CN114235917A - AuAg @ WP5/RGO-C3N4Composite material and preparation method and application thereof - Google Patents
AuAg @ WP5/RGO-C3N4Composite material and preparation method and application thereof Download PDFInfo
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- 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
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Abstract
The application discloses an AuAg @ WP5/RGO-C3N4Composite material, preparation method thereof and application thereof in Photoelectrochemical (PEC) detection of carcinoembryonic antigen (CEA). Coating a layer of water-soluble column [5 ] on the surface of the AuAg nanowire]Arene (WP5) loaded on reduced graphene and graphite carbon nitride composite (RGO-C)3N4) The AuAg @ WP5 is an optically active material, and a novel signal switch type Photoelectrochemical (PEC) biosensing system is designed for detecting a Cancer Embryo Antigen (CEA). This is the first use of AuAg @ WP5/RGO-C3N4As a sensing material. Utilizes the local surface plasma effect of the AuAg nano-wire under visible light, the host-guest complexation of water-soluble column aromatic hydrocarbon (WP5), the higher conductivity of RGO, the extraordinary thermochemical stability and C3N4And generating photo-generated electron holes under the irradiation of visible light to accelerate the oxidation-reduction reaction to cooperate with each other, and detecting the CEA. Based on AuAg @ WP5/RGO-C3N4Multiple signal amplification capability of, CEA detection Linear RangeFrom 0.0005ng mL‑1‑50 ng mL‑1The detection limit is 0.17 pg mL‑1(S/N=3)。
Description
Technical Field
The invention belongs to the technical field of photoelectrochemistry, and particularly relates to AuAg @ WP5/RGO-C3N4Composite material and method for producing the sameA preparation method and application.
Background
Carcinoembryonic antigen (CEA) is a group of highly related glycoproteins that are involved in cell adhesion. It was first discovered in human colon cancer tissue extracts in 1965 by Phil Gold and Samuel o. CEA is normally produced in gastrointestinal tissues during prenatal development, but production is stopped before birth. Therefore, CEA is usually present only at very low levels in the blood of healthy adults. However, elevated CEA levels in human serum can be used as a marker for tumorigenesis such as gastric, pancreatic, colorectal, lung and breast cancers. Many methods for detecting CEA have been developed, such as enzyme-linked immunosorbent assays, fluorescent immunoassays, electrochemiluminescence, and electrochemical immunoassays. Among them, electrochemiluminescence immunoassay (ECLI) is a standard method for CEA analysis, and is generally used for determining CEA in hospital assay. These methods generally require complex and expensive optical equipment and accurate image recognition software, whereas Photoelectrochemical (PEC) techniques have many advantages, such as low cost, simple instrumentation, wide detection range, and high sensitivity. Therefore, it is necessary to develop a sensitive, reliable and low-cost detection method to solve the above problems.
Graphene, one of the most promising two-dimensional materials, has attracted extensive attention in photoelectrochemical research due to its characteristics of high electrical conductivity, extraordinary thermochemical stability, high-quality crystals, and the like. Importantly, C3N4And the pi-like conjugated skeleton of graphene makes it easier to bond. Thus, RGO is combined with C3N4In combination, not only can effectively solve C3N4The problem of small specific surface area due to the recombination of photo-generated electron-hole pairs, and the possibility of combining RGO with C3N4In photoelectrochemical applications, such as RGO and C3N4The strong synergistic effect under visible light irradiation can significantly enhance the photoelectrochemical properties thereof. The proper plasma material is designed by regulating or optimizing the shape, size and the like of the plasma material, and the method is one of effective ways for improving the catalytic performance of the catalyst. BiOBr can be promoted by surface plasma resonance of gold nanoparticlesThe photoelectrochemical property of the material is improved by light adsorption. Gold nano-ions have become an important component of novel hybrid nano-materials due to the characteristics of easy synthesis, high chemical stability, easy surface functionalization and the like. The Au and Ag nanoparticles with specific size and morphology can generate plasma resonance (SPR) through excitation illumination, so that photogenerated electron hole recombination on the semiconductor photocatalyst can be inhibited, and the photogenerated current of the semiconductor photocatalyst is increased, and therefore the Au and Ag nanoparticles can be used as an effective photocatalyst. In particular, Au @ Ag with a core-shell structure is beneficial to improving the electronic performance of Au @ Ag due to the changed lattice parameter and the electronic effect of the core-shell structure, thereby attracting the attention of a plurality of scientific researchers. Meanwhile, macrocyclic hosts (cyclodextrins, calixarenes, cucurbiturils, etc.) have unique size-inaccessible luminal structures and exhibit special properties. Column [ n ]]The aromatic hydrocarbon is composed of hydroquinone or its derivative and methylene (-CH) at 2-and 5-positions2-) bridges are connected. Compared with crown ether and calixarene, the pillared arene has a stronger rigid structure; on the other hand, column [ n ] compared to cyclodextrin and cucurbitene]Aromatics are more easily modified. Column [ n ] as an emerging host family of macrocyclic arenes]Aromatic hydrocarbons are receiving wide attention due to their novel rigid symmetrical columnar structures, hydrophobic electron-donating cavities, unique and excellent host-guest functions, edges with adjustable functions, and the like. In recent years, the preparation of noble metal nano-doped organic materials has attracted great interest due to their advanced electronic, optical and biological properties. Thus, in RGO-C3N4The surface loaded AuAg @ WP5 not only provides a novel hybrid nano material, but also is expected to bring new performance, functions and applications.
Disclosure of Invention
The technical problem to be solved is as follows:
aiming at the defects of the prior art, the application solves the technical problems of low sensitivity, limited detection range, expensive instrument, special operator requirement, low efficiency, low speed, difficult operation and the like of the prior detection technology, and provides the AuAg @ WP5/RGO-C3N4Composite material and its preparation method and application.
The technical scheme is as follows:
in order to achieve the purpose, the application is realized by the following technical scheme:
AuAg @ WP5/RGO-C3N4Composite material of layered RGO-C3N4The surface is loaded with AuAg @ WP5 to prepare AuAg @ WP5/RGO-C3N4A composite material.
AuAg @ WP5/RGO-C3N4The preparation method of the composite material comprises the following specific steps:
in a first step, a water soluble column aromatic hydrocarbon (WP 5):
step two, preparing Ag nanowires: 10mL of a solution containing 150mM polyvinylpyrrolidone (PVP, M)w58000) of 1, 2-propanediol is added into a 25mL flask, and the flask is heated and stirred for 1h in an oil bath pot at the temperature of 160 ℃ and the rotating speed of 600 r/min; then 1mL of 1, 2-propanediol containing 1mM NaCl was injected; after 5min 4mL of 0.15M AgNO was added dropwise3Reacting 1, 2-propylene glycol for 40min to prepare a silver-white Ag nanowire crude solution, centrifuging the silver-white Ag nanowire crude solution for 5 times by using deionized water at 7000r/min to obtain a pure Ag nanowire, and dispersing the centrifuged Ag nanowire in 20mL of deionized water for storage;
thirdly, preparing the AuAg alloy nanowire by adopting a displacement method;
fourthly, preparing AuAg @ WP5 by adopting a ligand exchange method: taking 0.7mL of AuAg alloy nanowire, adding 4.3mL of deionized water, adding 6.31mg of WP5, controlling the rotating speed at 600r/min, stirring for 1.5h, and preparing the AuAg @ WP5 composite material;
the fifth step, preparation of RGO and RGO-C3N4A composite material;
and a sixth step: successively drop-coating RGO-C3N4And AuAg @ WP5 to the surface of a glassy carbon electrode to prepare AuAg @ WP5/RGO-C3N4a/GCE composite material.
The application also discloses the AuAg @ WP5/RGO-C3N4The application of the composite material in the photoelectric detection of carcinoembryonic antigen (CEA) comprises the following steps:
step 4, AuAg @ WP5/RGO-C in step 3 above3N4The surface of the/EDC-NHS/Ab/GCE electrode was coated with 5. mu.L of 1% Bovine Serum Albumin (BSA), incubated in an oven at 37 ℃ for 1h to prepare AuAg @ WP5/RGO-C3N4EDC-NHS/Ab/BSA/GCE electrode;
As a preferred technical scheme of the invention: the AuAg @ WP5/RGO-C3N4The composite material is AuAg @ WP5/RGO-C3N4EDC-NHS/Ab/BSA/CEA/GCE electrode; the AuAg @ WP5/RGO-C3N4The composite material is AuAg @ WP5/RGO-C3N4the/EDC-NHS/Ab/BSA/CEA/GCE electrode is placed in Ascorbic Acid (AA) solution for photoelectrochemical detection, and AA is used as an electron gain-loss donor; all experiments used a traditional three-electrode system with the GCE electrode as the working electrode, the platinum mesh as the counter electrode, and the Saturated Calomel Electrode (SCE) as the reference electrode.
As a preferred technical scheme of the invention: the third step of preparing the AuAg alloy nanowire by adopting a displacement method comprises the following specific steps:
s1: mu.L of HAuCl4(25.4mM), 2mL of NaOH solution and 17.9mL of deionized water were added thereto, and the mixture was stirred at room temperature for 1 hour to prepare 0.1mM Au (OH)4 -With 20mM NaOH;
s2: taking 1mL of 40mg/mL PVP, adding 2mL of deionized water, heating at 60 ℃, dropwise adding 500 mu L of ascorbic acid (AA,100mM) and 500 mu L of NaOH (200mM) solution after 2min, and controlling the rotation speed to be 400r/min during reaction (the subsequent heating temperature and stirring speed are unchanged);
s3: after 5min, 700 μ L of the Ag nanowire solution prepared in the second step is added;
s4: after 10min, the solution in S1 was added dropwise;
s5: and stopping the reaction after 10min, and centrifuging the reaction mixed solution for 5 times by using deionized water at 7000rpm to obtain the pure AuAg alloy nanowire.
As a preferred technical scheme of the invention: preparation of RGO and RGO-C in the fifth step3N4The composite material comprises the following specific steps:
(1) preparing a Reduced Graphene (RGO) dispersion: adding 14mg of Graphene Oxide (GO) and 10mL of deionized water into a flask, stirring at a rotating speed of 600r/min for two hours to obtain a Reduced Graphene Oxide (RGO) dispersion liquid;
(2) adding the prepared Reduced Graphene (RGO) dispersion liquid and 46mL of ethanol into a reaction kettle, adjusting the pH to 9 by using a 1M KOH solution, then placing the reaction kettle in an oven at 80 ℃ for reaction for two hours, finally centrifugally rinsing the black suspension by using deionized water, uniformly dispersing the black suspension in 23mL of deionized water, carrying out centrifugal washing at the centrifugal rotation speed of 7000r/min for 3 times to obtain 0.6mg/mL RGO;
(3)11mg C3N4the powder was mixed well with 4.4mL of isopropanol to prepare 2.5mg/mL of C3N4Suspension, and mixing 1mL of RGO with 1mL of C3N4Mixing and stirring at the rotating speed of 600r/min to prepare the RGO-C with the mass ratio of 1:13N4And (3) a complex suspension.
As a preferred technical scheme of the invention: the EDC-NHS in the step 2 is prepared by a mixed solution of EDC and 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and a mixed solution of NHS and N-hydroxysuccinimide according to the dosage ratio of 1:1, wherein the EDC is 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and is 400 mM/L; NHS: n-hydroxysuccinimide, 100 mM/L.
Has the advantages that:
the application provides an AuAg @ WP5/RGO-C3N4Compared with the prior art, the composite material and the preparation method and the application thereof have the following beneficial effects:
1. the application designs an AuAg nanowire material which forms LSPR effect under visible light, WP5 with host-guest complexing ability, RGO-C with large specific surface area and good conductivity3N4Composite material for the photoelectrochemical detection of carcinoembryonic antigen (CEA).
2. The method solves the technical problems of low sensitivity, limited detection range, serious environmental pollution, expensive instrument, special operator requirement, low efficiency, low speed, difficult operation and the like of the prior detection technology.
3. The detection range of the application is 0.001-50ng mL-1With a detection limit of 0.33pg mL-1(S/N)。
Drawings
FIG. 1 shows Ag nanowire (a), AuAg nanowire (b), AuAg @ WP5/RGO-C in this application3N4(c) Transmission electron micrograph (D).
FIG. 2 is RGO-C in the present application3N4、AuAg@WP5、AuAg@WP5/RGO-C3N4XRD powder diffractogram of (a) and WP5, RGO-C3N4、AuAg@WP5、AuAg@WP5/RGO-C3N4The infrared spectrum (b) of (A).
FIG. 3 is AuAg @ WP5/RGO-C in the present application3N4、AuAg@WP5/RGO-C3N4/Ab、AuAg@WP5/RGO-C3N4Ab/BSA and AuAg @ WP5/RGO-C3N4Ab/BSA/CEA modified glassy carbon electrode at 5mM K3[Fe(CN)6]/K4[Fe(CN)6]And Cyclic Voltammograms (CVs) (a), Nyquist plots (EIS) (b) in 0.1M KCl.
FIG. 4 shows the biosensor pairs of 0.0005, 0.001, 0.01,0.02,0.05,0.1,0.5,1.0,5.0,10.0 and 50.0ng mL in this application-1I-t curve (a) of CEA, linear calibration curve (b).
FIG. 5 is AuAg @ WP5/RGO-C of the present application3N4Time-current curve (a) of the PEC biosensor against CEA at a CEA concentration of 10.0ng/mL for the/Ab/BSA/CEA-modified glassy carbon electrode, and (b) for the PEC biosensor to have 10ng/mL for a- 1CEA+100ng mL-1Glucose (Glu); b is 10ng mL-1CEA+100ng mL-1Uric Acid (UA); c is 10ng mL-1CEA+100ng mL-1Dopamine (DA); d is 10ng mL-1CEA+100ng mL-1Bovine hemoglobin (BHb) and e 10ng mL-1CEA。
FIG. 6 is a flow chart of the synthesis method of WP5 in the present application.
Detailed Description
The present invention is further described with reference to the following examples, which are intended to be illustrative only and not to be limiting of the scope of the claims, and other alternatives which may occur to those skilled in the art are within the scope of the claims.
Example 1:
AuAg @ WP5 and RGO-C3N4The preparation method of the composite material comprises the following steps:
in the first step, a water soluble pillared aromatic hydrocarbon (WP5) is prepared as shown in fig. 6:
step two, preparing Ag nanowires: 10mL of a solution containing 150mM polyvinylpyrrolidone (PVP, M)w58000) of 1, 2-propanediol was added into a 25mL flask, heated and stirred in an oil bath kettle at 160 ℃ with a stirring speed of 600r/min for 1 h; then 1mL of 1, 2-propanediol containing 1mM NaCl was injected; after 5min 4mL of 0.15M AgN were added dropwiseO3Reacting 1, 2-propylene glycol for 40min to prepare a silver-white Ag nanowire crude solution, centrifugally washing the silver-white Ag nanowire crude solution for 5 times by using deionized water at 7000r/min to obtain pure Ag nanowires, and dispersing the centrifugal Ag nanowires in 20mL of deionized water for storage;
thirdly, preparing the AuAg alloy nanowire by adopting a displacement method;
fourthly, preparing AuAg @ WP5 by adopting a ligand exchange method: taking 0.7mL of AuAg alloy nanowire, adding 4.3mL of deionized water, adding 6.31mg of WP5, controlling the rotating speed at 600r/min, stirring for 1.5h, and preparing the AuAg @ WP5 composite material;
the fifth step, preparation of RGO and RGO-C3N4A composite material;
sixthly, sequentially dripping RGO-C3N4And AuAg @ WP5 to the surface of a glassy carbon electrode to prepare AuAg @ WP5/RGO-C3N4The composite material of/GCE: preparation of RGO and RGO-C3N4The composite material comprises the following specific steps:
(1) preparing a Reduced Graphene (RGO) dispersion: adding 14mg of Graphene Oxide (GO) and 10mL of deionized water into a flask, stirring at a rotating speed of 600r/min for two hours to obtain a Reduced Graphene Oxide (RGO) dispersion liquid;
(2) adding the prepared Reduced Graphene (RGO) dispersion liquid and 46mL of ethanol into a reaction kettle, adjusting the pH to 9 by using a 1M KOH solution, then placing the reaction kettle in an oven at 80 ℃ for reaction for two hours, finally centrifugally rinsing the black suspension by using deionized water, uniformly dispersing the black suspension in 23mL of deionized water, carrying out centrifugal washing at the centrifugal rotation speed of 7000r/min for 3 times to obtain 0.6mg/mL RGO;
(3)11mg C3N4the powder was mixed well with 4.4mL of isopropanol to prepare 2.5mg/mL of C3N4Suspension, and mixing 1mL of RGO with 1mL of C3N4Mixing and stirring at the rotating speed of 600r/min to prepare the RGO-C with the mass ratio of 1:13N4And (3) a complex suspension.
The third step of preparing the AuAg alloy nanowire by adopting a displacement method comprises the following specific steps:
s1: mu.L of HAuCl4(25.4mM), 2mL of NaOH solution and 17.9mL of NaOH solution were addedDeionized Water, stirring at ambient temperature for 1h, 0.1mM Au (OH) was prepared4 -With 20mM NaOH;
s2: 1mL of 40mg/mL PVP is taken, 2mL of deionized water is added, heating is carried out at 60 ℃, and 500 mu L of ascorbic acid (AA,100mM) and 500 mu L of NaOH (200mM) solution are dropwise added after 2 min;
s3: after 5min, 700 μ L of the Ag nanowire solution prepared in the second step is added;
s4: after 10min, the solution in S1 was added dropwise;
s5: and stopping the reaction after 10min, and centrifuging the reaction mixed solution for 5 times by using deionized water at 7000rpm to obtain the pure AuAg alloy nanowire.
Example 2:
AuAg @ WP5/RGO-C3N4The application of the composite material in the photoelectric detection of carcinoembryonic antigen (CEA) comprises the following steps:
step 4, AuAg @ WP5/RGO-C in step 3 above3N4/EDC-NHS/AbThe surface of the/GCE electrode is coated with 5 mu L of 1% Bovine Serum Albumin (BSA), incubated in an oven at 37 ℃ for 1h, and prepared into AuAg @ WP5/RGO-C3N4EDC-NHS/Ab/BSA/GCE electrode;
Example 3:
AuAg@WP5/RGO-C3N4the/EDC-NHS/Ab/BSA/CEA/GCE electrode was placed in a 0.2M Ascorbic Acid (AA) solution for photoelectrochemical detection (AA was used as an electron gain-loss donor in this experiment). All experiments used a traditional three-electrode system with the GCE electrode as the working electrode, the platinum mesh as the counter electrode, and the Saturated Calomel Electrode (SCE) as the reference electrode. A visible light source is simulated by using a xenon lamp to irradiate the surface of the GCE electrode, the shading interval time is controlled to be adjustable on-off, and then an electrochemical workstation is used for photoelectrochemical detection.
Performance testing
Ag nanowires, AuAg nanowires and AuAg @ WP5/RGO-C3N4Topography determination of
FIG. 1 (a-C) shows Ag nanowires, AuAg nanowires and AuAg @ WP5/RGO-C prepared in step 1 of example 1, respectively3N4Transmission electron micrographs. From the graphs (a, b), the prepared Ag and AuAg nanowires have good dispersibility and the diameter of about 70 nm. From the graph (d-f), it can be seen that the Au element of the prepared AuAg nanowire is uniformly distributed on the outer ring of the Ag nanowire. Panel (C) shows RGO-C prepared3N4The AuAg nano-wires are relatively uniformly dispersed in the RGO-C3N4In the sheet of (A), AuAg @ WP5/RGO-C is illustrated3N4And (4) successfully preparing the composite material.
XRD powder diffraction and infrared characterization of Au NPs @ WP5/BiOBr composite.
FIG. 2(a) is RGO-C3N4、AuAg@WP5、AuAg@WP5/RGO-C3N4The XRD powder diffractogram of the composite material can be seen from the figure, for Au NPs @ WP5/BiOBr, crystal planes (101), (102), (110), (200) and (212) of BiOBr are respectively at 21.51 DEG, 25.07 DEG, 25.29 DEG, 43.90 DEG and 57.53 DEG, crystal planes (111), (200) and (311) of Au NPs are respectively present at 38.34 DEG, 42.96 DEG and 78.68 DEG, and the result shows that AuAg @ WP5/RGO-C3N4And (4) successfully synthesizing the composite material.
3. Electrochemical characterization
As shown in FIG. 3a, by adding 5.0mM K3[Fe(CN)6]/K4[Fe(CN)6]And cyclic voltammograms in 0.1M KCl solution to explore AuAg @ WP5/RGO-C3N4/GCE、AuAg@WP5/RGO-C3N4/Ab/GCE、AuAg@WP5/RGO-C3N4Ab/BSA/GCE and AuAg @ WP5/RGO-C3N4Electrochemical activity of/Ab/BSA/CEA/GCE. It can be seen from the figure that the photocurrent gradually decreased with the Ab, BSA and CEA coating. This is because the protein substance is in AuAg @ WP5/RGO-C3N4The attachment to the electrode hinders the electron transfer rate of the system and to some extent the reaction of the electron donor with the photo-generated electron hole. The manufacturing process of the PEC immunosensor was also characterized by Electrochemical Impedance Spectroscopy (EIS). Figure 3b shows nyquist plots for different modified electrodes. As shown, the impedance spectrum includes a semicircular portion in the high frequency region and a linear portion in the low frequency region. After Ab anchoring (curve d), BSA blocking (curve c) and CEA specific binding (curve d), the resistance increases with increasing modification steps, which may be due to the non-conductive nature of the protein. The results also indicated successful fixation at each step. For all the above results, a label-free PEC immunosensor was successfully achieved
4. Detection of CEA
As shown in fig. 4, the concentration of CEA can be detected by monitoring the photocurrent intensity of the PEC immunosensor. The photocurrent response of the immunosensor was directly related to the concentration of CEA. Figure 5a shows that the photocurrent decreased with increasing CEA concentration. And FIG. 5b shows photocurrent response at 0.0005ng mL-1To 50ng mL-1Linearly decreasing with logarithmically increasing CEA concentration. The calibration equation is-0.9952 log c +2.8918 with a correlation coefficient of 0.9956. As the CEA concentration increases, more and more Ab-CEA binder binds specifically to the electrode surface, competitively absorbs the excitation light, partially consumes the AA electron donor and blocks electron transfer, resulting in a gradual decrease in photocurrent intensity. The PEC immunosensor showed a better detection limit of 0.33pg mL-1This suggests that the proposed biosensor may meet the improved requirements for future CEA analysis.
5. Stability, repeatability, interference immunity
Stability of
Stability is an important parameter for evaluating the fabricated sensors by modifying AuAg @ WP5/RGO-C in 0.2M AA solution3N4The corresponding test was carried out on the/Ab/BSA/CEA (CEA concentration 10ng/mL) electrode. After cycling for about 600 seconds, there was little change in photocurrent density, as shown in fig. 5 (a).
Repeatability:
under the same conditions, by using a solution of the three components in five parallel AuAg @ WP5/RGO-C3N4The reproducibility of the prepared PEC sensors was evaluated by measuring 0.2M AA solution on a/Ab/BSA/CEA electrode. The Relative Standard Deviation (RSD) was calculated to be 3.93%, which illustrates the excellent reproducibility of the sensor.
Anti-interference performance:
as shown in FIG. 5(b), to evaluate AuAg @ WP5/RGO-C3N4The selectivity of the/Ab/BSA/CEA electrode on CEA analysis is that glucose (Glu), Uric Acid (UA), Dopamine (DA) and bovine hemoglobin (BHb) are taken as anti-interference substances, and the concentration of each molecule is 100ng mL-1。AuAg@WP5/RGO-C3N4The corresponding photocurrent response on/Ab/BSA/CEA changed to the original (Ipa/Ip): 92.45%, 90.17%, 86.05%, 86.75%, while the photocurrent response of BHb was only 7.7% remaining. These results indicate that AuAg @ WP5/RGO-C3N4the/Ab/BSA/CEA electrode has higher selectivity on the template protein BHb.
Selectivity is also a very important criterion for immunoassays, and may be affected by non-specific adsorption. As shown in FIG. 5(b), glucose (Glu) and urine were selectedAcid (UA), Dopamine (DA) and bovine hemoglobin (BHb) were used for interference testing. All samples were under the same experimental conditions. The specificity of the biosensor is determined by measuring 10ng mL-1Evaluation of the photocurrent response of CEA containing 100ng mL of each-1A solution of an interfering substance. The standard deviation (RSD) of PEC response of different materials is 1.4-3.2%, and the PEC immunosensor is proved to have good selectivity.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (7)
1. AuAg @ WP5/RGO-C3N4A composite material characterized by: from a layered RGO-C3N4The surface is loaded with AuAg @ WP5 to prepare AuAg @ WP5/RGO-C3N4A composite material.
2. AuAg @ WP5/RGO-C3N4The preparation method of the composite material is characterized by comprising the following steps: the preparation method comprises the following specific steps:
in a first step, a water soluble column aromatic hydrocarbon (WP 5):
step two, preparing Ag nanowires: 10mL of a solution containing 150mM polyvinylpyrrolidone (PVP, M)w58000) of 1, 2-propanediol is added into a 25mL flask, and the flask is heated and stirred for 1h in an oil bath pot at the temperature of 160 ℃ and the rotating speed of 600 r/min; then 1mL of 1, 2-propanediol containing 1mM NaCl was injected; after 5min 4mL of 0.15M AgNO was added dropwise31 of (a) or (b) is,2-propylene glycol, reacting for 40min to prepare a silver-white Ag nanowire crude solution, centrifuging 5 times by using deionized water at 7000r/min to obtain a pure Ag nanowire, and dispersing the centrifuged Ag nanowire in 20mL of deionized water for storage;
thirdly, preparing the AuAg alloy nanowire by adopting a displacement method;
fourthly, preparing AuAg @ WP5 by adopting a ligand exchange method: taking 0.7mL of AuAg alloy nanowire, adding 4.3mL of deionized water, adding 6.31mg of WP5, controlling the rotating speed at 600r/min, stirring for 1.5h, and preparing the AuAg @ WP5 composite material;
the fifth step, preparation of RGO and RGO-C3N4A composite material;
and a sixth step: successively drop-coating RGO-C3N4And AuAg @ WP5 to the surface of a glassy carbon electrode to prepare AuAg @ WP5/RGO-C3N4a/GCE composite material.
3. AuAg @ WP5/RGO-C3N4The application of the composite material in the photoelectric detection of carcinoembryonic antigen (CEA) is characterized by comprising the following steps:
step 1, AuAg @ WP5/RGO-C3N4Coating on the surface of a glassy carbon electrode GCE: 10 μ L of RGO-C were successively applied dropwise3N4And 10. mu.L of AuAg @ WP5 to the surface of a glassy carbon electrode to prepare AuAg @ WP5/RGO-C3N4a/GCE nanocomposite electrode;
step 2, AuAg @ WP5/RGO-C in step 1 above3N4The surface of the/GCE nano composite electrode is coated with 5 mu L of EDC-NHS and stored in an oven at 37 ℃ for 1h to activate-COOH to prepare AuAg @ WP5/RGO-C3N4EDC-NHS/GCE electrode;
step 3, AuAg @ WP5/RGO-C in step 2 above3N45 μ L of 10 μ g/mL Ab was coated on the surface of the/EDC-NHS/GCE electrode and incubated in an oven at 37 ℃ for 1h to prepare AuAg @ WP5/RGO-C3N4EDC-NHS/Ab/GCE electrode;
step 4, AuAg @ WP5/RGO-C in step 3 above3N4the/EDC-NHS/Ab/GCE electrode was coated with 5. mu.L of 1% Bovine Serum Albumin (BSA) and incubated in an oven at 37 deg.C1h, preparation of AuAg @ WP5/RGO-C3N4EDC-NHS/Ab/BSA/GCE electrode;
step 5, AuAg @ WP5/RGO-C in step 4 above3N4EDC-NHS/Ab/BSA/GCE electrode surface was coated with 5. mu.L of different concentrations (0.0005ng mL)-1-50ng mL-1) The CEA of (a), was incubated in an oven at 37 ℃ for 1h to prepare AuAg @ WP5/RGO-C3N4EDC-NHS/Ab/BSA/CEA/GCE electrode detection solution Ascorbic Acid (AA) solution, AA as electron gain and loss donor in this experiment.
4. AuAg @ WP5/RGO-C according to claim 33N4The application of the composite material in the photoelectric detection of carcinoembryonic antigen (CEA) is characterized in that: the AuAg @ WP5/RGO-C3N4The composite material is AuAg @ WP5/RGO-C3N4the/EDC-NHS/Ab/BSA/CEA/GCE electrode is placed in Ascorbic Acid (AA) solution for photoelectrochemical detection, and AA is used as an electron gain-loss donor; all experiments used a traditional three-electrode system with the GCE electrode as the working electrode, the platinum mesh as the counter electrode, and the Saturated Calomel Electrode (SCE) as the reference electrode.
5. The AuAg @ WP5/RGO-C of claim 23N4The preparation method of the composite material is characterized by comprising the following steps: the third step of preparing the AuAg alloy nanowire by adopting a displacement method comprises the following specific steps:
s1: mu.L of HAuCl4(25.4mM), 2mL of NaOH solution and 17.9mL of deionized water were added thereto, and the mixture was stirred at room temperature for 1 hour to prepare 0.1mM Au (OH)4 -With 20mM NaOH;
s2: taking 1mL of 40mg/mL PVP, adding 2mL of deionized water, heating at 60 ℃, dropwise adding 500 mu L of ascorbic acid (AA,100mM) and 500 mu L of NaOH (200mM) solution after 2min, and controlling the rotation speed to be 400r/min during reaction (the subsequent heating temperature and stirring speed are unchanged);
s3: after 5min, 700 μ L of the Ag nanowire solution prepared in the second step is added;
s4: after 10min, the solution in S1 was added dropwise;
s5: and stopping the reaction after 10min, and centrifuging the reaction mixed solution for 5 times by using deionized water at 7000rpm to obtain the pure AuAg alloy nanowire.
6. The AuAg @ WP5/RGO-C of claim 23N4A method for preparing a composite material, characterized in that RGO and RGO-C are prepared in the fifth step3N4The composite material comprises the following specific steps:
(1) preparing a Reduced Graphene (RGO) dispersion: adding 14mg of Graphene Oxide (GO) and 10mL of deionized water into a flask, stirring at a rotating speed of 600r/min for two hours to obtain a Reduced Graphene Oxide (RGO) dispersion liquid;
(2) adding the prepared Reduced Graphene (RGO) dispersion liquid and 46mL of ethanol into a reaction kettle, adjusting the pH to 9 by using a 1M KOH solution, then placing the reaction kettle in an oven at 80 ℃ for reaction for two hours, finally centrifugally rinsing the black suspension by using deionized water, uniformly dispersing the black suspension in 23mL of deionized water, carrying out centrifugal washing at the centrifugal rotation speed of 7000r/min for 3 times to obtain 0.6 mg/mLRGO;
(3)11mg C3N4the powder was mixed well with 4.4mL of isopropanol to prepare 2.5mg/mL of C3N4Suspension, and mixing 1mL of RGO with 1mL of C3N4Mixing and stirring at the rotating speed of 600r/min to prepare the RGO-C with the mass ratio of 1:13N4And (3) a complex suspension.
7. AuAg @ WP5/RGO-C according to claim 33N4The application of the composite material in the photoelectric detection of carcinoembryonic antigen (CEA) is characterized in that: the EDC-NHS in the step 2 is prepared by a mixed solution of EDC and 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and a mixed solution of NHS and N-hydroxysuccinimide according to the dosage ratio of 1:1, wherein the EDC is 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and is 400 mM/L; NHS: n-hydroxysuccinimide, 100 mM/L.
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