CN106959329A - A kind of metal esters complex Cu Dada and its preparation method and application - Google Patents
A kind of metal esters complex Cu Dada and its preparation method and application Download PDFInfo
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- sgc8c
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- 150000002148 esters Chemical class 0.000 title claims abstract description 59
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 49
- 239000002184 metal Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 90
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 48
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 43
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 43
- 108091023037 Aptamer Proteins 0.000 claims abstract description 19
- 230000004044 response Effects 0.000 claims abstract description 19
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Natural products C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000001548 drop coating Methods 0.000 claims abstract description 12
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 201000011510 cancer Diseases 0.000 claims abstract description 4
- 239000010949 copper Substances 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 14
- 239000000725 suspension Substances 0.000 claims description 9
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 7
- 150000004780 naphthols Chemical class 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- FNGGVJIEWDRLFV-UHFFFAOYSA-N anthracene-1,2-dicarboxylic acid Chemical class C1=CC=CC2=CC3=C(C(O)=O)C(C(=O)O)=CC=C3C=C21 FNGGVJIEWDRLFV-UHFFFAOYSA-N 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 claims 1
- 238000001514 detection method Methods 0.000 abstract description 74
- 230000035945 sensitivity Effects 0.000 abstract description 24
- 238000000034 method Methods 0.000 abstract description 20
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 44
- 239000002048 multi walled nanotube Substances 0.000 description 41
- 238000002484 cyclic voltammetry Methods 0.000 description 28
- 239000000463 material Substances 0.000 description 18
- 239000000126 substance Substances 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 10
- 230000008859 change Effects 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 9
- 238000000970 chrono-amperometry Methods 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 206010028980 Neoplasm Diseases 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- 238000001903 differential pulse voltammetry Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 150000000996 L-ascorbic acids Chemical class 0.000 description 5
- HVDGDWCHFUHZMF-UHFFFAOYSA-N anthracene-1,8-dicarboxylic acid Chemical class C1=CC(C(O)=O)=C2C=C3C(C(=O)O)=CC=CC3=CC2=C1 HVDGDWCHFUHZMF-UHFFFAOYSA-N 0.000 description 5
- SUHZCEULOZMCHP-UHFFFAOYSA-N azanide;ruthenium(1+) Chemical compound [Ru]N SUHZCEULOZMCHP-UHFFFAOYSA-N 0.000 description 5
- 230000033116 oxidation-reduction process Effects 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 150000003384 small molecules Chemical class 0.000 description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000002041 carbon nanotube Substances 0.000 description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 230000005518 electrochemistry Effects 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229920001021 polysulfide Polymers 0.000 description 4
- 239000005077 polysulfide Substances 0.000 description 4
- 150000008117 polysulfides Polymers 0.000 description 4
- 238000001338 self-assembly Methods 0.000 description 4
- 238000002604 ultrasonography Methods 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- 238000001262 western blot Methods 0.000 description 4
- 102000004190 Enzymes Human genes 0.000 description 3
- 108090000790 Enzymes Proteins 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 150000004696 coordination complex Chemical class 0.000 description 3
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- 102000004169 proteins and genes Human genes 0.000 description 3
- 108090000623 proteins and genes Proteins 0.000 description 3
- KUUVQVSHGLHAKZ-UHFFFAOYSA-N thionine Chemical compound C=1C=CC=CSC=CC=1 KUUVQVSHGLHAKZ-UHFFFAOYSA-N 0.000 description 3
- 229940088594 vitamin Drugs 0.000 description 3
- 229930003231 vitamin Natural products 0.000 description 3
- 235000013343 vitamin Nutrition 0.000 description 3
- 239000011782 vitamin Substances 0.000 description 3
- 150000003722 vitamin derivatives Chemical class 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- 206010000830 Acute leukaemia Diseases 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 description 2
- 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 2
- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical compound N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-UHFFFAOYSA-N 0.000 description 2
- TVWHNULVHGKJHS-UHFFFAOYSA-N Uric acid Natural products N1C(=O)NC(=O)C2NC(=O)NC21 TVWHNULVHGKJHS-UHFFFAOYSA-N 0.000 description 2
- 229930003268 Vitamin C Natural products 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 235000015165 citric acid Nutrition 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical class C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000000835 electrochemical detection Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 238000000825 ultraviolet detection Methods 0.000 description 2
- 229940116269 uric acid Drugs 0.000 description 2
- 235000019154 vitamin C Nutrition 0.000 description 2
- 239000011718 vitamin C Substances 0.000 description 2
- 208000031261 Acute myeloid leukaemia Diseases 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 102000014914 Carrier Proteins Human genes 0.000 description 1
- 102100039813 Inactive tyrosine-protein kinase 7 Human genes 0.000 description 1
- 101710099452 Inactive tyrosine-protein kinase 7 Proteins 0.000 description 1
- 206010058467 Lung neoplasm malignant Diseases 0.000 description 1
- 208000033776 Myeloid Acute Leukemia Diseases 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 102000004278 Receptor Protein-Tyrosine Kinases Human genes 0.000 description 1
- 108090000873 Receptor Protein-Tyrosine Kinases Proteins 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 208000005718 Stomach Neoplasms Diseases 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 108091008324 binding proteins Proteins 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 208000029742 colonic neoplasm Diseases 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
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- 230000021615 conjugation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000012718 coordination polymerization Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
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- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000008236 heating water Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000012308 immunohistochemistry method Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
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- 201000005202 lung cancer Diseases 0.000 description 1
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- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 235000006109 methionine Nutrition 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011027 product recovery Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 201000011549 stomach cancer Diseases 0.000 description 1
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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
- G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
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- 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)
- Measuring Or Testing Involving Enzymes Or Micro-Organisms (AREA)
Abstract
The invention discloses a kind of metal esters complex Cu Dada and its preparation method and application.Metal esters complex Cu Dada, are 1 by mol ratio：The 1 of (3 5), 8 anthracene dimethyl dicarboxylates and copper nitrate are prepared from.The metal esters complex Cu Dada of the present invention prepare simple, pollution-free, can use the method drop coating of drop coating on electrode and stably, it is not necessary to polymerize using high voltage；Metal esters complex Cu Dada are combined with aptamers Sgc8c can prepare the electrochemica biological sensor for detecting malignant tumour mark PTK7K；Metal esters complex Cu Dada can be prepared for detecting H simultaneously2O2With the electrochemical sensor of ascorbic acid.The electrochemica biological/electrochemical sensor is prepared simply, easy to use, and detection sensitivity is high, and the response time is short, high specificity, with reappearance and stability.
Description
Technical field
The invention belongs to metal complex, and in particular to a kind of metal esters complex Cu-Dada (Cu-1,8
Anthracene dimethyl dicarboxylate) and its preparation method and application.
Background technology
Tumour turns into the global problem of human health, and protein tyrosine kinase -7 (PTK7K) is disliked in a variety of mankind
Property tumour in the member of deficiency receptor protein tyrosine kinase that is overexpressed, include it is several may be such as colon cancers, lung cancer, stomach cancer
With acute myelocytic leukemia etc..Current existing detection method is difficult to qualitatively evaluate and quantify PTK7K albumen in cancerous tissue
Expression.The detection to PTK7K mainly has ImmunohistochemistryMethods Methods detection, and Western blotting at present.But the side of the detection
Method detection line is higher, high cost, and detection method is complicated, it is impossible to realize the early detection of malignant tumour.Therefore new detection is proposed
PTK7K method is very necessary.Such as detection of the tumor markers for PTK7K acute leukemia, entered in early days with polysulfide violet
Row detection, mainly by polymerizeing thionine on electrode.Combined by thionine and aptamers, produce steric hindrance, cause curent change to produce
Signal is given birth to detect acute leukemia.But electrode can be caused to damage due to forming polysulfide violet, and the less stable of itself,
So gradually adopting the LBL self-assembly pattern of foreign countries to detect now.Detected with the pattern of LBL self-assembly.Typically all
The biocompatibility combination aptamers that decorated by nano-gold is recycled to nanogold on electrode are first layer.Aptamers combination tumour
Label is the second layer, is loaded with the material of aptamers and relevant enzyme and can combine tumor markers for third layer, finally by
Enzyme is catalyzed related substances, produces electric signal.Because the success rate and efficiency of LBL self-assembly are all very low, its test limit is resulted in
It is not too low.And the relatively expensive cost that also results in of nanogold is higher, actual application value is not high.And Sgc8c aptamers
(Apt) it is the DNA of being capable of binding proteins specific EGFR-TK -7 (PTK7K).And traditional detection can not realize molecular water
Flat detection, and electrochemical sensor detection tumor markers PTK7K albumen is built with Cu-Dada can reach molecular level
Detection.
It is being that we live a kind commonly used material that hydrogen peroxide, which is, is also the important material of organism, its concentration shadow
The function of cell and the metabolism of organism are rung, the hydrogen peroxide of high concentration even can cause the death of cell.And in clinical, ring
Had a wide range of applications in terms of border, pharmacy, mining industry, textile industry and manual manufacturing industry, such as the identification of many Ag-Abs, enzymatic
Reaction and protein gather during also can with hydrogen peroxide generation or consumption.Therefore the detection of hydrogen peroxide is in biology
There is actual application value in terms of, environment and industry.The survey method of traditional hydrogen peroxide has chemoluminescence method, fluorescence point
Analysis method, AAS etc., but these method comparative costs are high, and time-consuming, and detection method is complicated.Electrochemistry rule is faster
Fast, simple, sensitive and cheap the advantages of, causes people's extensive concern.
Ascorbic acid is one of necessary vitamin of human body, for maintaining the life and health of people very important.Traditional
The method of detection ascorbic acid has a variety of including iodimetric titration, colorimetric method, AAS and high performance liquid chromatography etc., and
Electrochemical analysis method relative to these it is traditional have analyze speed fast, easy to operation, low cost and reagent dosage are few,
The advantages of detection sensitivity is high, overcomes the high cost of conventional method, and operating technology requires high, the shortcomings of experiment condition is strict,
It is the indispensable powerful measure that ascorbic acid content is determined.
The content of the invention
Goal of the invention：The problem of existing for prior art, the present invention provides a kind of metal esters complex Cu-
Dada (Dada represents 1,8 anthracene dimethyl dicarboxylates), the compound can use the method drop coating of drop coating on electrode and steady
It is fixed, it is not necessary to be polymerize using high voltage, while metal esters complex Cu-Dada can be effectively combined aptamers
Sgc8c formation Cu-Dada-Sgc8c is used to prepare electrochemica biological sensor, the electricity for detecting PTK7K and Cu-Dada preparations
Chemical sensor can be used for detecting H2O2And ascorbic acid, and Detection results are good, and reappearance is high.
Present invention also offers metal esters complex Cu-Dada preparation method and application.
Technical scheme：To achieve these goals, a kind of metal esters complex Cu-Dada as described herein
(1,8 anthracene dimethyl dicarboxylate), is 1 by mol ratio：The 1 of (3-5), 8 anthracene dimethyl dicarboxylates and copper nitrate are prepared from, except
1,8 anthracene dimethyl dicarboxylate, the ester type compound can also other have dibasic esters of three aromatic rings planar structures conjugation small
Molecule chemical combination structure thing.
Wherein, the part of the compound is ester, and coordination center is Cu, and the mol ratio of Cu and part ester and nitrate anion is
2：1：2.
Metal esters complex Cu-Dada of the present invention preparation method, comprises the following steps：
(1) by 1,8 anthracene dimethyl dicarboxylates and copper nitrate are mixed and soluble in water in proportion, obtain mixed solution A；
(2) mixed solution A is added to after heating response in reactor, Temperature fall and dries product centrifuge washing, obtained
To metal esters complex Cu-Dada.
Wherein, the temperature of step (2) described heating response is 130-150 DEG C, and the time is 6-8d.
Applications of the metal esters complex Cu-Dada of the present invention on detector is prepared.
Wherein, the detector is for detecting that the electrochemica biological of malignant tumour marker protein EGFR-TK -7 is passed
Sensor.
Further, the detector is for detecting H2O2With the electrochemical sensor of ascorbic acid.
The electrochemica biological sensor is Cu-Dada-Sgc8c/GCE, by metal esters complex Cu-Dada and
Aptamers Sgc8c is combined, and generates Cu-Dada-Sgc8c, and Cu-Dada-Sgc8c is made into suspension and drop coating is in glass-carbon electrode table
Face is made.
The metal esters complex Cu-Dada and aptamers Sgc8c are in molar ratio (10-1)：(1-2) is tied
Close.
Further, the specific preparation method of the electrochemica biological sensor, comprises the following steps：Metal esters are coordinated
Compound Cu-Dada and aptamers Sgc8c is combined, and generates Cu-Dada-Sgc8c；Cu-Dada-Sgc8c is dissolved in second distillation
In water and naphthols, ultrasonic disperse obtains Cu-Dada-Sgc8c suspensions, after the suspended drop-coateds of Cu-Dada-Sgc8c are managed everywhere
Glassy carbon electrode surface, place dry at room temperature, that is, electrochemica biological sensor Cu-Dada-Sgc8c/ glass-carbon electrodes are made
(Cu-Dada-Sgc8c/GCE)。
Electrochemical sensing implement body preparation method, comprises the following steps：Metal esters complex Cu-Dada is dissolved in
In redistilled water and naphthols, ultrasonic disperse obtains Cu-Dada suspensions, the glass after the suspended drop-coateds of Cu-Dada are managed everywhere
Carbon electrodes, place dry at room temperature, that is, electrochemical sensor Cu-Dada/ glass-carbon electrodes (Cu-Dada/GCE) are made.
Electrochemica biological sensor Cu-Dada-Sgc8c/ glass-carbon electrodes.It can be used for detecting PTK7K, concretely comprise the following steps：
Cu-Dada-Sgc8c/ glass-carbon electrodes are placed in three-electrode system in the range of -0.5-0.3V and are circulated volt-ampere test,
The PTK7K for continually adding various concentrations obtains different electric currents drafting standard curves.Sample is added during detection and obtains electric current, root
Corresponding concentration is obtained according to the electric current on standard curve.
Electrochemical sensor is used to detect H2O2It is to use chronoamperometry generation with the method for the small-molecule substance such as ascorbic acid
For cyclic voltammetry, by being continuously added H2O2Standard curve is made according to concentration and current-responsive size with ascorbic acid, detected
When add sample obtain electric current, corresponding concentration is obtained according to the electric current on standard curve.
The present invention has synthesized the part ester type compound in a kind of new metal complex Cu-Dada, compound
It is the molecule chemical combination of 1,8 anthracene dimethyl dicarboxylates or other dibasic esters with three aromatic rings planar conjugate structures
Structure thing.The molecular structure of esters can make it easily insert DNA molecular, but it is also possible to produce strong electrostatic attraction and DNA,
So it can be combined with DNA.Thus synthesized metal complex Cu-Dada can combine Sgc8c formation Cu-
Dada-Sgc8c.Develop a kind of electrochemica biological biography that PTK7K is targetted based on Cu-Dada-Sgc8c first for these reasons
Sensor.Electrochemica biological sensor is made with reference to aptamers there is presently no the synthesis that document report crosses Cu-Dada, and by it
Detection PTK7K also has no report.Commonly use the method for western blot to detect albumen, electrochemically detect albumen and albumen print
Mark method, which is compared, has relatively low test limit and higher detection range.
Cu-Dada used by the present invention is a kind of new complex, and there is activated centre Cu makes it in electrochemistry
Be present potential application in sensory field, and due to being that carboxyl coordination structure compares Wen Ding, can repeatedly measure.Do not have also at present
There is the possibility for exploring this new complexes of Cu-Dada in detection small-molecule substance.The present invention is a kind of new
Cu-Dada metal complexes, and it is applied to Electrochemical Detection first, can be with effective detection H2O2With ascorbic acid etc.
Small-molecule substance.
Beneficial effect：Prior art is compared, the invention has the advantages that：
(1) the metal esters complex Cu-Dada of preparation synthesis of the invention is a kind of new compound, relative to
Existing material polysulfide violet, because synthesis polysulfide violet needs to carry out for a long time under high potential, and the compound of the present invention need not
Prepared for a long time under high potential, the destruction to electrode can be reduced, and preparation method is simple, and low cost is pollution-free.
(2) electrochemica biological sensor prepared by metal esters complex Cu-Dada of the present invention, prepares simply, makes
With convenient, PTK7K can be effectively detected, it is easy to use, PTK7K can be effectively detected, and the detector sensitivity is high,
Response time is short, high specificity, with reappearance and stability.Relative to the electrode assembling method of LBL self-assembly, it is not necessary to
Layer assembly is carried out, assembled layers are reduced, it is possible to increase efficiency；And because layer assembly is passed through frequently with nanogold, nanogold sheet
Body carries negative electrical charge, and does not have on glass-carbon electrode redox summit hinder thionine electron transmission, and life prepared by the present invention
Thing sensor can improve transmission electronic capability, and electro-chemical activity is high, can reduce detection line.
(3) electrochemical sensor prepared by metal esters complex Cu-Dada of the present invention, prepares simple, user
Just, H can effectively be detected2O2With the small-molecule substance such as ascorbic acid, and with selectivity, sensitivity is high, reproducible.
(4) electrochemica biological sensor prepared by metal esters complex Cu-Dada of the present invention can be used for electrification
Bio-sensing is learned, relative to the western blot in the technology for detecting albumen and the method with SABC, electrochemica biological
Method for sensing has specificity high, the good advantage of detection performance.
Brief description of the drawings
Fig. 1 is the XRD of the metal esters complex Cu-Dada prepared by the embodiment of the present invention 1；
Fig. 2 is that (A is red for the infrared and uv-spectrogram of the metal esters complex Cu-Dada prepared by the present embodiment 1
Outside, B is ultraviolet, and a is 1,8 anthracene dimethyl dicarboxylates, and b is Cu-Dada)；
The XRD of powder after metal esters complex Cu-Dada heat treatments prepared by Fig. 3 embodiments 1；
Fig. 4 is differential pulse voltammetries of the Cu-Dada-Sgc8c/GCE of the preparation of the embodiment of the present invention 6 in amino ruthenium solution
Scheme (DPV)；
Fig. 5 is the circulation volt that Cu-Dada-Sgc8c/GCE prepared by the embodiment of the present invention 6 adds PTK7K in PBS solution
Antu；Wherein a is the CV of bare electrode, and b is Cu-Dada/GCE CV, and c is that Cu-Dada/GC adds 2.5 × 10-5mg mL-
1PTK7K CV, d are Cu-Dada-Sgc8c/GCE CV, and e is that Cu-Dada-Sgc8c/GCE adds 2.5 × 10-5mg mL-
1PTK7K CV；
Fig. 6 is Cu-Dada-Sgc8c/GCE prepared by the embodiment of the present invention 6 quantitative cyclic voltammogram and standard curve
Scheme (insert)；
Fig. 7 is that Cu-Dada-Sgc8c/GCE prepared by the embodiment of the present invention 6 adds various concentrations PTK7K in PBS solution
Reappearance figure；
Cu-Dada/GCE detections H prepared by Fig. 8 embodiment of the present invention 72O2Volt-ampere curve figure (CV)；
Cu-Dada/MWCNTs/GCE detections H prepared by Fig. 9 embodiment of the present invention 82O2Volt-ampere curve figure (CV)；
Figure 10 is Cu-Dada/MWCNTs/ prepared by Cu-Dada/GCE (A) prepared by the embodiment of the present invention 7 and embodiment 8
GCE (B) detects H respectively2O2Chronoa mperometric plot figure (I-T)；
Figure 11 is Cu-Dada/GCE of the present invention (A) and Cu-Dada/MWCNTs/GCE (B) detections H2O2It is anti-interference；
Cu-Dada/GCE prepared by Figure 12 embodiment of the present invention 7 detects the volt-ampere curve figure (CV) of ascorbic acid；
Cu-Dada/GCE prepared by Figure 13 embodiment of the present invention 7 detects the chronoa mperometric plot figure (I- of ascorbic acid
T)；
Cu-Dada/GCE prepared by Figure 14 embodiment of the present invention 7 detects the figure of the anti-interference detection of ascorbic acid.
Embodiment
Below in conjunction with drawings and Examples, the invention will be further described.
The synthesis and application of metal esters complex Cu-Dada materials of the present invention, comprise the following steps：
The first step, synthesizing new metal esters complex Cu-Dada materials；
Second step, synthesis metal esters complex Cu-Dada materials are scattered in the aqueous solution and Sgc8c is mixed,
NaCl concentration is controlled, under a period of time, it is fully combined, is cleaned, centrifugal drying；
3rd step, the solid after combination is scattered in aqueous, and drop coating is in glass-carbon electrode, you can obtain Cu-Dada-
Sgc8c/ glass-carbon electrodes (Cu-Dada-Sgc8c/GCE)；
4th step, Cu-Dada-Sgc8c/GCE is placed in three-electrode system in the range of 0-0.9V by circulating volt
Peace test detection chemical property and addition PTK7K explore the recognition reaction to PTK7K；
In the range of 5th step, the result selection -0.5-0.3V detected according to cyclic voltammetry, by adding various concentrations
PTK7K, the standard curve obtained.
In the range of 6th step, the result selection -0.5-0.3V detected according to cyclic voltammetry, by adding various concentrations
PTK7K, test in triplicate；
7th step, Cu-Dada/GCE is placed in three-electrode system in the range of -0.8-1V by cyclic voltammetry
Detect chemical property and add H2O2Research is to H2O2Recognition reaction, and draw performance improvement of the CNT to it；
8th step, using the result selection -0.55V detected according to cyclic voltammetry as chrono-amperometric operating potential,
By being continuously added H2O2, Cu-Dada/GCE and Cu-Dada/MWCNTs/GCE the detection H obtained2O2Standard curve；
9th step, selection -0.55V adds 0.25mM H as the operating potential of chrono-amperometric2O2, 3 are studied respectively puts down
Row electrode Cu-Dada/GCE and Cu-Dada/MWCNTs/GCE are to H2O2Response；
Tenth step, Cu-Dada/MWCNTs/GCE is surveyed to H with simulation full pattern detection method2O2Full pattern detection；
11st step, Cu-Dada/GCE is placed in three-electrode system and surveyed in the range of -0.8-1V by cyclic voltammetric
Examination detection chemical property and the recognition reaction for adding ascorbic acid research Ascorbic Acid；
12nd step, 0.4V is selected as the operating potential of chrono-amperometric using the result detected according to cyclic voltammetry,
By being continuously added ascorbic acid, show that Cu-Dada/GCE detects the standard curve of ascorbic acid；
13rd step, selects operating potentials of the 0.4V as chrono-amperometric, adds 0.25mM ascorbic acid, and 3 are studied respectively
The response of parallel pole Cu-Dada/GCE Ascorbic Acids；
14th step, by electrode room temperature preservation, carries out the detection of stability, detects Cu-Dada/GCE pairs after 3 months
The response of 0.25mM ascorbic acid, and Cu-Dada/MWCNTs/GCE0.25mM H2O2Response.
Embodiment 1
Metal esters complex Cu-Dada preparation：
0.05mmol Dada (1,8 anthracene dimethyl dicarboxylate) is taken, the copper nitrate for adding 0.2mmol is dissolved in 15ml water in anti-
150 DEG C of reaction 6d in kettle are answered, the nitric acid of 3 drop volume fraction 1% is in reactor, Temperature fall.By product ethanol and hot water from
Heart separating, washing, obtains metal esters complex Cu-Dada.
Embodiment 2
Metal esters complex Cu-Dada preparation：
Take 0.05mmol Dada (1,8 anthracene dimethyl dicarboxylate), add 0.15mmol copper nitrate be dissolved in 15ml water in
150 DEG C of reaction 6d in reactor, the nitric acid of 3 drop volume fraction 1% is in reactor, Temperature fall.By product ethanol and hot water
Washing is centrifuged, metal esters complex Cu-Dada is obtained.
Embodiment 3
Embodiment 3 is formulated with embodiment 1 and preparation method is identical, and difference is Dada and copper nitrate mol ratio is 1：
5,130 DEG C of reaction 8d in reactor.
Embodiment 4
Cu-Dada-sgc8c synthesis：
1ODsgc8c aptamers are placed in 3ml centrifuge tube 12000 turns, 30-60s is centrifuged, 25ul deionized waters are added
In sgc8c aptamers, 100 μM are diluted to；1.86ul 100uM aptamers are taken, 2mL, 95 DEG C of heating water bath 5min are diluted to,
Naturally cool to room temperature.Add after embodiment 1 prepares Cu-Dada complexes 1.86umol, ultrasonic 30min and react 16h, plus
Enter 0.0032gNaCl, concentration is 0.05M, react 6h, add 0.0032gNaCl, the increased 0.1M. reactions 10h of concentration, from
The heart, adds deionized water washing centrifugation, obtains solid as Cu-Dada-sgc8c.
Embodiment 5
Embodiment 5 is formulated with embodiment 4 and preparation method is identical, and difference is metal esters complex Cu-
Dada and aptamers Sgc8c mol ratios are 1:2.
Embodiment 6
Cu-Dada-Sgc8c/GCE (Cu-Dada-Sgc8c/ glass-carbon electrodes) preparation：
Cu-Dada-Sgc8c prepared by embodiment 4 takes 3.7mg to be dissolved in 800 μ L redistilled waters and 200ul naphthols
In, ultrasonic disperse obtains Cu-Dada-Sgc8c suspensions.With liquid-transfering gun by after 6 μ L Cu-Dada-Sgc8c drop coatings to processing
(glass-carbon electrode GCE processing method is to be polished by a diameter of 3mm through nylon polishing cloth to glassy carbon electrode surface, then uses particle diameter
Size is respectively 1.0,0.3,0.05 μm of Al2O3Minute surface is polished to successively, is then cleaned by ultrasonic in redistilled water and ethanol
Alternately ultrasonic, each 30s dries standby after taking-up), place dry at room temperature, as electrochemica biological sensor Cu-Dada-
Sgc8c/ glass-carbon electrodes (Cu-Dada-Sgc8c/GCE).
Embodiment 7
Cu-Dada/GCE (Cu-Dada/ glass-carbon electrodes) preparation：
Cu-Dada prepared by embodiment 1 takes 3.7mg to be dissolved in 800 μ L redistilled waters and 200ul naphthols, ultrasound
It is scattered, Cu-Dada suspensions.Glassy carbon electrode surface (glass-carbon electrode with liquid-transfering gun by 6 μ L Cu-Dada drop coatings to after handling
GCE processing method is to be polished by a diameter of 3mm through nylon polishing cloth, is respectively then 1.0,0.3,0.05 with particle size
μm Al2O3Minute surface is polished to successively, alternately ultrasound is then cleaned by ultrasonic in redistilled water and ethanol, and each 30s takes out
After dry it is standby), place dry at room temperature, as electrochemical sensor Cu-Dada/ glass-carbon electrodes (Cu-Dada/GCE).
Embodiment 8
Cu-Dada/MWCNTs/GCE (Cu-Dada/ multi-walled carbon nano-tubes/glass-carbon electrode) preparation：
Cu-Dada prepared by embodiment 1 takes 3.7mg to be dissolved in 800 μ L redistilled waters and 200ul naphthols, ultrasound
It is scattered, obtain i.e. Cu-Dada suspensions.(glass-carbon electrode GCE processing method is to pass through diameter to glass-carbon electrode first after treatment
Polished for 3mm through nylon polishing cloth, be respectively then 1.0 with particle size, 0.3,0.05 μm of Al2O3Minute surface is polished to successively,
Then it is cleaned by ultrasonic alternately ultrasound in redistilled water and ethanol, each 30s dries standby after taking-up) 6 μ L of surface drop coating
The multi-walled carbon nano-tubes (MWCNTs) of 5mg/mL carboxylated, it is outstanding after room temperature is dried, then with liquid-transfering gun drop coating 6 μ L Cu-Dada
Turbid liquid, dries standby, obtained Cu-Dada/MWCNTs/GCE at room temperature.
Embodiment 9
Preparing metal esters complex Cu-Dada with micro- sem observation embodiment 1 does not have impurity, illustrates the thing of synthesis
Matter is pure material.Its XRD is as shown in figure 1, according to metal oxide (the CuO PDF#65-2309, Cu2OPDF#65- of XRD and copper
3288) XRD peaks and the peak of other known substances existed can not be overlapped, and illustrate to generate new material, peak it is strong
Larger, more intensive explanation better crystallinity degree is spent, and does not do impurity under the microscope.According to XRD and micro- sem observation, synthesis is judged
New material.More sharp by microscope and XRD peak shape, it is a kind of pure material to determine the material, is crystal, passes through
XRD shows that Cu-Dada compounds are new compound.
Embodiment 10
To the carry out infrared detection of the metal esters complex Cu-Dada prepared by the present embodiment 1, infared spectrum is such as
Shown in Fig. 2A, a is the infrared absorption peak of 1,8 anthracene dimethyl dicarboxylates, in 1719cm-1Characteristic peak shakes for the flexible of C=O in COO-
Dynamic absworption peak, 1200-1566cm-1There are the absworption peak of the stretching vibration 4 of phenyl ring, 670-1000cm in left and right-1There is phenyl ring left and right
The upper C-H of C=C-H absworption peak.B is metal esters complex Cu-Dada infrared absorption peak, in 1200-1500cm-1It is left
The absworption peak and phenyl ring 670-1000cm of the stretching vibration of right phenyl ring-1Absworption peak still have, and in 1719cm-1Feature
Peak disappears, and illustrates that part is not destroyed, and is present in the material of generation and C=O disappears, it may be possible to C=O oxygen atom and gold
Belong to ion formation coordinate bond.The 1676cm in b-2, and 1566cm-2There is Vascoo- and Vscoo- characteristic peak in annex, enters one
Step has said that copper ion is coordinated with carbonyl, and △ v=Vascoo--Vs coo- are less than 200cm-1, this sends out with carboxyl in theory
The asymmetric stretching vibration absorption frequency of raw double coordination carboxyl and the difference of symmetrical stretching vibration absorption frequency are less than or equal to
200cm-2It is consistent.Further illustrate that 1,8 anthracene dimethyl dicarboxylates there occurs and be hydrolyzed into 1,8 anthracene dicarboxylic acids, C=O's therein
Oxygen atom is coordinated with copper atom and is double coordination.
To the carry out ultraviolet detection of the metal esters complex Cu-Dada prepared by the present embodiment 1, ultraviolet detection figure
As shown in Figure 2 B, a is that 1.8 anthracene dimethyl dicarboxylates a strong peak Soret band occur in 260nm to spectrum, is occurred in 384nm two low
The Q bands of energy.S bands are blue shifted to 238nm b metal esters complexes Cu-Dada ultraviolet peak by 260nm, and Q is blue by 384nm
Move to 378nm or so.This is due to coordination polymerization, caused by the cloud density for reducing phenyl ring.Pass through infrared and ultraviolet table
It is bright to have synthesized using copper as coordination center, with the complex that 1,8 anthracene dicarboxylic acids is part.Analysis obtains our conjunctions more than
Into one kind using esters as part, the new metallo-organic compound by coordination center of Cu.
Made a concrete analysis of according to elementary analysis, and thermogravimetric.Polymer is dried at low temperature before elementary analysis, removes and inhales
Attached water, without causing the crystallization water to lose.According to the result of elementary analysis, C 36.38%, N 5.36%, O：32.24%, H
1.66%.
Pass through XRD points to the powder after the metal esters complex Cu-Dada heat analysis prepared by embodiment 1
Analysis, as shown in figure 3, by being compareed with standard spectrogram (b is standard spectrogram), it is found that generation material is CuO, water of coordination is at high temperature
React and generate the oxide of copper, the content for obtaining copper is 24.3%, wherein Cu：N mol ratios are 1:1, and N element can only be come
Nitrate anion is come from, then shows Cu:NO3 -Mol ratio is 1：1.According to infrared, the carboxylic acid in 1,8 anthracene dicarboxylic acids take part in coordination, and
Cu:C mol ratios are 1：8, all C are only possible to derive from 1,8 anthracene dicarboxylates.Show Cu:1,8 anthracene dicarboxylic acids mol ratios are
2:1.It is 0 so according to polymer compound valency, wherein nitric acid shows -1 valency, and 1,8 anthracene dicarboxylic acids show-divalent after coordination, infers copper
Valence state is+divalent, because the highest valence state of copper is+divalent.Thus, other anion are not present in polymer.And+2 copper added
The ligancy of ion is 4-6, thus shows that nitro take part in coordination, and the mol ratio of Cu and part ester and nitrate anion is 2：1：
2。
Embodiment 11
By synthetic method hydro-thermal reaction, Cu-Dada-Sgc8c that embodiment 4 is synthesized is dispersed in aqueous simultaneously
Drip in glassy carbon electrode surface.And with the method differential pulse voltammetry of electrochemistry, DPV is surveyed in concentration is 5 μM of amino ruthenium solution,
Potential range is -0.6V-1.0V.Judge whether Sgc8c is combined with Cu-Dada.
The differential pulse voltammetry figure (DPV) of Cu-Dada-Sgc8c/GCE prepared by embodiment 6 in amino ruthenium solution, such as
(a does not add amino ruthenium, and b adds amino ruthenium) shown in Fig. 4, Cu-Dada combined with Sgc8c after due to Sgc8c can and ruthenium
, with reference to rear, there is ruthenium ion in electrostatical binding, in the case where applying voltage, the oxidation peak of ruthenium ion, two just occurs on electrode
Valency is to trivalent, in 0.3V or so.Because copper ion can be reduced in -0.26V or so, be divalence to monovalence, with ruthenium ion shape
Into redox so that larger displacement occurs for spike potential, and peak current is significantly increased, thus shows Cu-Dada ligand compounds
Thing and sgc8c are combined.
Embodiment 12
Cyclic voltammetry detects PTK7K：
Cu-Dada-Sgc8c/GCE prepared by embodiment 6 is circulated volt-ampere test in the range of -0.5-0.3V.
Cyclic voltammetric, as shown in figure 5, Cu-Dada-sgc8c/GCE electrochemical properties are have studied using cyclic voltammetry (CV) first,
In pH=7 0.1molL-1Bare electrode and Cu-Dada/GCE CV curves in PBS electrolyte solutions.0.3V scopes are arrived -0.5
Interior, there is not redox peaks (curve a), and Cu-Dada-sgc8c/GCE (curve c) electricity in this potential range in bare electrode
Stream increase, and a pair of redox peaks of appearance are respectively labeled as peak 1 ' and 2 ' at -0.039/-0.230V, are classified as Cu (II)/Cu
(I) oxidation-reduction process.As 2.5 × 10-6mgmL-1After PTK7K is added, the electric current at peak 1 and peak 2 has obvious decrease
(c→b).As a result show that avtive spot Cu electric current declines, show the impedance increase of the material on electrode, be i.e. PTK7K belongs to high
Aptamers Sgc8c on molecule protein and electrode is combined so that impedance increases, thus electric current reduction.Electrode Cu-Dada/
GCE, a pair of redox peaks of appearance are respectively labeled as peak 1 and 2 at -0.039/-0.230V, are classified as Cu (II)/Cu (I) oxygen
Change reduction process, as 2.5 × 10-6mg mL-1After PTK7K is added, peak 1 and peak 2 all do not change significantly (e → d).As a result table
It is bright in Cu-Dada-sgc8c/GCE electrodes, can be specifically bound with PTK7K only Sgc8c, and bare electrode and
With PTK7K specific combination can not occur for Cu-Dada, show that electrode Cu-Dada-sgc8c/GCE can be specifically bound
Sgc8c。
Cu-Dada-Sgc8c/GCE prepared by embodiment 6 is circulated volt-ampere test in the range of -1-1V.Constantly
Ground adds the PTK7K (abscissa of the concentration with reference to Fig. 6 standard curve) of various concentrations, is explored according to concentration and the relation of electric current
Standard curve, obtains standard curve, obtains standard curve, and its minimum detection is limited to 2.56 × 10-7mg mL-1, sensitivity is
2.36mA mL mg-1cm-2, the range of linearity 5.6 × 10-7-9.9×10-7mg mL-1(R=0.99)
It is 0.5-1V to change volt-ampere curve sweep limits, as shown in fig. 6, its minimum detection is limited to 1.45 × 10-7mgmL-1,
Sensitivity is 2.89mA mL mg-1cm-2, the range of linearity 4.23 × 10-7-1.36×10-6mg mL-1(R=0.993).
It is that -0.5-0.3V detection the ranges of linearity are 6.25 × 10 to change volt-ampere curve sweep limits-7–3.75×10-6mgmL-1, detect and be limited to 1.5 × 10-8mg mL-1, sensitivity is 3.87mA mL mg-1cm-2(R=0.997).Selection -0.5-0.3V's
The electrode of current potential has superior chemical property.
The analysis of the above is occupy, because aptamers and PTK7K combination are not to complete moment, thus selection cyclic voltammetry
Cu-Dada-sgc8c/GCE detections PTK7K is carried out determining quantifier elimination.In pH=7 0.1M-1In PBS electrolyte solutions-
In the range of 0.5 to 0.3V, add the PTK7K of various concentrations (concentration is shown in Fig. 5 standard curve abscissa).And carry out cyclic voltammetric
Scanning, stable to curve, the curve for selecting each concentration stable is mapped, and continually adds the PTK7K of various concentrations, according to
Concentration and the relation of electric current explore standard curve, obtain standard curve, as shown in fig. 6, this electrochemical method detects the range of linearity
For 6.25 × 10-7–3.75×10-6mg mL-1, minimum detection be limited to 1.5 × 10-8mg mL-1, sensitivity is 3.87mAmL mg- 1cm-2.A-j represents to add the response of the PTK7K electric currents of various concentrations in Fig. 6, and j is Cmax, and a is Cmin.
As a result show that the electrochemica biological sensor has preferable performance in -0.5-0.3V current potentials, sensitivity is high, response
Time is short, high specificity.At present on PTK7K detection be mainly SABC method, and western blot method.Not
See with the method for electrochemistry to detect PTK7K.
Embodiment 13
Detection of Stability and reappearance detection：
The result selection 0-0.9V detected according to the cyclic voltammetry of embodiment 12 makees the operating potential of cyclic voltammetry,
Under the concentration specified, parallel test detection PTK7K is repeated 3 times, the detection of repeatability is carried out, the PTK7K concentration of addition is respectively
The concentration of addition is respectively 3.125 × 10-7, 6.25 × 10-7, 9.375 × 10-7, 1.25 × 10-6, 1.5625 × 10-6, 1.875
×10-6, 2.1875 × 10-6, 2.5 × 10-6, 2.8125 × 10-6, 3.125 × 10-6mgmL-1Carry out parallel laboratory test.Each
The reappearance of concentration all illustrates that detection of the electrochemica biological sensor to PTK7KK has preferable reappearance and stably very well
Property, as shown in Figure 7.
Embodiment 14
Cu-Dada/GCE prepared by embodiment 7 is circulated volt-ampere test.As shown in figure 8, using cyclic voltammetric first
Method (CV) have studied Cu-Dada electrochemical properties.Bare electrode and Cu- in pH=7.0 0.1M PBS electrolyte solutions
Dada/GCE CV curves.In the range of -0.8 to 1.0V, redox peaks does not occur in bare electrode, and (curve a), works as addition
0.5mM H2O2Afterwards, significant change (a → b) does not occur for curve, shows bare electrode to H2O2There is no electrocatalysis；And Cu-
(curve c) electric currents in this potential range increase Dada/GCE, a pair of redox peaks occur in -0.05/-0.31V, mark respectively
Peak 1 and peak 2 are designated as, Cu (I)/Cu (II) oxidation-reduction process is attributed to.And for Cu-Dada/GCE, when adding
Enter 0.5mM H2O2Afterwards, the electric current at peak 1 has significant enhancing (c → d).As a result show, avtive spot Cu is to H2O2Reduction tool
There is electrocatalysis.
CNT can often improve electricity as a kind of electrode modification agent with specific function, modification on electrode
The electric conductivity of pole and sensitivity, improve the performance of sensor.As shown in figure 9, comparing embodiment 8 prepares Cu-Dada/MWCNTs/
0.1molLs of the GCE and Cu-Dada/GCE in pH=7.0-1CV curves in PBS electrolyte solutions are, it is apparent that -0.8
To in the range of 1.0V, there are a pair of oxidations in Cu-Dada/GCE (a) and Cu-Dada/MWCNTs/GCE (c) -0.05/-0.31V
Reduction peak, is respectively labeled as peak 1 and peak 2, and peak 1 ' and peak 2 ' are attributed to Cu (I)/Cu (II) oxidation-reduction process.Add
After carbon nano tube modified, the electric conductivity of electrode is significantly improved (a → c), and Cu-Dada/MWCNTs/GCE (c) electric conductivity is more
Well.Cu-Dada/MWCNTs/GCE peak position is compared compared with Cu-Dada/GCE, and redox peaks all do not change, but Cu-
Dada/MWCNTs peak positions 1 ' and the peak position 1 and 2 of the electric current compared with Cu-Dada at peak 2 ', which have, significantly to be increased, and shows the conduction of electrode
Property improve.And for Cu-Dada/GCE, as the H for adding 0.5mM2O2Afterwards, the intensifying current (a → b) at peak 1, but enhanced
Size is substantially more much smaller than Cu-Dada/MWCNTs/GCE (c → d) enhancings amplitude, illustrates the electrode after carbon nano tube modified
To detection the comparing with more superior performance with and without modified of hydrogen peroxide.
It is placed according to Cu-Dada/GCE in three-electrode system in the range of -0.8-1V by cyclic voltammetry result.
Cu-Dada/GCE prepared by embodiment 7, as the operating potential of chronoamperometry, continually adds various concentrations in -0.5V
Hydrogen peroxide, standard curve is explored according to concentration and the relation of electric current, Cu-Dada/GCE detections H is obtained2O2The range of linearity
For 9.7 × 10-7-1.9×10-3M (R=0.994), sensitivity is 178.3mAM-1cm-2, minimum detectability is 6.4 × 10-7M。
Cu-Dada/MWCNTs/GCE detects H2O2The range of linearity is 8.7 × 10-7-1.8×10-1M (R=0.996), the spirit of the sensor
Sensitivity is 424.3mAM-1cm-2, minimum detectability is 7.5 × 10-8M。
Change operating potential -0.55V, the Cu-Dada/GCE detection H of chronoamperometry2O2The range of linearity be 5 × 10-7-
2.6×10-3M (R=0.997), sensitivity is 199.6mAM-1cm-2, minimum detectability is 2.6 × 10-7M。Cu-Dada/
MWCNTs/GCE detects H2O2The range of linearity is 5 × 10-7-1.8×10-1M (R=0.997), the sensitivity of the sensor is
424.3mAM-1cm-2, minimum detectability is 2.4 × 10-8M。
Change operating potential -0.6V, the Cu-Dada/GCE detection H of chronoamperometry2O2The range of linearity be 8.4 × 10-6-1.3×10-4M (R=0.99), sensitivity is 108.7mAM-1cm-2, minimum detectability is 2.7 × 10-6M。Cu-Dada/
MWCNTs/GCE detects H2O2The range of linearity is 1.4 × 10-6-3.8×10-2M (R=0.992), the sensitivity of the sensor is
354.9mAM-1cm-2, minimum detectability is 9.4 × 10-7M。
The electrode of selection -0.55V current potential has superior chemical property.
Compared to cyclic voltammetry, chronoamperometry is sensitiveer, using chronoamperometry (I-T), can be detected
The parameters such as limit, the range of linearity, while the data such as sensitivity can be calculated, the performance of sensor can be understood in more detail.By CV
Curve map, selection -0.55V does standard curve as detection current potential.Figure 10 is Cu-Dada/GCE (A) and Cu-Dada/ respectively
MWCNTs/GCE (B) is in pH=7.0 0.1M PBS deoxygenation cushioning liquid to H2O2Response time map of current.With adding
Enter H2O2That measures increases, and the electric current of response also gradually increases, within the specific limits linearly.Illustration in A and B is response current
And H2O2The graph of a relation of concentration, Cu-Dada/GCE detections H2O2The range of linearity be 5 × 10-7-2.6×10-3M (R=0.997),
Sensitivity is 199.6mAM-1cm-2, minimum detectability is 2.6 × 10-7M.Cu-Dada/MWCNTs/GCE detects H2O2The range of linearity
For 5 × 10-7-1.8×10-1M (R=0.997), the sensitivity of the sensor is 424.3mAM-1cm-2, minimum detectability is 2.4
×10-6M。
In order to investigate the accuracy of data, three Cu-Dada/GCE electrodes and three Cu-Dada/MWCNTs/ are respectively prepared
GCE, compares each of three electrodes to 0.25mM H2O2Response current and standard deviation is calculated to show the quality of its reappearance.Table 1
For the response current and standard deviation of electrode, as can be seen from Table 1, Cu-Dada/GCE and Cu-Dada/MWCNTs/GCE pairs
In H2O2Detection have relatively good reappearance.
Table 1Cu-Dada/GCE, Cu-Dada/MWCNTs/GCE detection H2O2Reappearance
It has studied the selectivity that 8 two kinds of sensors of embodiment 7 and embodiment are detected for hydrogen peroxide.(A as shown in figure 11
Anti-interference for Cu-Dada/GCE survey hydrogen peroxide, B is that Cu-Dada/MWCNTs/GCE survey hydrogen peroxide is anti-interference), in deoxygenation
0.1molL-11 hydrogen peroxide (0.5mM), 2 dopamines (0.5mM), 3 uric acid (0.5mM), 4 Vitamin Cs are separately added into PBS solution
Sour (0.5mM), 5 citric acids (0.5mM), 6 natrium nitrosums (0.5mM), 7 hydrogen peroxide (0.5mM), 8 glucose (0.5mM), 9
Ammonia (0.5mM), 10L- methionines (0.5mM), 11 hydrogen peroxide (0.5mM) show Cu-Dada/MWCNTs/GCE and Cu-
Detections of the Dada to hydrogen peroxide is not influenceed by other materials substantially, is shown when detecting hydrogen peroxide with good selection
Property.And Cu-Dada/MWCNTs/GCE antijamming capability is more stronger than Cu-Dada, Cu-Dada/MWCNTs/GCE is for H2O2's
Selectivity is more preferable.
The Cu-Dada/MWCNTs/GCE prepared using embodiment 8 to medical disinfectant (storage 15 months) it is effective into
Hydrogen peroxide is divided to be detected, as a result as shown in table 2, Electrochemical Detection takes 1 μ l sample to add in 0.1M, 4mlPBS, surveys
Surely the concentration of the sample obtained is 0.097mM, is with the concentration of hydrogen peroxide in permanganate titration in proportion dilute sample
0.102mM.Experiment reagent volume fraction is matched somebody with somebody for 13% hydrogen peroxide (Chemical Reagent Co., Ltd., Sinopharm Group analyzes pure)
The standard sample of various concentrations is put, the concentration of the standard sample of electrolyte kind is respectively 0.176,0.225,0.264mM, test sample product
Recovery of standard addition, table 2 shows that Cu-Dada/MWCNTs/GCE detects H2O2With high-recovery.
Table 2Cu-Dada/MWCNTs/GCE detects H2O2Full pattern detection
Embodiment 15
As shown in figure 12, the Cu-Dada/GCE prepared using naked glass-carbon electrode and embodiment 7 is whetheing there is Vitamin C respectively
The 0.1molL of acid-1CV curves in PBS (pH=7.0) supporting electrolyte.- 0.8 arrive 1.0V, bare electrode non-oxidation reduction peak,
Generating new peak position 3 after 1.0mM ascorbic acid is added, in curve, " (a → b) shows that bare electrode has electricity for ascorbic acid
Catalysed oxidn；And for Cu-Dada/GCE, a pair of redox peaks occurs in -0.05/-0.31V, it is respectively labeled as
Peak 1 and peak 2, are attributed to Cu (I)/Cu (II) oxidation-reduction process.After 1.0mM ascorbic acid is added, the peak 2 of peak 1
Electric current have enhancing (c → d), show that avtive spot Cu has electrocatalytic oxidation effect for ascorbic acid.Meanwhile, add
After 1.0mM ascorbic acid, new peak position peak 3 ' is generated in d curves in 0.4V or so, and the more original peak position of curent change is more
Substantially, thus selection 0.4V as ascorbic acid detection current potential.
It is placed according to Cu-Dada/GCE in three-electrode system in the range of -0.8-1V by cyclic voltammetry result.
Cu-Dada/GCE prepared by embodiment 7 selects 0.35V as the operating potential of chronoamperometry, continually adds different dense
The ascorbic acid of degree, standard curve is explored according to concentration and the relation of electric current, obtains Cu-Dada/GCE detection ascorbic acid standards
Curve, minimum detectability 2.6 × 10-7M, sensitivity is 24..3mA mol-1L cm-2, the range of linearity 4.5 × 10-5-1.5×10-3M (R=0.993).
The operating potential 0.4V for changing chronoamperometry obtains standard curve, and detection range is 1.6 × 10-5-2.2×10- 3M, sensitivity is 37.5mA mol-1L cm-2, minimum detectability is 1.37 × 10-6M (R=0.997).
The operating potential 0.45V for changing chronoamperometry obtains standard curve, minimum detectability 3.54 × 10-7M, sensitivity
For 19.8mA mol-1L cm-2, the range of linearity 6.7 × 10-5-9.5×10-4M (R=0.99).
As a result the electrode of selection 0.4V current potential has superior chemical property.
By CV curve maps, selection 0.4V does standard curve as detection current potential.0.1Ms of the Cu-Dada/GCE in pH=7.0
The response time map of current of Ascorbic Acid in PBS deoxygenation cushioning liquid, as shown in figure 13.With addition ascorbic acid amount
Increase, the electric current of response also gradually increases, within the specific limits linearly.Calculated by the standard curve of illustration, Cu-Dada/
The range of linearity of GCE detection ascorbic acid is 1.6 × 10-5-2.2×10-3M (R=0.997), sensitivity is 37.5mA mol L-1cm-2, minimum detectability is 1.37 × 10-6M.Equally, table 3 compared for three Cu-Dada/GCE electrode detection ascorbic acid
Response current numerical value, Cu-Dada/GCE has preferable reappearance for the detection of ascorbic acid.
Table 3Cu-Dada/GCE detects the reappearance of ascorbic acid
The Cu-Dada/GCE prepared by have studied embodiment 7 detects the selectivity of ascorbic acid.As shown in figure 14, it is
1 ascorbic acid (1.0mM), 2 sodium chloride (0.5mM), 3 potassium nitrate (0.5mM), 4 calcium chloride are added when detecting ascorbic acid
(0.5mM), 5 glucose (0.5mM), 6 citric acids (0.5mM), 7 uric acid (0.5mM), 8 ascorbic acid (1.0mM) interfering material
I-t curve maps.Found by Figure 14, the addition of non-oxidizing inorganic salts and some organic matters is not disturbed or for Vitamin C
The detection interference of acid is little, shows that Cu-Dada/GCE has preferable selectivity for the detection of ascorbic acid.
The sensor of testing example 7 and 8 detects the stability of ascorbic acid：
1. electrode was placed after two weeks, Cu-Dada/GCE Ascorbic Acids stability is 99.8%, with Cu-Dada/
MWCNTs/GCE is to H2O2Stability be 99.9%.
2. after electrode is placed one month, Cu-Dada/GCE Ascorbic Acids stability is 99.4%, with Cu-Dada/
MWCNTs/GCE is to H2O2Stability be 99.9%.
3. after electrode is placed two months, Cu-Dada/GCE Ascorbic Acids stability is 99.1%, with Cu-Dada/
MWCNTs/GCE is to H2O2Stability be 99.7%.
4. after electrode is placed three months, Cu-Dada/GCE Ascorbic Acids stability is 98.7%, with Cu-Dada/
MWCNTs/GCE is to H2O2Stability be 99.6%.
As a result show that this electrode has preferable stability.
By electrode room temperature preservation, the detection of stability is carried out after 3 months, Cu-Dada/GCE is to 0.25mM Vitamin Cs for detection
The response of acid, as a result shows that response current is original 98.7% after three months.And Cu-Dada/MWCNTs/GCE0.25mM
H2O2Response, it is original 99.6% as a result to show response current after three months.
Pass through Cu-Dada, Cu-Dada/MWCNTs and some other hydrogen peroxide sensor performance parameter.It can send out
The Integrated comparative Cu- such as existing Cu-Dada and metal coordinating polymer, the composite of carbon nanotubes, noble metal, enzyme, oxide
Dada has very big advantage in terms of detection limit, while the range of linearity is also wider, it is the electrification of an excellent hydrogen peroxide
Learn sensor.After using carbon nano-tube modification, the performance of sensor is improved, and its sensitivity is improved nearly twice,
Meanwhile, the range of linearity of sensor has also increased.Equally, Cu-Dada and Cu-Dada/MWCNTs anti-interference curve is contrasted,
It can be found that Cu-Dada/MWNCTs current-responsive is bigger, antijamming capability more preferably, equally, is doped with the Cu- of CNT
More preferably, the influence for receiving systematic error and accidental error is smaller for Dada/MWCNTs reappearance.In summary, Cu-Dada is one
The electrochemical sensor of more excellent detection hydrogen peroxide is planted, meanwhile, doped carbon nanometer pipe can play modification to Cu-Dada
Effect, significantly improve the performance of the sensor.
Cu-Dada detects ascorbic acid better performances compared with the materials such as graphene, and its detection limit and the range of linearity have
Some advantages.Cu-Dada provides a kind of new method for the detection of ascorbic acid, and Cu-Dada is in terms of ascorbic acid is detected
With certain prospect.
Claims (10)
1. a kind of metal esters complex Cu-Dada, it is characterised in that by mol ratio be 1：The 1 of (3-5), 8 anthracene dicarboxylic acids
Dimethyl ester and copper nitrate are prepared from.
2. metal esters complex Cu-Dada according to claim 1, it is characterised in that the compound is matched somebody with somebody
Body is ester, and coordination center is Cu, and the mol ratio of Cu and part ester and nitrate anion is 2：1：2.
3. a kind of metal esters complex Cu-Dada as claimed in claim 1 preparation method, it is characterised in that bag
Include following steps：
(1) by 1,8 anthracene dimethyl dicarboxylates and copper nitrate are mixed and soluble in water in proportion, obtain mixed solution A；
(2) mixed solution A is added to after heating response in reactor, Temperature fall and dries product centrifuge washing, obtain gold
Belong to esters complex Cu-Dada.
4. preparation method according to claim 3, it is characterised in that the temperature of step (2) described heating response is 130-
150 DEG C, the time is 6-8d.
5. a kind of applications of metal esters complex Cu-Dada as claimed in claim 1 on detector is prepared.
6. application according to claim 5, it is characterised in that the detector is for detecting malignant tumour mark egg
The electrochemica biological sensor of white EGFR-TK -7.
7. application according to claim 5, it is characterised in that the detector is for detecting H2O2With ascorbic acid
Electrochemical sensor.
8. application according to claim 6, the electrochemica biological sensor is Cu-Dada-Sgc8c/GCE, by metal
Esters complex Cu-Dada and aptamers Sgc8c are in molar ratio (10-1)：(1-2) is combined, and generates Cu-Dada-
Sgc8c, is made suspension by Cu-Dada-Sgc8c and drop coating is made in glassy carbon electrode surface.
9. application according to claim 7, the electrochemical sensor is Cu-Dada/GCE, by metal esters coordinationization
Suspension is made in compound Cu-Dada and drop coating is made in glassy carbon electrode surface.
10. application according to claim 8, the electrochemica biological bio-sensing implement body preparation method, including it is as follows
Step：Metal esters complex Cu-Dada and aptamers Sgc8c are combined, Cu-Dada-Sgc8c is generated；By Cu-
Dada-Sgc8c is dissolved in redistilled water and naphthols mixed liquor, ultrasonic disperse, obtains Cu-Dada-Sgc8c suspensions, by Cu-
The suspended drop-coateds of Dada-Sgc8c manage everywhere after glassy carbon electrode surface, at room temperature place dry, that is, be made electrochemica biological pass
Sensor Cu-Dada-Sgc8c/ glass-carbon electrodes.
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