CN102175729A - Photoinduced electrochemical sensor manufactured by assembling functional grapheme and nano particle layer by layer - Google Patents
Photoinduced electrochemical sensor manufactured by assembling functional grapheme and nano particle layer by layer Download PDFInfo
- Publication number
- CN102175729A CN102175729A CN201110021525XA CN201110021525A CN102175729A CN 102175729 A CN102175729 A CN 102175729A CN 201110021525X A CN201110021525X A CN 201110021525XA CN 201110021525 A CN201110021525 A CN 201110021525A CN 102175729 A CN102175729 A CN 102175729A
- Authority
- CN
- China
- Prior art keywords
- graphene
- layer
- photoelectric
- grapheme
- electrode
- 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.)
- Granted
Links
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 9
- 230000000694 effects Effects 0.000 claims abstract description 18
- 125000000524 functional group Chemical group 0.000 claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 33
- 229910021389 graphene Inorganic materials 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 29
- 239000000463 material Substances 0.000 claims description 16
- 238000001514 detection method Methods 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- 229920002125 Sokalan® Polymers 0.000 claims description 9
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 claims description 9
- 239000002131 composite material Substances 0.000 claims description 9
- 108091023037 Aptamer Proteins 0.000 claims description 8
- 239000004584 polyacrylic acid Substances 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 229920006317 cationic polymer Polymers 0.000 claims description 6
- 230000005622 photoelectricity Effects 0.000 claims description 6
- 101710186708 Agglutinin Proteins 0.000 claims description 4
- 102000003886 Glycoproteins Human genes 0.000 claims description 4
- 108090000288 Glycoproteins Proteins 0.000 claims description 4
- 101710146024 Horcolin Proteins 0.000 claims description 4
- 101710189395 Lectin Proteins 0.000 claims description 4
- 101710179758 Mannose-specific lectin Proteins 0.000 claims description 4
- 101710150763 Mannose-specific lectin 1 Proteins 0.000 claims description 4
- 101710150745 Mannose-specific lectin 2 Proteins 0.000 claims description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 4
- 239000000910 agglutinin Substances 0.000 claims description 4
- 229920006318 anionic polymer Polymers 0.000 claims description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 4
- 239000000427 antigen Substances 0.000 claims description 4
- 108091007433 antigens Proteins 0.000 claims description 4
- 102000036639 antigens Human genes 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 230000009881 electrostatic interaction Effects 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 claims description 4
- 238000007306 functionalization reaction Methods 0.000 claims description 3
- 108010020346 Polyglutamic Acid Proteins 0.000 claims description 2
- 108010039918 Polylysine Proteins 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 claims description 2
- 229920000831 ionic polymer Polymers 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 229910052755 nonmetal Inorganic materials 0.000 claims description 2
- SLIUAWYAILUBJU-UHFFFAOYSA-N pentacene Chemical compound C1=CC=CC2=CC3=CC4=CC5=CC=CC=C5C=C4C=C3C=C21 SLIUAWYAILUBJU-UHFFFAOYSA-N 0.000 claims description 2
- 229920000962 poly(amidoamine) Polymers 0.000 claims description 2
- 229920002643 polyglutamic acid Polymers 0.000 claims description 2
- 229920000656 polylysine Polymers 0.000 claims description 2
- CQPRXCARUJOTNF-UHFFFAOYSA-N pyridine;ruthenium Chemical compound [Ru].C1=CC=NC=C1.C1=CC=NC=C1 CQPRXCARUJOTNF-UHFFFAOYSA-N 0.000 claims description 2
- 230000004044 response Effects 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 2
- 125000003118 aryl group Chemical group 0.000 abstract 1
- 230000000975 bioactive effect Effects 0.000 abstract 1
- 230000003993 interaction Effects 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 abstract 1
- 150000003384 small molecules Chemical class 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 8
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000002096 quantum dot Substances 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- -1 amido modified CdSe Chemical class 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 238000011010 flushing procedure Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 102000009123 Fibrin Human genes 0.000 description 3
- 108010073385 Fibrin Proteins 0.000 description 3
- BWGVNKXGVNDBDI-UHFFFAOYSA-N Fibrin monomer Chemical compound CNC(=O)CNC(=O)CN BWGVNKXGVNDBDI-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229960005070 ascorbic acid Drugs 0.000 description 3
- 235000010323 ascorbic acid Nutrition 0.000 description 3
- 239000011668 ascorbic acid Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229950003499 fibrin Drugs 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 238000006392 deoxygenation reaction Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-N 1H-imidazole Chemical compound C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- 230000005355 Hall effect Effects 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 108090000190 Thrombin Proteins 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000001652 electrophoretic deposition Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- ZUHZZVMEUAUWHY-UHFFFAOYSA-N n,n-dimethylpropan-1-amine Chemical compound CCCN(C)C ZUHZZVMEUAUWHY-UHFFFAOYSA-N 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- FUKCQLQHFFKTBW-UHFFFAOYSA-N pyren-1-amine hydrochloride Chemical compound Cl.NC=1C=CC2=CC=C3C=CC=C4C=CC1C2=C43 FUKCQLQHFFKTBW-UHFFFAOYSA-N 0.000 description 1
- RGNMXKKNDSHTFD-UHFFFAOYSA-N pyren-1-ylmethylazanium;chloride Chemical compound Cl.C1=C2C(CN)=CC=C(C=C3)C2=C2C3=CC=CC2=C1 RGNMXKKNDSHTFD-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000002109 single walled nanotube Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 229960004072 thrombin Drugs 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Images
Landscapes
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
- Light Receiving Elements (AREA)
Abstract
By utilizing the characteristic that grapheme can strengthen the photoinduced electrochemical activity of nano particles, the grapheme is firstly functionlized; an electrified polymer is anchored to the surface of grapheme by virtue of the interaction of aromatic organic small molecules with a large pi conjugated structure and the pi-pi of the grapheme, so that the grapheme is electrified. And the functional grapheme and the nano particle layer with opposite charges are assembled layer by layer, so as to obtain a sensitive photoelectric response interface reserved with active functional groups at the surface. The sensing interface can be used for detecting bioactive substances, and a highly sensitive photoinduced electrochemical sensor is obtained.
Description
Technical field
Semi-conductor nano particles has photic electrochemical activity, and the present invention utilizes Graphene to strengthen the photic electrochemical activity of semi-conductor nano particles, and utilizes this method to prepare photic electrochemica biological sensor.
Background technology
Since Becquerel found photoelectric effect first, light emission had developed in the electrochemical system one independently research contents.Utilize inorganic, the organic semiconductor functional material of photic electrochemical principle exploitation function admirable, improve the solar cell photoelectric conversion efficiency and become one of research focus.Yet photic electrochemical method is just at the early-stage in the applied research in analytical chemistry field.Photoelectric activity material commonly used at present comprises the nail complex, the dye well semiconductor nano.Wherein because nanocrystal uniqueness structurally makes the breakthrough of photoelectric material on performance become possibility.One of key of the efficient photoelectricity transition interface that the development based semiconductor is nanocrystalline is effectively to separate the photoproduction electron-hole pair and realize the transfer of electronics to electrode.Is to realize this purpose effective method and utilize the nano material that suitable band energy is arranged as electron accepter.Material with carbon element is the field, forward position of scientific and technical innovation as eco-friendly cheap material always.Fullerene of finding in 1985 and the carbon nano-tube of finding in 1991 all have been applied in the photoelectric material of semiconductor nano at present.Yet at present the photoelectric transformation efficiency based on the semiconductor nano of carbon nanomaterial of report is still lower.2004, the Britain scientist found by carbon atom with sp
2Novel two-dimentional atomic crystal-Graphene that the monoatomic layer that hydridization connects constitutes has begun to surmount carbon nano-tube and has become international forward position and the focus that gets most of the attention.
Graphene is a kind of novel two dimensional surface nano material, the monoatomic layer structures shape that it is special it have abundant and novel physical property, have outstanding heat conductivility and mechanical property, and at a high speed an electron mobility under the room temperature.The structure that Graphene is special, a series of character such as conductivity that make it have perfect quantum tunneling effect, half integral quantum Hall effect, never disappear.Because its good electric conductivity has lot of documents to report at present Graphene is applied in the research of galvanochemistry and fluorescent optical sensor, and it is less relatively that Graphene is used for photic electrochemical research report.Report Graphenes such as Guo in 2010 can strengthen the photoelectric response of CdS quantum dot, and its strengthen effect be higher than Single Walled Carbon Nanotube (Angew.Chem.Int.Ed., 2010,49,1-5).In the literary composition method of Graphene by electrophoretic deposition is fixed in the ITO electrode, again this electrode repeated multiple times immersed CdCl
2And Na
2In the S solution, directly synthetic CdS quantum dot on the electrode of pre-deposition Graphene.This method can obtain having the corresponding photoelectricity system of high photoelectricity, is used for the research of solar cell.But this method is unfavorable for further finishing, is not suitable for the preparation biology sensor.
Summary of the invention
Purpose of the present invention utilizes the Graphene of functionalization and semiconductor nano to be raw material, the photoelectric sensing interface that preparation is sensitive, and, be convenient to further assemble sensor in this interface reservation ripple alive functional group.
Method provided by the present invention may further comprise the steps:
(1) preparation negative ion or cationic polymer and have the compound of the aromaticity organic molecule of big pi-conjugated structure.
Described method, its described aromaticity organic molecule with big pi-conjugated structure can be compound and derivants thereof such as benzene, naphthalene, anthracene, pyrene, pentacene.
Described method, its described anionic polymer can be polyacrylic acid, polyglutamic acid etc.
Described method, its described cationic polymer can be polylysine, shitosan and branch molecule PAMAM etc.
(2) π-π takes place and interacts in aromaticity organic molecule that utilizes non-covalent bonding action to make to have big pi-conjugated structure and Graphene, prepares compound or the cationic polymer of positively charged and the compound of Graphene of electronegative anionic polymer and Graphene.
(3) will adopt the method for electrostatic interaction with Graphene that has negative charge in the step (2) and the photoelectric activity material that has positive electricity, be fixed in electrode surface; To adopt the method for electrostatic interaction with Graphene that has positive charge in the step (a) and the photoelectric activity material that has negative electricity, be fixed in electrode surface.
Described method, CdS, CdSe or CdSe@CdS nano particle that its described photoelectric activity material is amino or carboxyl modified, or be the ruthenium dipyridine complex of amino or carboxyl modified.
(4) the photoelectricity interface that forms in the step (3) is replaced further layer assembly by positive and negative charge, obtain the sensing interface that multilayer has Graphene and photoelectric activity material, outermost layer is the photoelectric activity material.
(5) utilize the active functional groups bioactivator of reserving on the photoelectric sensing interface that obtains in the step (4), behind the bioactivator and object effect of combination, the intensity that the compound that generates can influence photocurrent realizes the detection to object in view of the above.
Described method, its described active functional groups aptamer of reserving on the photoelectric sensing interface that obtains in the step (4) that utilizes, the intensity that the composite structure that forms after aptamer combines with object can influence photocurrent realizes the detection to target molecule in view of the above.
Described method, its described active functional groups antibody of reserving on the photoelectric sensing interface that obtains in the step (c) that utilizes, the intensity that the composite structure that forms after antigen and the antibodies can influence photocurrent realizes in view of the above to detection of antigens.
The intensity that the composite structure that forms after described method, its described active functional groups agglutinin of reserving on the photoelectric sensing interface that obtains in the step (c) that utilizes, agglutinin combine with glycoprotein can influence photocurrent realizes the detection to glycoprotein in view of the above.
(6) detection of photocurrent.The electrode immersion is contained in the solution of electron transmitter, adopt the rayed of suitable wavelength, detect photocurrent.
Described method, its described working electrode are metal electrode, nonmetal electrode or metal oxide electrode.
Described method, its described electron transmitter is ascorbic acid or triethanolamine.
Description of drawings
Accompanying drawing 2 is the influences of the different assembling numbers of plies to photocurrent.
Embodiment
Following examples will help those of ordinary skill in the art further to understand the present invention, but not limit the present invention in any form.
The structure (see figure 1) at Graphene-CdSe photoelectric sensing interface
One, this step of the preparation of polyacrylic acid-graphene complex list of references Langmuir, 2010,15022-15026 is synthetic.
(1) preparation of polyacrylic acid-pyrene compound
1.0g polyacrylic acid (PAA) is joined in the there-necked flask that contains 50mL N-Methyl pyrrolidone (NMP), and 60 ℃ of lower magnetic forces stir 2h, logical nitrogen deoxygenation.Add then with 5mL and dissolve 0.0956g 1-pyrene methylamine hydrochloride, 0.0947g dicyclohexylcarbodiimide (DCC) and 65 μ L triethylamine (Et that 5mL dissolves with NMP with NMP
3N), 60 ℃ of dark place reaction 24h.After reaction finishes, reactant liquor is placed under the condition of ice bath, the NaOH solution that adds high concentration to there being precipitation to produce, filters, with the NMP washing precipitation of 60 ℃ of 20mL three times, and then with the cold methanol wash of 20mL three times, vacuum drying, water dissolving then, use the ion exchange column desalination, freeze drying obtains white solid product polyacrylic acid-pyrene compound (PAA-pyrene).
(2) preparation of graphene oxide
Natural scale graphite (G) 12g, 10g K
2S
2O
8, 10g P
2O
5Join and be equipped with in the conical beaker that 50mL concentration is 98% the concentrated sulphuric acid, 80 ℃ of following stirring reaction 6h add the dilution of 2L water again, with the water wettability nylon microporosity membrane filtration washing drying of 0.2 μ m.The graphite oxide for preparing is put into stirring reaction in 0 ℃ the concentrated sulphuric acid that contains 460mL, with 60gKMnO
4Slowly join in the reactant liquor, the control temperature of reaction is reacted 1.5h below 10 ℃.Subsequently beaker is placed 35 ℃ of waters bath with thermostatic control, continue reaction 2h, slowly add 920mL water again, temperature is controlled at below 50 ℃, reacts 2h, adds the H of 2.8L water and 50mL 30% again
2O
2, the yellow mixture that obtains becoming clear leaves standstill a night, and the centrifugal sediment that gets with HCl and the 5L deionized water wash of 5L 10%, is removed the SO in the solution
4 2-
(3) preparation of polyacrylic acid-Graphene
Get the graphene oxide (0.5mg/mL) of the ultrasonic dispersion of 25mL, the PAA-pyrene of 25mL 0.5mg/mL, the NaOH of 10mg and the hydrazine hydrate of 1mL join in the there-necked flask, and 80 ℃ of following heated and stirred 24h get the Graphene (G-pyrene-PAA) that desired polyacrylic acid is modified.
Two, the preparation of amido modified CdSe
The 0.1M NaHTe of new system is joined the CdCl of the 1.25mM that contains 2-mercaptoethylmaine (AET)
2In the solution, pH regulator is between the 5.6-5.9.Cd
2+/ AET/HTe
-The molal weight ratio be 1: 2.4: 0.5, vigorous stirring 10min under the nitrogen deoxygenation, the 3h that refluxes then obtains amido modified CdSe.
Three, layer assembly method modified electrode
At first, at round dot of one section center mark of electrode,, leave standstill distilled water flushing behind the 15min, dry up at the polydiene propyl-dimethyl amine hydrochlorate (PDDA) of round dot center Dropwise 5 μ L.The polyacrylic acid of Dropwise 5 μ L-Graphene solution again, behind the 15min, with distilled water flushing, dry up, Dropwise 5 μ L CdSe quantum dot solution repeats above-mentioned steps again.Making outermost layer is amido modified nano-tube/CdS e.
Four, the detection of photocurrent
Using Zahner ENNIIUM electrochemical workstation at the PBS of the ascorbic acid that contains 0.1M solution (0.1M, pH=7.4), is to detect under the 50mV at bias voltage, and the light source of employing is that wavelength is 430nm, and radiant illumination is 48.22Wm
2The response (see figure 2) of photocurrent under the relatively more different assembling numbers of plies.
The photic electrochemical properties that utilizes Graphene to strengthen quantum dot detects fibrin ferment
The aptamer sequence that this experiment is used: 5 ' phosphorylated cdna: TTTTTTGGTTGGTGTGGTTGG
One, the preparation of sensor
Get the carbodiimide crosslinking chemical EDC 40 μ L of 0.2M, the imidazole buffer solution 40 μ L of the pH=6.8 of 0.1M join in the solution that contains the fit DNA of 20 μ L phosphate fibrin ferments, the activation phosphate.Getting the dna solution that 10 μ L activate drops on the electrode of layer assembly, reaction overnight with distilled water flushing, dry up, drips 10 μ L 2%BSA solution and seals unreacted active site (1h), with electrode with distilled water flushing, dry up, be dipped in the solution that contains fibrin ferment.
Two, the detection of photocurrent
Using Zahner ENNIIUM electrochemical workstation at the PBS of the ascorbic acid that contains 0.1M solution (0.1M, pH=7.4), is to detect under the 50mV at bias voltage, and the light source of employing is that wavelength is 430nm, and radiant illumination is 48.22Wm
2The variation of the different assembling stage photocurrents of sensor as shown in Figure 3.
Claims (9)
1. functionalization graphene and nano particle are assembled the method for the photic electrochemical sensor of preparation layer by layer.Step comprises:
(a) at first prepare negative ion or cationic polymer and have the compound of the aromaticity organic molecule of big pi-conjugated structure.π-π takes place and interacts in aromaticity organic molecule that utilizes non-covalent bonding action to make then to have big pi-conjugated structure and Graphene, prepares compound or the cationic polymer of positively charged and the compound of Graphene of electronegative anionic polymer and Graphene;
(b) will adopt the method for electrostatic interaction with the photoelectric activity material of Graphene that has negative charge in the step (a) and positively charged, be fixed in electrode surface; To adopt the method for electrostatic interaction with Graphene that has positive charge in the step (a) and electronegative photoelectric activity material, be fixed in electrode surface;
(c) the photoelectricity interface that forms in the step (b) is replaced further layer assembly by positive and negative charge, obtain the sensing interface that multilayer has Graphene and photoelectric activity material, outermost layer is the photoelectric activity material;
(d) utilize the active functional groups bioactivator of reserving on the photoelectric sensing interface that obtains in the step (c), when the bioactivator of combination with after object combines, the intensity that the compound that generates can influence photocurrent realizes the detection to object in view of the above.
2. method according to claim 1 is characterized in that: the aromaticity organic molecule that has big pi-conjugated structure in the step (a) can be compound and derivants thereof such as benzene, naphthalene, anthracene, pyrene, pentacene.
3. method according to claim 1 is characterized in that: the anionic polymer in the step (a) can be polyacrylic acid, polyglutamic acid etc.
4. method according to claim 1 is characterized in that: the cationic polymer in the step (a) can be polylysine, shitosan and branch molecule PAMAM etc.
5. method according to claim 1 is characterized in that: the photoelectric activity material in the step (b) is CdS, CdSe or the CdSe@CdS nano particle of amino or carboxyl modified, or is the ruthenium dipyridine complex of amino or carboxyl modified.
6. method according to claim 1, it is characterized in that: utilize the active functional groups aptamer of reserving on the photoelectric sensing interface that obtains in the step (c), the intensity that the composite structure that forms after aptamer combines with object can influence photocurrent realizes the detection to target molecule in view of the above;
7. method according to claim 1, it is characterized in that: utilize the active functional groups antibody of reserving on the photoelectric sensing interface that obtains in the step (c), the intensity that the composite structure that forms after antigen and the antibodies can influence photocurrent realizes in view of the above to detection of antigens.
8. method according to claim 1, it is characterized in that: utilize the active functional groups agglutinin of reserving on the photoelectric sensing interface that obtains in the step (c), the intensity that the composite structure that forms after agglutinin combines with glycoprotein can influence photocurrent realizes the detection to glycoprotein in view of the above.
9. method according to claim 1 is characterized in that: working electrode is metal electrode, nonmetal electrode or metal oxide electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110021525.XA CN102175729B (en) | 2011-01-13 | 2011-01-13 | Photoinduced electrochemical sensor manufactured by assembling functional grapheme and nano particle layer by layer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110021525.XA CN102175729B (en) | 2011-01-13 | 2011-01-13 | Photoinduced electrochemical sensor manufactured by assembling functional grapheme and nano particle layer by layer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102175729A true CN102175729A (en) | 2011-09-07 |
| CN102175729B CN102175729B (en) | 2013-10-09 |
Family
ID=44518934
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110021525.XA Expired - Fee Related CN102175729B (en) | 2011-01-13 | 2011-01-13 | Photoinduced electrochemical sensor manufactured by assembling functional grapheme and nano particle layer by layer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102175729B (en) |
Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102504807A (en) * | 2011-10-18 | 2012-06-20 | 西北师范大学 | Eu (III)-1,10-phenanthroline/graphene optoelectronic composite and preparation thereof |
| CN103310873A (en) * | 2012-03-08 | 2013-09-18 | 中国科学院理化技术研究所 | Transparent conductive graphene film and preparation method and application thereof |
| CN103441186A (en) * | 2013-08-29 | 2013-12-11 | 江苏大学 | Ultraviolet detector manufacturing method |
| CN103616357A (en) * | 2013-12-02 | 2014-03-05 | 江苏大学 | Visual biosensor device and preparation method thereof |
| CN103623864A (en) * | 2013-11-25 | 2014-03-12 | 天津大学 | Method for preparing Pt-based anode catalyst of direct liquid flow methanol fuel cell |
| CN103855305A (en) * | 2014-03-19 | 2014-06-11 | 北京科技大学 | Manufacturing method of fluorine-containing graphene decorative layer organic field effect transistor |
| CN103937234A (en) * | 2014-04-19 | 2014-07-23 | 中山市永威新材料有限公司 | Thermal conductive plastic applying modified carbon material, and preparation method thereof |
| CN104597082A (en) * | 2015-01-23 | 2015-05-06 | 清华大学 | Preparation method of hybridized hierarchical structure sensitive thin-film sensing device based on two-dimensional material |
| CN104589725A (en) * | 2014-12-30 | 2015-05-06 | 昆明理工大学 | Graphene-ruthenium coordination compound multilayer composite membrane and preparation method thereof |
| CN104600133A (en) * | 2014-12-30 | 2015-05-06 | 昆明理工大学 | Ruthenium complex/graphene composite film and method for producing ruthenium complex/graphene composite film on HOPG |
| CN104616895A (en) * | 2014-12-30 | 2015-05-13 | 昆明理工大学 | Ruthenium complex monomolecular film and method for preparing monomolecular film by self-assembling ruthenium complex on graphene |
| CN104649258A (en) * | 2014-12-30 | 2015-05-27 | 昆明理工大学 | Graphene-symmetrical ruthenium complex composite film and graphene self-assembly method by use of spin-coating method |
| CN104681282A (en) * | 2014-12-30 | 2015-06-03 | 昆明理工大学 | Grapheme-based composite functional membrane material and preparing method thereof |
| CN104698055A (en) * | 2015-03-08 | 2015-06-10 | 北京工业大学 | Method for orderly assembling DNA and graphene on gold electrode surface |
| CN104726603A (en) * | 2015-04-07 | 2015-06-24 | 中国科学院上海高等研究院 | Graphene quantum dot based molecular beacon sensor as well as preparation method and application of sensor |
| CN105259349A (en) * | 2015-11-03 | 2016-01-20 | 青岛农业大学 | Preparation of fixation-free biological sensing electrode and application of fixation-free biological sensing electrode to label-free homogeneous photo-electrochemical pesticide residue detection and cancer diagnosis |
| CN105694892A (en) * | 2016-03-16 | 2016-06-22 | 山东大学 | Preparation method of CdSe quantum dot with surface carrying positive charges |
| CN106596672A (en) * | 2017-01-06 | 2017-04-26 | 金华市中心医院 | Double-channel cell membrane glycosyl electrochemical sensing array and preparing method thereof |
| CN106596654A (en) * | 2016-12-11 | 2017-04-26 | 苏州大学 | Three-dimensional porous graphene ultrathin film based vertical responding gas sensor and preparation method thereof |
| CN107248452A (en) * | 2017-06-02 | 2017-10-13 | 大连理工大学 | A kind of ultrafast hydrogen ion composite eletrode material and preparation method thereof |
| CN108148810A (en) * | 2017-12-14 | 2018-06-12 | 临沂大学 | A kind of aptamer and the RNA films of luminol-gold nanoparticle functionalization and its preparation method and application |
| CN108459066A (en) * | 2018-03-21 | 2018-08-28 | 安徽大学 | Photoelectrochemistry biological immunosensor, preparation method thereof and application of photoelectrochemistry biological immunosensor in detection of specific base sequence |
| CN111175507A (en) * | 2020-03-13 | 2020-05-19 | 河南中医药大学 | Lung cancer early diagnosis kit based on signal amplification of ring-opening polymerization reaction initiated by hydroxyl functionalized graphene oxide |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101354374A (en) * | 2008-07-07 | 2009-01-28 | 浙江大学 | Chitosan-carbon nano-tube-dye-enzyme multi-layer film prepared by self-assembling for layer upon layer |
| CN101450800A (en) * | 2008-11-19 | 2009-06-10 | 北京理工大学 | Coordination layer-by-layer self-assembly of terpyridyl covalent modified multi-wall carbon nanotube and transition metal ion on functional substrate surface |
-
2011
- 2011-01-13 CN CN201110021525.XA patent/CN102175729B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101354374A (en) * | 2008-07-07 | 2009-01-28 | 浙江大学 | Chitosan-carbon nano-tube-dye-enzyme multi-layer film prepared by self-assembling for layer upon layer |
| CN101450800A (en) * | 2008-11-19 | 2009-06-10 | 北京理工大学 | Coordination layer-by-layer self-assembly of terpyridyl covalent modified multi-wall carbon nanotube and transition metal ion on functional substrate surface |
Non-Patent Citations (4)
| Title |
|---|
| 《Chem. Commun》 20101231 Xiaoru Zhang.et al "Photoelectrochemical biosensor for detection of adenosine triphosphate in the extracts of cancer cells" 第9173-9175页 1-9 第46卷, * |
| 《分析化学研究简报》 20070731 尹峰等 "基于多壁碳纳米管和聚丙烯胺层层自组装的葡萄糖生物传感器" 第1021-1.23页 1-9 第35卷, 第7期 * |
| XIAORU ZHANG.ET AL: ""Photoelectrochemical biosensor for detection of adenosine triphosphate in the extracts of cancer cells"", 《CHEM. COMMUN》 * |
| 尹峰等: ""基于多壁碳纳米管和聚丙烯胺层层自组装的葡萄糖生物传感器"", 《分析化学研究简报》 * |
Cited By (34)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102504807A (en) * | 2011-10-18 | 2012-06-20 | 西北师范大学 | Eu (III)-1,10-phenanthroline/graphene optoelectronic composite and preparation thereof |
| CN103310873B (en) * | 2012-03-08 | 2015-08-19 | 中国科学院理化技术研究所 | Transparent conductive graphene film and preparation method and application thereof |
| CN103310873A (en) * | 2012-03-08 | 2013-09-18 | 中国科学院理化技术研究所 | Transparent conductive graphene film and preparation method and application thereof |
| CN103441186A (en) * | 2013-08-29 | 2013-12-11 | 江苏大学 | Ultraviolet detector manufacturing method |
| CN103441186B (en) * | 2013-08-29 | 2016-04-06 | 江苏大学 | A kind of preparation method of ultraviolet detector |
| CN103623864A (en) * | 2013-11-25 | 2014-03-12 | 天津大学 | Method for preparing Pt-based anode catalyst of direct liquid flow methanol fuel cell |
| CN103616357A (en) * | 2013-12-02 | 2014-03-05 | 江苏大学 | Visual biosensor device and preparation method thereof |
| CN103855305A (en) * | 2014-03-19 | 2014-06-11 | 北京科技大学 | Manufacturing method of fluorine-containing graphene decorative layer organic field effect transistor |
| CN103855305B (en) * | 2014-03-19 | 2016-09-07 | 北京科技大学 | A kind of preparation method of fluorine-containing graphene modified layer organic field effect tube |
| CN103937234A (en) * | 2014-04-19 | 2014-07-23 | 中山市永威新材料有限公司 | Thermal conductive plastic applying modified carbon material, and preparation method thereof |
| CN103937234B (en) * | 2014-04-19 | 2016-03-23 | 中山市永威新材料有限公司 | Heat-conducting plastic of a kind of applying modified carbon material and preparation method thereof |
| CN104649258A (en) * | 2014-12-30 | 2015-05-27 | 昆明理工大学 | Graphene-symmetrical ruthenium complex composite film and graphene self-assembly method by use of spin-coating method |
| CN104681282A (en) * | 2014-12-30 | 2015-06-03 | 昆明理工大学 | Grapheme-based composite functional membrane material and preparing method thereof |
| CN104589725A (en) * | 2014-12-30 | 2015-05-06 | 昆明理工大学 | Graphene-ruthenium coordination compound multilayer composite membrane and preparation method thereof |
| CN104616895A (en) * | 2014-12-30 | 2015-05-13 | 昆明理工大学 | Ruthenium complex monomolecular film and method for preparing monomolecular film by self-assembling ruthenium complex on graphene |
| CN104681282B (en) * | 2014-12-30 | 2017-08-25 | 昆明理工大学 | A kind of graphene-based compound functional film material and preparation method thereof |
| CN104600133A (en) * | 2014-12-30 | 2015-05-06 | 昆明理工大学 | Ruthenium complex/graphene composite film and method for producing ruthenium complex/graphene composite film on HOPG |
| CN104597082A (en) * | 2015-01-23 | 2015-05-06 | 清华大学 | Preparation method of hybridized hierarchical structure sensitive thin-film sensing device based on two-dimensional material |
| CN104597082B (en) * | 2015-01-23 | 2017-02-22 | 清华大学 | Preparation method of hybridized hierarchical structure sensitive thin-film sensing device based on two-dimensional material |
| CN104698055A (en) * | 2015-03-08 | 2015-06-10 | 北京工业大学 | Method for orderly assembling DNA and graphene on gold electrode surface |
| CN104698055B (en) * | 2015-03-08 | 2017-02-22 | 北京工业大学 | Method for orderly assembling DNA and graphene on gold electrode surface |
| CN104726603A (en) * | 2015-04-07 | 2015-06-24 | 中国科学院上海高等研究院 | Graphene quantum dot based molecular beacon sensor as well as preparation method and application of sensor |
| CN104726603B (en) * | 2015-04-07 | 2017-05-17 | 中国科学院上海高等研究院 | Graphene quantum dot based molecular beacon sensor as well as preparation method and application of sensor |
| CN105259349A (en) * | 2015-11-03 | 2016-01-20 | 青岛农业大学 | Preparation of fixation-free biological sensing electrode and application of fixation-free biological sensing electrode to label-free homogeneous photo-electrochemical pesticide residue detection and cancer diagnosis |
| CN105694892A (en) * | 2016-03-16 | 2016-06-22 | 山东大学 | Preparation method of CdSe quantum dot with surface carrying positive charges |
| CN106596654A (en) * | 2016-12-11 | 2017-04-26 | 苏州大学 | Three-dimensional porous graphene ultrathin film based vertical responding gas sensor and preparation method thereof |
| CN106596654B (en) * | 2016-12-11 | 2019-09-17 | 苏州大学 | Vertical response type gas sensor based on three-dimensional porous graphene extra-thin film and preparation method thereof |
| CN106596672A (en) * | 2017-01-06 | 2017-04-26 | 金华市中心医院 | Double-channel cell membrane glycosyl electrochemical sensing array and preparing method thereof |
| CN107248452A (en) * | 2017-06-02 | 2017-10-13 | 大连理工大学 | A kind of ultrafast hydrogen ion composite eletrode material and preparation method thereof |
| CN108148810A (en) * | 2017-12-14 | 2018-06-12 | 临沂大学 | A kind of aptamer and the RNA films of luminol-gold nanoparticle functionalization and its preparation method and application |
| CN108148810B (en) * | 2017-12-14 | 2020-06-12 | 临沂大学 | Aptamer and luminol-gold nanoparticle functionalized RNA membrane and preparation method and application thereof |
| CN108459066A (en) * | 2018-03-21 | 2018-08-28 | 安徽大学 | Photoelectrochemistry biological immunosensor, preparation method thereof and application of photoelectrochemistry biological immunosensor in detection of specific base sequence |
| CN108459066B (en) * | 2018-03-21 | 2020-06-05 | 安徽大学 | Photoelectrochemistry biological immunosensor, preparation method thereof and application of photoelectrochemistry biological immunosensor in detection of specific base sequence |
| CN111175507A (en) * | 2020-03-13 | 2020-05-19 | 河南中医药大学 | Lung cancer early diagnosis kit based on signal amplification of ring-opening polymerization reaction initiated by hydroxyl functionalized graphene oxide |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102175729B (en) | 2013-10-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102175729B (en) | Photoinduced electrochemical sensor manufactured by assembling functional grapheme and nano particle layer by layer | |
| Shao et al. | Large-scale production of flexible, high-voltage hydroelectric films based on solid oxides | |
| Chen et al. | Gold nanoparticle-graphite-like C3N4 nanosheet nanohybrids used for electrochemiluminescent immunosensor | |
| Lin et al. | Dual-mode triboelectric nanogenerator for harvesting water energy and as a self-powered ethanol nanosensor | |
| Gao et al. | Crystalline Si/graphene quantum dots heterojunction solar cells | |
| Joshi et al. | Assembly of one dimensional inorganic nanostructures into functional 2D and 3D architectures. Synthesis, arrangement and functionality | |
| Hasobe | Porphyrin-based supramolecular nanoarchitectures for solar energy conversion | |
| Wang et al. | Silicon nanowires for biosensing, energy storage, and conversion | |
| Cassagneau et al. | Optical and electrical characterizations of ultrathin films self-assembled from 11-aminoundecanoic acid capped TiO2 nanoparticles and polyallylamine hydrochloride | |
| Faulkner et al. | Rapid assembly of photosystem I monolayers on gold electrodes | |
| Che et al. | Interfacial engineering of organic nanofibril heterojunctions into highly photoconductive materials | |
| Lin et al. | Poly (N-phenylglycine)/MoS2 nanohybrid with synergistic solar-thermal conversion for efficient water purification and thermoelectric power generation | |
| Li et al. | Asymmetric charged conductive porous films for electricity generation from water droplets via capillary infiltrating | |
| Gao et al. | Supersandwich nanowire/quantum dots sensitization structure-based photoelectrochemical “signal-on” platform for ultrasensitive detection of thrombin | |
| Shen et al. | Competitive displacement triggering DBP photoelectrochemical aptasensor via cetyltrimethylammonium bromide bridging aptamer and perovskite | |
| Ji et al. | Integration of functionalized two-dimensional TaS 2 nanosheets and an electron mediator for more efficient biocatalyzed artificial photosynthesis | |
| Wang et al. | Highly flexible coaxial nanohybrids made from porous TiO2 nanotubes | |
| Nagy et al. | Photosynthetic machineries in nano-systems | |
| Zhao et al. | Graphite-like carbon nitride nanotube for electrochemiluminescence featuring high efficiency, high stability, and ultrasensitive ion detection capability | |
| Kim et al. | Poly (3-hexylthiophene)/multiwalled carbon hybrid coaxial nanotubes: Nanoscale rectification and photovoltaic characteristics | |
| Zhao et al. | A tunable photosensor | |
| Kohmoto et al. | Controlling the adsorption of ruthenium complexes on carbon surfaces through noncovalent bonding with pyrene anchors: An electrochemical study | |
| Zhang et al. | Solar-driven evaporation device based on coal-derived nanomaterials for efficient and stable desalination | |
| Chen et al. | Highly sensitive photoelectrochemical immunosensor based on organic multielectron donor nanocomposite as signal probe | |
| Wang et al. | Designed ionic microchannels for ultrasensitive detection and efficient removal of formaldehyde in an aqueous solution |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C53 | Correction of patent of invention or patent application | ||
| CB02 | Change of applicant information |
Address after: 266061 Shandong Province, Qingdao city Laoshan District Songling Road No. 99 Applicant after: Qingdao University of Science & Technology Address before: 266042 Zhengzhou Road, Sifang District, Shandong, China, No. 53, No. Applicant before: Qingdao University of Science & Technology |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20131009 Termination date: 20150113 |
|
| EXPY | Termination of patent right or utility model |