A composite metal material with tunable electrochemical chiral recognition effect and its preparation method

Abstract

This invention belongs to the field of nanomaterials technology and provides a method for preparing a composite metal material with tunable electrochemical chiral recognition effect. The method includes the following steps: S1: preparing a metal nano-spiral arrow solution using a seed growth method; S2: mixing the metal nano-spiral arrow solution with a phosphate buffer solution of bovine serum albumin, stirring at room temperature in the dark, to obtain a composite metal material solution with tunable electrochemical chiral recognition effect. The composite metal material with tunable electrochemical chiral recognition effect prepared by the method provided by this invention exhibits different binding abilities with tyrosine residues of different configurations before and after near-infrared light irradiation. The composite metal material with tunable electrochemical chiral recognition effect provided by this invention has good chiral recognition ability, and the control method is simple and rapid, facilitating its application in detection and treatment fields.

Description

Technical Field

[0001] This invention belongs to the field of nanomaterials technology, specifically relating to a composite metal material with tunable electrochemical chiral recognition effect and its preparation method. Background Technology

[0002] Chirality refers to the mirror symmetry property of an object or molecule, meaning it cannot be perfectly superimposed on its mirror image by rotation or translation. Chirality is ubiquitous in nature, permeating various fields such as chemistry, biology, and physics. In living organisms, amino acids and carbohydrate molecules possess chirality, which is crucial for the function and metabolism of organisms. For example, L-tyrosine is an important precursor to many neurotransmitters, including L-DOPA, dopamine, norepinephrine, and epinephrine, and is frequently added to food and pharmaceutical preparations. D-tyrosine, a non-protein amino acid, is a biochemical agent that promotes growth and a probe for studying protein configuration and dynamics. Therefore, chiral recognition is of significant importance to human health.

[0003] Because chiral materials with the same configuration exhibit varying affinities for different target chiral molecules, precise modulation of the chirality of chiral materials based on the chirality of the target substance is crucial. Current methods for regulating the chiral recognition effect of chiral materials include temperature-induced modulation and pH-induced modulation. However, these methods suffer from drawbacks such as difficulty in control and complexity in the modulation process.

[0004] To facilitate the application of materials with chiral recognition capabilities in fields such as detection and treatment, we look forward to proposing simpler and more effective chiral modulation methods. Summary of the Invention

[0005] This invention provides a method for preparing a composite metal material with tunable electrochemical chiral recognition effect. The composite metal material with tunable electrochemical chiral recognition effect obtained by this method has good chiral recognition ability, and the control method is simple and quick, which is convenient for application in detection and treatment fields.

[0006] This invention provides a method for preparing a composite metal material with tunable electrochemical chiral recognition effect, comprising the following steps:

[0007] S1: Preparation of metal nano-spiral arrowhead solution using seed growth method;

[0008] S2: Mix the metal nano-spiral arrow solution with a phosphate buffer solution of bovine serum albumin until homogeneous, and stir at room temperature in the dark to obtain a composite metal material solution with adjustable electrochemical chiral recognition effect.

[0009] Further, in S2, the concentration of the metal nano-spiral arrow solution is 0.2-2 mM, the concentration of the bovine serum albumin phosphate buffer solution is 5-10 mg / mL, the volume of the metal nano-spiral arrow solution and the bovine serum albumin phosphate buffer solution is 1-5 mL, and the pH is 6.0-8.0.

[0010] Further, in S2, the concentration of the metal nano-spiral arrow solution is 0.4 mM, the concentration of the bovine serum albumin phosphate buffer solution is 10 mg / mL, the volume of the metal nano-spiral arrow solution and the bovine serum albumin phosphate buffer solution is 1 mL, and the pH is 6.0-8.0.

[0011] Furthermore, the metal is gold.

[0012] The present invention also provides a composite metal material with tunable electrochemical chiral recognition effect, which is prepared by the preparation method of the composite metal material with tunable electrochemical chiral recognition effect as described in any of the above claims.

[0013] The present invention also provides a photosensitizer comprising a composite metal material having tunable electrochemical chiral recognition effects as described above.

[0014] The present invention also provides a drug based on photothermal therapy, comprising a composite metal material with tunable electrochemical chiral recognition effect as described above.

[0015] The present invention also provides a screening or detection device, comprising a composite metal material with adjustable electrochemical chiral recognition effect as described above.

[0016] This invention also provides the application of the composite metal material with adjustable electrochemical chiral recognition effect as described above in the fields of detection and treatment.

[0017] The present invention also provides a method for controlling the electrochemical chiral recognition effect of the composite metal material as described above, comprising irradiating the composite metal material with the controllable electrochemical chiral recognition effect with near-infrared light, wherein the wavelength of the near-infrared light is 600-900nm and the irradiation time is 0.5-5h.

[0018] The composite metal material with tunable electrochemical chiral recognition effect prepared by the method provided in this invention exhibits a high binding capacity with L-tyrosine before near-infrared light irradiation. After near-infrared light irradiation, the composite metal material with tunable electrochemical chiral recognition effect absorbs light energy and converts it into heat energy, exhibiting a high binding capacity with D-tyrosine. The composite metal material with tunable electrochemical chiral recognition effect provided by this invention has excellent chiral recognition ability, and the control method is simple and rapid, facilitating its application in detection, treatment, and other fields. Attached Figure Description

[0019] 1. Figure 1 This is a flowchart of the preparation method of the composite metal material with adjustable electrochemical chiral recognition effect provided by the present invention;

[0020] Figure 2 These are the extinction spectra of AuNRs and AuNAs provided by this invention;

[0021] 2. Figure 3 The bare glassy carbon electrode (GCE), AuNAs / GCE, BSA / GCE, AuNAs / BSA / GCE, and AuNAs / BSA / NIR / GCE provided by this invention contain 5 mM [Fe(CN)6]. 4- / 3- Cyclic voltammograms in 0.1 MkCl solution;

[0022] 3. Figure 4 The GCE, AuNAs / GCE, BSA / GCE, AuNAs / BSA / GCE, and AuNAs / BSA / NIR / GCE provided by this invention contain 5 mM [Fe(CN)6]. 4- / 3- AC impedance diagram of 0.1 MkCl solution;

[0023] 4. Figure 5 This invention provides zeta potential diagrams for BSA, AuNRs, AuNAs, AuNAs / BSA, and AuNAs / BSA / NIR.

[0024] 5. Figure 6 This is the differential pulse voltammogram of unmodified GCE recognizing tyrosine enantiomers provided by the present invention;

[0025] 6. Figure 7 This invention provides a differential pulse voltammogram of AuNAs / GCE recognizing tyrosine enantiomers.

[0026] 7. Figure 8 This invention provides a differential pulse voltammetry diagram of BSA / GCE recognition of tyrosine enantiomers.

[0027] 8. Figure 9 This invention provides a differential pulse voltammetry diagram of AuNAs / BSA / GCE recognizing tyrosine enantiomers.

[0028] 9. Figure 10 This invention provides a differential pulse voltammetry diagram of AuNAs / BSA / NIR / GCE recognizing tyrosine enantiomers. Detailed Implementation

[0029] To make the above-mentioned objects, features and advantages of the present invention more apparent and understandable, the specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings, but this should not be construed as limiting the scope of the present invention.

[0030] Photothermal therapy, through laser irradiation, converts light energy into heat energy to kill cancer cells. Metal nanomaterials often exhibit high photothermal conversion efficiency. This invention provides a composite metal material with tunable electrochemical chiral recognition effects. This material exhibits different binding capacities for L-tyrosine and D-tyrosine before and after near-infrared light irradiation, thereby achieving recognition of protein amino acids. Furthermore, after near-infrared light irradiation, the material heats up, denaturing the bound protein amino acids and thus killing specific cells, such as cancer cells.

[0031] See Figure 1 The preparation method of composite metal materials with tunable electrochemical chiral recognition effect includes the following steps:

[0032] S1: Preparation of metal nano-spiral arrowhead solution using seed growth method;

[0033] S2: Mix the metal nano-spiral arrow solution with the phosphate buffer solution of bovine serum albumin until homogeneous, and stir at room temperature in the dark to obtain a composite metal material solution with adjustable electrochemical chiral recognition effect.

[0034] Step S1 can be achieved by referring to existing literature on the preparation of metal nano-spiral arrow solutions using seed growth methods. This invention provides one method for preparing metal nano-spiral arrow solutions using seed growth methods.

[0035] The method for preparing metal nano-spiral arrow solutions using seed growth includes steps S11, S12, and S13.

[0036] S11: Add 0.25 mL of 10 mmol / L chloroauric acid solution to 9.75 mL of 100 mmol / L hexadecyltrimethylammonium bromide solution, and then quickly add 0.65 mL of 10 mmol / L sodium borohydride solution while stirring vigorously. The mixed solution immediately turns light brown. Stop stirring after 2 min, and then let it stand at 28 °C for 2 h to obtain AuNRs seed solution.

[0037] S12: Preparation of AuNRs solution: 95 mL of 100 mmol / L hexadecyltrimethylammonium bromide solution, 4 mL of 10 mmol / L chloroauric acid solution, and 2 mL of 5 mmol / L silver nitrate solution were mixed thoroughly under stirring. Then, 0.64 mL of 100 mmol / L ascorbic acid solution was rapidly added under vigorous stirring to prepare the AuNRs growth solution. Next, 0.2 mL of the AuNRs seed solution prepared in step S11 was added to the AuNRs growth solution, and the mixture was stirred vigorously for 30 s and then allowed to stand for 10 min. The solution was observed to change from colorless to dark purple. The mixture was then allowed to stand at 28 °C for 12 h. The resulting AuNRs were centrifuged twice (8000 rpm, 5 min) to remove unreacted reagents, and the solution volume was concentrated 10-fold. The solution was then redispersed in 1 mmol / L hexadecyltrimethylammonium bromide solution for storage to obtain the AuNRs solution.

[0038] S13: Preparation of Gold Nanoparticle Spiral Arrows (AuNAs) Solution: 10 mL of 100 mmol / L hexadecyltrimethylammonium chloride solution, 460 μL of 10 mmol / L chloroauric acid solution, 150 μL of 10 mmol / L silver nitrate solution, and 200 μL of 1 mol / L hydrochloric acid solution were mixed uniformly under slow stirring. Then, 150 μL of 100 mmol / L ascorbic acid solution was rapidly added while stirring. After vigorous stirring for 30 s, 100 μL of 0.58 mmol / L D-cysteine ​​solution and 425 μL of the AuNRs solution obtained in step S12 were added. The mixture was then allowed to stand at 27 °C for 2 h, during which time the solution slowly changed from purplish-red to deep blue. Unreacted reagents were removed by two centrifugations (5000 rpm, 4 min), and the solution was redispersed in 1 mmol / L hexadecyltrimethylammonium bromide solution for storage, yielding the AuNAs solution.

[0039] See Figure 2 The extinction spectra of AuNRs and AuNAs solutions were characterized. The extinction band at 780 nm was attributed to the longitudinal plasmon resonance peak of AuNRs, and the extinction band around 520 nm was attributed to the transverse plasmon resonance peak of AuNRs, thus proving the successful synthesis of AuNRs. Furthermore, the extinction peak at 610 nm of AuNRs originated from the extinction peak of byproducts generated during the AuNRs formation process.

[0040] During the transition of AuNRs to AuNAs, the decrease in the aspect ratio of AuNRs leads to a red shift in the transverse plasmon resonance peak and a significant blue shift in the longitudinal plasmon resonance peak. Furthermore, the two characteristic extinction peaks merge into a single extinction peak (570 nm). The extinction spectrum of AuNAs confirms that AuNRs have gradually grown into AuNAs, thus verifying the successful synthesis of AuNAs.

[0041] In this invention, the metal in the composite metal material with adjustable electrochemical chiral recognition effect can be any metal selected from those prepared by seed growth method to form metal nano-spiral arrow solutions and which have photothermal conversion capabilities, with gold being preferred.

[0042] In one embodiment:

[0043] S1: Gold nano-spiral arrow solution was obtained by the above-described method of preparing metal nano-spiral arrow solution using seed growth.

[0044] S2: Mix the 0.4 mM gold nano-spiral arrow solution (represented by the concentration of gold) prepared in S1 with a phosphate buffer solution of bovine serum albumin with a concentration of 5-10 mg / mL. The volume of both the gold nano-spiral arrow solution and the phosphate buffer solution of bovine serum albumin is 1-5 mL. Stir at room temperature in the dark for 1-20 h to obtain a composite metal material solution with adjustable electrochemical chiral recognition effect. The phosphate buffer solution has a concentration of 0.01-1 mol / L and a pH of 6.0-8.0.

[0045] Different concentrations of gold nano-spiral arrow solutions were obtained by adjusting the amount and concentration of the reagent in S1. Optionally, the concentration of the gold nano-spiral arrow solution was 0.2-2 mM.

[0046] In a composite metal material with tunable electrochemical chiral recognition, bovine serum albumin (BSA) is attached to the surface of gold nano-helical arrows (AuNAs).

[0047] Example 1

[0048] S1: Gold nano-spiral arrow solution was obtained by the above-described method of preparing metal nano-spiral arrow solution using seed growth.

[0049] S2: 1 mL of the AuNAs solution obtained in Example S1 was mixed with 1 mL of 0.1 mol / L phosphate buffer solution of 10 mg / mL BSA at pH 7.0 and stirred at room temperature in the dark for 10 h. The concentration of the AuNAs solution was 0.4 mM.

[0050] The present invention also provides a method for controlling the electrochemical chiral recognition effect of composite metal materials, namely, irradiating the composite metal materials with near-infrared light with a wavelength of 600-900nm for 0.5-5h.

[0051] Before near-infrared light irradiation, bovine serum albumin (BSA) possesses natural chiral sites and a high binding affinity to L-tyrosine, enabling it to recognize tyrosine enantiomers. After near-infrared light irradiation, the composite metal material with tunable electrochemical chiral recognition absorbs light energy and converts it into heat, denaturing bovine serum albumin (BSA) on its surface. The destruction of BSA leads to the exposure of AuNAs. AuNAs have a high binding affinity to D-tyrosine, causing D-tyrosine to accumulate on the surface of the composite metal material with tunable electrochemical chiral recognition. In summary, the recognition effect of this composite metal material on tyrosine enantiomers can be controlled by irradiating it with near-infrared light.

[0052] Recognition performance test:

[0053] Preparation of test electrodes:

[0054] (1) Preparation of AuNAs modified electrode: Take 5 μL of AuNAs solution from step S1 of Example 1 and drop it onto the electrode surface, let it air dry naturally to obtain AuNAs / BSA modified electrode.

[0055] (2) Preparation of BSA modified electrode: 5 μL of 0.1 mol / L phosphate buffer solution of 5 mg / mL BSA at pH 7.0 was dropped onto the electrode surface and allowed to air dry to obtain BSA modified electrode.

[0056] (3) Preparation of AuNAs / BSA modified electrode: Take 5 μL of AuNAs / BSA solution from Example 1 and drop it onto the electrode surface, let it air dry naturally to obtain AuNAs / BSA modified electrode.

[0057] (4) Preparation of AuNAs / BSA / NIR modified electrode: The AuNAs / BSA solution obtained in Example 1 was irradiated with near-infrared light at a wavelength of 808 nm. After irradiation for 2 h, the supernatant was removed by centrifugation, and the solution was redispersed in 0.1-1 mmol / L hexadecyltrimethylammonium bromide solution to obtain AuNAs / BSA / NIR solution. 5 μL of AuNAs / BSA / NIR solution was drop-coated onto the electrode surface and allowed to air dry to obtain the AuNAs / BSA / NIR modified electrode.

[0058] The base electrodes used as modified electrodes mentioned above are all bare GCE electrodes.

[0059] 1. Using bare GCE, AuNAs-modified electrodes, BSA-modified electrodes, AuNAs / BSA-modified electrodes, and AuNAs / BSA / NIR-modified electrodes as working electrodes, the chiral recognition effect of composite metal materials with tunable electrochemical chiral recognition was tested using cyclic voltammetry and electrochemical impedance spectroscopy.

[0060] Cyclic voltammetry is used for identification as follows: Identification efficiency = IL / ID; IL represents the oxidation peak current of the modified electrode in L tyrosine solution; ID represents the oxidation peak current of the modified electrode in D tyrosine solution.

[0061] The AuNAs-modified electrode, BSA-modified electrode, AuNAs / BSA-modified electrode, AuNAs / BSA / NIR-modified electrode, and unmodified GCE electrode prepared above were used as working electrodes, a platinum sheet electrode as a counter electrode, and a silver / silver chloride electrode as a reference electrode. These electrodes were then placed in an atmosphere containing 5 mM [Fe(CN)6]. 4- / 3- Cyclic voltammetry was performed in 0.1 M KCl solution within an electrochemical window of -0.2–0.6 V and a scan rate of 100 mV / s. The test results show… Figure 3 .

[0062] The AuNA-modified electrode, BSA-modified electrode, AuNA / BSA-modified electrode, AuNA / BSA / NIR-modified electrode, and unmodified GCE electrode prepared above were used as working electrodes, a platinum sheet electrode as a counter electrode, and a silver / silver chloride electrode as a reference electrode. These electrodes were then placed in an atmosphere containing 5 mM [Fe(CN)6]. 4- / 3- Electrochemical impedance spectroscopy was performed in 0.1 M KCl solution at an open-circuit potential of ~0.24 V and a frequency range of 10⁵–0.01 Hz. The test results show… Figure 4 .

[0063] like Figure 3 As shown, when the electrode surface is unmodified, a pair of distinct [Fe(CN)6] electrodes are observed. 4- / 3- The redox peaks are attributed to the presence of [Fe(CN)6] in the solution. 4- / 3- The redox process. Due to the presence of a large amount of surfactant (such as hexadecyltrimethylammonium bromide) on the surface of AuNAs, the [Fe(CN)6] of AuNAs / GCE is affected. 4- / 3- The redox peak current is weaker than that of GCE itself. When the electrode surface is modified with BSA, because BSA is a protein and proteins have poor conductivity, the [Fe(CN)6] ratio of BSA / GCE is weakened. 4- / 3-The redox peak current values ​​are relatively small. When AuNAs are combined with BSA, the poor conductivity of the BSA coating on the AuNAs surface leads to the [Fe(CN)6] formation in the AuNAs / BSA / GCE composition. 4- / 3- The redox peak current is significantly lower compared to AuNAs / GCE. However, AuNAs have significantly higher conductivity than proteins, resulting in a lower [Fe(CN)6] current in AuNAs / BSA / GCE. 4- / 3- The redox peak current intensity is between that of BSA / GCE and AuNAs / GCE.

[0064] Due to their excellent photothermal conversion capabilities, AuNAs gradually convert light energy into heat energy upon near-infrared light irradiation, leading to an increase in the overall temperature of the AuNAs / BSA structure. This, in turn, causes the BSA on the AuNAs surface to pyrolyze and break down, exposing the AuNAs. Furthermore, thanks to the excellent electrical conductivity of AuNAs themselves, the [Fe(CN)6] structure of AuNAs / BSA / NIR / GCE is effectively exposed. 4- / 3- The redox peak current intensity is enhanced to some extent compared to AuNAs / BSA / GCE. Figure 4 The AC impedance diagrams for different modified electrodes show the following trends in charge transfer impedance: BSA / GCE (424Ω) > AuNAs / BSA / GCE (343Ω) > AuNAs / BSA / NIR / GCE (124Ω) > AuNAs / GCE (112Ω) > GCE (88Ω). The AC impedance test results for different electrodes are consistent with the cyclic voltammetry results for each electrode.

[0065] 2. Zeta potential characterization of composite metal materials with tunable electrochemical chiral recognition effect

[0066] The zeta potentials of the following solutions used in the preparation of the test electrodes—5 mg / mL BSA in 0.1 mol / L phosphate buffer (pH 7.0), AuNRs solution, AuNAs solution, AuNAs / BSA solution, and AuNAs / BSA / NIR solution—were measured. The test results showed... Figure 5 .

[0067] like Figure 5As shown, BSA has an isoelectric point of approximately 4.7, thus it carries a negative charge in a phosphate buffer solution at pH 7.0, with a Zeta potential of -10.6 mV. Since both AuNRs and AuNAs are stored in a solution of the cationic surfactant cetyltrimethylammonium bromide, they are both positively charged, with Zeta potentials of 30.8 mV and 24.2 mV, respectively. Because AuNAs and BSA have opposite charges, the Zeta potential of the composite metal nanomaterial AuNAs / BSA becomes -0.59 mV, approaching electroneutrality, thus indicating the successful composite of AuNAs / BSA. Upon introduction of near-infrared light, the photothermal conversion capability of AuNAs increases the overall material temperature, causing the BSA on the AuNAs surface to be destroyed, leading to the exposure of the AuNAs. Therefore, the zeta potential of AuNAs / BSA / NIR recovered to approximately 20.3 mV, close to that of AuNAs, and the electrical reversal of AuNAs / BSA was achieved through near-infrared laser irradiation. These zeta potential test results not only demonstrate the successful synthesis of the composite material but also confirm the feasibility of reversing the chiral recognition effect.

[0068] 3. The GCE electrode, and the prepared test electrodes, AuNAs-modified electrode, AuNAs / BSA-modified electrode, and the electrode modified with 5 μL of 5 mg / mL BSA in 0.1 mol / L phosphate buffer solution at pH 7.0, were used to test the recognition effect by differential pulse voltammetry.

[0069] The GCE electrode, along with the prepared test electrodes—an AuNAs-modified electrode, an AuNAs / BSA-modified electrode, and a 5 μL (5 mg / mL) BSA-modified electrode in a 0.1 mol / L phosphate buffer solution at pH 7.0—were used as working electrodes. A platinum sheet electrode served as the counter electrode, and a silver / silver chloride electrode as the reference electrode. All electrodes were placed in 25 mL of a 0.1 M phosphate buffer solution containing 1 mM L-tyrosine and D-tyrosine at pH 7.0. Differential pulse voltammetry was used for testing within an electrochemical window of 0.4–1.2 V. The test results showed… Figure 6-9 .

[0070] like Figure 6 As shown, after the naked GCE electrode was placed in L-tyrosine and D-tyrosine solutions, an oxidation peak current of tyrosine was observed at approximately 0.65 V, proving that tyrosine was oxidized on the surface of the naked GCE electrode. However, since the GCE surface lacks chiral sites, it is impossible to effectively distinguish tyrosine enantiomers. Figure 6The oxidation peak currents of L-tyrosine and D-tyrosine are almost equal, and their differential pulse voltammetric curves almost completely overlap, indicating that the bare GCE cannot recognize the tyrosine enantiomer. This proves that the subsequent signal difference originates solely from the material itself, not from interference by the bare GCE. Figure 7 As shown, when AuNAs are modified on the GCE surface, the chiral source D-cysteine ​​of AuNAs has a better adsorption effect with the isomorphic D-tyrosine, leading to the oxidation of more D-tyrosine on the electrode surface. It can be observed that the oxidation peak current signal of D-tyrosine is stronger than that of L-tyrosine (IL>ID), and the peak current ratio (IL / ID) is 0.74, indicating that AuNAs can efficiently recognize D-tyrosine. When differential pulse voltammetry is performed using BSA / GCE, BSA, due to its natural chiral sites, can recognize tyrosine enantiomers, such as... Figure 8 The oxidation peak current signal of L-tyrosine is significantly stronger than that of D-tyrosine (ID>IL), and the peak current ratio (IL / ID) reaches 1.63. Furthermore, due to the poor conductivity of BSA, the current signal of BSA / GCE is relatively weak. It is worth noting that when AuNAs are complexed with BSA (e.g., ... Figure 9 As shown in the figure, the peak current ratio (IL / ID) becomes 1.50 (IL>ID). This demonstrates that after AuNAs and BSA are combined, the chiral recognition effect is reversed, with BSA dominating chiral recognition. This reversal lays the foundation for subsequent regulation of the chiral recognition ability of metal nanomaterials based on photothermal conversion. Furthermore, a comparison of the oxidation peak current diagrams shows that the conductivity of AuNAs is significantly higher than that of BSA. Therefore, the conductivity of the AuNAs / BSA combination is weaker than that of AuNAs alone, but slightly higher than that of BSA, thus confirming the successful combination of AuNAs and BSA.

[0071] 4. The recognition performance of the prepared AuNAs / BSA / NIR / GCE differential pulse voltammetry was tested.

[0072] The prepared AuNAs / BSA / NIR / GCE was used as the working electrode, a platinum sheet electrode as the counter electrode, and a silver / silver chloride electrode as the reference electrode. The electrodes were placed in 25 mL of 0.1 M phosphate buffer solution (pH 7.0) containing 1 mM L-tyrosine and D-tyrosine, respectively. Differential pulse voltammetry was used for testing within an electrochemical window of 0.4–1.2 V. The changes in the oxidation peak current of tyrosine were recorded using differential pulse voltammetry. The test results show… Figure 10 .

[0073] Due to the introduction of near-infrared light, AuNAs convert light energy into heat energy凭借其良好的光热转化能力将光能转化为热能,AuNAs使得材料整体温度提升,通过高温使得蛋白质变性的原理破坏了AuNAs表面复合的BSA,导致原本被包裹于BSA之中的AuNAs的暴露。见 Figure 10 ,当使用AuNAs / BSA / NIR修饰电极后,与AuNAs / BSA / GCE相比,酪氨酸的氧化峰电流强度有所提升。此外,由于BSA的热解、以及AuNAs的暴露,此时的AuNAs / BSA / NIR的手性是由AuNAs所主导的,因此AuNAs / BSA / NIR对D-酪氨酸具有更佳的选择性(IL<ID),识别效率(IL / ID)可达0.83,由此实现了基于光热转化调控金属纳米材料电化学手性识别的翻转。通过以上数据,表明本发明所提出的基于光热转化调控金属纳米材料电化学手性识别效果的方法的有效性。

[0074] The present invention also provides a photosensitizer, characterized in that it comprises the composite metal material capable of regulating the electrochemical chiral recognition effect as described in any one of the above.

[0075] The present invention also provides a drug based on photothermal therapy, comprising the composite metal material capable of regulating the electrochemical chiral recognition effect as described in any one of the above.

[0076] The present invention also provides a screening device or a detection device, comprising the composite metal material capable of regulating the electrochemical chiral recognition effect as described in any one of the above.

[0077] The present invention also provides the application of the composite metal material capable of regulating the electrochemical chiral recognition effect as described in any one of the above in the fields of detection and treatment. [[ID=,15]]<>

[0078] 1. Since AuNAs with high efficient recognition ability for D-tyrosine is selected as the substrate material in this application, and then it is compounded with BSA which has high affinity for L-tyrosine, the chiral recognition ability of the composite material AuNAs / BSA is reversed, showing amino acid enantiomer chiral recognition dominated by BSA. Due to the introduction of near-infrared light into the composite material system, the overall temperature of the material is increased through the photothermal conversion ability of AuNAs itself, and the BSA on the surface of AuNAs is thermally decomposed and destroyed, so that the chiral recognition ability of AuNAs / BSA / NIR can be restored, and it shows high efficient recognition for D-tyrosine again;

[0079] 2. The metal nanomaterials in this application have sensitive optical response, good biocompatibility, and excellent morphology controllability. The method proposed in this application for controlling the electrochemical chiral recognition effect of metal nanomaterials based on photothermal conversion is a novel, simple, and efficient control method. The AuNAs, AuNAs / BSA, and AuNAs / BSA / NIR involved all have excellent chiral recognition capabilities, laying the foundation for the construction of subsequent control processes.

[0080] 3. This application introduces near-infrared light into a composite metal nanomaterial system to achieve photothermal conversion and thus precisely control the chiral recognition effect of metal nanomaterials. This allows for on-demand control of the chiral recognition effect, expanding the application of the photothermal properties of metal nanomaterials in the field of electrochemical chiral control. It provides a reference for the on-demand control of chiral materials and opens up new avenues for constructing intelligent and convenient chiral sensing platforms with variable enantioselectivity.

Claims

1. A composite metal material with tunable electrochemical chiral recognition effect, characterized in that, The composite metal material with tunable electrochemical chiral recognition effect includes metal nanoparticles and bovine serum albumin disposed on the surface of the metal nanoparticles; wherein the metal nanoparticles have photothermal conversion capability. Before near-infrared light irradiation, the composite metal material with adjustable electrochemical chiral recognition effect has the ability to bind with L-tyrosine; after near-infrared light irradiation, the composite metal material with adjustable electrochemical chiral recognition effect absorbs light energy, converts it into heat energy, and transforms into a material with the ability to bind with D-tyrosine. The preparation method of the composite metal material with tunable electrochemical chiral recognition effect includes the following steps: S1: Preparation of metal nano-spiral arrowhead solution using seed growth method; S2: Mix the metal nano-spiral arrow solution with a phosphate buffer solution of bovine serum albumin until homogeneous, and stir at room temperature in the dark to obtain a composite metal material solution with adjustable electrochemical chiral recognition effect.

2. The composite metal material with tunable electrochemical chiral recognition effect as described in claim 1, characterized in that, In S2, the concentration of the metal nano-spiral arrow solution is 0.2-2 mM, the concentration of the bovine serum albumin phosphate buffer solution is 5-10 mg / mL, the volume of the metal nano-spiral arrow solution and the bovine serum albumin phosphate buffer solution is 1-5 mL, and the pH is 6.0-8.

0.

3. The composite metal material with tunable electrochemical chiral recognition effect as described in claim 1, characterized in that, In S2, the concentration of the metal nano-spiral arrow solution is 0.4 mM, the concentration of the bovine serum albumin phosphate buffer solution is 10 mg / mL, the volume of the metal nano-spiral arrow solution and the bovine serum albumin phosphate buffer solution is 1 mL, and the pH is 6.0-8.

0.

4. The composite metal material with tunable electrochemical chiral recognition effect as described in claim 1, characterized in that, The metal is gold.

5. A photosensitizer, characterized in that, Including the composite metal material with tunable electrochemical chiral recognition effect as described in claim 4.

6. A medicine based on photothermal therapy, characterized in that, Including the composite metal material with tunable electrochemical chiral recognition effect as described in claim 4.

7. A screening device, characterized in that, Including the composite metal material with tunable electrochemical chiral recognition effect as described in claim 4.

8. A detection device, characterized in that, Including the composite metal material with tunable electrochemical chiral recognition effect as described in claim 4.

9. The application of the composite metal material with adjustable electrochemical chiral recognition effect as described in claim 4 in the fields of detection and treatment.

10. The method for controlling the electrochemical chiral recognition effect of composite metal materials as described in claim 4, characterized in that, This includes irradiating the composite metal material with adjustable electrochemical chiral recognition effect with near-infrared light, wherein the wavelength of the near-infrared light is 600-900nm and the irradiation time is 0.5-5h.

Images