CN111474225B - Chiral electrochemical sensor and application thereof - Google Patents

Chiral electrochemical sensor and application thereof Download PDF

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CN111474225B
CN111474225B CN202010454529.6A CN202010454529A CN111474225B CN 111474225 B CN111474225 B CN 111474225B CN 202010454529 A CN202010454529 A CN 202010454529A CN 111474225 B CN111474225 B CN 111474225B
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CN111474225A (en
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牛文新
李风华
贾菲
吴峰霞
鲍海波
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Changchun Institute of Applied Chemistry of CAS
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Abstract

The invention relates to a chiral electrochemical sensor based on intrinsic chiral nanocrystals and application thereof, belonging to the technical field of electrochemical sensors. The technical problems that the existing chiral electrochemical sensor has poor enantiomer distinguishing capability, cannot realize complete distinguishing, cannot distinguish in situ at the same time and has extremely short service life are solved. The chiral electrochemical sensor of the present invention comprises: an electrode and an intrinsic chiral nanocrystal fixed on the surface of the electrode. The invention firstly proposes that the chiral electrochemical sensor is constructed based on the intrinsic chiral nanocrystal, the chiral interface modified by the chiral nanocrystal material has intrinsic chiral recognition capability, and the difference is generated between the chiral interface and the non-covalent bond acting force between the chiral interface and the electrode. Such non-covalent bond forces in association with the chiral groups of the molecule can enable true discrimination between the target chiral molecular isomers. The electrochemical chiral sensor can be used for identifying amino acid in food, active ingredients in chiral drugs and chiral isomers in human bodies.

Description

Chiral electrochemical sensor and application thereof
Technical Field
The invention relates to the technical field of electrochemical sensors, in particular to a chiral electrochemical sensor based on intrinsic chiral nanocrystals and application thereof.
Background
Most of the existing chiral electrochemical sensors are constructed by adopting chiral selective reagents. Researchers have successfully constructed different chiral electrochemical sensors with multiple chiral selective reagents. According to different interaction mechanisms of chiral selective reagents and chiral enantiomers, electrochemical chiral recognition is divided into: host-guest recognition, chiral reagent transfer recognition, chiral biomacromolecule adsorption recognition, molecular imprinting recognition and the like. All the chiral identifications are in essence that chiral molecules participate as main bodies and then interact with target chiral molecules. The chirality of the prepared chiral electrochemical interface is derived from a chiral reagent and is not the electrode material, so that the chiral identification effect is poor, characteristic peaks of target chiral isomers are almost at the same potential in most cases, and only the difference of current intensity is the current type chiral electrochemical sensor. In the sensor, chiral molecules with different configurations interact with an electrode interface, and only the difference of the amount has no qualitative difference, which means that the two isomers cannot be distinguished if the two isomers exist in the solution to be detected simultaneously. The potential type chiral electrochemical sensor does not realize complete separation of enantiomers, when the two exist at the same time, the characteristic peaks are overlapped, and only the peak positions move along with the difference of the proportion of the two.
Professor Nam of seoul university in 2018 and co-workers thereof propose a simple, large-scale and high-yield synthesis method of three-dimensional intrinsic chiral gold nanostructure, which adopts chiral Cys/glutathione as a guiding reagent, Cetyl Trimethyl Ammonium Bromide (CTAB) as a protective agent, Ascorbic Acid (AA) as a reducing agent, and a 30 ℃ seed growth method to prepare helical chiral gold nanoparticles, wherein the nanostructure has super-strong anisotropy factors (Lee, h. -e., Ahn, h. -y., Mun, j., Lee, y.y., Kim, m., Cho, n.h., Chang, k.k.m., Kim, w.s., Rho, j., Nam, k.t., Amino-acid-and peptide-synthesized synthesis of chiral platinum nanoparticles, Nature,2018,556, 360). The article draws a research heat tide of chiral nano precious metal materials after being published in Nature, and further develops a novel spiral structure (Lee, H. -E., Kim, R.M., Ahn, H. -Y., Lee, Y.Y., Byun, G.H., Im, S.W., Mun, J., Rho, J., Nam, K.T., Cysteine-encoded chirality in plasma rare solution, Nam, K.T.), the final nano material is coated on a glass sheet, and the glass sheet is irradiated by polarized light with different wavelengths to form a film, so that the film presents different colors, thereby establishing a novel analysis and detection method. Professor topic group from Xu of Jiangnan university adopts hexadecylamine to grow a polycrystalline copper structure on one side of a gold nanorod, and adopts diamine to prepare an AuCuAu Chiral hetero nanorod (Wang, J., Wu, X., Ma, W., Xu, C., Chiral AuCuAu heteronenous nanoparticles with a targeted optical activity, adv.Funct.Mater.,2020,2000670.), and tries potential application of the Au Chiral hetero nanorod in photothermal therapy.
The chiral nanotubes were identified by the university of Qinghua university Shih Chu (Chen, L., Chang, F., Meng, L., Li, M., Zhu, Z., A novel electrochemical chip sensor for 3,4-dihydroxyphenyl alkane based on the combination of single-walled carbon nanotubes, Sulfuric acid and square wave voltametry, analysis, 2014,139, 2243-. However, no research has been made to use intrinsic chiral nanocrystals as chiral recognition matrices.
Disclosure of Invention
The invention provides a chiral electrochemical sensor based on intrinsic chiral nanocrystals and application thereof, aiming at solving the technical problems that the existing chiral electrochemical sensor has poor enantiomer distinguishing capability (small difference of electric signals), cannot realize complete distinguishing, cannot realize in-situ simultaneous distinguishing and has extremely short service life (within 2 times). The invention firstly proposes that the chiral electrochemical sensor is constructed based on the intrinsic chiral nanocrystal, and the chiral interface modified by the chiral nanocrystal material has intrinsic chiral recognition capability, namely, the difference between two different enantiomers and the noncovalent bond acting force between the chiral interface of the electrode is generated due to the difference of mirror image structures. Such non-covalent bond forces in association with the chiral groups of the molecule can enable true discrimination between the target chiral molecular isomers.
In order to solve the technical problems, the technical scheme of the invention is as follows:
the invention provides a chiral electrochemical sensor comprising:
an electrode;
and intrinsic chiral nanocrystals fixed on the surface of the electrode.
In the above technical solution, it is preferable that: the intrinsic chiral nanocrystal is a high-index noble metal nanocrystal with intrinsic chirality or a composite metal nanocrystal with intrinsic chirality.
In the above technical solution, it is further preferable that: the high-index noble metal nanocrystalline with intrinsic chirality is Au, Pd, Ag or Pt nanocrystalline.
In the above technical solution, it is further preferable that: the composite metal nanocrystalline with intrinsic chirality is Au-Pd, Au-Ag, Au-Pt, Au-Cu, Pd-Ag, Pt-Ag, Pd-Pt or Pd-Cu composite nanocrystalline.
In the above technical solution, it is preferable that: the intrinsic chiral nanocrystal is a Cu nanocrystal. In the above technical solution, it is preferable that: the intrinsic chiral nanocrystalline is fixed on the surface of the electrode in an electrostatic assembly mode, a chemical bonding mode or an electrochemical deposition mode.
In the above technical solution, it is preferable that: the electrode is a metal electrode, a glassy carbon electrode or an ITO electrode.
In the above technical solution, it is further preferable that: the metal electrode is an Au, Ag or Pt electrode.
The invention also provides an application of the chiral electrochemical sensor, and particularly relates to the identification of amino acids in food, active ingredients in chiral drugs and chiral isomers in human bodies.
The invention has the beneficial effects that:
the invention firstly proposes that the chiral electrochemical sensor is constructed based on the intrinsic chiral nanocrystal, and the chiral interface modified by the chiral nanocrystal material has intrinsic chiral recognition capability, namely, the difference between two different enantiomers and the noncovalent bond acting force between the chiral interface of the electrode is generated due to the difference of mirror image structures. Such non-covalent bond forces in association with the chiral groups of the molecule can enable true discrimination between the target chiral molecular isomers.
The chirality of the chiral electrochemical sensor is derived from the nano material, and most of the current researches are broken through from the recognition principle.
The chiral electrochemical sensor of the invention can realize simultaneous chiral recognition: the anisotropy factor of the intrinsic chiral nanocrystalline material can reach 10-1The electrode interface has strong chiral recognition capability, and the chiral isomers can be distinguished in real meaning, so that the purpose of simultaneous detection is achieved.
The chiral electrochemical sensor can realize multiple chiral identification: the host-guest inclusion compound is formed based on a host-guest method, the sensor prepared by the specificity recognition principle of biological macromolecules such as DNA molecules is disposable and can not be used repeatedly, and the chiral recognition of the intrinsic chiral electrochemical sensor is based on the strong chiral environment of a chiral interface, so that the repeated use and repeatable chiral recognition effect of a common electrochemical sensor can be realized.
The electrochemical chiral sensor with high discrimination, high sensitivity and long service life prepared by the invention can be used for identifying amino acid in food, active ingredients in chiral drugs and chiral isomers in human bodies.
Drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
FIG. 1 is a diagram of the chiral gold electrochemical sensor prepared in example 1 for molecular specific recognition of chiral amino acids.
FIG. 2 is a diagram of the right-handed chiral gold electrochemical sensor prepared in example 2 for the specific recognition of chiral amino acid molecules.
Fig. 3 is a scanning electron microscope image of the L-cysteine chiral nanogold prepared in example 1.
Fig. 4 is a scanning electron microscope image of the d-cysteine chiral nanogold prepared in example 2.
Fig. 5 is a scanning electron microscope image of the levo glutathione chiral nanogold prepared in example 3.
FIG. 6 is the scanning electron microscope image of the dextral glutathione chiral nanogold prepared in example 4.
FIG. 7 is a scanning electron microscope image of the glutathione chiral nano Au-Ag prepared in example 5.
FIG. 8 is a scanning electron microscope image of the glutathione chiral nano Au-Cu prepared in example 6.
Detailed Description
The invention provides a chiral electrochemical sensor comprising: an electrode; and intrinsic chiral nanocrystals fixed on the surface of the electrode. It is preferable that: the intrinsic chiral nanocrystal is a high-index noble metal nanocrystal with intrinsic chirality or a composite metal nanocrystal with intrinsic chirality. Further preferred are: the high-index noble metal nanocrystalline with intrinsic chirality is Au, Pd, Ag or Pt nanocrystalline. Further preferred are: the composite metal nanocrystalline with intrinsic chirality is Au-Pd, Au-Ag, Au-Pt, Au-Cu, Pd-Ag, Pt-Ag, Pd-Pt or Pd-Cu composite nanocrystalline. It is preferable that: the intrinsic chiral nanocrystal is a Cu nanocrystal. It is preferable that: the intrinsic chiral nanocrystalline is fixed on the surface of the electrode in an electrostatic assembly mode, a chemical bonding mode or an electrochemical deposition mode. It is preferable that: the electrode is a metal electrode, a glassy carbon electrode or an ITO electrode. Further preferred are: the metal electrode is an Au, Ag or Pt electrode.
The invention also provides a chiral electrochemical sensor which can be used for identifying amino acid in food, active ingredients in chiral drugs and chiral isomers in human bodies.
The preparation process of the chiral electrochemical sensor of the invention is as follows:
designing and synthesizing a high-index noble metal nanocrystalline with intrinsic chirality:
(1) au cubic, octahedral and dodecahedral seeds protected by cetylpyridinium chloride (CPC) are prepared by adopting a method proposed in the past in the subject group, and 1.5nm gold seeds protected by CTAB are synthesized by a sodium borohydride reduction method in the approximate process; on the basis, AA is reduced and synthesized into gold nanorods with the assistance of silver ions; after the gold nanorods grow for the second time, chloroauric acid is added to carry out oxidative corrosion on the gold nanorods so as to convert the gold nanorods into CPC-protected gold seeds. Gold seeds protected by CPC can grow into Au cubic, octahedral and dodecahedral seeds by regulating and controlling growth kinetics and thermodynamics under the protection of CPC.
(2) According to the literature [ Lee, H. -E., Ahn, H. -Y., Mun, J., Lee, Y.Y., Kim, M., Cho, N.H., Chang, K., Kim, W.S., Rho, J., Nam, K.T., Amino-acid-and peptide-directed synthesis of spinal planar diamond nanoparticles, Nature,2018,556, 360-reservoir 365.]Chiral cysteine/glutathione is adopted as a chiral inducing reagent, 0.1-2.0mL100mM CTAB is sequentially added into 3.95mL water as a protective agent, and 0.1-0.5mL 10mM HAuCl40.2-1.0mL of 100mM AA as a reducing agent, 10-200 muL of cube/octahedron/dodecahedron CPC gold seeds, 10-300 muL of 100 mu M L/D cysteine, and growing at 30 ℃ to prepare spiral chiral gold nanoparticles. The same method can be adopted to realize the growth of chiral nanocrystals such as Pd, Ag, Pt, Cu and the like, and the chiral inducing reagent can also adopt a series of chiral reagents such as chiral penicillamine, chiral phenylalanine, chiral lysine, chiral tryptophan, chiral arginine, chiral tyrosine and the like.
(3) Based on the synthesis of the spiral chiral gold, 0.1-2.0mL100mM CTAB serving as a protective agent and 0.1-0.5mL 10mM HAuCl are sequentially added into 3.95mL of water4，0.01-0.10mL 10mM H2PdCl42-1.0mL of 100mM AA as a reducing agent, 10-200 muL of cube/octahedron/dodecahedron CPC gold seeds and 10-300 muL of 100 mu M L/D cysteine, and growing at 30 ℃ to prepare the Au-Pd composite nanocrystal with intrinsic chirality. The composite metal nanocrystalline also comprises Au-Ag, Au-Pt, Au-Cu, Pd-Ag, Pt-Ag, Pd-Pt, Pd-Cu and other transformations, and the chiral inducing reagent can adopt a series of chiral reagents such as chiral penicillamine, chiral phenylalanine, chiral lysine, chiral tryptophan and the like besides cysteine/glutathione.
(4) The electrode interface with chiral recognition capability is prepared by adopting methods such as electrostatic assembly, chemical bonding, electrochemical deposition and the like, so that the real, simultaneous and multiple chiral recognition of the electrochemical chiral sensor is realized. Specifically, the method comprises the following steps: polishing, cleaning and electrically activating a gold electrode, immersing the gold electrode in 0.1-100mM organic molecular solution with sulfydryl at two ends for overnight, taking out the gold electrode, and washing and drying the gold electrode; soaking in 0.01-1.0mM of the above chiral Au, Au-Pd, etc. solution for 1-12 hr, and cleaning; and the prepared chiral electrode is used for identifying the target chiral reagent by adopting methods such as DPV (differential pulse voltage)/square wave voltammetry/cyclic voltammetry and the like.
Example 1: preparation of cubic Au seeds: synthesizing 1.5nm gold seeds protected by CTAB by sodium borohydride reduction method at 30 ℃; under the assistance of silver ions, CTAB is used as a protective agent, and a weak reducing agent AA is reduced to generate gold nanorods; after the gold nanorods grow for the second time, adding chloroauric acid to carry out oxidative corrosion on the gold nanorods so as to convert the gold nanorods into CPC-protected gold seeds; CPC is used as a protective agent, and crystal faces are introducedInducer Br-And finally obtaining the CPC-protected golden cubic seeds by using AA as a reducing agent.
Preparation of cysteine-induced intrinsic chiral gold nanocrystals: 3.95mL of water were added 0.8mL of 100mM CTAB, 0.2mL of 10mM HAuCl40.475mL of 100mM AA as a reducing agent, 50. mu.L of cubic CPC gold seeds were incubated for 5min, 50. mu.L of 10. mu. M L cysteine was added, and the seeds were grown at 30 ℃ for 2 h. Chiral gold nanoparticles were prepared as helices in FIG. 3.
Preparing an intrinsic chiral electrochemical sensor: polishing, cleaning and electrically activating a gold electrode, immersing the gold electrode in a 5mM bifunctional mercaptan solution overnight, and cleaning; immersing the substrate in 0.5mM of the chiral Au solution for 1 hour, and cleaning the substrate to be used as a working electrode; the prepared chiral electrode is used for identifying chiral amino acid by adopting a DPV method and setting a parameter sweep range of 0.3-1.8V, a potential increment of 1mV and an amplitude of 10 mV. The result is shown in figure 1, the levorotatory chiral gold sensor has obvious identification peak to levorotatory tryptophan, and does not identify dextrorotatory tryptophan. .
Example 2: preparation of cubic Au seeds: synthesizing 1.5nm gold seeds protected by CTAB by sodium borohydride reduction method at 30 ℃; under the assistance of silver ions, CTAB is used as a protective agent, and a weak reducing agent AA is reduced to generate gold nanorods; after the gold nanorods grow for the second time, adding chloroauric acid to carry out oxidative corrosion on the gold nanorods so as to convert the gold nanorods into CPC-protected gold seeds; CPC is used as a protective agent, and a crystal face inducer Br is introduced-And finally obtaining the CPC-protected golden cubic seeds by using AA as a reducing agent.
Preparation of cysteine-induced intrinsic chiral gold nanocrystals: 3.95mL of water were added 0.8mL of 100mM CTAB, 0.2mL of 10mM HAuCl40.475mL of 100mM AA as a reducing agent, 100. mu.L of cubic CPC gold seeds were incubated for 5min, 50. mu.L of 10. mu. M D cysteine was added, and the seeds were grown at 30 ℃ for 2 h. Chiral gold nanoparticles with dextrorotation as shown in FIG. 4 were prepared.
Preparing an intrinsic chiral electrochemical sensor: polishing, cleaning and electrically activating a gold electrode, immersing the gold electrode in a 5mM bifunctional mercaptan solution overnight, and cleaning; immersing the electrode into 2mM of the chiral Au solution for assembly for 1 hour, and cleaning the electrode to be used as a working electrode; the prepared chiral electrode is used for identifying chiral amino acid by adopting a DPV method. As shown in FIG. 2, the D-chiral gold sensor showed a distinct peak for D-tryptophan, but little for L-tryptophan.
Example 3: preparation of cubic Au seeds: synthesizing 1.5nm gold seeds protected by CTAB by sodium borohydride reduction method at 30 ℃; under the assistance of silver ions, CTAB is used as a protective agent, and a weak reducing agent AA is reduced to generate gold nanorods; after the gold nanorods grow for the second time, adding chloroauric acid to carry out oxidative corrosion on the gold nanorods so as to convert the gold nanorods into CPC-protected gold seeds; CPC is used as a protective agent, and a crystal face inducer Br is introduced-And finally obtaining the CPC-protected golden cubic seeds by using AA as a reducing agent.
Preparing an intrinsic chiral gold nanocrystal induced by L-glutathione (L-Glu): 158mL H2O32 mL of 100mM CTAB, 8mL of 10mM HAuCl were added in sequence419mL of 100mM AA, 1mL of 2mM L-Glu, 1mL of cubic gold seeds, grown at 30 ℃ for 2 hours. Prepare the fan-shaped rotating chiral gold nanoparticles as shown in FIG. 5.
Preparing an intrinsic chiral electrochemical sensor: polishing, cleaning and electrically activating a gold electrode, immersing the gold electrode in a bifunctional mercaptan solution overnight, and cleaning; immersing the substrate into the chiral Au solution with certain concentration for assembly for 1 hour, and cleaning; the prepared chiral electrode is used for identifying chiral amino acid by adopting a DPV method and setting a parameter sweep range of 0.3-1.8V, a potential increment of 1mV and an amplitude of 10 mV. The left/right chiral gold sensor selectively recognizes the left/right tryptophan respectively, has obvious recognition peaks, and hardly recognizes target amino acids with opposite chirality.
Example 4: preparation of cubic Au seeds: synthesizing 1.5nm gold seeds protected by CTAB by sodium borohydride reduction method at 30 ℃; under the assistance of silver ions, CTAB is used as a protective agent, and a weak reducing agent AA is reduced to generate gold nanorods; after the gold nanorods grow for the second time, adding chloroauric acid to carry out oxidative corrosion on the gold nanorods so as to convert the gold nanorods into CPC-protected gold seeds; CPC is used as a protective agent, and a crystal face inducer Br is introduced-And finally obtaining the CPC-protected golden cubic seeds by using AA as a reducing agent.
D-Glu induced intrinsic chiral gold nanocrystalThe preparation of (1): 158mL H2O32 mL of 100mM CTAB, 8mL of 10mM HAuCl were added in sequence419mL of 100mM AA, 1mL of 2mM D-Glu, 1mL of cubic gold seeds, grown at 30 ℃ for 2 hours. Chiral gold nanoparticles with dextrorotation as shown in FIG. 6 were prepared.
Preparing an intrinsic chiral electrochemical sensor: polishing, cleaning and electrically activating a gold electrode, immersing the gold electrode in a bifunctional mercaptan solution overnight, and cleaning; immersing the substrate into the chiral Au solution with certain concentration for assembly for 1 hour, and cleaning; the prepared chiral electrode is used for identifying chiral amino acid by adopting a DPV method and setting a parameter sweep range of 0.3-1.8V, a potential increment of 1mV and an amplitude of 10 mV. The left/right chiral gold sensor selectively recognizes the left/right tryptophan respectively, has obvious recognition peaks, and hardly recognizes target amino acids with opposite chirality.
Example 5: preparation of cubic Au seeds: synthesizing 1.5nm gold seeds protected by CTAB by sodium borohydride reduction method at 30 ℃; under the assistance of silver ions, CTAB is used as a protective agent, and a weak reducing agent AA is reduced to generate gold nanorods; after the gold nanorods grow for the second time, adding chloroauric acid to carry out oxidative corrosion on the gold nanorods so as to convert the gold nanorods into CPC-protected gold seeds; CPC is used as a protective agent, and a crystal face inducer Br is introduced-And finally obtaining the CPC-protected golden cubic seeds by using AA as a reducing agent.
Preparing an intrinsic chiral Au-Ag nano alloy crystal induced by glutathione: 158mL H2O32 mL of 100mM CTAB, 8mL of 10mM HAuCl were added in sequence4，0.01mL 5mM AgNO39mL of 100mM AA, 1mL of 2mM Glu, 1mL of cubic gold seeds, grown at 30 ℃ for 2 hours. Prepare chiral Au-Ag nanoparticles as helices in FIG. 7.
Preparing an intrinsic chiral electrochemical sensor: polishing, cleaning and electrically activating a gold electrode, immersing the gold electrode in a bifunctional mercaptan solution overnight, and cleaning; immersing the substrate into the chiral Au-Ag solution with certain concentration for assembly for 1 hour, and cleaning; the prepared chiral electrode is used for identifying chiral amino acid by adopting a DPV method and setting a parameter sweep range of 0.3-1.8V, a potential increment of 1mV and an amplitude of 10 mV. The left/right chiral gold sensor selectively recognizes the left/right tryptophan respectively, has obvious recognition peaks, and hardly recognizes target amino acids with opposite chirality.
Example 6: preparation of cubic Au seeds: synthesizing 1.5nm gold seeds protected by CTAB by sodium borohydride reduction method at 30 ℃; under the assistance of silver ions, CTAB is used as a protective agent, and a weak reducing agent AA is reduced to generate gold nanorods; after the gold nanorods grow for the second time, adding chloroauric acid to carry out oxidative corrosion on the gold nanorods so as to convert the gold nanorods into CPC-protected gold seeds; CPC is used as a protective agent, and a crystal face inducer Br is introduced-And finally obtaining the CPC-protected golden cubic seeds by using AA as a reducing agent.
Preparing an intrinsic chiral Au-Cu nano alloy crystal induced by glutathione: 158mL H2O32 mL of 100mM CTAB, 8mL of 10mM HAuCl were added in sequence4，0.01mL 2.5mM CuCl29mL of 100mM AA, 1mL of 2mM Glu, 1mL of cubic gold seeds, grown at 30 ℃ for 2 hours. Chiral Au-Cu nanoparticles were prepared as helices in FIG. 8.
Preparing an intrinsic chiral electrochemical sensor: polishing, cleaning and electrically activating a gold electrode, immersing the gold electrode in a bifunctional mercaptan solution overnight, and cleaning; immersing the substrate into the chiral Au-Cu solution with certain concentration for assembly for 1 hour, and cleaning; the prepared chiral electrode is used for identifying chiral amino acid by adopting a DPV method and setting a parameter sweep range of 0.3-1.8V, a potential increment of 1mV and an amplitude of 10 mV. The left/right chiral gold sensor selectively recognizes the left/right tryptophan respectively, has obvious recognition peaks, and hardly recognizes target amino acids with opposite chirality.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.

Claims (7)

1. A chiral electrochemical sensor, comprising:
an electrode;
and intrinsic chiral nanocrystals fixed on the surface of the electrode;
the intrinsic chiral nanocrystal is a high-index noble metal nanocrystal with intrinsic chirality or a high-index composite metal nanocrystal with intrinsic chirality or a high-index Cu nanocrystal with intrinsic chirality;
when the intrinsic chiral nanocrystal is a high-index noble metal Au nanocrystal with intrinsic chirality or a high-index Au-Pd composite metal nanocrystal with intrinsic chirality, the preparation process of the chiral electrochemical sensor is as follows:
(1) firstly, synthesizing 1.5nm gold seeds protected by cetyl trimethyl ammonium bromide CTAB by a sodium borohydride reduction method; on the basis, under the assistance of silver ions, the ascorbic acid AA is reduced to synthesize the gold nanorods; after the gold nanorods grow for the second time, adding chloroauric acid to carry out oxidative corrosion on the gold nanorods, and converting the gold nanorods into gold seeds protected by cetylpyridinium chloride (CPC); gold seeds protected by CPC are adopted, and are grown into Au cubic, octahedral or dodecahedral seeds by regulating and controlling growth kinetics and thermodynamics under the protection of CPC;
(2) chiral cysteine, chiral glutathione, chiral penicillamine, chiral phenylalanine, chiral lysine, chiral tryptophan, chiral arginine or chiral tyrosine are used as chiral inducing reagents, 0.1-2.0mL of 100mM CTAB protective agent and 0.1-0.5mL of 10mM HAuCl are sequentially added into 3.95mL of water40.2-1.0mL of 100mMAA reducing agent, 10-200 muL of cubic, octahedral or dodecahedral CPC gold seeds, 10-300 muL of 100 muM chiral inducing reagent, and growing at 30 ℃ to prepare spiral chiral gold nanoparticles;
(3) on the basis of the synthesis of the spiral chiral gold nanoparticles, 0.1-2.0mL of 100mM CTAB protective agent and 0.1-0.5mL of 10mM HAuCl are sequentially added into 3.95mL of water4，0.01-0.10mL 10mM H2PdCl42-1.0mL of 100mMAA reducing agent, 10-200 muL of cubic, octahedral or dodecahedral CPC gold seeds and 10-300 muL of 100 muM chiral inducing reagent, and growing at 30 ℃ to prepare the Au-Pd composite nanocrystalline with intrinsic chirality; the chiral inducing reagent is chiral cysteine, chiral glutathione, chiral penicillamine, chiral phenylalanine, chiral lysine or chiral tryptophan；
(4) Polishing, cleaning and electrically activating a gold electrode, immersing the gold electrode in 0.1-100mM organic molecular solution with sulfydryl at two ends for overnight, taking out the gold electrode, and washing and drying the gold electrode; immersing the solution into 0.01-1.0mM chiral gold nano particle solution prepared in the step (2) or 0.01-1.0mM chiral Au-Pd composite nanocrystalline solution prepared in the step (3) for assembling for 1-12 hours, and cleaning to prepare the chiral electrochemical sensor;
when the intrinsic chiral nanocrystal is other noble metal nanocrystals or Cu nanocrystals, the corresponding chiral electrochemical sensor can be prepared by only replacing the Au raw material with the corresponding noble metal nanocrystal or Cu raw material;
when the intrinsic chiral nanocrystal is other composite metal nanocrystals, the corresponding chiral electrochemical sensor can be prepared only by replacing Au and Pd raw materials with corresponding metal raw materials.
2. The chiral electrochemical sensor of claim 1 wherein the high index noble metal nanocrystals having intrinsic chirality are Au, Pd, Ag, or Pt nanocrystals.
3. The chiral electrochemical sensor of claim 1, wherein the high index composite metal nanocrystal with intrinsic chirality is an Au-Pd, Au-Ag, Au-Pt, Au-Cu, Pd-Ag, Pt-Ag, Pd-Pt, or Pd-Cu composite nanocrystal.
4. The chiral electrochemical sensor of claim 1, wherein the intrinsic chiral nanocrystals are immobilized on the electrode surface by electrostatic assembly, chemical bonding, or electrochemical deposition.
5. The chiral electrochemical sensor of claim 1, wherein the electrode is a metal electrode, a glassy carbon electrode, or an ITO electrode.
6. The chiral electrochemical sensor of claim 5, wherein the metal electrode is an Au, Ag, or Pt electrode.
7. Use of a chiral electrochemical sensor according to any one of claims 1 to 6 for the recognition of amino acids in food, active ingredients in chiral drugs, or chiral isomers in the human body.
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