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
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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)
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