CN110836919B - Chiral recognition material and preparation method thereof - Google Patents

Chiral recognition material and preparation method thereof Download PDF

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CN110836919B
CN110836919B CN201911196788.7A CN201911196788A CN110836919B CN 110836919 B CN110836919 B CN 110836919B CN 201911196788 A CN201911196788 A CN 201911196788A CN 110836919 B CN110836919 B CN 110836919B
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chiral
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long
cysteine
afterglow luminescent
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CN110836919A (en
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张文妍
杨晓莉
管航敏
叶原丰
郝凌云
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Jinling Institute of Technology
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    • G—PHYSICS
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    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28—Electrolytic cell components
    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
    • G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/416—Systems
    • G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7701—Chalogenides
    • C09K11/7703—Chalogenides with alkaline earth metals

Abstract

The invention relates to the technical field of chiral identification materials, in particular to a chiral identification material and a preparation method thereof; it comprises a long afterglow luminescent material with metal nano particles loaded on the surface; and chiral cysteine, and forming a chiral molecular layer on the surface of the metal nano-particle through self-assembly. According to the invention, long-life electrons are transferred from the long-afterglow material to the surface of the chiral identification material by utilizing the heterojunction between the long-afterglow material and the chiral identification material, and a large amount of long-life electrons are injected to the surface of the chiral identification material, so that the current density on an electrode is effectively enhanced, and an electrochemical identification signal is amplified. Meanwhile, by utilizing the spin filtering effect of the chiral molecules on electrons, the electrons are spin-polarized when flowing through the chiral molecular layer assembled on the surface of the metal nano particles, so that the electromagnetic field on the surface of the electrode is changed, the difference between the electromagnetic field and the acting force of L and D amino acid enantiomers in the electrolyte is amplified, and the detection sensitivity is improved.

Description

Chiral recognition material and preparation method thereof
Technical Field
The invention relates to the technical field of chiral identification materials, in particular to a chiral identification material and a preparation method thereof.
Background
Chiral molecules refer to molecules having a configuration or conformation that does not coincide with their mirror images. Chirality is closely related to life phenomena, which significantly affects the properties of a substance. For example, the R configuration thalidomide molecule has a sedative or antitussive effect, whereas the S configuration thalidomide molecule has a strong teratogenic effect. Due to the understandings of chiral isomers, abusing thalidomide without resolution of R and S configurations results in the birth of a large number of malformations, and thus, chiral isomers are widely regarded by people.
Amino acids are the most basic chiral enantiomers, L-amino acids are a basic unit constituting proteins, and D-amino acids are rarely involved in protein formation and even cause some side effects on life systems. The chiral identification and detection of amino acid has important theoretical and practical research significance in the fields of life, environment, pesticide, material and the like, and the development of chiral identification materials and chiral identification technologies with low detection cost and short detection period is urgently needed to distinguish the enantiomers of amino acid. The electrochemical method has the advantages of simple and convenient operation, higher identification sensitivity, low cost and the like. The principle of the electrochemical method for realizing chiral recognition is that a chiral recognition material capable of reacting with chiral molecules is used as an electrode, when the chiral recognition material is close to two chiral enantiomers in electrolyte, two acting forces with different intensities can be generated, and the difference of the intensities of the two acting forces can cause the difference of electrochemical signals to realize chiral recognition.
Obviously, in order to improve the signal sensitivity of electrochemical chiral recognition, it is necessary to try to improve the difference of the acting force intensity of the chiral recognition material and the two chiral enantiomers. In addition, there is a need to improve the electron transport efficiency and lifetime of the surface of the chiral recognition material.
At present, no literature or patent reports such studies.
Disclosure of Invention
The invention aims to provide a long-afterglow luminescent material which utilizes the chiral molecular spin filtering effect and the long-life electronic gain of a long-afterglow material and is loaded with metal nano-particles on the surface, and a preparation method thereof, aiming at the defects and the defects of the prior art.
The chiral recognition material comprises a long-afterglow luminescent material with metal nano-particles loaded on the surface; and chiral cysteine, and forming a chiral molecular layer on the surface of the metal nano-particle through self-assembly.
In addition, the chiral identification material disclosed by the invention also has the following additional technical characteristics:
further, the long afterglow luminescent material is CaTiO3:Pr3+Long persistence luminescent materials.
Further, the size of the long afterglow luminescent material is 1-10 μm.
Further, the metal nanoparticles are selected from any one or more of gold nanoparticles, silver nanoparticles or platinum nanoparticles.
Furthermore, in the long afterglow luminescent material with the surface loaded with the metal nano particles, the weight percentage of the long afterglow luminescent material is 99-99.9%, and the weight percentage of the surface loaded with the metal nano particles is 0.1-1%.
The preparation method of any one of the chiral recognition materials comprises the following steps:
s1, loading metal nanoparticles on the surface of the long-afterglow luminescent material by a microwave reduction method to form a heterojunction between the metal nanoparticles and the long-afterglow luminescent material, and obtaining the long-afterglow luminescent material loaded with the metal nanoparticles on the surface;
s2, adopting the chiral cysteine to self-assemble the chiral molecular layer on the surface of the metal nano-particle of the long-afterglow luminescent material with the metal nano-particle loaded on the surface by the in-situ bonding method, and obtaining the chiral identification material.
In addition, the preparation method of the chiral identification material disclosed by the invention also has the following additional technical characteristics:
further, the method for loading the metal nano-particles on the surface of the long-afterglow luminescent material by adopting a microwave reduction method to form a heterojunction between the metal nano-particles and the long-afterglow luminescent material to obtain the long-afterglow luminescent material loaded with the metal nano-particles on the surface comprises the following steps:
dipping the long-afterglow luminescent material in a metal salt solution, carrying out ultrasonic treatment for 20-60 minutes, then carrying out microwave heating for 2-10 minutes, taking the solid, and washing to obtain the long-afterglow luminescent material with the surface loaded with the metal nano-particles.
Further, the metal salt solution is selected from any one or more of silver nitrate solution, potassium chloroplatinate solution and tetrachloroauric acid solution.
Further, the solvent of the metal salt solution is water and glycol in a volume ratio of (10-20): 1.
Further, the method for preparing the chiral recognition material by self-assembling chiral cysteine on the surface of the metal nano-particles of the long-afterglow luminescent material with the metal nano-particles loaded on the surface by adopting an in-situ bonding method to form a chiral molecular layer comprises the following steps:
and immersing the long-afterglow luminescent material with the surface loaded with the metal nano-particles in the cysteine aqueous solution for 24-72 hours to obtain the chiral recognition material.
The invention has the advantages that:
(1) according to the invention, the heterojunction between the long afterglow material and the chiral identification material is utilized to transfer long-life electrons from the long afterglow material to the surface of the chiral identification material, and a large amount of long-life electrons are injected to the surface of the chiral identification material, so that the current density on an electrode is effectively enhanced, and an electrochemical identification signal is amplified.
(2) The invention utilizes the spin filtering effect of chiral molecules on electrons: l-cysteine or D-cysteine is self-assembled into a chiral molecular layer on the surface of the metal nano-particle through hydrogen bond action and electrostatic action, and electrons are spin-polarized when flowing through the chiral molecular layer assembled on the surface of the metal nano-particle, so that an electromagnetic field on the surface of the electrode is changed, the difference of acting force between the electrode and L and D amino acid enantiomers in electrolyte is amplified, and the detection sensitivity is improved.
(3) Under the excitation of ultraviolet light, long-life electrons generated in the long-afterglow material are transferred to the surface of the chiral identification material through a heterojunction between the long-afterglow material and the chiral identification material, and a large amount of long-life electrons are injected into the surface of the chiral identification material, so that the current density on the electrode is effectively enhanced.
(4) The reduction and the loading of the metal nanoparticles are realized by an ultraviolet illumination reduction method, the assembly of chiral molecules on the metal nanoparticles is realized by the formation of chemical valence bonds, special equipment and harsh conditions are not needed, the preparation method is simple, the process is fast and easy to implement, the controllability is strong, and large-area preparation and large-scale production are easy to realize.
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 application, and are not to be considered limiting of the invention, in which:
FIG. 1 is an SEM photograph of a chiral discrimination material of example 1 of the present invention;
FIG. 2 is a schematic diagram of the mechanism of chiral discrimination of the chiral discrimination material of examples 1 to 4 of the present invention using the long-life electron gain chiral discrimination of the long-afterglow material;
FIG. 3 is a graph showing electrochemical recognition signals of L-arginine and D-arginine in an electrolyte by the chiral recognition material of example 1 of the present invention;
FIG. 4 is a diagram of electrochemical recognition signals of the chiral recognition material of example 1 of the present invention on L-arginine and D-arginine in an electrolyte under the excitation of ultraviolet light irradiation;
FIG. 5 is a graph showing electrochemical recognition signals of L-arginine and D-arginine in an electrolyte by the chiral recognition material of example 2 of the present invention;
FIG. 6 is a graph showing electrochemical recognition signals of L-glutamic acid and D-glutamic acid in an electrolyte by the chiral recognition material of example 4 of the present invention.
Detailed Description
The present invention will now be described in detail with reference to the drawings and specific embodiments, wherein the exemplary embodiments and descriptions are provided only for the purpose of illustrating the present invention and are not to be construed as limiting the present invention.
< example 1>
A preparation method of a chiral identification material comprises the following steps:
s1, mixing 0.01g CaTiO with particle size of 1-10 μm3:Pr3+The long afterglow luminescent material is soaked in 20mL of 0.1mol/L silver nitrate solution and is subjected to ultrasonic treatment at 50W power for half an hour to ensure that the metal solution and CaTiO3:Pr3+The surfaces of the long afterglow luminescent materials are fully contacted; placing the solution in a microwave digestion instrument, reducing for 5min under 800W microwave power to load Ag nano particles on CaTiO3:Pr3+Forming Ag nano-particles and CaTiO on the surface of the long-afterglow luminescent material3:Pr3+The heterojunction of the long afterglow luminescent material is washed for 2 times by distilled water and absolute ethyl alcohol respectively, and residual Ag on the surface of the material is washed away+Ions are carried out to obtain CaTiO of which the surface is loaded with Ag nano particles3:Pr3+A long persistence luminescent material;
s2, 0.01g of CaTiO with Ag nano particles loaded on the surface3:Pr3+The long afterglow luminescent material is immersed in 50mL of 20mM L-cysteine aqueous solution for 72 hours, the mercapto (-SH) of L-cysteine molecules is bonded with the surface of metal nano particles to form chemical bonds, and the chemical bonds are self-assembled into chiral molecular layers to obtain chiral recognitionOther materials (CaTiO)3:Pr3+@ Ag @ L-cysteine).
The chiral identification material (CaTiO) provided in this example3:Pr3+@ Ag @ L-cysteine) as shown in FIG. 1.
10mg of the chiral discrimination material (CaTiO) prepared in this example was taken3:Pr3+@ Ag @ L-cysteine), ultrasonically dispersing in 100 mu L of ultrapure water, transferring the dispersion by using a liquid transfer gun, dropwise adding the dispersion to the surface of a glassy carbon electrode, standing for 24 hours at normal temperature to obtain CaTiO3:Pr3+The glassy carbon electrode modified by the material is chiral recognition of @ Ag @ L-cysteine.
The electrolyte is 20mM L-arginine aqueous solution (containing 50mM potassium chloride) or 20mM D-glycine aqueous solution (containing 0.1mol/L potassium chloride).
Adding CaTiO3:Pr3+The glassy carbon electrode modified by the @ Ag @ L-cysteine chiral recognition material is placed in electrolyte, a saturated calomel electrode is used as a reference electrode, and a cyclic voltammetry curve is scanned between-0.1 and 0.5V.
FIG. 3 is a graph showing electrochemical recognition signals of L-arginine and D-arginine in an electrolyte by the chiral recognition material of example 1 of the present invention. FIG. 4 is a diagram of electrochemical recognition signals of the chiral recognition material of example 1 of the present invention on L-arginine and D-arginine in an electrolyte under the excitation of ultraviolet light.
As shown in FIG. 3, the electrolyte has high electrochemical signal of L-arginine and weak electrochemical signal of D-arginine, which indicates that CaTiO3:Pr3+The @ Ag @ L-glycine has good recognition on L-arginine, which is mainly caused by the spin filtering effect of chiral molecules.
As shown in FIG. 4, the electrochemical signal was significantly improved after 5W of 365nm UV radiation, mainly due to the excitation of the UV radiation except CaTiO3:Pr3+The long-life electrons are transferred to the surface of the chiral recognition material through a heterojunction, a large number of long-life electrons are injected into the surface of the chiral recognition material, the current density on the electrode is effectively enhanced, and the electrochemical recognition signal is amplified.
< example 2>
A preparation method of a chiral identification material comprises the following steps:
s1, mixing 0.01g of CaTiO with the size of 1-10 μm3:Pr3+The long afterglow luminescent material is soaked in 20mL of 0.1mol/L tetrachloroauric acid aqueous solution, and 50W power ultrasonic is carried out for half an hour to ensure that the tetrachloroauric acid aqueous solution and CaTiO3:Pr3+The surfaces of the long afterglow luminescent materials are fully contacted; placing the solution in a microwave digestion instrument, reducing for 5min under 800W microwave power to load gold nanoparticles on CaTiO3:Pr3+Forming gold nanoparticles and CaTiO on the surface of the long-afterglow luminescent material3:Pr3+A heterojunction of long persistence luminescent material; respectively washing with distilled water and absolute ethyl alcohol for 2 times, and washing off residual gold ions on the surface of the material to obtain the CaTiO with gold nanoparticles loaded on the surface3:Pr3+A long persistence luminescent material;
s2, loading 0.01g of CaTiO with gold nanoparticles on the surface3:Pr3+The long afterglow luminescent material is immersed in 50mL of 20mM D-cysteine aqueous solution for 72 hours, the sulfydryl (-SH) of a D-cysteine molecule is bonded with the surface of a metal nanoparticle to form a chemical bond, and the chemical bond is self-assembled into a chiral molecular layer to obtain a chiral identification material (CaTiO)3:Pr3+@ Au @ D-cysteine).
10mg of the chiral discrimination material (CaTiO) prepared in this example was taken3:Pr3+@ Au @ D-cysteine), ultrasonically dispersing in 100 mu L of ultrapure water, transferring the dispersion by using a liquid transfer gun, dropwise adding the dispersion to the surface of a glassy carbon electrode, and standing for 24 hours at normal temperature to obtain CaTiO3:Pr3+The glassy carbon electrode modified by the @ Au @ D-cysteine chiral recognition material.
The electrolyte is 40mM L-arginine (containing 0.1mol/L potassium chloride) or 0.1mol/L D-arginine aqueous solution (containing 0.1mol/L potassium chloride).
Adding CaTiO3:Pr3+The glassy carbon electrode modified by the @ Au @ D-cysteine chiral recognition material is placed in electrolyte, a saturated calomel electrode is used as a reference electrode, and a cyclic voltammetry curve is scanned between-0.1 and 0.5V.
FIG. 5 is a graph showing electrochemical recognition signals of L-arginine and D-arginine in an electrolyte by the chiral recognition material of example 2 of the present invention.
As can be seen from FIG. 5, the electrolyte has a higher electrochemical signal for D-arginine and a weaker electrochemical signal for L-arginine, indicating CaTiO3:Pr3+@ Ag @ D-cysteine has good recognition for D-cysteine.
< example 3>
A preparation method of a chiral identification material comprises the following steps:
s1, mixing 0.01g CaTiO with particle size of 1-10 μm3:Pr3+Soaking the long-afterglow luminescent material in 20mL of 0.1mol/L potassium chloroplatinate aqueous solution, and performing ultrasonic treatment at 50W power for half an hour to ensure that the potassium chloroplatinate aqueous solution and CaTiO are mixed3:Pr3+The surfaces of the long afterglow luminescent materials are fully contacted; placing the solution in a microwave digestion instrument, reducing for 5min under 800W microwave power to load platinum nanoparticles on CaTiO3:Pr3+Forming platinum nanoparticles and CaTiO on the surface of the long afterglow luminescent material3:Pr3+A heterojunction of long persistence luminescent material; respectively washing with distilled water and absolute ethyl alcohol for 2 times, and washing off residual platinum ions on the surface of the material to obtain the CaTiO with gold nanoparticles loaded on the surface3:Pr3+A long persistence luminescent material;
s2, loading 0.01g of CaTiO with gold nanoparticles on the surface3:Pr3+The long afterglow luminescent material is immersed in 50mL of D-cysteine aqueous solution for 72 hours, the mercapto (-SH) of the D-cysteine molecule is bonded with the surface of the metal nano particle to form a chemical bond, and the chemical bond is self-assembled into a chiral molecular layer to obtain the chiral identification material (CaTiO)3:Pr3+@ Pt @ D-cysteine).
10mg of the chiral discrimination material (CaTiO) prepared in this example was taken3:Pr3+@ Pt @ D-cysteine), ultrasonically dispersing in 100 mu L of ultrapure water, transferring the dispersion by using a liquid transfer gun, dropwise adding the dispersion to the surface of a glassy carbon electrode, standing for 24 hours at normal temperature to obtain CaTiO3:Pr3+The material is modified by a @ Pt @ D-cysteine chiral recognition material.
The electrolyte was 50mM L-glutamic acid aqueous solution (containing 0.1mol/L potassium chloride) or 50mM D-glutamic acid aqueous solution (containing 0.1mol/L potassium chloride).
Adding CaTiO3:Pr3+The glassy carbon electrode modified by the @ Pt @ D-cysteine chiral recognition material is placed in electrolyte, a saturated calomel electrode is used as a reference electrode, and a cyclic voltammetry curve is scanned between-0.1 and 0.5V.
D-glutamic acid in the electrolyte has higher electrochemical signal, and L-glutamic acid has weaker electrochemical signal, which shows that CaTiO3:Pr3+The @ Pt @ D-cysteine has good recognition on D-glutamic acid.
< example 4>
A preparation method of a chiral identification material comprises the following steps:
s1, mixing 0.01g CaTiO with particle size of 1-10 μm3:Pr3+The long afterglow luminescent material is soaked in 20mL of 0.1mol/L silver nitrate solution, and is subjected to 50W power ultrasonic treatment for half an hour to ensure that the silver nitrate solution and CaTiO3:Pr3+The surfaces of the long afterglow luminescent materials are fully contacted; placing the solution in a microwave digestion instrument, reducing for 5min under 800W microwave power to load platinum nanoparticles on CaTiO3:Pr3+Forming platinum nanoparticles and CaTiO on the surface of the long afterglow luminescent material3:Pr3+A heterojunction of long persistence luminescent material; respectively washing with distilled water and anhydrous ethanol for 2 times, and washing off residual silver ions on the surface of the material to obtain CaTiO loaded with silver nanoparticles on the surface3:Pr3+Long persistence luminescent materials.
S2, 0.01g of CaTiO with silver nano particles loaded on the surface3:Pr3+The long afterglow luminescent material is immersed in 50mL of 20mM L-cysteine aqueous solution for 72 hours, the mercapto (-SH) of L-cysteine molecules is bonded with the surface of metal nano particles to form chemical bonds, and the chemical bonds are self-assembled into chiral molecular layers to obtain the chiral identification material (CaTiO)3:Pr3+@ Ag @ L-cysteine).
10mg of the chiral discrimination material (CaTiO) prepared in this example was taken3:Pr3+@ Ag @ L-cysteine),
ultrasonically dispersing in 100 μ L of ultrapure water, transferring the dispersion with a liquid-transferring gun, dropwise adding the dispersion to the surface of a glassy carbon electrode, and standing at normal temperature for 24 hours to obtain CaTiO3:Pr3+The glass carbon electrode modified by the material is characterized by comprising a material with chiral recognition of @ Ag @ L-cysteine.
The electrolyte is 20mM L-glutamic acid aqueous solution (containing 0.1mol/L potassium chloride) or glutamic acid D-glutamic acid aqueous solution (containing 0.1mol/L potassium chloride).
FIG. 6 is a graph showing electrochemical recognition signals of L-glutamic acid and D-glutamic acid in an electrolyte by the chiral recognition material of example 4 of the present invention.
As shown in FIG. 6, the CaTiO compound is added3:Pr3+The glassy carbon electrode modified by the @ Ag @ L-cysteine chiral recognition material is placed in electrolyte, a saturated calomel electrode is used as a reference electrode, and a cyclic voltammetry curve is scanned between-0.1 and 0.5V. L-glutamic acid in the electrolyte has higher electrochemical signal, and D-glutamic acid has weaker electrochemical signal, which indicates that CaTiO3:Pr3+The @ Ag @ L-cysteine has good identification property on the L-glutamic acid.
The beneficial effects of the above embodiment are as follows:
(1) in the embodiment, the heterojunction between the long afterglow material and the chiral identification material is utilized to transfer long-life electrons from the long afterglow material to the surface of the chiral identification material, and a large amount of long-life electrons are injected to the surface of the chiral identification material, so that the current density on the electrode is effectively enhanced, and the electrochemical identification signal is amplified.
(2) The above examples utilize the spin filtering effect of chiral molecules on electrons: l-cysteine or D-cysteine is self-assembled into a chiral molecular layer on the surface of the metal nano-particle through hydrogen bond action and electrostatic action, and electrons are spin-polarized when flowing through the chiral molecular layer assembled on the surface of the metal nano-particle, so that an electromagnetic field on the surface of the electrode is changed, the difference of acting force between the electrode and L and D amino acid enantiomers in electrolyte is amplified, and the detection sensitivity is improved.
(3) Under the excitation of ultraviolet light, long-life electrons generated in the long-afterglow material are transferred to the surface of the chiral identification material through a heterojunction between the long-afterglow material and the chiral identification material, and a large amount of long-life electrons are injected into the surface of the chiral identification material, so that the current density on the electrode is effectively enhanced.
(4) The reduction and the loading of the metal nanoparticles are realized by an ultraviolet illumination reduction method, the assembly of chiral molecules on the metal nanoparticles is realized by the formation of chemical valence bonds, special equipment and harsh conditions are not needed, the preparation method is simple, the process is fast and easy to implement, the controllability is strong, and large-area preparation and large-scale production are easy to realize.
The above description is only a preferred embodiment of the present invention, and all equivalent changes or modifications of the structure, characteristics and principles described in the present invention are included in the scope of the present invention.

Claims (1)

1. A method for chiral recognition of D-glutamic acid, which is characterized by comprising the following steps: the method comprises the following specific steps:
(1) preparing a glassy carbon electrode modified by a chiral recognition material, wherein the chiral recognition material comprises a long afterglow luminescent material and chiral cysteine, the surface of the long afterglow luminescent material is loaded with platinum nanoparticles, a chiral molecular layer is formed on the surface of the platinum nanoparticles through self assembly, and the long afterglow luminescent material is CaTiO3:Pr3+；
The preparation method of the chiral recognition material comprises the following steps:
s1, mixing 0.01g CaTiO with particle size of 1-10 μm3:Pr3+The long afterglow luminescent material is soaked in 20mL of 0.1mol/L potassium chloroplatinate aqueous solution, and 50W power ultrasound is carried out for half an hour to ensure the potassium chloroplatinate aqueous solution and the CaTiO3:Pr3+The surfaces of the long afterglow luminescent materials are fully contacted; placing the solution in a microwave digestion instrument, reducing for 5min under 800W microwave power to load platinum nanoparticles on CaTiO3:Pr3+Forming platinum nanoparticles and CaTiO on the surface of the long afterglow luminescent material3:Pr3+A heterojunction of long persistence luminescent material; respectively washing with distilled water and absolute ethyl alcohol for 2 times, and washing off residual platinum ions on the surface of the material to obtain the CaTiO with gold nanoparticles loaded on the surface3:Pr3+Long surplusA glow-emitting material;
s2, loading 0.01g of CaTiO with gold nanoparticles on the surface3:Pr3+The long afterglow luminescent material is immersed in 50mL of D-cysteine aqueous solution for 72 hours, the sulfydryl of D-cysteine molecules is bonded with the surface of metal nano particles to form chemical bonds, and the chemical bonds are self-assembled into chiral molecular layers to obtain the chiral recognition material CaTiO3:Pr3+@ Pt @ D-cysteine;
(2) adding CaTiO3:Pr3+The glassy carbon electrode modified by the @ Pt @ D-cysteine chiral recognition material is placed in electrolyte, a saturated calomel electrode is used as a reference electrode, a cyclic voltammetry curve is scanned between-0.1 and 0.5V, D-glutamic acid in the electrolyte has a high electrochemical signal, and an electrochemical signal of L-glutamic acid is weak, so that the situation that CaTiO is proved3:Pr3+@ Pt @ D-cysteine has good recognition for D-glutamic acid.
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