimental water is ultrapure water, and methanol, ethyl alcohol are respectively anhydrous methanol, dehydrated alcohol, the name of remaining agents useful for same
Title, specification, manufacturer are listed in the following table:
Embodiment one
(1) monohydrate potassium, histidine and M are weighed in beaker, wherein the molar ratio of monohydrate potassium and histidine
For 1:0.1, the mass ratio of monohydrate potassium and M are 1:0.05, and 5ml water is added, is put into 150 DEG C of constant temperature blast drying oven 6h systems
Standby His-M-GQD；
1:0.1 weighs monohydrate potassium and histidine in molar ratio, and 5ml water is added, is put into 150 DEG C of constant temperature forced air dryings
Case 6h prepares His-GQD；
It weighs 0.1g monohydrate potassium to be added in 5ml water, is put into 150 DEG C of constant temperature blast drying oven 5h and prepares graphene amount
Sub- point GQD；
His-M-GQD, His-GQD and GQD are made into the aqueous solution of 25mg/ml respectively, adjust pH to neutrality；Due to dimethyl
Biguanide hydrochloride highly basic there are in the environment of it is unstable, using PBS buffer solution adjust His-M-GQD solution pH；
(2) UCNP of Coated with Oleic Acid is prepared by high temperature pyrolytic cracking (HTP), concrete operations are as follows:
A. the YCl of 0.78mmol is weighed3·6H2O, the YbCl36H of 0.2mmol2O, the ErCl of 0.02mmol3·6H2O and
Tm (the CH of 0.005mmol3COO)3In 100mL three-necked flask, then 8mLOA and 15mL1-ODE is added thereto；Flask is close
It closes, vacuumizes, lead to nitrogen 30min, 110 DEG C of set temperature, when system temperature rises to 70-80 DEG C, start to vacuumize water removal and remove
Oxygen continues to take out 20min after system temperature reaches 110 DEG C；Logical nitrogen, is warming up to 160 DEG C, constant temperature 1h；Heating is closed, it is natural
It is cooled to 50 DEG C or less；
B. the NaOH of 2.5mmol is dissolved in preparation NaOH methanol solution in 10mL methanol, 4mmolNH is added after dissolution4F,
Ultrasonic dissolution obtained solution A；
C. solution A is added dropwise in step (1) in reaction flask, setting jacket temperature is 47 DEG C of constant temperature 45min；If
Setting temperature is 110 DEG C, starts to vacuumize except methanol, after temperature rises to 110 DEG C, vacuumizes 30min, leads to nitrogen 30min；Finally set
Determine 320 DEG C of temperature, after constant temperature 1h, removing heating mantle makes product up-conversion nano material quickly be down to room temperature；With excessive anhydrous
Ethanol precipitation product, and product is repeatedly washed with the mixed solution of dehydrated alcohol and hexamethylene, finally by reaction product
12h is dried in vacuo at 60 DEG C；
It in the hexamethylene that prepared UCNP ultrasound is dispersed in, takes 1mL dispersion liquid in centrifuge tube, ethyl alcohol is added
Precipitate nanoparticle, centrifuge separation juxtaposition is dried in a vacuum drying oven, and the HCl that pH is 4 is added into dry obtained solid
Solution, vortex oscillation dispersion；
(3) PVP of 1mg is added into step (2) acquired solution, at room temperature magnetic agitation 6h；Then it is buffered with alkalinity PBS
System pH is adjusted to neutrality by solution, then system constant volume to 15ml is made to the upper conversion material of PVP cladding with neutrality PBS buffer solution
Material；The UCNP for taking 3 parts of 1ml PVP to coat is added 0.1ml step (1) thereto respectively and His-M-GQD, His-GQD is prepared
With GQD aqueous solution, oscillation respectively obtains histidine-dimethylbiguanide hydrochloride function fossil alkene quantum dot modification after mixing dilute
Composite material and graphene quantum are converted on the rare earth that conversion composite material, histidine functionalization graphene quantum dot are modified on soil
Composite material (converting composite material on three kinds of graphene-rare earths) is converted on the rare earth of point modification；In use, being with excitation wavelength
The laser of 980nm does light source, carries out the scanning of the fluorescence spectrum of material.
Embodiment two
(1) monohydrate potassium, histidine and M are weighed in beaker, wherein the molar ratio of monohydrate potassium and histidine
For 1:1, the mass ratio of monohydrate potassium and M are 1:0.3, and 25ml water is added, is put into 2000 DEG C of constant temperature blast drying oven 10h systems
Standby His-M-GQD；
1:1 weighs monohydrate potassium and histidine in molar ratio, and 25ml water is added, is put into 180 DEG C of constant temperature forced air dryings
Case 10h prepares His-GQD；
It weighs 10g monohydrate potassium to be added in 30ml water, is put into 2100 DEG C of constant temperature blast drying oven 10h and prepares graphene
Quantum dot GQD；
His-M-GQD, His-GQD and GQD are made into the aqueous solution of 60mg/ml respectively, adjust pH to neutrality；Due to dimethyl
Biguanide hydrochloride highly basic there are in the environment of it is unstable, using PBS buffer solution adjust His-M-GQD solution pH；
(2) UCNP of Coated with Oleic Acid is prepared by high temperature pyrolytic cracking (HTP), concrete operations are as follows:
A. 0.78:0.2:0.02:0.005 weighs YCl in molar ratio3·6H2O、YbCl3·6H2O、ErCl3·6H2O and Tm
(CH3COO)3In flask, then OA and 1-ODE is added thereto；Flask is closed, it vacuumizes, leads to nitrogen 30min, set temperature
110 DEG C, when system temperature rises to 70-80 DEG C, starts to vacuumize water removal deoxygenation, after system temperature reaches 110 DEG C, continue to take out
20min；Logical nitrogen, is warming up to 160 DEG C, constant temperature 1h；Heating is closed, naturally cools to 50 DEG C or less；
B. NaOH methanol solution is prepared, NH is added after dissolution4F, ultrasonic dissolution obtained solution A；
C. solution A is added dropwise in step (1) in reaction flask, setting jacket temperature is 47 DEG C of constant temperature 45min；If
Setting temperature is 110 DEG C, starts to vacuumize except methanol, after temperature rises to 110 DEG C, vacuumizes 30min, leads to nitrogen 30min；Finally set
Determine 320 DEG C of temperature, after constant temperature 1h, removing heating mantle makes product up-conversion nano material quickly be down to room temperature；With excessive anhydrous
Ethanol precipitation product, and product is repeatedly washed with the mixed solution of dehydrated alcohol and hexamethylene, finally by reaction product
12h is dried in vacuo at 60 DEG C；
It in the hexamethylene that prepared UCNP ultrasound is dispersed in, takes 5.5mL dispersion liquid in centrifuge tube, second is added
Alcohol precipitates nanoparticle, and centrifuge separation juxtaposition is dried in a vacuum drying oven, and it is 4 that pH is added into dry obtained solid
HCl solution, vortex oscillation dispersion；
(3) PVP of 6mg is added into step (2) acquired solution, at room temperature magnetic agitation 4h；Then the PBS for being 8 with pH
System pH is adjusted to neutrality by buffer solution, then PVP cladding is made in system constant volume to 15ml with neutrality PBS buffer solution
UCNP；The UCNP for taking 3 parts of 3ml PVP to coat is added 10ml step (1) thereto respectively and His-M-GQD, His- is prepared
GQD and GQD aqueous solution converts composite material on three kinds of graphene-rare earths after oscillation mixing；In use, using excitation wavelength
Light source is done for the laser of 980nm, carries out the scanning of the fluorescence spectrum of material.
Embodiment three
(1) monohydrate potassium, histidine and M are weighed in beaker, wherein the molar ratio of monohydrate potassium and histidine
For 1:10, the mass ratio of monohydrate potassium and M are 1:0.5, and 50ml water is added, is put into 250 DEG C of constant temperature blast drying oven 0.5h
Prepare His-M-GQD；
1:10 weighs monohydrate potassium and histidine in molar ratio, and 50ml water is added, is put into 250 DEG C of constant temperature forced air dryings
Case 0.5h prepares His-GQD；
It weighs 100g monohydrate potassium to be added in 5ml water, is put into 250 DEG C of constant temperature blast drying oven 0.5h and prepares graphene
Quantum dot GQD；
His-M-GQD, His-GQD and GQD are made into the aqueous solution of 100mg/ml respectively, adjust pH to neutrality；Due to diformazan
Base biguanide hydrochloride highly basic there are in the environment of it is unstable, using PBS buffer solution adjust His-M-GQD solution pH；
(2) UCNP of Coated with Oleic Acid is prepared by high temperature pyrolytic cracking (HTP), concrete operations are as follows:
A. 0.78:0.2:0.02:0.005 weighs YCl in molar ratio3·6H2O、YbCl3·6H2O、ErCl3·6H2O and Tm
(CH3COO)3In flask, then OA and 1-ODE is added thereto；Flask is closed, it vacuumizes, leads to nitrogen 30min, set temperature
110 DEG C, when system temperature rises to 70-80 DEG C, starts to vacuumize water removal deoxygenation, after system temperature reaches 110 DEG C, continue to take out
20min；Logical nitrogen, is warming up to 160 DEG C, constant temperature 1h；Heating is closed, naturally cools to 50 DEG C or less；
B. NaOH methanol solution is prepared, NH is added after dissolution4F, ultrasonic dissolution obtained solution A；
C. solution A is added dropwise in step (1) in reaction flask, setting jacket temperature is 47 DEG C of constant temperature 45min；If
Setting temperature is 110 DEG C, starts to vacuumize except methanol, after temperature rises to 110 DEG C, vacuumizes 30min, leads to nitrogen 30min；Finally set
Determine 320 DEG C of temperature, after constant temperature 1h, removing heating mantle makes product up-conversion nano material quickly be down to room temperature；With excessive anhydrous
Ethanol precipitation product, and product is repeatedly washed with the mixed solution of dehydrated alcohol and hexamethylene, finally by reaction product
12h is dried in vacuo at 60 DEG C；
It in the hexamethylene that prepared UCNP ultrasound is dispersed in, takes 10mL dispersion liquid in centrifuge tube, second is added
Alcohol precipitates nanoparticle, and centrifuge separation juxtaposition is dried in a vacuum drying oven, and it is 4 that pH is added into dry obtained solid
HCl solution, vortex oscillation dispersion；
(3) PVP of 1mg is added into step (2) acquired solution, at room temperature magnetic agitation 6h；Then the PBS for being 8 with pH
System pH is adjusted to neutrality by buffer solution, then with neutrality PBS buffer solution by system constant volume to 15ml be made PVP cladding upper turn
Conversion materials；The UCNP for taking 3 parts of 5ml PVP to coat is added 6ml step (1) thereto respectively and His-M-GQD, His- is prepared
GQD and GQD aqueous solution converts composite material on three kinds of graphene-rare earths after oscillation mixing；In use, using excitation wavelength
Light source is done for the laser of 980nm, carries out the scanning of the fluorescence spectrum of material.
Application Example one
Application of the composite material in combined toxicity of pesticides evaluation is converted on graphene-rare earth, on the graphene-rare earth
Composite material is converted as composite material is converted on three kinds of graphene-rare earths made from above-described embodiment；Concrete operations are as follows:
(1) processing group: the A549 cell of logarithmic growth phase is processed into the single cell suspension of dispersion through attached cell, and
It is 1 × 10 with complete medium adjustment cell concentration4A/100 μ L, according to the volume of every 200 μ L single cell suspension of hole by A549
Cell inoculation is placed in 5%CO in 96 porocyte culture plates2Stationary culture 8 hours in saturated humidity, 37 DEG C of constant incubators；
After cell is adherent, change liquid to A549 cell with the culture medium of different pesticide poisoning dosages, 4 Duplicate Samples of every group of setting,
Respectively contamination processing for 24 hours, 48h；It contaminates after treatment, any preparation side 20 μ L such as claim 1-4 is added in every hole
Graphene made from method-rare earth upconversion nano material continues to cultivate 4h so that graphene-rare earth up-conversion enters carefully
Born of the same parents；Supernatant is siphoned away to terminate culture along edge with pipettor, and the PBS buffer solution of 100 μ L is added in every hole, vibrates 10min, makes
Cell dispersion as much as possible on tissue culture plate is in the solution；
Wherein, the concrete operations of contamination are as follows: take out the pesticide storing liquid for being dissolved in dimethyl sulfoxide, it is quick to be placed in constant temperature water tank
After dissolution, it is centrifuged with centrifuge；The dilution of pesticide storing liquid is become into 200 μM, 100 μM, 50 μM, 25 μM and 0 μ with complete medium
The working concentration of M；It is thin to A549 using the form for changing liquid according to the culture medium dosage of 200 μ L after to be processed group of cell is adherent
Born of the same parents carry out contamination processing, in 5%CO2, be incubated for 1-48h in 37 DEG C of constant incubators；
(2) by step (1) acquired solution after centrifuge washing, the polyvinyl pyrrolidon modified graphite not acted on is removed
Composite material is converted on alkene-rare earth, and fluorescence spectrum then is carried out to material using the external laser that excitation wavelength is 980nm and is swept
It retouches；Measuring zeroing group respectively simultaneously, (DMEM/F12 (1:1) contains+0.5%100 × penicillin of phenol red+5% import fetal calf serum-chain
Composite material and PBS buffer solution are converted on graphene-rare earth that mycin solution, 1mg/ml PVP are modified) it is (thin with control group
Born of the same parents, 0.5% acetone of volumetric concentration, culture solution, DPA-GQD-His and PBS buffer solution) 980nm excitation under emissive porwer；
According to: cell survival rate=(processing group fluorescence intensity-zeroing group fluorescence intensity)/(control group fluorescence intensity-zeroing
Group fluorescence intensity) × 100%, combined toxicity of pesticides is judged according to cell survival rate.
The His-GQD being prepared is characterized, as shown in Figure 1, Figure 1A TEM map analysis can obtain being averaged for His-GQD
Size is in 3.3nm or so；Six bright spots are presented in FFT figure, disclose His-GQD with hexagonal lattice structure, further analyze
The spacing of lattice that HRTEM figure can obtain His-GQD is 0.22nm；AFM analysis the result shows that, the average thickness of His-GQD is about
0.9nm, i.e., the thickness of major part His-GQD is between one layer to two layers graphene nanometer sheet thickness.Fig. 1 D is His-GQD's
Infared spectrum, wherein 3100-3700cm-1Absorption band in range is generated by the stretching vibration of O-H key and N-H key, 2200-
3100cm-1Absorption band in range is generated by the stretching vibration of c h bond.1699cm-1The absorption peak at place shows-C=in acyl group
The stretching vibration of O key, and 1594cm-1The absorption peak at place is generated by-C=N key the stretching vibration in imidazole ring, 1167cm-1Place
Absorption peak is then generated by the stretching vibration of C-O key.The result shows that histidine is successfully introduced in GQD, GQD function is imparted
The imidazole group of change also brings a large amount of-NH2Group.
Fig. 2 is the TEM figure and XRD diagram of upper conversion nano crystal.As can be seen that the upper conversion nano of synthesis is brilliant from figure A
Body size uniformity, average grain diameter are about 20nm.Figure B shows that the XRD of upper conversion nano crystal has 5 strong and point diffraction maximum, position
In 17.1 °, 29.8 °, 30.4 °, 42.9 °, 53.1 °, (100) are corresponded respectively to, (110), (101), (201), (211) crystal face
These diffraction maximums can find (JCPDS No.27-0809) in standard card, it was demonstrated that form conversion nano crystal in β phase.
Take isometric upper conversion nano crystal aqueous solution, be separately added into thereto isometric three kinds of quantum dot solutions or
Pure water is after mixing.980nm used as excitation wavelength measure respectively the up-conversion fluorescence transmitting of four samples, obtained fluorescence light
Spectrogram is as shown in Figure 3: compared with blank sample, up-conversion fluorescence weakens after His-M-GQD is added；And after GQD or His-GQD is added
Up-conversion fluorescence has different degrees of enhancing, wherein His-GQD, which is added, to be enhanced more.
His-GQD solution, the Cu of equivalent are separately added into the upper conversion nano crystal aqueous solution of same concentrations2+Solution,
His-GQD+Cu2+Solution and pure water, the up-conversion fluorescence intensity of system and comparison are as shown in Figure 4.The result shows that: each solution is added
The spectral shape of system and peak position are unchanged afterwards；System Up-conversion emission is remarkably reinforced in His-GQD, on its basis plus
Enter Cu2+Then make the fluorescent quenching of strengthening part, and is individually added into Cu2+System fluorescence is had no significant effect.
Fig. 5 is that the change of different amounts of GQD system fluorescence intensity is added in the case that upper conversion nano crystal concentration is certain
Change.As seen from the figure, the GQD of addition has different degrees of enhancing to system fluorescence, when the mass concentration ratio of upper conversion crystal and GQD
When for 1:5, conversion composite material fluorescence intensity is maximum on graphene-rare earth.
For Fig. 6 for not same amount His-GQD is added in the upper conversion nano crystalloid solution water under same concentrations, system fluorescence is strong
The variation of degree is the results show that introducing system up-conversion fluorescence after His-GQD enhances, and works as upper conversion nano crystal and His-GQD
Mass concentration ratio when being 1:5, the fluorescence intensity of up-conversion luminescent material of histidine functionalization graphene quantum dot modification reaches
To maximum.Compared with the up-conversion luminescent material of the modified by graphene quantum dot of same concentrations, histidine functionalization graphene amount
The up-conversion fluorescence intensity of the up-conversion luminescent material of son point modification is bigger, has also confirmed optics of the introducing to GQD of histidine
Performance increases, best in the application effect in combined toxicity of pesticides is evaluated.
Fig. 7 is that not same amount His-M-GQD, system fluorescence is added in upper conversion nano crystal aqueous solution under same concentrations
The variation of intensity is as the result is shown: when the mass concentration ratio of upper conversion nano crystal and His-M-GQD are 1:0.5 or 1:1, body
It is that fluorescence intensity is enhanced；When the mass concentration ratio of upper conversion nano crystal and His-M-GQD are 1:5 or 1:10, system
Quenching occurs for fluorescence.
Claims (5)
1. converting the preparation method of composite material on graphene-rare earth, which comprises the following steps:
(1) monohydrate potassium, histidine and dimethylbiguanide hydrochloride are weighed in beaker, 5-50ml water is added, is put into 150-
250 DEG C of constant temperature blast drying oven 0.5-10 h prepare histidine-dimethylbiguanide hydrochloride functionalization graphene quantum dot；
Monohydrate potassium and histidine are weighed, 5-50ml water is added, is put into 150-250 DEG C of constant temperature blast drying oven 0.5-10 h
Prepare histidine functionalization graphene quantum dot；
It weighs monohydrate potassium to be added in 5-50ml water, is put into 150-250 DEG C of constant temperature blast drying oven 0.5-10 h and prepares stone
Black alkene quantum dot；
Respectively by histidine-dimethylbiguanide hydrochloride functionalization graphene quantum dot, histidine functionalization graphene quantum dot
It is made into the aqueous solution of 25-100mg/ml with graphene quantum dot, adjusts pH to neutrality；
(2) up-conversion nano material of Coated with Oleic Acid is prepared by high temperature pyrolytic cracking (HTP), by prepared upper conversion nano material
In the hexamethylene that material ultrasound is dispersed in, take 1-10 mL dispersion liquid in centrifuge tube, ethyl alcohol, which is added, precipitates nanoparticle,
Centrifuge separation juxtaposition is dried in a vacuum drying oven, and HCl solution, vortex oscillation dispersion are added into dry obtained solid；
(3) polyvinylpyrrolidone of 1-10 mg is added into step (2) acquired solution, at room temperature magnetic agitation 4-10 h；So
System pH is adjusted to neutrality with alkalinity PBS buffer solution afterwards, then system constant volume is made to 15 ml with neutrality PBS buffer solution
The up-conversion of polyvinylpyrrolidone cladding；The up-conversion nano material for taking 3 parts of 1-5ml polyvinylpyrrolidones to coat,
0.1-10ml step (1) is added thereto respectively, histidine-dimethylbiguanide hydrochloride functionalization graphene quantum is prepared
Point, histidine functionalization graphene quantum dot and graphene quantum dot aqueous solution, oscillation respectively obtain histidine-diformazan after mixing
Composite material, histidine functionalization graphene quantum dot are converted on the rare earth of base biguanide hydrochloride function fossil alkene quantum dot modification
It is converted on the rare earth of modification and converts composite material on the rare earth of composite material and modified by graphene quantum dot；In use, with excitation
Wavelength is that the laser of 980nm does light source, carries out the scanning of the fluorescence spectrum of material.
2. converting the preparation method of composite material on graphene-rare earth as described in claim 1, which is characterized in that the step
Suddenly the molar ratio of monohydrate potassium and histidine is 1:0.1-10, monohydrate potassium and dimethylbiguanide hydrochloric acid in (1)
The mass ratio of salt is 1:0.05-0.5.
3. converting the preparation method of composite material on graphene-rare earth as described in claim 1, which is characterized in that the step
Suddenly histidine-dimethylbiguanide hydrochloride functionalization graphene quantum dot solution pH is adjusted using PBS buffer solution in (1).
4. converting the preparation method of composite material on graphene-rare earth as described in claim 1, which is characterized in that the step
Suddenly the concrete operations for the up-conversion nano material preparation of Coated with Oleic Acid being prepared by high temperature pyrolytic cracking (HTP) in (2) are as follows:
(1) 0.78:0.2:0.02:0.005 weighs YCl in molar ratio3•6H2O、YbCl3•6H2O、ErCl3•6H2O and Tm
(CH3COO)3In flask, then oleic acid and 1- octadecylene are added thereto；Flask is closed, it vacuumizes, leads to nitrogen 30min, if
Determine 110 DEG C of temperature, when system temperature rises to 70-80 DEG C, starts to vacuumize water removal deoxygenation, after system temperature reaches 110 DEG C,
Continue to take out 20 min；Logical nitrogen, is warming up to 160 DEG C, constant temperature 1h；Heating is closed, naturally cools to 50 DEG C or less；
(2) NaOH methanol solution is prepared, NH is added after dissolution4F, ultrasonic dissolution obtained solution A；
(3) solution A is added dropwise in step (1) in reaction flask, setting jacket temperature is 47 DEG C of 45 min of constant temperature；Setting
Temperature is 110 DEG C, starts to vacuumize except methanol, after temperature rises to 110 DEG C, vacuumizes 30 min, leads to 30 min of nitrogen；Finally set
Determine 320 DEG C of temperature, after constant temperature 1h, removing heating mantle makes product up-conversion nano material quickly be down to room temperature；With excessive anhydrous
Ethanol precipitation product, and product is repeatedly washed with the mixed solution of dehydrated alcohol and hexamethylene, finally by reaction product
12h is dried in vacuo at 60 DEG C.
5. converting application of the composite material in combined toxicity of pesticides evaluation on graphene-rare earth, turn on the graphene-rare earth
Changing composite material is that histidine function made from the preparation method of composite material is converted on graphene-rare earth as described in claim 1
Composite material can be converted on the rare earth of graphite alkene quantum dot modification.
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