CN115011337B - Boric acid functionalized carbon dot and preparation method and application thereof - Google Patents
Boric acid functionalized carbon dot and preparation method and application thereof Download PDFInfo
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- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000004327 boric acid Substances 0.000 title claims abstract description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 34
- 239000008103 glucose Substances 0.000 claims abstract description 34
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 31
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 17
- 102000002260 Alkaline Phosphatase Human genes 0.000 claims abstract description 14
- 108020004774 Alkaline Phosphatase Proteins 0.000 claims abstract description 14
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 claims abstract description 14
- 235000003704 aspartic acid Nutrition 0.000 claims abstract description 14
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003987 organophosphate pesticide Substances 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 4
- LXAATRGTGHYGJH-UHFFFAOYSA-N OP(O)(O)=O.[O-][N+](=O)C1=CC=C([Na])C=C1 Chemical compound OP(O)(O)=O.[O-][N+](=O)C1=CC=C([Na])C=C1 LXAATRGTGHYGJH-UHFFFAOYSA-N 0.000 claims abstract 2
- 238000001514 detection method Methods 0.000 claims description 20
- 239000000575 pesticide Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000006228 supernatant Substances 0.000 claims description 6
- 210000004369 blood Anatomy 0.000 claims description 5
- 239000008280 blood Substances 0.000 claims description 5
- 238000011534 incubation Methods 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 238000001917 fluorescence detection Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- 238000000502 dialysis Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 238000003556 assay Methods 0.000 claims description 2
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- 238000004627 transmission electron microscopy Methods 0.000 abstract description 2
- 238000005054 agglomeration Methods 0.000 abstract 1
- 238000012512 characterization method Methods 0.000 abstract 1
- 238000004062 sedimentation Methods 0.000 abstract 1
- 238000002211 ultraviolet spectrum Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 15
- XZKIHKMTEMTJQX-UHFFFAOYSA-N 4-Nitrophenyl Phosphate Chemical compound OP(O)(=O)OC1=CC=C([N+]([O-])=O)C=C1 XZKIHKMTEMTJQX-UHFFFAOYSA-N 0.000 description 11
- 238000012360 testing method Methods 0.000 description 7
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 5
- 238000004220 aggregation Methods 0.000 description 5
- ZNOLGFHPUIJIMJ-UHFFFAOYSA-N fenitrothion Chemical compound COP(=S)(OC)OC1=CC=C([N+]([O-])=O)C(C)=C1 ZNOLGFHPUIJIMJ-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 150000002903 organophosphorus compounds Chemical class 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 3
- 230000003013 cytotoxicity Effects 0.000 description 3
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- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 2
- 239000005944 Chlorpyrifos Substances 0.000 description 2
- 241000276457 Gadidae Species 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 2
- SBPBAQFWLVIOKP-UHFFFAOYSA-N chlorpyrifos Chemical compound CCOP(=S)(OCC)OC1=NC(Cl)=C(Cl)C=C1Cl SBPBAQFWLVIOKP-UHFFFAOYSA-N 0.000 description 2
- OEBRKCOSUFCWJD-UHFFFAOYSA-N dichlorvos Chemical compound COP(=O)(OC)OC=C(Cl)Cl OEBRKCOSUFCWJD-UHFFFAOYSA-N 0.000 description 2
- 229950001327 dichlorvos Drugs 0.000 description 2
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012091 fetal bovine serum Substances 0.000 description 2
- RWSXRVCMGQZWBV-WDSKDSINSA-N glutathione Chemical compound OC(=O)[C@@H](N)CCC(=O)N[C@@H](CS)C(=O)NCC(O)=O RWSXRVCMGQZWBV-WDSKDSINSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
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- 239000002609 medium Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 108010024636 Glutathione Proteins 0.000 description 1
- 206010058467 Lung neoplasm malignant Diseases 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- 239000012980 RPMI-1640 medium Substances 0.000 description 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical compound N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-UHFFFAOYSA-N 0.000 description 1
- TVWHNULVHGKJHS-UHFFFAOYSA-N Uric acid Natural products N1C(=O)NC(=O)C2NC(=O)NC21 TVWHNULVHGKJHS-UHFFFAOYSA-N 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 229960005261 aspartic acid Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000003833 cell viability Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- VIYFPAMJCJLZKD-UHFFFAOYSA-L disodium;(4-nitrophenyl) phosphate Chemical compound [Na+].[Na+].[O-][N+](=O)C1=CC=C(OP([O-])([O-])=O)C=C1 VIYFPAMJCJLZKD-UHFFFAOYSA-L 0.000 description 1
- 229960003638 dopamine Drugs 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229960001031 glucose Drugs 0.000 description 1
- 229960003180 glutathione Drugs 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 201000005202 lung cancer Diseases 0.000 description 1
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- 238000005259 measurement Methods 0.000 description 1
- VMGAPWLDMVPYIA-HIDZBRGKSA-N n'-amino-n-iminomethanimidamide Chemical compound N\N=C\N=N VMGAPWLDMVPYIA-HIDZBRGKSA-N 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 210000005036 nerve Anatomy 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- BOLDJAUMGUJJKM-LSDHHAIUSA-N renifolin D Natural products CC(=C)[C@@H]1Cc2c(O)c(O)ccc2[C@H]1CC(=O)c3ccc(O)cc3O BOLDJAUMGUJJKM-LSDHHAIUSA-N 0.000 description 1
- 210000002966 serum Anatomy 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
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- 241000894007 species Species 0.000 description 1
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- 229910021642 ultra pure water Inorganic materials 0.000 description 1
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- 229940116269 uric acid Drugs 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
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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
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
-
- G—PHYSICS
- G01—MEASURING; TESTING
- 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"
-
- G—PHYSICS
- G01—MEASURING; TESTING
- 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"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
-
- G—PHYSICS
- G01—MEASURING; TESTING
- 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
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- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Abstract
The invention belongs to the technical field of fluorescence sensing, and relates to a boric acid functionalized carbon dot, a preparation method and application thereof. The preparation method comprises the steps of synthesizing aspartic acid and phenylboronic acid through a hydrothermal method. Characterization is performed by means of transmission electron microscopy, ultraviolet spectrum, fluorescence spectrum and the like. Based on non-radiative energy conversion, decomposing the 4-nitrophenyl sodium phosphate by means of alkaline phosphatase, wherein the absorption peak position of the decomposed product coincides with the fluorescence emission position of the carbon quantum dots, so that the fluorescence of the carbon dots is quenched, and the organophosphorus pesticide can inhibit enzymolysis reaction, so that the fluorescence of the carbon quantum dots is not quenched; glucose can promote agglomeration and sedimentation of the carbon quantum dots, so that fluorescence quenching of the carbon quantum dots is caused. The method is simple and easy to implement, has easily available raw materials, and has good prospect in production.
Description
Technical Field
The invention belongs to the technical field of fluorescence sensing, and relates to a boric acid functionalized carbon dot, a preparation method and application thereof.
Background
The disclosure of this background section is only intended to increase the understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art already known to those of ordinary skill in the art.
Organophosphorus compounds (OPs) are widely used in agriculture for pest control, nerve agents and flame retardants. A large amount of organophosphorus waste residue is detected in air, soil, water, agricultural products such as fruits, vegetables, and crops. Glucose in blood is called blood glucose and diabetics need to monitor blood glucose frequently.
Carbon quantum dots (CQDs, carbon dots) are used as an emerging fluorescent nanomaterial, and have the advantages of small size, high light stability, excellent water solubility, low biotoxicity and the like. The inventor researches show that no report on carbon points capable of simultaneously detecting the organophosphorus compounds and glucose exists at present.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides the boric acid functionalized carbon dot, and the preparation method and the application thereof.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
on the one hand, the preparation method of the boric acid functionalized carbon point is characterized in that aspartic acid and phenylboric acid are synthesized by a hydrothermal method to obtain the boric acid functionalized carbon point.
According to the invention, the boric acid functionalized carbon point can be synthesized by a hydrothermal method by taking aspartic acid and phenylboric acid as raw materials, and can be used for detecting organophosphorus pesticides based on non-radiative energy transfer, and can also be directly applied to the detection of glucose by utilizing the modified surface of the boric acid functionalized carbon point.
Preferably, the process is as follows: adding aspartic acid and phenylboronic acid into water, mixing, adjusting the pH to 8.5-9.5, introducing nitrogen, and performing hydrothermal reaction.
Preferably, the temperature of the hydrothermal reaction is 160 to 200 ℃, more preferably 185 to 195 ℃.
Preferably, the hydrothermal reaction time is 14 to 20 hours, more preferably 15.5 to 16.5 hours.
Preferably, the material after the hydrothermal reaction is centrifuged, the supernatant after centrifugation is taken, the supernatant is filtered, and then the uncarbonated raw materials are removed by dialysis.
Preferably, the mass ratio of the aspartic acid to the phenylboronic acid is 0-7:7-0, and the mass ratio of the aspartic acid to the phenylboronic acid is not 0, preferably 1:0.9-1.1.
In another aspect, a boric acid functionalized carbon dot is obtained by the above preparation method.
In a third aspect, a boric acid functionalized carbon dot is used for detecting an organic phosphorus compound, detecting glucose and/or preparing a blood glucose detection reagent.
Specifically, the method for detecting glucose comprises the following steps: and adding the glucose-containing sample into the aqueous solution of the boric acid functionalized carbon point, dissolving and mixing, and then carrying out fluorescence detection.
In a fourth aspect, a method for detecting an organophosphorus pesticide comprises adding a sample to be detected into a solution containing sodium 4-nitrophenyl phosphate (NPP) and alkaline phosphatase (ALP), incubating, adding a terminator and the boric acid functionalized carbon point, and performing fluorescence detection.
Preferably, the terminator is Na 3 VO 4 。
In a fifth aspect, a glucose test reagent comprises the above-described boronic acid functionalized carbon spot.
The mechanism for detecting the organic phosphorus compound by the boric acid functionalized carbon point provided by the invention is as follows: the hydrolysis of 4-nitrophenyl phosphate (NPP) to 4-Nitrophenol (NTP) by ALP also shifts the corresponding absorption band from 310 to 405nm, whereas the fluorescence emission of the boric acid functionalized carbon point provided by the present invention is also at 405nm, resulting in a decrease in fluorescence emission intensity due to non-radiative energy conversion. The organic phosphorus pesticide has an inhibition effect on the hydrolysis reaction of alkaline phosphatase, can influence the degree of hydrolysis of NPP into NTP, and can not quench the fluorescence intensity, thereby realizing the fluorescence signal sensing of the organic phosphorus pesticide.
The mechanism of detecting glucose by boric acid functionalized carbon dots provided by the invention is as follows: the cis-diol of glucose can be quickly and covalently combined with boric acid on the surface of the boric acid functionalized carbon dot, so that aggregation-induced fluorescence quenching of the carbon quantum dot occurs, and along with the increase of the concentration of glucose, the faster the aggregation phenomenon of the carbon quantum dot is, the lower the fluorescence signal is.
The beneficial effects of the invention are as follows:
1. the invention provides a boric acid modified fluorescent carbon dot, which is prepared from aspartic acid and phenylboronic acid by a hydrothermal method, and researches show that the carbon dot can sensitively detect organophosphorus pesticides and glucose.
2. Experiments show that the boric acid functionalized carbon dot provided by the invention has strong selectivity to organophosphorus pesticides and glucose.
3. The preparation method of the boric acid functionalized carbon dot provided by the invention is simple, low in cost, universal and easy for mass production.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention.
FIG. 1 is a TEM image of boric acid functionalized carbon quantum dots prepared in example 1 of the present invention;
fig. 2 is a working principle diagram of the carbon quantum dot detection of the organophosphorus pesticide prepared in the embodiment 1 of the present invention;
FIG. 3 is a schematic diagram of the carbon quantum dot for detecting glucose prepared in example 1 of the present invention;
FIG. 4 is a fluorescence diagram for verifying feasibility of a fluorescent sensing platform construction idea in an embodiment of the invention;
FIG. 5 shows fluorescence emission spectra of detection platforms added with fenitrothion (0-25 mug/L) with different concentrations under 320nm excitation and corresponding linear fitting curves (1-6 mug/L);
FIG. 6 is a diagram showing the selective detection of organophosphorus pesticides by a fluorescence sensing platform in an embodiment of the invention;
FIG. 7 is a TEM image of aggregation of carbon quantum dots in a 3mM glucose solution in an embodiment of the present invention;
FIG. 8 is a graph of fluorescence quenching of glucose to carbon quantum dots and corresponding linear fitting curve in an embodiment of the present invention;
FIG. 9 is a graph showing the selective detection of glucose by carbon quantum dots in an embodiment of the present invention;
FIG. 10 is a bar graph of carbon quantum dot versus cytotoxicity detection in an example of the present invention.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the present invention. As used herein, the singular is also intended to include the plural unless the context clearly indicates otherwise, and furthermore, it is to be understood that the terms "comprises" and/or "comprising" when used in this specification are taken to specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof.
The hydrothermal method is a method for synthesizing by adopting a hydrothermal reaction, wherein the hydrothermal reaction is a reaction which is carried out by heating a reaction system taking water as a solvent under a closed condition, generating a high-pressure condition after heating and carrying out the condition.
In order to enable those skilled in the art to more clearly understand the technical scheme of the present invention, the technical scheme of the present invention will be described in detail with reference to specific embodiments.
Example 1 synthesis of boronic acid functionalized carbon quantum dots: and preparing the carbon quantum dots by direct carbonization through a one-step hydrothermal method.
0.1g of phenylboronic acid and 0.1g of aspartic acid were dissolved in 20mL of ultrapure water, naOH (0.1M) was added with stirring to adjust the pH to 9.0, and then N was bubbled in 2 One hour to remove dissolved O 2 . Finally, the solution was transferred to an autoclave lined with polytetrafluoroethylene and maintained in a heated environment at 190 ℃ for 16 hours. After cooling to room temperature, centrifugation was performed at 10000rpm for 30min, and only the supernatant was taken to remove large precipitates, followed by removal of large impurities by a water-based nanofiltration head (0.22 μm). To further purify CQDs, the supernatant was dialyzed in a dialysis bag (molecular weight cut-off=1000) for 24 hours to remove the uncarbonated starting material. The purified CQDs solution was stored at 4 ℃ for later use.
The purified CQDs solution was freeze-dried and then characterized by transmission electron microscopy, as shown in fig. 1, and fig. 1 shows that the present example obtained CQDs of uniform particle size.
Example 2 fluorescence detection of Organophosphorus Pesticides (OPs) based on the CQDs fluorescence sensing detection platform prepared in example 1:
the detection mechanism is shown in FIG. 2, in which 4-nitrophenyl phosphate (NPP) is hydrolyzed by ALP to 4-Nitrophenol (NTP), the corresponding absorption band is shifted from 310 to 405nm, and the fluorescence emission of CQDs prepared in example 1 is also at 405nm, so that the fluorescence emission intensity is reduced due to non-radiative energy conversion. The alkaline phosphatase can hydrolyze the organophosphorus pesticide, and the affinity of the alkaline phosphatase to the organophosphorus pesticide is higher than that of NPP, so that the organophosphorus pesticide can be hydrolyzed preferentially, the inhibition effect on the hydrolysis reaction of NPP is achieved, the fluorescence intensity can not be quenched, and the fluorescence signal sensing of the organophosphorus pesticide is realized.
And verifying the feasibility of the experimental thought. 200. Mu.L of the CQDs solution prepared in example 1 was mixed with NPP solutions (0-80. Mu.M) of different concentrations and NPP solutions (0-80. Mu.M) after reaction with ALP of different concentrations, respectively, and after standing for 10min, fluorescence test was performed to investigate effective fluorescence quenching process and optimal formulation of other components in the system, and the results are shown in FIG. 4.
Mixing fenitrothion (0-25 μg/L) with ALP (0.2U), standing for 15min, adding into NPP (2 mL of 0.03mM containing 2 μM MgSO) 4 ) In an aqueous solution. The resulting solution was incubated at 37℃for 30 minutes, and the solution turned from clear to pale yellow. At the end of incubation, 10. Mu.L of terminator solution (Na 3 VO 4 10 mM). Then, 800. Mu.L of the reacted sample with different concentrations of fenitrothion inhibition was taken, 200. Mu.L of the CQDs solution prepared in example 1 was added, and the mixture was shaken and thoroughly mixed. Fluorescence spectra of different samples emitted at 405nm under 320nm excitation wavelength are collected, and fluorescence intensities of organophosphorus pesticides in a concentration range of 1-6 mug/L are subjected to linear fitting, wherein a linear correlation coefficient is 0.9879, and a detection limit is 0.087 mug/L through a detection limit formula, and a result is shown in fig. 5.
Example 3 fluorescence sensing detection platform selectivity test:
because the fluorescence sensing platform is sensitive to organophosphorus pesticides and is not a carbon quantum dot, the interference efficiency of alkaline phosphatase in the presence of different interfering species is directly tested.
In the process of selectively testing the platform, several substances which can interfere alkaline phosphatase or are common in soil and water quality are adoptedComprises fenitrothion, dichlorvos, chlorpyrifos and Al (NO) with the same concentration (25 mu g/L) and the concentration of 20 mu M 3 ) 3 、CaCl 2 NaCl, KCl and urea. The configuration of the samples and the parameters of the fluorescence test were the same as those set in example 2.
As shown in FIG. 6, the CQDs fluorescence sensing platform prepared based on example 1 has high selectivity to Organophosphorus Pesticides (OPs) such as fenitrothion, dichlorvos, chlorpyrifos and the like.
Example 4 carbon quantum dot to glucose detection:
the detection principle is shown in fig. 3, the cis-diol of glucose can be quickly and covalently combined with boric acid on the surface of the carbon quantum dots, so that the CQDs prepared in the embodiment 1 generate aggregation-induced fluorescence quenching, and the faster the aggregation phenomenon of the carbon quantum dots is, the lower the fluorescence signal is along with the increase of the concentration of glucose. A TEM image of the CQDs carbon quantum dots prepared in example 1 in a 3mM glucose solution is shown in fig. 7, indicating that CQDs can be aggregated in the presence of glucose.
mu.L of PBS buffer (0.1M, pH=7.4) and 100. Mu.L of the CQDs solution prepared in example 1 were placed in a series of 5mL cuvettes. Then, different amounts (0. Mu.M, 50. Mu.M, 80. Mu.M, 100. Mu.M, 200. Mu.M, 500. Mu.M, 800. Mu.M, 1000. Mu.M, 1500. Mu.M, 2000. Mu.M, 2500. Mu.M, 3000. Mu.M) of glucose were added. The mixture was diluted to 1mL with water and thoroughly mixed, and the concentration of glucose in the mixture was 0-3000. Mu.M. After 60 minutes, their fluorescence spectra were recorded by operating a fluorescence spectrophotometer, and fluorescence intensities in the concentration range of 5 to 1000. Mu.M of glucose were linearly fitted with a linear light-mascot of 0.998, and a detection limit of 28.54. Mu.M was obtained by a detection limit formula, and the result is shown in FIG. 8.
Example 5 carbon Quantum dot to glucose selectivity test
mu.L of PBS buffer (0.1M, pH=7.4) and 100. Mu.L of the CQDs solution prepared in example 1 were placed in a series of 5mL cuvettes. Then, the same amounts (20. Mu.M) of glucose, aspartic acid, dopamine, uric acid, ascorbic acid, glutathione and alkaline phosphatase were added. The mixture was diluted to 1mL with water and thoroughly mixed. After 60 minutes, their fluorescence spectra were recorded by operating a fluorescence spectrophotometer.
The results are shown in FIG. 9, which demonstrates that CQDs prepared in example 1 have higher selectivity for glucose detection.
Example 6 carbon quantum dot to cytotoxicity measurement:
human lung cancer A549 cells were selected to test the biocompatibility of CQDs. Cells were cultured in RPIM 1640 medium containing 10% (v/v) Fetal Bovine Serum (FBS) and 1% (v/v) penicillin-streptomycin solution (diabody) and then placed at 37℃in 5% CO 2 Humidification incubator. When the cell density reached 1X 105mL -1 At this time, the experiment was started. After overnight incubation, different volumes of CQDs were added to RPMI1640 medium containing only 10% fbs and incubation of the cells was continued for 20 hours. After incubation, 150. Mu.L of MTT in PBS (5 mg mL -1 ) Added to each well. The cells were further cultured for 4 hours. The medium was removed and formazan formed was dissolved in DMSO (150 μl). The Optical Density (OD) of each sample was recorded at 570nm using a Synergy H1 microplate reader (BioTeK, winooski, VT) to calculate relative cell viability (%).
As shown in FIG. 10, the cell activity after dropping 40. Mu.L of CODs was still 90% or more, indicating that the CODs prepared in example 1 did not damage the cell structure in serum or plasma during the assay, and were very low in cytotoxicity.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (14)
1. A preparation method of boric acid functionalized carbon dots is characterized in that aspartic acid and phenylboric acid are synthesized by a hydrothermal method, and the boric acid functionalized carbon dots are obtained.
2. The method for preparing the boric acid functionalized carbon dot according to claim 1, which is characterized by comprising the following steps: adding aspartic acid and phenylboronic acid into water, mixing, adding alkali to adjust the pH value to 8.5-9.5, introducing nitrogen, and performing hydrothermal reaction.
3. The method for preparing a boric acid functionalized carbon dot according to claim 1, wherein the temperature of the hydrothermal reaction is 160 to 200 ℃.
4. The method for preparing a boric acid functionalized carbon dot according to claim 3, wherein the temperature of the hydrothermal reaction is 185-195 ℃.
5. The method for preparing boric acid functionalized carbon dots according to claim 1, wherein the hydrothermal reaction time is 14-20 hours.
6. The method for preparing boric acid functionalized carbon dots according to claim 5, wherein the hydrothermal reaction time is 15.5-16.5 h.
7. The method for preparing boric acid functionalized carbon dots according to claim 1, wherein the material after hydrothermal reaction is centrifuged, the supernatant after centrifugation is taken, the supernatant is filtered, and then dialysis is performed to remove the raw material that is not carbonized.
8. The method for preparing a boric acid functionalized carbon dot according to claim 1, wherein the mass ratio of aspartic acid to phenylboric acid is 0-7:7-0, and neither aspartic acid nor phenylboric acid is 0.
9. The method for preparing a boric acid functionalized carbon dot according to claim 8, wherein the mass ratio of aspartic acid to phenylboric acid is 1:0.9-1.1.
10. Boric acid functionalized carbon dot, characterized in that it is obtained by the preparation method according to any one of claims 1 to 9.
11. Use of a boric acid functionalized carbon dot according to claim 10 for organophosphorus pesticide detection, glucose detection and/or for the preparation of a blood glucose detection reagent.
12. A method for detecting organophosphorus pesticides is characterized in that a sample to be detected is added into a solution containing 4-nitrophenyl sodium phosphate and alkaline phosphatase, after incubation, a terminator and the boric acid functionalized carbon point of claim 10 are added, and then fluorescence detection is carried out.
13. The method for detecting organophosphorus pesticide according to claim 12, wherein the terminator is Na 3 VO 4 。
14. A glucose assay reagent comprising the boronic acid functionalized carbon dot of claim 10.
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| CN109852373A (en) * | 2019-01-07 | 2019-06-07 | 温州大学 | A kind of boric acid functional fluorescence nano material and the application for detecting glucose |
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| Standoff Optical Glucose Sensing in Photosynthetic Organisms by a Quantum Dot Fluorescent Probe;Jinming Li et al.;ACS Appl. Mater. Interfaces(第第10期期);第28279-28289页 * |
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