CN114235917B - AuAg@WP5/RGO-C3N4Composite material, preparation method and application thereof - Google Patents
AuAg@WP5/RGO-C3N4Composite material, preparation method and application thereof Download PDFInfo
- Publication number
- CN114235917B CN114235917B CN202111452047.8A CN202111452047A CN114235917B CN 114235917 B CN114235917 B CN 114235917B CN 202111452047 A CN202111452047 A CN 202111452047A CN 114235917 B CN114235917 B CN 114235917B
- Authority
- CN
- China
- Prior art keywords
- rgo
- auag
- electrode
- cea
- edc
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000463 material Substances 0.000 title abstract description 7
- 102000012406 Carcinoembryonic Antigen Human genes 0.000 claims abstract description 59
- 108010022366 Carcinoembryonic Antigen Proteins 0.000 claims abstract description 59
- 239000002131 composite material Substances 0.000 claims abstract description 39
- 239000002070 nanowire Substances 0.000 claims abstract description 28
- 238000001514 detection method Methods 0.000 claims abstract description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 15
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 46
- 108091003079 Bovine Serum Albumin Proteins 0.000 claims description 30
- 229940098773 bovine serum albumin Drugs 0.000 claims description 30
- 239000008367 deionised water Substances 0.000 claims description 28
- 229910021641 deionized water Inorganic materials 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 26
- 229960005070 ascorbic acid Drugs 0.000 claims description 23
- 235000010323 ascorbic acid Nutrition 0.000 claims description 23
- 239000011668 ascorbic acid Substances 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 15
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 13
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide Substances CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 claims description 12
- 239000000956 alloy Substances 0.000 claims description 12
- 229910045601 alloy Inorganic materials 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 12
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 11
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 9
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 9
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 9
- 229960004063 propylene glycol Drugs 0.000 claims description 9
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 8
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 238000002474 experimental method Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000002114 nanocomposite Substances 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 235000013772 propylene glycol Nutrition 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 101710134784 Agnoprotein Proteins 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 230000001276 controlling effect Effects 0.000 claims description 3
- 239000012045 crude solution Substances 0.000 claims description 3
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 3
- 238000011549 displacement method Methods 0.000 claims description 3
- 239000003446 ligand Substances 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 238000006467 substitution reaction Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 230000005693 optoelectronics Effects 0.000 claims 4
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 230000000536 complexating effect Effects 0.000 abstract description 2
- 206010028980 Neoplasm Diseases 0.000 abstract 1
- 230000001133 acceleration Effects 0.000 abstract 1
- 239000000427 antigen Substances 0.000 abstract 1
- 102000036639 antigens Human genes 0.000 abstract 1
- 108091007433 antigens Proteins 0.000 abstract 1
- 201000011510 cancer Diseases 0.000 abstract 1
- 229910002804 graphite Inorganic materials 0.000 abstract 1
- 239000010439 graphite Substances 0.000 abstract 1
- 210000001161 mammalian embryo Anatomy 0.000 abstract 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 abstract 1
- 238000006479 redox reaction Methods 0.000 abstract 1
- 239000011540 sensing material Substances 0.000 abstract 1
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 12
- 239000010931 gold Substances 0.000 description 9
- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical compound N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-UHFFFAOYSA-N 0.000 description 6
- TVWHNULVHGKJHS-UHFFFAOYSA-N Uric acid Natural products N1C(=O)NC(=O)C2NC(=O)NC21 TVWHNULVHGKJHS-UHFFFAOYSA-N 0.000 description 6
- 229960003638 dopamine Drugs 0.000 description 6
- 229910052737 gold Inorganic materials 0.000 description 6
- 230000004044 response Effects 0.000 description 6
- 229940116269 uric acid Drugs 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 5
- 239000011258 core-shell material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 241000283690 Bos taurus Species 0.000 description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 3
- 102000001554 Hemoglobins Human genes 0.000 description 3
- 108010054147 Hemoglobins Proteins 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000008103 glucose Substances 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 230000036039 immunity Effects 0.000 description 3
- 238000003018 immunoassay Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 241001120493 Arene Species 0.000 description 2
- 206010009944 Colon cancer Diseases 0.000 description 2
- 229920000858 Cyclodextrin Polymers 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- VTJUKNSKBAOEHE-UHFFFAOYSA-N calixarene Chemical class COC(=O)COC1=C(CC=2C(=C(CC=3C(=C(C4)C=C(C=3)C(C)(C)C)OCC(=O)OC)C=C(C=2)C(C)(C)C)OCC(=O)OC)C=C(C(C)(C)C)C=C1CC1=C(OCC(=O)OC)C4=CC(C(C)(C)C)=C1 VTJUKNSKBAOEHE-UHFFFAOYSA-N 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000011984 electrochemiluminescence immunoassay Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 230000002496 gastric effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 206010006187 Breast cancer Diseases 0.000 description 1
- 208000026310 Breast neoplasm Diseases 0.000 description 1
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- 208000001333 Colorectal Neoplasms Diseases 0.000 description 1
- 238000002965 ELISA Methods 0.000 description 1
- 102000003886 Glycoproteins Human genes 0.000 description 1
- 108090000288 Glycoproteins Proteins 0.000 description 1
- 206010058467 Lung neoplasm malignant Diseases 0.000 description 1
- 206010061902 Pancreatic neoplasm Diseases 0.000 description 1
- 208000005718 Stomach Neoplasms Diseases 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 230000036952 cancer formation Effects 0.000 description 1
- 231100000504 carcinogenesis Toxicity 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000021164 cell adhesion Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 208000029742 colonic neoplasm Diseases 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- MSBXTPRURXJCPF-DQWIULQBSA-N cucurbit[6]uril Chemical compound N1([C@@H]2[C@@H]3N(C1=O)CN1[C@@H]4[C@@H]5N(C1=O)CN1[C@@H]6[C@@H]7N(C1=O)CN1[C@@H]8[C@@H]9N(C1=O)CN([C@H]1N(C%10=O)CN9C(=O)N8CN7C(=O)N6CN5C(=O)N4CN3C(=O)N2C2)C3=O)CN4C(=O)N5[C@@H]6[C@H]4N2C(=O)N6CN%10[C@H]1N3C5 MSBXTPRURXJCPF-DQWIULQBSA-N 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 229940097362 cyclodextrins Drugs 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 206010017758 gastric cancer Diseases 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 210000004072 lung Anatomy 0.000 description 1
- 201000005202 lung cancer Diseases 0.000 description 1
- 208000020816 lung neoplasm Diseases 0.000 description 1
- 208000015486 malignant pancreatic neoplasm Diseases 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003550 marker Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 201000002528 pancreatic cancer Diseases 0.000 description 1
- 208000008443 pancreatic carcinoma Diseases 0.000 description 1
- 230000009237 prenatal development Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 210000002966 serum Anatomy 0.000 description 1
- 230000009870 specific binding Effects 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 201000011549 stomach cancer Diseases 0.000 description 1
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Powder Metallurgy (AREA)
Abstract
The application discloses an AuAg@WP5/RGO-C 3N4 composite material, a preparation method thereof and application thereof in Photoelectrochemical (PEC) detection of carcinoembryonic antigen (CEA). A layer of water-soluble column [5] arene (WP 5) is wrapped on the surface of the AuAg nanowire, auAg@WP5 loaded on a reduced graphene and graphite carbon nitride composite material (RGO-C 3N4) is taken as a photoactive material, and a novel signal switch type Photoelectrochemistry (PEC) biosensing system is designed and used for detecting Cancer Embryo Antigens (CEA). This is the first time that AuAg@WP5/RGO-C 3N4 is used as the sensing material. The CEA is detected by utilizing the local surface plasma effect of the AuAg nanowire under visible light, the main guest complexing action of water-soluble column arene (WP 5), the high conductivity of RGO, the extraordinary thermochemical stability and the photo-generated electron-hole acceleration redox reaction of C 3N4 under visible light. Based on the multiple signal amplifying capabilities of auag@wp5/RGO-C 3N4, CEA detection linearity ranges from 0.0005 ng mL ‑1-50 ng mL‑1 with a detection limit of 0.17 pg mL ‑1 (S/n=3).
Description
Technical Field
The invention belongs to the technical field of photoelectrochemistry, and particularly relates to an AuAg@WP5/RGO-C 3N4 composite material as well as a preparation method and application thereof.
Background
Carcinoembryonic antigen (CEA) is a group of highly related glycoproteins that are involved in cell adhesion. It was first discovered in 1965 in human colon cancer tissue extracts by Canadian Phil Gold and Samuel O.freedman. CEA is usually produced in gastrointestinal tissue during prenatal development, but ceases to be produced before birth. Thus, CEA is typically 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 of tumorigenesis such as gastric, pancreatic, colorectal, lung and breast cancer. Numerous methods of detecting CEA have been developed, such as enzyme-linked immunosorbent assays, fluorescent immunoassays, electrochemiluminescence and electrochemical immunoassays. Among them, electrochemiluminescence immunoassay (ECLI) is the standard method for CEA analysis, commonly used in hospital assays to determine CEA. However, these methods typically require complex and expensive optical equipment and accurate image recognition software, while Photoelectrochemical (PEC) technology has many advantages such as low cost, simple instrumentation, wide detection range, and high sensitivity. Therefore, in order to solve the above problems, it is necessary to develop a sensitive, reliable, low-cost detection method.
Graphene, one of the most promising two-dimensional materials, has attracted extensive attention in photoelectrochemistry research due to its high conductivity, exceptional thermochemical stability, high quality crystals, and the like. Importantly, the p-like conjugated backbone of C 3N4 and graphene makes it easier to bond. Therefore, the combination of RGO and C 3N4 not only can effectively solve the problems of the photo-generated electron-hole pair recombination and smaller specific surface area of C 3N4, but also can combine the advantages of RGO and C 3N4 in photoelectrochemistry application, for example, the strong synergistic effect of RGO and C 3N4 under irradiation of visible light can obviously enhance the photoelectrochemistry performance. The proper plasma material is designed by regulating or optimizing the shape, the size and the like of the plasma material, so that the method is one of effective ways for improving the catalytic performance of the catalyst. The surface plasmon resonance of the gold nanoparticles can promote the photo-adsorption of the BiOBr and improve the photoelectrochemical property of the gold nanoparticles. Gold nano-ions 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 nano particles with specific size and morphology can generate plasma resonance (SPR) through excitation illumination, so that photo-generated electron-hole recombination on the semiconductor photocatalyst can be inhibited, and the photo-generated current of the Au and Ag nano particles is increased, and therefore the Au and Ag nano particles can be used as an effective photocatalyst. Especially, au@Ag with a core-shell structure is beneficial to improving the electronic performance of the core-shell structure due to the changed lattice parameter and the electronic effect of the core-shell structure, so that the core-shell structure attracts attention of a plurality of scientific researchers. Meanwhile, macrocyclic hosts (cyclodextrins, calixarenes, cucurbiturils, etc.) have unique cavity structures that are not accessible in size and exhibit special properties. The column [ n ] arene is formed by connecting hydroquinone or derivatives thereof at the 2 and 5 positions by methylene (-CH 2 -) bridges. The column aromatics have a stronger rigid structure than the crown ethers and calixarenes; on the other hand, the column [ n ] arene is more easily modified than cyclodextrin and cucurbituril. As an emerging host family of macrocyclic arenes, pillar [ n ] arenes are receiving attention because of their novel rigid symmetrical columnar structure, hydrophobic electron donating cavities, unique and excellent guest functions, and edges of tunable functions. 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. Therefore, the AuAg@WP5 loaded on the surface of RGO-C 3N4 not only provides a novel hybrid nanomaterial, but also is expected to bring new performances, functions and applications.
Disclosure of Invention
The technical problems to be solved are 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, low efficiency, low speed, difficult operation and the like of the prior detection technology, and provides the AuAg@WP5/RGO-C 3N4 composite material and the preparation method and application thereof.
The technical scheme is as follows: in order to achieve the above purpose, the present application is realized by the following technical scheme:
An AuAg@WP5/RGO-C 3N4 composite material is prepared by loading Au Ag@WP5 on the surface of a layered RGO-C 3N4.
A preparation method of an AuAg@WP5/RGO-C 3N4 composite material comprises the following specific steps:
In the first step, water-soluble column aromatics (WP 5) are prepared:
；
Secondly, preparing Ag nano wires: 10 mL of 1, 2-propanediol containing 150 mM polyvinylpyrrolidone (PVP, M w =58000) was added to a 25 mL flask and heated and stirred in an oil bath at 160 ℃ and a rotation speed of 600 r/min for 1 hour; 1mL 1, 2-propanediol containing 1mM NaCl was then injected; after 5 min, dropwise adding 4mL of 1, 2-propylene glycol containing AgNO 3 of 0.15M, reacting 40 min to prepare a silvery white Ag nanowire crude solution, centrifuging 5 times with deionized water at 7000 r/min to obtain pure Ag nanowires, and dispersing the centrifuged Ag nanowires in deionized water of 20mL for preservation;
thirdly, preparing the AuAg alloy nanowire by adopting a displacement method;
Fourthly, preparing AuAg@WP5 by adopting a ligand exchange method: taking 0.7 mL AuAg alloy nanowire, adding 4.3 mL deionized water, adding 6.31 WP5 of mg, and stirring at a rotating speed of 600 r/min for 1.5 h to prepare an AuAg@WP5 composite material;
Fifthly, preparing RGO and RGO-C 3N4 composite materials;
Sixth step: and sequentially dripping RGO-C 3N4 and AuAg@WP5 on the surface of the glassy carbon electrode to prepare the AuAg@WP5/RGO-C 3N4/GCE composite material.
The application also discloses an application of the AuAg@WP5/RGO-C 3N4 composite material in photoelectric detection of carcinoembryonic antigen (CEA), which comprises the following steps:
Step 1, auAg@WP5/RGO-C 3N4 is coated and dripped on the surface of a glassy carbon electrode GCE: sequentially dripping 10 mu L of RGO-C 3N4 and 10 mu L of AuAg@WP5 on the surface of the glassy carbon electrode to prepare an AuAg@WP5/RGO-C 3N4/GCE nano composite electrode;
Step 2, dripping 5 mu L of EDC-NHS on the surface of the AuAg@WP5/RGO-C 3N4/GCE nano composite electrode in the step 1 and storing in a baking oven at 37 ℃ for 1h to activate-COOH, so as to prepare an AuAg@WP5/RGO-C 3N4/EDC-NHS/GCE electrode;
Step 3, dripping 5 mu L of 10 mu g/mL Ab on the surface of the AuAg@WP5/RGO-C 3N4/EDC-NHS/GCE electrode in the step 2, incubating 1h in a baking oven at 37 ℃ to prepare an AuAg@WP5/RGO-C 3N4/EDC-NHS/Ab/GCE electrode;
Step 4, dripping 5 mu L of 1% Bovine Serum Albumin (BSA) on the surface of the AuAg@WP5/RGO-C 3N4/EDC-NHS/Ab/GCE electrode in the step 3, and incubating for 1h in an oven at 37 ℃ to prepare an AuAg@WP5/RGO-C 3N4/EDC-NHS/Ab/BSA/GCE electrode;
Step 5, dripping 5 mu L of CEA with different concentrations (0.0005 ng.mL -1- 50 ng·mL-1) on the surface of the AuAg@WP5/RGO-C 3N4/EDC-NHS/Ab/BSA/GCE electrode in the step 4, incubating 1 h in an oven at 37 ℃ to prepare an AuAg@WP5/RGO-C 3N4/EDC-NHS/Ab/BSA/CEA/GCE electrode detection solution Ascorbic Acid (AA) solution, wherein AA is taken as an electron donor in the experiment.
As a preferred technical scheme of the invention: the AuAg@WP5/RGO-C 3N4 composite material is an AuAg@WP5/RGO-C 3N4/EDC-NHS/Ab/BSA/CEA/GCE electrode; the AuAg@WP5/RGO-C 3N4 composite material is formed by placing an AuAg@WP5/RGO-C 3N4/EDC-NHS/Ab/BSA/CEA/GCE electrode in an Ascorbic Acid (AA) solution for photoelectrochemical detection, wherein the AA is used as an electron donor; all experiments used a conventional three electrode system with a GCE electrode as the working electrode, a platinum mesh as the counter electrode, and a Saturated Calomel Electrode (SCE) as the reference electrode.
As a preferred technical scheme of the invention: the specific steps of preparing the AuAg alloy nanowire by adopting the substitution method in the third step are as follows:
S1: 100. Mu.L of HAuCl 4 (25.4 mM) was added with 2mL of NaOH solution and 17.9 mL deionized water and stirred at room temperature for 1 h to prepare 0.1mM Au (OH) 4 − and 20 mM NaOH;
S2: taking 1 mL of PVP (polyvinyl pyrrolidone) of 40 mg/mL, adding 2 mL of deionized water, heating at 60 ℃, dropwise adding 500 mu L of ascorbic acid (AA, 100 mM) and 500 mu L of NaOH (200 mM) solution into the mixture after 2 min of deionized water, and controlling the rotating speed to be 400 r/min (the subsequent heating temperature and stirring speed are unchanged) in the reaction;
S3: after 5 min, 700 μl of the Ag nanowire solution prepared in the second step was added;
s4:10 After min, dropwise adding the solution in the step S1;
s5:10 After the min, the reaction is stopped, and the reaction mixture is centrifuged for 5 times with deionized water at 7000 rpm to obtain pure AuAg alloy nano-wires.
As a preferred technical scheme of the invention: the preparation method of the RGO and RGO-C 3N4 composite material in the fifth step comprises the following specific steps:
(1) Preparing a reduced graphene RGO dispersion liquid: adding 14 mg graphene oxide GO and 10 mL deionized water into a flask, stirring at the rotating speed of 600 r/min, and stirring for two hours to obtain a reduced graphene RGO dispersion;
(2) Adding the prepared reduced graphene RGO dispersion liquid and 46 mL ethanol into a reaction kettle, regulating the pH value 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 deionized water, uniformly dispersing the black suspension in 23 mL deionized water, and centrifugally washing for 3 times at a centrifugal speed of 7000 r/min to obtain RGO of 0.6 mg/mL;
(3) 11 mg C 3N4 powder and 4.4. 4.4 mL isopropyl alcohol were thoroughly mixed to prepare a 2.5. 2.5 mg/mL C 3N4 suspension, and RGO of 1.1mL was mixed with 1mL C 3N4 and stirred at 600: 600 r/min to prepare a RGO-C 3N4 complex suspension having a mass ratio of 1:1.
As a preferred technical scheme of the invention: the EDC-NHS in the step2 is prepared from 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, 400 mM/L; NHS: n-hydroxysuccinimide, 100 mM/L.
The beneficial effects are that: the application provides an AuAg@WP5/RGO-C 3N4 composite material and a preparation method and application thereof, and compared with the prior art, the AuAg@WP5/RGO-C 3N4 composite material has the following beneficial effects:
The application designs an AuAg nanowire material forming LSPR effect under visible light, and an RGO-C 3N4 composite material with large specific surface area and good conductivity, which has the complexing ability with a host and guest, and is used for the photoelectrochemical detection of carcinoembryonic antigen (CEA).
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 original detection technology.
3. The detection range of the application is 0.001-50 ng.mL -1, and the detection limit is 0.33 pg.mL -1 (S/N).
Drawings
FIG. 1 is a transmission electron microscope image of an Ag nanowire (a), an AuAg nanowire (b), and an AuAg@WP5/RGO-C 3N4 (C) in the present application.
FIG. 2 is an XRD powder diffraction pattern (a) of RGO-C 3N4、AuAg@WP5、AuAg@WP5/ RGO-C3N4 and an infrared spectrum (b) of WP5, RGO-C 3N4、AuAg@WP5、AuAg@WP5/RGO-C3N4 in the present application.
FIG. 3 is a Cyclic Voltammogram (CVs) (a), nyquist diagram (EIS) (b) plot of AuAg@WP5/RGO-C3N4、AuAg@WP5/RGO-C3N4/Ab、AuAg@WP5/RGO-C3N4/Ab/BSA and AuAg@WP5/RGO-C 3N4/Ab/BSA/CEA modified glassy carbon electrode in 5 mM K 3[Fe(CN)6]/ K4[Fe(CN)6 ] and 0.1M KCl of the present application.
FIG. 4 is a graph of the i-c curve (a), linear calibration curve (b) for the biosensor pair of the present application for 0.0005, 0.001, 0.01, 0.02, 0.05, 0.1, 0.5, 1.0, 5.0, 10.0 and 50.0 ng mL -1 CEA.
FIG. 5 is a time-current curve (a) of an AuAg@WP5/RGO-C 3N4/Ab/BSA/CEA modified glassy carbon electrode of the present application at a CEA concentration of 10.0 ng/mL, the interference immunity (b) of the PEC biosensor to CEA, a being 10 ng.mL - 1CEA+100 ng·mL-1 glucose (Glu); b is 10 ng.mL -1CEA +100 ng·mL-1 Uric Acid (UA); c is 10 ng.mL -1CEA + 100 ng·mL-1 Dopamine (DA); d is 10ng mL -1CEA + 100 ng·mL-1 bovine hemoglobin (BHb) and e is 10ng mL -1 CEA.
FIG. 6 is a flow chart of the synthesis method of WP5 of the application.
Detailed Description
The invention is further described below with reference to examples, which are intended to be illustrative only and not to limit the scope of the claims, as other alternatives, which can be envisaged by a person skilled in the art, are within the scope of the claims.
Examples
A preparation method of an AuAg@WP5 and RGO-C 3N4 composite material comprises the following steps:
In the first step, water-soluble column aromatics (WP 5) are prepared as shown in fig. 6:
；
Secondly, preparing Ag nano wires: 10 mL of 1, 2-propanediol containing 150 mM polyvinylpyrrolidone (PVP, M w =58000) was added to a flask of 25mL and stirred with heating in an oil bath at 160 ℃ at a stirring speed of 600 r/min for 1 hour; 1mL 1, 2-propanediol containing 1 mM NaCl was then injected; after 5 min, dropwise adding 4 mL of 1, 2-propylene glycol containing AgNO 3 of 0.15M, reacting 40 min to prepare a silvery white Ag nanowire crude solution, centrifugally washing 5 times with deionized water at 7000 r/min to obtain pure Ag nanowires, dispersing the centrifuged Ag nanowires in deionized water of 20 mL, and preserving;
thirdly, preparing the AuAg alloy nanowire by adopting a displacement method;
Fourthly, preparing AuAg@WP5 by adopting a ligand exchange method: taking 0.7 mL AuAg alloy nanowire, adding 4.3 mL deionized water, adding 6.31 WP5 of mg, and stirring at a rotating speed of 600 r/min for 1.5 h to prepare an AuAg@WP5 composite material;
Fifthly, preparing RGO and RGO-C 3N4 composite materials;
Step six, sequentially dripping RGO-C 3N4 and AuAg@WP5 on the surface of the glassy carbon electrode to prepare an AuAg@WP5/RGO-C 3N4/GCE composite material: the preparation method of the RGO and RGO-C 3N4 composite material comprises the following specific steps:
(1) Preparing a reduced graphene RGO dispersion liquid: adding 14 mg graphene oxide GO and 10 mL deionized water into a flask, stirring at the rotating speed of 600 r/min, and stirring for two hours to obtain a reduced graphene RGO dispersion;
(2) Adding the prepared reduced graphene RGO dispersion liquid and 46 mL ethanol into a reaction kettle, regulating the pH value 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 deionized water, uniformly dispersing the black suspension in 23 mL deionized water, and centrifugally washing for 3 times at a centrifugal speed of 7000 r/min to obtain RGO of 0.6 mg/mL;
(3) 11 mg C 3N4 powder and 4.4. 4.4 mL isopropyl alcohol were thoroughly mixed to prepare a 2.5. 2.5 mg/mL C 3N4 suspension, and RGO of 1.1mL was mixed with 1mL C 3N4 and stirred at 600: 600 r/min to prepare a RGO-C 3N4 complex suspension having a mass ratio of 1:1.
The specific steps of preparing the AuAg alloy nanowire by adopting the substitution method in the third step are as follows:
S1: 100. Mu.L of HAuCl 4 (25.4 mM) was added with 2mL of NaOH solution and 17.9 mL deionized water and stirred at room temperature for 1 h to prepare 0.1mM Au (OH) 4 − and 20 mM NaOH;
S2: 1mL of 40 mg/mL PVP was taken, 2 mL deionized water was added, heated at 60℃and 2 min, to which 500. Mu.L of ascorbic acid (AA, 100 mM) and 500. Mu.L of NaOH (200 mM) solution were added dropwise;
S3: after 5min, 700 μl of the Ag nanowire solution prepared in the second step was added;
s4:10 After min, dropwise adding the solution in the step S1;
s5:10 After the min, the reaction is stopped, and the reaction mixture is centrifuged for 5 times with deionized water at 7000 rpm to obtain pure AuAg alloy nano-wires.
Example 2:
the application of the AuAg@WP5/RGO-C 3N4 composite material in photoelectric detection of carcinoembryonic antigen (CEA) comprises the following steps:
Step 1, auAg@WP5/RGO-C 3N4 is coated and dripped on the surface of a glassy carbon electrode GCE: sequentially dripping 10 mu L of RGO-C 3N4 and 10 mu L of AuAg@WP5 on the surface of the glassy carbon electrode to prepare an AuAg@WP5/RGO-C 3N4/GCE nano composite electrode;
Step 2, dripping 5 mu L of EDC-NHS on the surface of the AuAg@WP5/RGO-C 3N4/GCE nano composite electrode in the step 1 and storing in a baking oven at 37 ℃ for 1h to activate-COOH, so as to prepare an AuAg@WP5/RGO-C 3N4/EDC-NHS/GCE electrode; the EDC-NHS in the step 2 is prepared from 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, 400 mM/L; NHS: n-hydroxysuccinimide, 100 mM/LL.
Step 3, dripping 5 mu L of 10 mu g/mL Ab on the surface of the AuAg@WP5/RGO-C 3N4/EDC-NHS/GCE electrode in the step 2, incubating 1h in a baking oven at 37 ℃ to prepare an AuAg@WP5/RGO-C 3N4/EDC-NHS/Ab/GCE electrode;
step 4, dripping 5 mu L of 1% Bovine Serum Albumin (BSA) on the surface of the AuAg@WP5/RGO-C 3N4/EDC-NHS/Ab/GCE electrode in the step 3, incubating 1h in an oven at 37 ℃ to prepare an AuAg@WP5/RGO-C 3N4/EDC-NHS/Ab/BSA/GCE electrode;
Step 5, dripping 5 mu L of CEA with different concentrations (0.0005, 0.01, 0.02, 0.05, 0.1, 0.5, 1.0, 5.0, 10.0, 50.0 ng/mL) on the surface of the AuAg@WP5/RGO-C 3N4/EDC-NHS/Ab/BSA/GCE electrode in the step 4, and incubating 1 h in an oven at 37 ℃ to prepare the AuAg@WP5/RGO-C 3N4/EDC-NHS/Ab/BSA/CEA/GCE electrode.
Example 3:
The AuAg@WP5/RGO-C 3N4/EDC-NHS/Ab/BSA/CEA/GCE electrode was placed in 0.2M Ascorbic Acid (AA) solution for photoelectrochemical detection (AA was used as electron donor in this experiment). All experiments used a conventional three electrode system with a GCE electrode as the working electrode, a platinum mesh as the counter electrode, and a Saturated Calomel Electrode (SCE) as the reference electrode. And simulating a visible light source by using a xenon lamp to irradiate the surface of the GCE electrode, controlling the shading interval time as adjustable on-off, and then carrying out photoelectrochemical detection by using an electrochemical workstation.
Performance testing
1. Morphology determination of Ag nanowires, auAg nanowires and AuAg@WP5/RGO-C 3N4
FIG. 1 (a-C) is a transmission electron microscope image of the Ag nanowire, the AuAg nanowire and the AuAg@WP5/RGO-C 3N4 prepared in step 1 of example 1, respectively. It can be seen from the figures (a, b) that the prepared Ag and AuAg nanowires have good dispersibility and a diameter of about 70 nm. Fig. (C) shows that the prepared RGO-C 3N4 is in a layered structure, and the augg nanowires are relatively uniformly dispersed in the lamellae of RGO-C 3N4, demonstrating the successful preparation of the augg@wp5/RGO-C 3N4 composite.
2. XRD powder diffraction and infrared characterization of the composite.
FIG. 2 (a) is an XRD powder diffraction pattern of RGO-C 3N4、AuAg@WP5、AuAg@WP5/RGO-C3N4 composite, indicating successful synthesis of AuAg@WP5/RGO-C 3N4 composite.
3. Electrochemical characterization
The electrochemical activity of AuAg@WP5/RGO-C3N4/GCE、AuAg@WP5/RGO-C3N4/Ab/GCE、AuAg@WP5/RGO-C3N4/Ab/BSA/GCE and AuAg@WP5/RGO-C 3N4/Ab/BSA/CEA/GCE was studied by cyclic voltammograms in solutions containing 5.0 mM K 3[Fe(CN)6]/K4[Fe(CN)6 and 0.1M KCl, as shown in FIG. 3 a. It can be seen from the figure that the photocurrent gradually decreased with the dripping of Ab, BSA and CEA. This is because the attachment of proteinaceous material to the AuAg@WP5/RGO-C 3N4 electrode impedes the electron transfer rate of the system and to some extent the reaction of the electron donor with the photogenerated electron holes. The manufacturing process of PEC immunosensors is also characterized by Electrochemical Impedance Spectroscopy (EIS). Fig. 3 b shows the nyquist plot 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 increased with the addition of the modification step, possibly due to the non-conductive nature of the protein. The results also indicate successful immobilization for each step. For all of the above results, a label-free PEC immunosensor was successfully implemented
4. CEA detection
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 is directly related to the concentration of CEA. Fig. 4 (b) shows that the photocurrent decreases with increasing CEA concentration. And (a) in fig. 4 shows that the photocurrent response linearly decreases with increasing logarithm of CEA concentration in the range of 0.0005 ng-mL -1 to 50 ng-mL -1. The calibration equation is i= -0.9952 logc + 2.8918, and the correlation coefficient is 0.9956. As CEA concentration increases, more and more Ab-CEA conjugates specifically bind to the electrode surface, competitively absorb excitation light, partially deplete AA electron donors and hinder electron transfer, resulting in a gradual decrease in photocurrent intensity. The PEC immunosensor exhibits a better detection limit of 0.33 pg-mL -1, indicating that the proposed biosensor may meet the improvement requirements of future CEA analysis.
5. Stability, repeatability, and interference immunity
Stability of
Stability is an important parameter in evaluating the fabricated sensor by performing corresponding tests on modified AuAg@WP5/RGO-C 3N4/Ab/BSA/CEA (CEA concentration 10 ng/mL) electrodes in 0.2M AA solution. After about 600 seconds of cycling, the photocurrent density was hardly changed as shown in fig. 5 (a).
Repeatability:
the reproducibility of the prepared PEC sensor was evaluated under the same conditions by measuring 0.2M AA solution on five parallel aucag@wp5/RGO-C 3N4/Ab/BSA/CEA electrodes. The Relative Standard Deviation (RSD) was calculated to be 3.93%, which demonstrates the excellent repeatability of the sensor.
Interference immunity:
As shown in fig. 5 (b), to evaluate the selectivity of the auag@wp5/RGO-C 3N4/Ab/BSA/CEA electrode to CEA analysis, we used glucose (Glu), uric Acid (UA), dopamine (DA) and bovine hemoglobin (BHb) as anti-interference substances, and the corresponding photocurrent response on each molecule was 100 ng ·ml -1.AuAg@WP5/ RGO-C3N4/Ab/BSA/CEA as the original (Ipa/Ip): 92.45 % 90.17%, 86.05%, 86.75%, while the photocurrent response of BHb is only 7.7%. These results indicate that the AuAg@WP5/RGO-C 3N4/Ab/BSA/CEA electrode has higher selectivity to template protein BHb.
Selectivity is also a very important criterion for immunoassays and may be affected by nonspecific adsorption. As shown in fig. 5 (b), glucose (Glu), uric Acid (UA), dopamine (DA) and bovine hemoglobin (BHb) were selected for the interference test. All samples were under the same experimental conditions. The specificity of the biosensor was evaluated by measuring the photocurrent response of 10 ng mL -1 CEA in a solution containing 100 ng mL -1 interfering substances, respectively. The standard deviation (RSD) of the PEC responses of different substances is 1.4-3.2%, and the PEC immunosensor has good selectivity.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments 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-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (5)
1. The application of the AuAg@WP5/RGO-C 3N4 composite material in photoelectric detection of carcinoembryonic antigen (CEA) is characterized in that the AuAg@WP5/RGO-C 3N4 composite material is prepared by loading Au Ag@WP5 on the surface of layered RGO-C 3N4, and the application specifically comprises the following steps:
Step 1, auAg@WP5/RGO-C 3N4 is coated and dripped on the surface of a glassy carbon electrode GCE: sequentially dripping 10 mu L of RGO-C 3N4 and 10 mu L of AuAg@WP5 on the surface of the glassy carbon electrode to prepare an AuAg@WP5/RGO-C 3N4/GCE nano composite electrode;
Step 2, dripping 5 mu L of EDC-NHS on the surface of the AuAg@WP5/RGO-C 3N4/GCE nano composite electrode in the step 1 and storing in a baking oven at 37 ℃ for 1h to activate-COOH, so as to prepare an AuAg@WP5/RGO-C 3N4/EDC-NHS/GCE electrode;
Step 3, dripping 5 mu L of 10 mu g/mL Ab on the surface of the AuAg@WP5/RGO-C 3N4/EDC-NHS/GCE electrode in the step 2, incubating 1h in a baking oven at 37 ℃ to prepare an AuAg@WP5/RGO-C 3N4/EDC-NHS/Ab/GCE electrode;
step 4, dripping 5 mu L of 1% Bovine Serum Albumin (BSA) on the surface of the AuAg@WP5/RGO-C 3N4/EDC-NHS/Ab/GCE electrode in the step 3, incubating 1h in an oven at 37 ℃ to prepare an AuAg@WP5/RGO-C 3N4/EDC-NHS/Ab/BSA/GCE electrode;
Step 5, respectively coating 5 mu L of CEA with different concentrations on the surface of the AuAg@WP5/RGO-C 3N4/EDC-NHS/Ab/BSA/GCE electrode in the step 4, incubating 1 h in a 37 ℃ oven, and preparing an Ascorbic Acid (AA) solution of an AuAg@WP5/RGO-C 3N4/EDC-NHS/Ab/BSA/CEA/GCE electrode detection solution, wherein AA is used as an electron donor in the experiment;
the AuAg@WP5/RGO-C 3N4 composite material is prepared by the following steps:
In the first step, water-soluble column aromatics (WP 5) are prepared:
；
Secondly, preparing Ag nano wires: adding 10 mL of 1, 2-propylene glycol containing 150 mM polyvinylpyrrolidone into 25 mL flask, heating at 160deg.C at 600 r/min, and stirring for 1 hr; 1 mL 1, 2-propanediol containing 1 mM NaCl was then injected; after 5min, dropwise adding 4 mL of 1, 2-propylene glycol containing AgNO 3 of 0.15M, reacting 40 min to prepare a silvery white Ag nanowire crude solution, centrifuging 5 times with deionized water at 7000 r/min to obtain pure Ag nanowires, and dispersing the centrifuged Ag nanowires in deionized water of 20 mL for preservation;
thirdly, preparing the AuAg alloy nanowire by adopting a displacement method;
Fourthly, preparing AuAg@WP5 by adopting a ligand exchange method: taking 0.7 mL AuAg alloy nanowire, adding 4.3 mL deionized water, adding 6.31 WP5 of mg, and stirring at a rotating speed of 600 r/min for 1.5 h to prepare an AuAg@WP5 composite material;
Fifthly, preparing RGO and RGO-C 3N4 composite materials;
Sixth step: and sequentially dripping RGO-C 3N4 and AuAg@WP5 on the surface of the glassy carbon electrode to prepare the AuAg@WP5/RGO-C 3N4/GCE composite material.
2. The use of the auag@wp5/RGO-C 3N4 composite material according to claim 1 in the optoelectronic detection of carcinoembryonic antigen (CEA), characterized in that: the AuAg@WP5/RGO-C 3N4 composite material is formed by placing an AuAg@WP5/RGO-C 3N4/EDC-NHS/Ab/BSA/CEA/GCE electrode in an Ascorbic Acid (AA) solution for photoelectrochemical detection, wherein the AA is used as an electron donor; all experiments used a conventional three electrode system with a GCE electrode as the working electrode, a platinum mesh as the counter electrode, and a Saturated Calomel Electrode (SCE) as the reference electrode.
3. The use of the auag@wp5/RGO-C 3N4 composite material according to claim 1 in the optoelectronic detection of carcinoembryonic antigen (CEA), characterized in that: the EDC-NHS in the step 2 is prepared from 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, 400 mM/L; NHS: n-hydroxysuccinimide, 100 mM/L.
4. The use of the auag@wp5/RGO-C 3N4 composite material according to claim 1 in the optoelectronic detection of carcinoembryonic antigen (CEA), characterized in that: the specific steps of preparing the AuAg alloy nanowire by adopting the substitution method in the third step are as follows:
S1: 100. Mu.L of HAuCl 4 was added with 2mL of NaOH solution and 17.9: 17.9 mL deionized water, and stirred at room temperature for 1.1 h to prepare 0.1: 0.1mM Au (OH) 4 − and 20: 20mM NaOH;
S2: taking PVP of 40 mg/mL of 1mL, adding deionized water of 2 mL, heating at 60 ℃, dropwise adding 500 mu L of ascorbic acid and 500 mu L of NaOH solution into the mixture after 2min ℃, and controlling the rotating speed to 400r/min in the reaction;
S3: after 5 min, 700 μl of the Ag nanowire solution prepared in the second step was added;
s4:10 After min, dropwise adding the solution in the step S1;
s5:10 After the min, the reaction is stopped, and the reaction mixture is centrifuged for 5 times with deionized water at 7000 rpm to obtain pure AuAg alloy nano-wires.
5. The use of the auag@wp5/RGO-C 3N4 composite material according to claim 1 in the optoelectronic detection of carcinoembryonic antigen (CEA), characterized in that: the preparation method of the RGO and RGO-C 3N4 composite material in the fifth step comprises the following specific steps:
(1) Preparing a Reduced Graphene (RGO) dispersion: adding 14 mg Graphene Oxide (GO) and 10 mL deionized water into a flask, stirring at a rotating speed of 600 r/min, and stirring for two hours to obtain a Reduced Graphene (RGO) dispersion;
(2) Adding the prepared Reduced Graphene (RGO) dispersion liquid and 46 mL ethanol into a reaction kettle, regulating 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 deionized water, uniformly dispersing the black suspension in 23 mL deionized water, centrifugally washing for 3 times at a centrifugal speed of 7000 r/min to obtain RGO of 0.6 mg/mL;
(3) 11 mg C 3N4 powder and 4.4. 4.4 mL isopropyl alcohol were thoroughly mixed to prepare a 2.5. 2.5 mg/mL C 3N4 suspension, and RGO of 1. 1 mL was mixed with 1 mL C 3N4 and stirred at 600: 600 r/min to prepare a RGO-C 3N4 complex suspension having a mass ratio of 1:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111452047.8A CN114235917B (en) | 2021-12-01 | 2021-12-01 | AuAg@WP5/RGO-C3N4Composite material, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111452047.8A CN114235917B (en) | 2021-12-01 | 2021-12-01 | AuAg@WP5/RGO-C3N4Composite material, preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114235917A CN114235917A (en) | 2022-03-25 |
| CN114235917B true CN114235917B (en) | 2024-05-03 |
Family
ID=80752577
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111452047.8A Active CN114235917B (en) | 2021-12-01 | 2021-12-01 | AuAg@WP5/RGO-C3N4Composite material, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114235917B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104391113A (en) * | 2014-12-17 | 2015-03-04 | 济南大学 | Preparation method and application of biosensor built based on gold copper nanowires and 3-mercaptopropyltriethoxysilane graphene |
| CN106111175A (en) * | 2016-06-20 | 2016-11-16 | 江苏大学 | A kind of preparation method of tri compound semi-conducting material |
| CN106442675A (en) * | 2016-11-01 | 2017-02-22 | 济南大学 | Preparation and application of carcino-embryonic antigen electrochemical immunosensor based on Au@Ag@Au marker |
| CN109283235A (en) * | 2018-11-13 | 2019-01-29 | 汕头大学 | One kind being based on NSCQDs/Bi2S3Optical electro-chemistry sensor and its preparation and application |
| CN109507256A (en) * | 2018-11-06 | 2019-03-22 | 商丘师范学院 | A kind of unmarked electrochemical luminescence aptamer sensor and preparation method thereof and application method detecting carcinomebryonic antigen |
| CN110124063A (en) * | 2019-04-18 | 2019-08-16 | 武汉中毅博生物科技有限公司 | A kind of multimode molecular probe and the preparation method and application thereof based on Supramolecular Assembling |
| CN110980666A (en) * | 2019-12-04 | 2020-04-10 | 山西大学 | g-C3N4Nano thin sheet/graphene oxide composite material and preparation method and application thereof |
| CN113189188A (en) * | 2021-04-16 | 2021-07-30 | 南通大学 | Preparation method and application of Au NPs @ WP5/BiOBr composite material |
-
2021
- 2021-12-01 CN CN202111452047.8A patent/CN114235917B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104391113A (en) * | 2014-12-17 | 2015-03-04 | 济南大学 | Preparation method and application of biosensor built based on gold copper nanowires and 3-mercaptopropyltriethoxysilane graphene |
| CN106111175A (en) * | 2016-06-20 | 2016-11-16 | 江苏大学 | A kind of preparation method of tri compound semi-conducting material |
| CN106442675A (en) * | 2016-11-01 | 2017-02-22 | 济南大学 | Preparation and application of carcino-embryonic antigen electrochemical immunosensor based on Au@Ag@Au marker |
| CN109507256A (en) * | 2018-11-06 | 2019-03-22 | 商丘师范学院 | A kind of unmarked electrochemical luminescence aptamer sensor and preparation method thereof and application method detecting carcinomebryonic antigen |
| CN109283235A (en) * | 2018-11-13 | 2019-01-29 | 汕头大学 | One kind being based on NSCQDs/Bi2S3Optical electro-chemistry sensor and its preparation and application |
| CN110124063A (en) * | 2019-04-18 | 2019-08-16 | 武汉中毅博生物科技有限公司 | A kind of multimode molecular probe and the preparation method and application thereof based on Supramolecular Assembling |
| CN110980666A (en) * | 2019-12-04 | 2020-04-10 | 山西大学 | g-C3N4Nano thin sheet/graphene oxide composite material and preparation method and application thereof |
| CN113189188A (en) * | 2021-04-16 | 2021-07-30 | 南通大学 | Preparation method and application of Au NPs @ WP5/BiOBr composite material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114235917A (en) | 2022-03-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Label-free electrochemical immunosensor based on flower-like Ag/MoS2/rGO nanocomposites for ultrasensitive detection of carcinoembryonic antigen | |
| Atar et al. | A novel QCM immunosensor development based on gold nanoparticles functionalized sulfur-doped graphene quantum dot and h-ZnS-CdS NC for Interleukin-6 detection | |
| Huang et al. | A disposable electrochemical immunosensor for carcinoembryonic antigen based on nano-Au/multi-walled carbon nanotubes–chitosans nanocomposite film modified glassy carbon electrode | |
| Wang et al. | Label-free photoelectrochemical immunoassay for α-fetoprotein detection based on TiO2/CdS hybrid | |
| Butmee et al. | An ultrasensitive immunosensor based on manganese dioxide-graphene nanoplatelets and core shell Fe3O4@ Au nanoparticles for label-free detection of carcinoembryonic antigen | |
| Yan et al. | Photoelectrochemical competitive immunosensor for 17β-estradiol detection based on ZnIn2S4@ NH2-MIL-125 (Ti) amplified by PDA NS/Mn: ZnCdS | |
| Gao et al. | An enzyme-free immunosensor for sensitive determination of procalcitonin using NiFe PBA nanocubes@ TB as the sensing matrix | |
| Hasanzadeh et al. | Ultrasensitive immunoassay of tumor protein CA 15.3 in MCF-7 breast cancer cell lysates and unprocessed human plasma using gold nanoparticles doped on the structure of mesoporous silica | |
| Ghanavati et al. | A novel label-free impedimetric immunosensor for sensitive detection of prostate specific antigen using Au nanoparticles/MWCNTs-graphene quantum dots nanocomposite | |
| Zhang et al. | Gold–silver nanocomposite-functionalized graphene sensing platform for an electrochemiluminescent immunoassay of a tumor marker | |
| Anusha et al. | Fabrication of electrochemical immunosensor based on GCN-β-CD/Au nanocomposite for the monitoring of vitamin D deficiency | |
| Zhang et al. | Label-free immunosensor based on Au@ Ag2S nanoparticles/magnetic chitosan matrix for sensitive determination of ractopamine | |
| Han et al. | A photoelectrochemical immunosensor for detection of α-fetoprotein based on Au-ZnO flower-rod heterostructures | |
| Hasanzadeh et al. | Ultrasensitive immunoassay of glycoprotein 125 (CA 125) in untreated human plasma samples using poly (CTAB‑chitosan) doped with silver nanoparticles | |
| Han et al. | Gold nanoparticles enhanced electrochemiluminescence of graphite-like carbon nitride for the detection of Nuclear Matrix Protein 22 | |
| Zhai et al. | Near-infrared-light-triggered photoelectrochemical biosensor for detection of alpha-fetoprotein based on upconversion nanophosphors | |
| Ge et al. | Photoelectrochemical detection of tumor markers based on a CdS quantum dot/ZnO nanorod/Au@ Pt-paper electrode 3D origami immunodevice | |
| Xu et al. | Renewable photoelectrochemical cytosensing platform for rapid capture and detection of circulating tumor cells | |
| Li et al. | Multi-amplification of the signal of voltammetric immunosensors: Highly sensitive detection of tumor marker | |
| Li et al. | Label-free photoelectrochemical biosensor for alpha-fetoprotein detection based on Au/CsxWO3 heterogeneous films | |
| Valverde et al. | Carbon/Inorganic Hybrid Nanoarchitectures as Carriers for Signaling Elements in Electrochemical Immunosensors: First Biosensor for the Determination of the Inflammatory and Metastatic Processes Biomarker RANK‐ligand | |
| Hu et al. | Layer-by-layer self-assembly of MoS2/PDDA hybrid film in microfluidic chips for ultrasensitive electrochemical immunosensing of alpha-fetoprotein | |
| Wang et al. | A paper-supported photoelectrochemical sensing platform based on surface plasmon resonance enhancement for real-time H 2 S determination | |
| Deng et al. | Electrochemiluminescence PSA assay using an ITO electrode modified with gold and palladium, and flower-like titanium dioxide microparticles as ECL labels | |
| Bajpai et al. | Au@ Zr-based metal–organic framework composite as an immunosensing platform for determination of hepatitis B virus surface antigen |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |