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WO2020113361A1 - Matériau composite phosphore noir/or fonctionnalisé et son application - Google Patents

Matériau composite phosphore noir/or fonctionnalisé et son application Download PDF

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Publication number
WO2020113361A1
WO2020113361A1 PCT/CN2018/118880 CN2018118880W WO2020113361A1 WO 2020113361 A1 WO2020113361 A1 WO 2020113361A1 CN 2018118880 W CN2018118880 W CN 2018118880W WO 2020113361 A1 WO2020113361 A1 WO 2020113361A1
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Prior art keywords
cysteine
black phosphorus
gold
modified
electrode
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Chinese (zh)
Inventor
吴立冬
刘欢
李晋成
韩刚
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Chinese Academy Of Fishery Science
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Chinese Academy Of Fishery Science
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Priority to PCT/CN2018/118880 priority Critical patent/WO2020113361A1/fr
Priority to KR1020217004147A priority patent/KR102623728B1/ko
Publication of WO2020113361A1 publication Critical patent/WO2020113361A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G7/00—Compounds of gold
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y15/00—Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

Definitions

  • the present application relates to the field of biosensors, in particular, to functionalized black phosphorus, functionalized black phosphorous gold nanocomposite, metal electrodes and biosensors including them, and applications of the biosensors.
  • BP black phosphorus
  • BP having a wide band nonlinear optical response characteristics, associated to a thickness of 0.3 to 2.0eV 9 from the band gap range, a strong in-plane anisotropy characteristics, high charge carrier mobility (around cm2 V -1 s - 1 ) 12 and the theoretical capacity of 2596mAh g -1 as the anode of Li/Na ion battery, so it has broad application prospects in the fields of optoelectronics, electronics, selective sensors, catalysis, biosensors, batteries, etc. Because of its biocompatibility, low cytotoxicity, and high charge carrier mobility, BP is a promising candidate for a biosensor platform. Although BP has attractive properties and is one of the most thermodynamically stable phosphorus allotropes, its degradation in oxygen-enriched and water environments is still quite serious, resulting in rapid loss of semiconductor properties. This limits the development of BP in electrochemical sensing.
  • the non-covalent functionalization of BP not only maintains its original honeycomb structure and good conductivity, but also improves its stability and dispersion in aqueous solution, providing it with good performance as a biosensing platform in aqueous solution Possibility.
  • Traditional non-covalent functionalization has the problem of high cost of modifiers.
  • the existing known non-covalent functional groups mainly rely on the NH 2 support, but only play a role in passivating black phosphorus, but do not make it have more functional groups.
  • the present invention uses L-cysteine self-assembled membrane to passivate BP, so that the obtained BP can overcome the problem of instability under oxygen and humidity conditions.
  • Au-S self-assembly connects functionalized BP to gold nanoparticles (AuNP), providing a binding site for further anchoring of aptamers.
  • Functionalized BP and aptamers work together to improve the sensitivity and selectivity of biosensors.
  • the aptamer has a specific recognition area for selective detection of environmental analytes.
  • An aptamer is a single-stranded DNA or RNA that has a high affinity for a target and is called a "chemical antibody.”
  • aptamers are easy to prepare, low cost, repeatable, and non-immunogenic, thus providing a promising option for the development of selective biosensors.
  • functionalized BP as a biosensing platform, high sensitivity and low detection limit (DL) can be achieved.
  • MG malachite green
  • functionalized BP as a biosensor material can be used to detect malachite green (MG).
  • MG is a cationic triphenylmethane dye, which can be used as the detection target of the biosensor constructed by functional BP. Since 1936, although MG has adverse effects on the immune system and reproductive system, such as infertility and respiratory diseases, it is still widely used in commercial aquaculture to resist saprophytic bacteria. In order to ensure food safety, it is urgent MG needs to be screened quickly, selectively and sensitively.
  • an L-cysteine-modified black phosphorus is provided.
  • the black phosphorus combines with L-cysteine to form functionalized black phosphorus, and the functionalized black phosphorus has a uniform protective layer on the surface.
  • the present invention introduces a thiol group, thereby making the mounting of gold nanoparticles easier.
  • Gold particles are currently the classic material for bio-immobilization, and the application range of black phosphorus materials has been expanded since then.
  • cysteine is cheap and readily available, making it an ideal black phosphorus modifier.
  • L-cysteine with NH 2 and SH groups was used for non-covalent coating of the BP surface at room temperature. According to the structure of BP and L-cysteine, L-cysteine is coated non-covalently through the electrostatic interaction between the NH 2 of L-cysteine and the lone pair of electrons of BP BP surface.
  • an L-cysteine-black phosphorus-gold nanocomposite includes L-cysteine-modified black phosphorus and gold nanoparticles, and the L-cysteine-modified black phosphorus and the gold nanoparticles are connected by Au-S self-assembly.
  • a method for preparing L-cysteine-modified black phosphorus includes the steps of: placing a sheet-shaped substrate on which black phosphorus is placed in a container and sealing, an oil bath Heat to 110°C ⁇ 140°C and keep warm for 10-30 minutes; then contact L-cysteine with black phosphorus at 100°C ⁇ 150°C for not less than 5 minutes to obtain the L-cysteine Modified black phosphorus.
  • a method for preparing L-cysteine-black phosphorus-gold nanocomposite includes the steps of preparing L-cysteine-modified black phosphorus, and: A solution containing the L-cysteine-modified black phosphorus is mixed with a solution in which gold nanoparticles are dispersed to obtain a mixture; the mixture is separated, and the resulting solid is washed to obtain the L-cysteine-black Phosphorus-gold nanocomposite; preferably, the mass ratio of L-cysteine-modified black phosphorus to gold nanoparticles in the mixture is 0.1 to 0.5: 0.5 to 5.
  • the gold nanoparticle-dispersed solution is prepared by a method including the following steps: mixing chloroauric acid and vitamin C with a mass of 0.2 to 1:20 to 60 in water.
  • a preferred embodiment is to mix 50 mL of 0.1-10 mg L -1 chloroauric acid and 1-10 mL of vitamin C (4 mg mL -1 ) for 2 hours.
  • a preferred embodiment is to mix 50 mL of 0.1-0.5 mg mL -1 functionalized BP solution with 0.1-5 mg mL -1 gold nanoparticle solution, and quickly Stir for 10 minutes.
  • a metal electrode comprising L-cysteine-modified black phosphorus or L-cysteine-black phosphorus-gold nanocomposite.
  • the metal electrode is a gold electrode.
  • the metal electrode further contains an aptamer solution, and the aptamer includes a specific recognition area to specifically bind to the analyte.
  • the user can select the aptamer solution according to the needs of the biochemical properties of the analyte.
  • aptamers such as polychlorinated biphenyl aptamers and aflatoxin aptamers can be used in the biosensor constructed in the present invention.
  • a method for preparing a metal electrode comprising the steps of preparing an L-cysteine-black phosphorus-gold nanocomposite, and: applying a series of alumina powder to the metal electrode After polishing, it was cleaned with ethanol and deionized water ultrasonically; the metal electrode was electrochemically polished by potential scanning; the obtained L-cysteine-black phosphorus-gold nanocomposite was oscillated with a vortex meter and added to On the surface of the metal electrode.
  • a preferred embodiment is to perform electrochemical polishing from 0 to 1.7 V in the range of 0.1-5 mol L -1 H 2 SO 4 .
  • the metal electrode may be gold, platinum, glassy carbon electrode and the like.
  • the metal electrode is a gold electrode.
  • the method further includes adding an aptamer solution to the metal electrode
  • the aptamer solution is a mercapto aptamer solution.
  • the sulfhydryl aptamer solution is selected from 5'-terminal thiol modified single-stranded DNA.
  • it is washed with deionized water to remove weakly adsorbed aptamers.
  • a biosensor including or modified from L-cysteine-modified black phosphorus, L-cysteine-black phosphorus-gold nanocomposite At least one of the metal electrodes.
  • the biosensor according to the present invention can be used to detect malachite green.
  • the present invention provides a black phosphorus modified with L-cysteine which is stable under water environment
  • the present invention provides an L-cysteine-black phosphorus-gold nanocomposite, which provides a binding site for further anchoring of aptamers;
  • the present invention provides a method for preparing L-cysteine-modified black phosphorus which is stable in an aqueous environment
  • This book provides a method for preparing L-cysteine-black phosphorus-gold nanocomposite
  • the present invention provides a metal electrode for detecting environmental targets, and further provides a biosensor including such an electrode, which has low DL, high sensitivity and high specificity, and is expected to become a rapid on-site measurement of the object to be tested Tool of.
  • FIG. 1 shows a schematic diagram of the preparation process and detection mechanism of the BP-AuNP-Ap/Au biosensor.
  • the BP and cysteine were immersed in DMSO, and then Au-S self-assembly was used to fix the gold nanoparticle particles on the BP surface.
  • the BP-AuNP nanocomposite was transferred from the solution to the gold electrode surface, and then the thioaptamer solution was added to the BP-AuNP modified gold electrode.
  • BP-AuNP-aptamer biosensor detects MG.
  • Figure 2 shows the results of atomic force microscopy (AFM): (A) BP, (B) BP in water for 12 hours, (C) BP functionalized with L-cysteine and (D) with L- Cysteine functionalized BP was in water for 12 hours. (E) Atomic force microscopy was used to characterize the thickness, position and height distribution of the same BP before and after coating L-cysteine as a protective layer. (F) Infrared spectra of L-cysteine and L-cysteine/BP.
  • Figure 3 shows the TEM image and SEM image results, where (A) is the TEM image of BP, (B) is the TEM image of gold nanoparticles and (C) is the TEM image of BP-AuNP nanocomposite, (D) Is the SEM image of BP, (E) is the SEM image of BP-AuNP nanocomposite.
  • Figure 4 shows the results of a cyclic voltammogram, where (A) is in 1 mol L -1 H 2 SO 4 , the bare gold electrode has a CV (20 times) from 0.3 to 1.55V, and (B) is a different gold electrode CV in 5 mmol L -1 [Fe(CN) 6 ] 3-/4- (a) bare gold electrode, (b) Ap/Au electrode, and (C)BP-AuNP-Ap/Au electrode.
  • Figure 5 shows a differential pulse voltammogram (DPV), where (A) the corresponding DPV of the biosensor at different concentrations of MG from 1pg L -1 to 10 ⁇ g L -1 , (B) the peak current of MG at different concentrations increase.
  • the standard deviations are all less than 5%.
  • Fig. 6(A) shows the reproducibility of the BP-AuNP-Ap/Au biosensor
  • Fig. 6(B) screens the MG and chloramphenicol (CP) by the BP-AuNP-Ap/Au biosensor
  • NF nitrofurans
  • MTS methyltestosterone
  • EG eugenol
  • MG methylene blue (MB), L-cysteine, dimethyl sulfoxide (DMSO), and other chemicals were purchased from Sigma Aldrich (USA). MG is dissolved in H 2 O to obtain a series of standard solutions.
  • PBS 50 mmol L L -1 phosphate buffer
  • TEM Transmission electron microscope
  • SEM scanning electron microscope
  • FTIR Fourier transform infrared spectroscopy
  • CV Cyclic voltammetry
  • DUV differential pulse voltammetry
  • Example 1 Preparation of BP, L-cysteine-coated BP and BP-AuNP nanocomposite Preparation of L-cysteine-coated BP
  • the preparation process of BP can be divided into several steps, all of which are operated in acrylic glove boxes.
  • the glove box needs to maintain a certain level of oxygen and water, which is necessary for the uniform oxidation and hydroxylation of the BP surface.
  • the first step is to perform ultrasonic assisted stripping of BP in DMSO under a nitrogen atmosphere to remove dissolved oxygen molecules. After centrifugation to remove non-shedding particles, BP was collected from the supernatant.
  • the second step is to transfer the BP onto the SiO 2 /Si wafer immersed in the glass bottle. The glass bottle was then capped and placed in silicone oil. The glass bottle was heated to 130°C and incubated for 20 minutes. After this step, -OH groups are present on the BP surface.
  • BP was transferred into DMSO with L-cysteine at 100°C for 20 minutes.
  • L-cysteine binds to BP via the formation of an ionic bond between -OH and -NH 2 .
  • a uniform protective monolayer is formed on the BP surface. Obtained functionalized BP.
  • Preparation of gold nanoparticles and BP nanocomposites by self-assembly method Preparation of gold nanoparticles in water by reduction of chloroauric acid by vitamin C. 50 mL of 0.1 mg L -1 chloroauric acid and 2.5 mL of vitamin C (4 mg mL -1 ) were mixed for 2 hours, and then 0.5 mL of sodium citrate (10 mg mL -1 ) was added to the solution to terminate the reaction. Gold nanoparticles were obtained. Then, 0.25 mg mL -1 functionalized BP solution (50 mL) was mixed with 0.5 mg mL -1 gold nanoparticle solution and stirred rapidly for 10 minutes. Through three centrifugations (1300g, 5 minutes), the bottom of the centrifuge bottle was washed and nanocomposite material G1# was obtained.
  • the BP-AuNP-Ap/Au electrode was constructed by the following method: After the gold electrode was polished with a series of alumina powder (0.3 and 0.05 ⁇ m diameter), it was ultrasonically cleaned three times with ethanol and deionized water. Then, the gold electrode was electrochemically polished from 0 to 1.7 V in 1 mol L -1 H 2 SO 4 by potential scanning. The construction process is shown in Figure 1: The BP-AuNP nanomaterial (0.5 mg mL -1 ) solution was vortexed for 20 minutes and added to the gold electrode surface. Then, 8 ⁇ L, 1 ⁇ mol L -1 thiol aptamer solution was added to the Au electrode at room temperature for 2 hours. All other electrodes are washed with deionized water to remove weakly adsorbed aptamers, and they have a similar preparation method as the BP-AuNP-Ap/Au electrode.
  • MG is classified as a Class II health hazard and can cause cancer.
  • Select MG as the target compound and add 8 ⁇ L of MG solution to the PBS solution for 3 minutes to provide sufficient time for the aptamer to recognize MG.
  • the BP-AuNP-Ap/Au biosensor is used to monitor the change of the response signal generated by the MG through the DPV method.
  • Example 4 Characterization of BP, L-cysteine-coated BP and BP-AuNP nanocomposites
  • the long-term stability of functionalized BP was characterized using atomic force microscopy (AFM). As shown in FIG. 2A and FIG. 2B, after applying L-cysteine, the passivation of BP stably exists in the aqueous solution for about 2 weeks. But without coating L-cysteine, BP degraded in aqueous solution within 12 hours. ( Figure 2C and Figure 2D). AFM was also used to characterize the functionalized BP and BP thickness. The sample G1# was used as a typical representative to observe the characterization of BP L-cysteine-coated BP and BP-AuNP nanocomposites. FIG. 2E shows that the coating thickness of L-cysteine is about 0.6 nm.
  • FIG. 3 shows representative TEM images of functionalized BP (A), gold nanoparticles (B), and BP-AuNP (C). Under the strong electron beams of TEM and SEM, the uncoated BP degrades within one minute, so the patterns of these uncoated BP cannot be captured by TEM and SEM.
  • Figure 3A shows that high-quality functionalized BP is obtained by liquid stripping and site functionalization.
  • FIG. 3B shows a TEM image of gold nanoparticles with a size of about 10 nm.
  • Figure 3C is a BP-AuNP nanocomposite.
  • Sample G2# ⁇ sample G5# have similar structure and morphology as sample G1#.
  • BP has excellent carrier mobility (1000 cm 2 /V ⁇ s), which is higher than that of molybdenum disulfide (MoS 2 , 200 cm 2 /V ⁇ s).
  • MoS 2 molybdenum disulfide
  • BP plays a key role in the development of biosensors as a biosensor platform.
  • CV was used to monitor the preparation process of Au electrodes.
  • FIG. 4A shows that the repeated CV of the bare electrode in mol L ⁇ 1 H 2 SO 4 is 0.2 ⁇ 1.55V. The results showed that the electrode was cleaned by electrochemical corrosion in 1mol L -1 H 2 SO 4 .
  • FIG. 4B shows the CV signals of the bare gold electrode, Ap/Au electrode, and BP-AuNP-Ap/Au electrode in 5 mmol L -1 [Fe(CN) 6 ] 3-/4- solution (curve A, curve B and curve C).
  • the response signal of the electrode (curve B) was significantly weakened. This is because the thiol aptamer covers the Au electrode surface through AU-S self-assembly.
  • the response signal was significantly enhanced. This is mainly due to the high conductivity of the BP-AuNP nanocomposite improving the electron mobility. The results showed that BP-AuNP was successfully fixed on the Au electrode.
  • Example 6 MG determination by BP-AuNP-Ap/Au electrode
  • MG is a cationic triphenylmethane dye that has been used in commercial aquaculture since 1936 to resist saprophytic bacteria. In recent years, due to its adverse effects on the immune and reproductive systems, infertility and respiratory diseases, it has attracted widespread attention. Based on the above reasons, a preferred embodiment of the present invention uses a BP-AuNP-Ap/Au biosensor to detect MG.
  • DPV is one of the most sensitive electrochemical methods, which is used to monitor the concentration of MG by BP-AuNP-Ap/Au biosensor.
  • the redox-active molecules MB electrochemical response signals for amplification, the redox potential of the low -0.25-0V, 33 can be reduced potential coexistence interference. As shown in FIG.
  • the response signal of this biosensor continuously increases with the addition of MG.
  • the peak current of the BP-AuNP-Ap/Au biosensor showed a linear correlation with the change in MG concentration from 1 pg L -1 to 10 ⁇ g L -1 ( Figure 5B).
  • the DL of the biosensor for MG is as low as 0.3 pg L -1 .
  • the DL of this biosensor (0.3 pg L -1 ) is significantly better than that of other biosensors (Table 2). This indicates that functionalized BP plays a key role in improving the performance of biosensors.
  • Figure 5 shows a possible mechanism by which MG is recognized by the aptamer.
  • the aptamer Before the aptamer binds to MG, there is no helix or hairpin structure. The aptamer showed a random linear structure to keep the MG away from the electrode. Therefore, in the absence of MG, this biosensor has no obvious response signal. After the aptamer binds to MG, a hairpin structure is formed. The hairpin structure of the aptamer brings the MB close to the electrode and has an enhanced response signal. The high conductivity BP significantly improves the DL of the biosensor.
  • the sensitivity of BP-AuNP-Ap/Au biosensor and Ap/Au biosensor are 95.1 ⁇ A cm -2 and 42.5 ⁇ A cm -2, respectively .
  • the selectivity of the biosensor is determined by the coexisting interfering substances, such as chloramphenicol (CP) and nitrofuran (NF) methyl testosterone (MTS) and eugenol (EG).
  • CP chloramphenicol
  • NF nitrofuran
  • MTS nitrofuran methyl testosterone
  • EG eugenol
  • Fig. 6B is the response signal of PP-AuNPs-Ap/Au biosensor to MG at 10ng L -1 for 8 times. This shows that under the output current, the functionalized BP with protective layer is very stable in the liquid, and it is not a disposable biosensor.
  • Example 7 Detection of breeding water samples by BP-AuNP-Ap/Au electrode
  • BP-AuNP-Ap/Au biosensors were used to evaluate the cultured water samples in 7 provinces of China.
  • BP-AuNP-Ap/Au biosensor showed that only three aquaculture water samples had MG, and their response signals increased by 33%, 24% and 16% respectively. As shown in Table 3, the differences between these values are 23.5%, 26.1%, and 8.3%, respectively.
  • the results show that the biosensor results are consistent with the LC-MS results.
  • the biosensor developed is an effective tool for selective determination of MG from coexisting aquaculture drugs, although it may not be very accurate.
  • the biosensor constructed by the present invention is not limited to detecting MG.
  • L-cysteine-coated BP can stably stay in water for two weeks. It overcomes the current shortcomings of BP.
  • a stable BP as a biosensing platform, a new BP-AuNP-Ap/Au biosensor was constructed. This biosensor is used to detect MG quickly and selectively. It shows a concentration-dependent response to MG as well as low DL and high selectivity. It is a useful early warning tool for the rapid and selective detection of MG in aquaculture water from coexisting drugs.

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Abstract

L'invention concerne un phosphore noir modifié par L-cystéine, comprenant une liaison ionique formée entre -OH et -NH2. Le phosphore noir modifié est utilisé pour préparer une électrode et un détecteur destiné à détecter le vert de malachite.
PCT/CN2018/118880 2018-12-03 2018-12-03 Matériau composite phosphore noir/or fonctionnalisé et son application Ceased WO2020113361A1 (fr)

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CN114804550A (zh) * 2022-06-10 2022-07-29 安徽新宇环保科技股份有限公司 一种基于神经网络模型的污水处理调控系统
CN114804550B (zh) * 2022-06-10 2023-06-02 安徽新宇环保科技股份有限公司 一种基于神经网络模型的污水处理调控系统
CN116593557A (zh) * 2023-05-17 2023-08-15 海南师范大学 二硫化钼/黑磷烯复合材料、制备的电化学传感器及其应用
CN116593557B (zh) * 2023-05-17 2024-01-23 海南师范大学 二硫化钼@黑磷烯复合材料制备的电化学传感器及其应用
CN119086657A (zh) * 2024-09-05 2024-12-06 西安交通大学医学院第一附属医院 传感层、包含其的湿度传感器、制备方法和用途

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