CN102901754A - Electropolymerization molecular imprinting technology-based double-parameter composite micro-sensor and preparation thereof - Google Patents
Electropolymerization molecular imprinting technology-based double-parameter composite micro-sensor and preparation thereof Download PDFInfo
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Abstract
Relating to sensors and molecular imprinting technologies, the invention discloses an electropolymerization molecular imprinting technology-based double-parameter composite micro-sensor and a preparation thereof. According to the invention, three electrochemical microelectrode systems are integrated on a same chip, and each electrochemical microelectrode system has its independent micro-electrochemical reaction pool. Through encapsulation by a sealant, the integrated chip can form an open composite measurement pool containing three electrochemical microelectrode systems. In the micro-reaction pool of each electrochemical microelectrode system, by injecting a solution from the outside, a molecular imprinting procedure containing in situ polymerization and ultrasonic elution of template molecules can be implemented separately, thus obtaining a molecularly imprinted sensor. The left and right microelectrode systems of the composite micro-sensor respectively recognize two corresponding molecules due to different molecularly imprinted sensitive membranes, and the electrochemical microelectrode system positioned in the middle is used as a differential detection reference so as to deduct background signals and environmental effects of a test system. The composite micro-sensor provided in the invention can recognize two molecules simultaneously.
Description
Technical field
The present invention relates to electrochemical sensor and molecular imprinting field, a kind of two-parameter compound microsensor and preparation method based on the electropolymerization molecular engram.
Background technology
Along with developing rapidly of hyundai electronics and biotechnology, biosensor technique has formed an independently emerging high-tech area.Based on the biology sensor of MEMS technology, have microminiaturization, integrated, intelligentized advantage, that its matching instrument has is portable, digitizing, the advantage such as easy to use.The characteristics effective, fast detecting of biology sensor will be brought new technological revolution for fields such as biomedicine, environment measuring, food, medical industries.
Engram technology is one of 20th century biology field three great discoveries.It has brought revolutionary progress for human bioengineering with discovery and the pcr gene amplification technique of restriction endonuclease.Before quantitative immuning engram technology (quantitative immunoblotting) is come out, main application enzyme immuno-chemical method is analyzed the antigen/epitope specificity of natural and disease association autoantibody, used antibody comes from the immunoglobulin (Ig) of blood plasma or the monoclonal antibody that the random hybridoma that merges produces, and antigen is autoantigen or the related polypeptide of purifying or restructuring.Biology sensor so that this specific recognition consists of as the basis because the biomolecule environment for use is had relatively high expectations, is difficult to long preservation etc., runs in actual applications much to be difficult for the obstacle that overcomes; Simultaneously, biomolecule derives from biological living, and preparation and purifying are loaded down with trivial details, expensive.Biology sensor face low stable, expensive, can not in pH value higher or on the low side and pyrosol, use, be difficult to do not have the corresponding series of problems such as identification target molecule with micro-processing technology compatibility, some analyte, become a key factor that affects its development.In addition, the immuno-chemical method take single albumen as antigen has the simple set that inevitable defective is namely regarded numerous and jumbled immune system as plurality of antigens-antibody response.The quantitative immuning engram technology then can reflect antibody to the characteristic of autoantigen reaction comprehensively, thereby overcomes above-mentioned deficiency.Detect mixed antibody (such as serum, saliva) to the reaction of one group of autoantigen by the quantitative immuning engram method, and the result is carried out multivariate statistical analysis, can quantitatively show the whole id reaction feature of autoantibody.By research and the understanding to antigen-antibody, enzyme and substrate reactions principle, scientist has courageously proposed the imagination by the synthetic analog antibody of chemical reaction, has started a brand-new technology-molecular imprinting.This obtains cheapness, stable bionical recognition component just, promotes one of key that biology sensor further develops.
Biology sensor is comprised of recognition component and signal converter, recognition component is fixed on the surface of converter by rights, when testing molecule when recognition component is combined, produce a physics or chemical signal, converter with this signal convert to one can be quantitative output signal, realize the real time measure to testing molecule by monitoring output signal.The recognition component of conventional biosensor is made of biomolecule, such as enzyme, antibody, microorganism, tissue even complete organ; Converter has microelectrode, field effect transistor, optical fiber, thermistor and piezoelectric crystal etc.Biology sensor high sensitivity and specific advantage make it be subject to extensive concern.At present, come some important biochemical reaction in the modeling effort biosome with the electrochemical method bind profile section of learning to do, study the electro-catalysis on the bionical interface, disclose metabolism and energy conversion in the biosome, development high sensitivity and the biochemical analysis method of high selectivity and the research of biomolecular device have become one of important front edge research field of analytical chemistry and life science.This is that biology sensor is inevitable to bionical molecular device development.
This society and having in 1,300,000,000 populous nations of substantially enjoying a fairly comfortable life in China, preventing and treating diseases is to uplift the people's living standard, affect the national economy significant problem.Biomedical research has entered a brand-new electronic age, and biology sensor plays vital impact to the intelligent development of biomedical research.Clinical medicine often need to detect two kinds of parameters simultaneously, and most typical is to detect creatinine and urea.The compound microsensor of creatinine/urea is for renal insufficiency patient's renal function state-detection creatinine and urea nitrogen levels.These indexs are higher, and the degree that represents renal dysfunction is more serious.These two parameters must detect simultaneously, and single urea nitrogen is high and creatinine is not high or opposite, and are then meaningless to diagnosis renal function state.The sign of creatinine and urea nitrogen levels also must in large hospital, adopt large-scale analyser to carry out at present.Therefore study the sensor that detects simultaneously creatinine and urea nitrogen index and have important clinical meaning.Two-parameter compound microsensor based on the electropolymerization molecular engram is not limited to detection creatinine and urea, replaces template molecule, just can detect different physiologically substance molecules.
The biosensors market occupation rate is compared with other sensors and is only had 1/8 in the world, and 95% is glucose and glucose oxidase sensor wherein.Domestic biology sensor is more rare on market.The impact of this low stability mainly due to sensor, expensive shortcoming.Bionical biology sensor has high stability and specific advantage, surely its potential of performance aspect medical science detection research.Southern at first came analyzing DNA with the engram technology method in 1975, was called Southern blot; Alwine was used for RNA research with this method in 1979, was called Northern blot; The same year, Towbin etc. expanded to it again protein analysis, was named as Western blot (WBT), was called again Immunoblot (IBT), i.e. Western blotting.Can copy in theory the MIPs of any material, nearly 300 kinds of the MIPs of the inorganic ions of making, nucleic acid, protein even cell, and the emphasis that will study the engram technology of polymerization science focuses on, and utilizes computer software that molecule is carried out three-dimensional design.At organic sphere, also begin MIPs is combined with large-sized analytic instrument as sensitive element, nucleic acid, protein even cell are detected, and obtain gratifying achievement.Little by little the MIPs technology is applied to sensor in recent years: Panasyuk etc. utilize the grafting polymerization technique to prepare the molecular engram capacitive transducer at polypropylene screen and hydrophobicity gold electrode surfaces, have good selectivity.The people such as Kriz are fixed on the morphine molecularly imprinted polymer on the platinum electrode, measure the morphine that discharges by current method, and its detectable concentration scope is 0.01-1mg/L, and detection limit reaches 0.1ng/mL.The Piletsky of Ukraine utilizes cholesterol as template molecule, and hexadecane mercaptan adopts cyclic voltammetry that polymkeric substance is carried out electropolymerization as function monomer, and its sensing range is 15-60 μ M.Mullett etc. combine molecular imprinting and have developed a kind of theophylline sensor with Applications of surface plasmon resonance, measure concentration range and can reach 0.4-6g/L.Domestic analytical chemistry field is also very active to the research of MIPs, in Peking University, the molecular recognition mechanism of research MIPs, design, synthesize, estimate the novel molecular engram polymkeric substance with specificity and compatibility by the modern instrumental analysis means such as ultraviolet, infrared, chromatogram, specific surface, nuclear-magnetism and computer aided animation, and the condition of molecularly imprinted polymer preparation is optimized.They have proposed the concept of molecular engram originality, are used for describing the ability that a compound can produce high selectivity and high-affinity molecularly imprinted polymer.Also enlarging by the coordination of indirect molecular engram method and metallic ion in addition can be by the molecular range of trace, solves some little molecules and contains the trace problem of intramolecular hydrogen bond compound.Simultaneously, they also are applied to molecularly imprinted polymer the simulation of some native enzyme, constantly explore molecularly imprinted polymer in the application of catalytic field.Chemical defence research institute the 4th research institute is with the template molecule of methylphosphonic acid p-nitrophenyl ester as molecularly imprinted polymer, N-phenyl-benzamide is as the function base, synthesize the novel molecular engram analog antibody enzyme MIP-3 with " nanochannel " by being embedded into ZnO nano material, studied this enzyme to carboxylic acid p-nitrophenyl ester catalyzing hydrolysis dynamics; Result of study shows, this analoglike abzyme not only has good structure selectivity, and the ability of catalysis carboxyester hydrolysis improves greatly, for the application of synthetic molecules trace analogue enztme and nano material provides new way.
The molecular engram concept has existed for many years, still, to its experimental technique and application thereof, is in recent years along with developing rapidly of hyundai electronics and biotechnology just had considerable progress, becomes the focus of research.The stability of MIPs is higher than the bio-molecules recognition component far away, can obtain than high selectivity and specific polymkeric substance, is the ideal material that solves the bio-sensitive film poor stability.Therefore, the research of molecularly imprinted polymer is subject to people's attention.The at present research of MIPs biology sensor is process for fixation and repeatability etc. more effectively, becomes the Main Bottleneck problem anxious to be resolved that MIPs is applied to biology sensor research.How research combines biosensor technique with intrinsic high stability advantage and the achievement in research of MIPs material, overcoming the present difficult problem that exists of MIPs is responsibility and the opportunity of our Research on Sensing.In recent years, the MEMS technology has possessed research and has made traditional molecular engram detection means by equipment is large, cost is higher and energy consumption is higher to technical conditions microminiaturized, low-cost and that low energy consumption changes just increasingly mature.
List of references:
1.Sergey?A.Piletsky，S.Subrahmanyam，Anthony?P.F.Turner?“Application?of?molecularly?imprinted?polymers?in?sensors?for?the?environment?and?biotechnology”Sensor?Review，Volume?21?Number?4?2001?pp.292-296.
2.Toshifumi?Takeuchi，Yuji?Minato?et?al.Molecularly?imprinted?polymers?with?halogen?bonding-based?molecular?recognition?sites.Tetrahedron?Letters?46(2005)9025-9027
3. what is forever red etc. " Study on Molecular Imprinting-Based Biomimetic Sensors progress " analytical chemistry, 2004,32 (10): 1407～1412.
4.Tzong-Rong?Ling，Yau?Zen?Syu?et?al.Size-selective?recognition?of?catecholamines?by?molecular?imprinting?on?silica-alumina?gel.Biosensors?and?Bioelectronics?21(2005)901-907
5?A.G.Mayes，M.J.Whitcombe.Synthetic?strategies?for?the?generation?of?molecularly?imprinted?organic?polymers.Advanced?Drug?Delivery?Reviews?57(2005)1742-1778.
6?Kal?Karim，Florent?Breton?et?al.How?to?find?effective?functional?monomers?for?effective?molecularly?imprinted?polymers.Advanced?Drug?Delivery?Reviews?57(2005)1795-1808
7?Michal?Lahav?et?al.Tailored?chemosensors?for?chloroaromatic?acides?using?molecular?imprinted?TiO2?thin?films?on?ion-sensitive?field-effect?transistors.Anal.Chem.(2001)73，720-723
Summary of the invention
The objective of the invention is to disclose a kind of two-parameter compound microsensor and preparation method based on the electropolymerization molecular engram, this two-parameter compound microsensor is measured in same duplex measurement pond, can identify simultaneously two kinds of molecules, have high consistance, advantage cheaply.
For achieving the above object, technical solution of the present invention is:
A kind of two-parameter compound microsensor based on the electropolymerization molecular imprinting, it is provided with three molecular engram microsensors at same chip; Wherein, three molecular engram microsensor one row dischargings are fixed in substrate upper surface; About two microsensors, can identify simultaneously two kinds of molecules, the microsensor in the middle of being positioned at is used for the benchmark of Differential Detection, background signal and the environmental impact of deduction test macro;
The substrate lower surface is fixed in P.e.c. resin plate upper surface, and P.e.c. resin plate one side is provided with a plurality of external electrodes, and a plurality of external electrodes are connected with the electrode of three molecular engram microsensors on the chip respectively through wire;
At P.e.c. resin plate upper surface, around the chip of microsensor, be provided with the protruding wall of sealing all around, form uncovered duplex measurement pond, top, a plurality of wires and chip edge are encapsulated in the protruding wall.
Described two-parameter compound microsensor based on the electropolymerization molecular imprinting, its described three molecular engram microsensors, be three galvanochemistry microelectrode systems, each microelectrode system comprises working electrode, electrode, contrast electrode and micro reaction pool is formed; Working electrode, be that concentric circles distributes to electrode, contrast electrode, micro reaction pool, be positioned at the silicon chip upper surface that there is insulation course on glass substrate or surface; Circular working electrode is positioned at the electrode system center, at circular working electrode upper surface, original position is prepared with molecular imprinted membrane, non-closed ring contrast electrode encloses in the working electrode cylindrical, non-closed ring is positioned at the outmost turns of electrode system to electrode, spacing between three electrodes equates, and electrically insulated from one another; Three molecular engram microsensors to the electrode mutual conduction;
Three molecular engram microsensors all have the sealing ring of ring seal, consist of circular micro reaction pool, micro reaction pool pool wall internal diameter is greater than to the electrode curved inner radius, is fixed in the substrate insulation course and to the top of electrode, with working electrode, electrode and contrast electrode are trapped among wherein;
Working electrode, electrode and contrast electrode are electrically connected with external electrode on the P.e.c. resin plate through wire respectively.
Described two-parameter compound microsensor based on the electropolymerization molecular imprinting, its described substrate is silicon chip or glass sheet; When substrate was silicon chip, the silicon chip upper surface covered silicon dioxide insulating layer; When substrate is glass, the naked layer; The micro reaction pool pool wall is organic material; Working electrode is the Au film, is the Pt film to electrode and contrast electrode, and electrode is positioned at substrate or insulation course upper surface; Wire is spun gold; Duplex measurement pond side-wall material is epoxy sealing glue.
Described two-parameter compound microsensor based on the electropolymerization molecular imprinting, the working electrode upper surface of its described three molecular engram microsensors has the sensitive membrane based on the preparation of electropolymerization molecular imprinting, about two microsensors, identify respectively corresponding molecule because of the difference of molecular imprinted membrane, middle microsensor is the molecular imprinted membrane without template.
A kind of preparation method of the two-parameter compound microsensor based on the electropolymerization molecular imprinting, the manufacture method of its two-parameter compound microsensor comprises that integrated chip preparation, encapsulation and sensitive membrane prepare three parts.
The preparation method of described two-parameter compound microsensor, the preparation of its described integrated chip comprises that step is as follows:
The a-substrate is selected, silicon chip or glass sheet, and conventional the cleaning;
B-is at the silicon chip surface silicon dioxide insulating layer of growing, and thickness is 1 μ m approximately;
C-is based on the Lift-off technology, with the technique of photoetching, sputter form the Pt film to electrode and contrast electrode, thickness is 400nm approximately;
D-is based on the Lift-off technology, and with the technique formation Au thin film work electrode of photoetching, sputter, thickness is 400nm approximately;
E-casts the highly approximately solid ring of 30 μ m based on the MEMS technology with SU8 glue on the silicon dioxide insulating layer surface of chip, with working electrode, contrast electrode, electrode is trapped among wherein, consist of micro reaction pool.
The preparation method of described two-parameter compound microsensor, its described packaging technology comprises that step is as follows:
A-is bonded at the integrated chip that processes on the P.e.c. resin plate;
B-is with the way of gold ball bonding, with the working electrode of chip, to electrode and contrast electrode, is connected with external electrode on the printed circuit board (PCB);
C-erects protruding wall with the manual package method of epoxy sealing glue around chip, all spun gold wires and chip edge are encapsulated in the protruding wall, consist of uncovered duplex measurement pond.
The preparation method of described two-parameter compound microsensor, its described sensitive membrane preparation is three sensors that are positioned at same chip, has separately independently three electrodes: working electrode, to electrode, contrast electrode, and micro reaction pool galvanochemistry microelectrode system; The preparation sensitive membrane is electricity consumption polymerizable molecular engram technology, prepares molecular imprinted membrane in the working electrode surface original position, comprises situ cleaning, in-situ polymerization and the original position demoulding three parts.
The preparation method of described two-parameter compound microsensor, the situ cleaning of its described sensitive membrane preparation is the situ cleaning before three galvanochemistry microelectrode system surface in situ prepare molecular imprinted membrane, comprising: (1) is carried out conventional chemical to chip and is cleaned; (2) chip bombards 1～3min with oxonium ion to electrode surface in plasma etching machine; (3) then, drip H in the electrochemical reaction cell on micro-electrode chip
2O
2: H
2SO
4=3: the mixed solution of 7, v/v soaks 2min; (4) again with three electrodes: working electrode, to the connection corresponding to electrochemical workstation of electrode and contrast electrode, carry out cyclic voltammetry scanning, by the in-situ oxidation reduction reaction, reach the purpose of purification at electrode surface, this process repeats 2-3 time; (5) last, repeatedly replace cleaning, drying dehydration with the second alcohol and water.
The preparation method of described two-parameter compound microsensor, the in-situ polymerization of its described sensitive membrane preparation, comprise step: (1) fills with respectively the electropolymerization solution for preparing in advance in three galvanochemistry micro reaction pools; (2) again with the working electrode of chip, to electrode, contrast electrode connection corresponding to electrochemical workstation, in-0.2V～1.0V scope, carry out polymerization with cyclic voltammetry respectively, the polymerization number of turns is 30 circles, generates non-conductive polymeric membrane; (3) about in two galvanochemistry micro reaction pools, inject the electropolymerization solution that is mixed with the corresponding template molecule, contain respectively creatinine molecule and urea molecule, and inject the electropolymerization solution that does not contain template molecule in the middle galvanochemistry micro reaction pool.The wherein said electropolymerization solution for preparing in advance, select o-aminophenol as polymerization single polymerization monomer, with the dissolving of the perchloric acid solution of 0.1mol/L and be adjusted to the pH value in faintly acid, and template molecule (creatinine or urea molecule) leads to high pure nitrogen and the oxygen in the solution is discharged rear for subsequent use with 10: 1 volumetric molar concentration mixing.
The manufacture method of described two-parameter compound microsensor, the original position demoulding of its described sensitive membrane preparation, to about two microsensors, wash-out is embedded in the polymeric membrane template molecule separately respectively, comprises step, and (1) is creatinine molecule and urea molecule for example, first in the galvanochemistry micro reaction pool of the relatively little sensor of template molecule amount, wherein contain urea molecule, the ammonia spirit of injection 1% carries out the demoulding to be processed: soaked 12 hours, the low power ultrasound that carried out again 1 minute cleans; (2) then change the program three times that fresh 1% ammonia spirit repeats (1) step; (3) finally use a large amount of deionized water rinsings clean; (4) then process another sensor electrical chemistry micro reaction pool, wherein contain the creatinine molecule, the sulfuric acid solution that injects 0.5mol/L in micro reaction pool soaked four hours; (5) then change the program three times that fresh 0.5mol/L sulfuric acid solution repeats (4) step, (6) finally use a large amount of deionized water rinsings clean; Embedded template molecule not in the polymeric membrane of middle microsensor is without wash-out.
The present invention proposes the two-parameter compound sensor that combines with the electropolymerization molecular imprinting based on the MEMS technology on molecular engram urea sensor and molecular engram creatinine sensor research basis to separation.The composite micro-electrode design has wherein been proposed; In micro reaction pool, implement to comprise the molecular engram program of original position electropolymerization and ultrasonic wash-out template molecule; The measuring method of two kinds of molecules of compound microsensor identification.Related content in the invention there is not yet report.
Description of drawings
Fig. 1 is the two-parameter compound micro-sensor structure schematic diagram based on the electropolymerization molecular engram of the present invention;
Fig. 2 is the A-A cut-open view among Fig. 1;
Fig. 3 is the B-B cut-open view among Fig. 1.
Label in graphic:
1-silicon chip or glass
2-silicon dioxide insulating layer (as just not needing with glass)
3-is to electrode (Pt)
4-contrast electrode (Pt)
5, working electrode (Au)
6-is without the molecular imprinted membrane of template
7-SU8 glue is cast micro reaction pool
8-P.e.c. resin plate
9-printed circuit board (PCB) external electrode
10-pressure welding spun gold
The 11-fluid sealant consists of uncovered duplex measurement pond
The printed circuit board (PCB) external electrode of 12-working electrode
13-is to the printed circuit board (PCB) external electrode of electrode
14-contrast electrode printed circuit board (PCB) external electrode
15-template molecule trace sensitive membrane (for example creatinine)
The another kind of template molecule trace sensitive membrane (for example urea) of 16-
Embodiment
A kind of two-parameter compound microsensor based on the electropolymerization molecular engram of the present invention, its implementation is illustrated take creatinine and urea as detected object.Select creatinine and urea as template molecule, o-aminophenol is as polymerization single polymerization monomer.
Embodiment:
The compound microsensor of a kind of creatinine/urea based on the electropolymerization molecular engram of the present invention.Such as Fig. 1, Fig. 2, shown in Figure 3, implementation step is as follows:
1, at first select silicon chip or glass as substrate (1);
2, at silicon chip surface growth silicon dioxide insulating layer (2) (as just not needing with glass);
3, based on the Lift-off technology, adopt the techniques such as photoetching and sputter Pt film 400nm to form electrode (3) and contrast electrode (4);
4, based on the Lift-off technology, adopt the techniques such as photoetching and sputter Au film 400nm to form working electrode (5);
5, based on the MEMS technology, adopting SU8 glue to cast at the silicon dioxide insulating layer of chip highly is the solid ring (7) of 30 μ m, with working electrode with electrode is trapped among wherein the formation micro reaction pool;
6, the integrated chip that processes is bonded on the P.e.c. resin plate (8);
7, adopt the way of gold ball bonding, with the working electrode of chip with to electrode, with the external electrode (9) on the printed circuit board (PCB), be connected to the printed circuit board (PCB) external electrode, (13) of (12) working electrode to the printed circuit board (PCB) external electrode of electrode, the printed circuit board (PCB) external electrode of (14) contrast electrode by Ф 30 μ m spun golds (10);
8, adopt the manual encapsulation of epoxy sealing glue (11) to consist of the duplex measurement pond;
9, on packaged integrated chip, adopt the electropolymerization mode to prepare molecular imprinted membrane (6) for not containing the blotting membrane of template molecule in the working electrode surface original position of microelectrode, (15) be the creatinine molecular imprinted membrane, (16) are urea molecule trace sensitive membrane.
10, preparation molecular imprinted membrane program comprises situ cleaning, in-situ polymerization, the original position demoulding three parts:
● three galvanochemistry microelectrode system surface in situ prepare the situ cleaning of molecular imprinted membrane, except the conventional chemical cleaning way to chip, chip in plasma etching machine with oxonium ion to electrode surface 1～3min; Then, drip H in the electrochemical reaction cell on micro-electrode chip
2O
2: H
2SO
4=3: the mixed solution of 7, v/v soaks 2min, and the access electrochemical workstation, carries out cyclic voltammetry scanning, by the in-situ oxidation reduction reaction, reaches the purpose of purification at electrode surface, and this process repeats 2-3 time; At last, repeatedly replace cleaning, drying dehydration with the second alcohol and water.
● three galvanochemistry microelectrode system surface in situ prepare the in-situ polymerization of molecular imprinted membrane, it is characterized in that filling with in the galvanochemistry micro reaction pool electropolymerization solution for preparing in advance, chip is communicated with electrochemical workstation, carry out polymerization with cyclic voltammetry in-0.2V～1.0V scope, the polymerization number of turns is 30 circles.About the electropolymerization solution that injects in two galvanochemistry micro reaction pools be mixed with template molecule, the electropolymerization solution that injects in the middle galvanochemistry micro reaction pool does not contain template molecule.The electropolymerization solution for preparing in advance, it is characterized in that selecting o-aminophenol as polymerization single polymerization monomer, with the dissolving of the perchloric acid solution of 0.1mol/L and be adjusted to the pH value in faintly acid, and template molecule (creatinine or urea molecule) leads to high pure nitrogen and the oxygen in the solution is discharged rear for subsequent use with 10: 1 volumetric molar concentration mixing.
● three original position demouldings that galvanochemistry microelectrode system surface in situ prepares molecular imprinted membrane is characterized in that: to two microsensors about in the compound sensor, wash-out is embedded in the polymeric membrane template molecule separately respectively.The relatively little creatinine molecule of template molecule amount that embeds in elder generation's wash-out polymeric membrane, the ammonia spirit of injection 1% carries out demoulding processing in this galvanochemistry micro reaction pool: soaked 12 hours, carry out again 1 minute lower powered ultrasonic cleaning, then change fresh ammonia spirit and repeat said procedure three times, finally use the clean way of a large amount of deionized water rinsings; Then process the another kind of template molecule urea that embeds in the wash-out polymeric membrane, 0.5mol/L is injected in employing in the galvanochemistry micro reaction pool sulfuric acid solution soaked four hours, then change fresh sulfuric acid solution and repeat said procedure three times, finally use a large amount of deionized water rinsings clean; Embedded template molecule not in the polymeric membrane of middle microsensor is without wash-out.
11, compound sensor makes three molecular engram microsensors be positioned at same duplex measurement pond and measures when detecting.Utilize electrochemical workstation, adopted differential pulse voltammetry (DPV) to characterize sensor characteristic, inject the K of 0.01mol/L in little measuring cell of sensor
3[Fe (CN)
6] end liquid, carry out the scanning of DPV, speed is 10mV/s, and pulse-response amplitude is 50mV, and pulse width is 50ms.For the microelectrode system of centre, the polymeric membrane of working electrode surface does not embed any template molecule, and the demoulding does not produce binding site, Fe (CN) after processing in the film
6 3-Ion can not arrive electrode surface, can not produce reduction current, so the DPV curve is a horizontal line substantially; And about two not electrode system formed a large amount of binding sites after the demoulding is processed again so that Fe (CN)
6 3-Ion can arrive electrode surface and produce reduction current by these sites, and the Δ i of this moment
0Value is maximum.When to liquid at the bottom of containing the detected material molecule to sneak into the potassium ferricyanide, carry out DPV scanning, the detected material molecule is combined with the site, thus reduce so that Fe (CN) in the hole of sensitive membrane
6 3-The amount that ion arrives electrode surface reduces relatively, and Δ i value also obviously reduces.Can obtain thus the relation that detected material molecular conecentration and Δ i value change.With its calibration curve as sensor, the average sensitivity of calculating sensor.Because sensor is at the mass of making, the original position trace of sensitive membrane, and characteristic cheaply, sensor can have under the good conforming condition as disposable sensor.According to demarcating good sensitivity, direct-detection contains the K of detected material molecule
3[Fe (CN)
6] solution, just can obtain the detected material molecular conecentration.
Two-parameter compound microsensor based on the electropolymerization molecular imprinting of the present invention, its three molecular engram microsensors are positioned at same duplex measurement pond to be measured, and can identify simultaneously two kinds of molecules; About two microsensors, can identify respectively corresponding molecule because of the difference of molecular imprinted membrane, microsensor is used for the benchmark of Differential Detection in the middle of being positioned at, background signal and the environmental impact of deduction test macro; Utilize the high consistance of sensor, advantage cheaply, sensor is done disposable use.To the demarcation of sampling of same batch of sensor, obtain average sensitivity, become the performance parameter of this batch sensor.
Experimental results show that compound sensor of the present invention has intersects more by force jamming performance, adopts sensors A (molecular engram creatinine sensor) identification urea molecule, and its response is comparison creatinine molecule little obviously.The remolding sensitivity of creatinine and urea is about 11, illustrates that sensor has preferably specific performance; Adopt sensor B (molecular engram urea sensor) identification creatinine molecule, the little of urea molecule obviously compared in its response, and both are about 10.7 by ratio.
Claims (11)
1. the two-parameter compound microsensor based on the electropolymerization molecular imprinting is characterized in that, is provided with three molecular engram microsensors at same chip; Wherein, three molecular engram microsensor one row dischargings are fixed in substrate upper surface; About two microsensors, can identify simultaneously two kinds of molecules, the microsensor in the middle of being positioned at is used for the benchmark of Differential Detection, background signal and the environmental impact of deduction test macro;
The substrate lower surface is fixed in P.e.c. resin plate upper surface, and P.e.c. resin plate one side is provided with a plurality of external electrodes, and a plurality of external electrodes are connected with the electrode of three molecular engram microsensors on the chip respectively through wire;
At P.e.c. resin plate upper surface, around the chip of microsensor, be provided with the protruding wall of sealing all around, form uncovered duplex measurement pond, top, a plurality of wires and chip edge are encapsulated in the protruding wall.
2. the two-parameter compound microsensor based on the electropolymerization molecular imprinting as claimed in claim 1, it is characterized in that, described three molecular engram microsensors, three galvanochemistry microelectrode systems, each microelectrode system comprises working electrode, electrode, contrast electrode and micro reaction pool is formed; Working electrode, be that concentric circles distributes to electrode, contrast electrode, micro reaction pool, be positioned at the silicon chip upper surface that there is insulation course on glass substrate or surface; Circular working electrode is positioned at the electrode system center, at circular working electrode upper surface, original position is prepared with molecular imprinted membrane, non-closed ring contrast electrode encloses in the working electrode cylindrical, non-closed ring is positioned at the outmost turns of electrode system to electrode, spacing between three electrodes equates, and electrically insulated from one another; Three molecular engram microsensors to the electrode mutual conduction;
Three molecular engram microsensors all have the sealing ring of ring seal, consist of circular micro reaction pool, micro reaction pool pool wall internal diameter is greater than to the electrode curved inner radius, is fixed in the substrate insulation course and to the top of electrode, with working electrode, electrode and contrast electrode are trapped among wherein;
Working electrode, electrode and contrast electrode are electrically connected with external electrode on the P.e.c. resin plate through wire respectively.
3. the two-parameter compound microsensor based on the electropolymerization molecular imprinting as claimed in claim 1 or 2 is characterized in that, described substrate is silicon chip or glass sheet; When substrate was silicon chip, the silicon chip upper surface covered silicon dioxide insulating layer; When substrate is glass, the naked layer; The micro reaction pool pool wall is organic material; Working electrode is the Au film, is the Pt film to electrode and contrast electrode, and electrode is positioned at substrate or insulation course upper surface; Wire is spun gold; Duplex measurement pond side-wall material is epoxy sealing glue.
4. the two-parameter compound microsensor based on the electropolymerization molecular imprinting as claimed in claim 1 or 2, it is characterized in that, the working electrode upper surface of described three molecular engram microsensors has the sensitive membrane based on the preparation of electropolymerization molecular imprinting, about two microsensors, identify respectively corresponding molecule because of the difference of molecular imprinted membrane, middle microsensor is the molecular imprinted membrane without template.
5. the preparation method based on the two-parameter compound microsensor of electropolymerization molecular imprinting is characterized in that, the manufacture method of two-parameter compound microsensor comprises that integrated chip preparation, encapsulation and sensitive membrane prepare three parts.
6. the preparation method of two-parameter compound microsensor as claimed in claim 5 is characterized in that, the preparation of described integrated chip comprises that step is as follows:
The a-substrate is selected, silicon chip or glass sheet, and conventional the cleaning;
B-is at the silicon chip surface silicon dioxide insulating layer of growing, and thickness is 1 μ m approximately;
C-is based on the Lift-off technology, with the technique of photoetching, sputter form the Pt film to electrode and contrast electrode, thickness is 400nm approximately;
D-is based on the Lift-off technology, and with the technique formation Au thin film work electrode of photoetching, sputter, thickness is 400nm approximately;
E-casts the highly approximately solid ring of 30 μ m based on the MEMS technology with SU8 glue on the silicon dioxide insulating layer surface of chip, with working electrode, contrast electrode, electrode is trapped among wherein, consist of micro reaction pool.
7. the preparation method of two-parameter compound microsensor as claimed in claim 5 is characterized in that, described packaging technology comprises that step is as follows:
A-is bonded at the integrated chip that processes on the P.e.c. resin plate;
B-is with the way of gold ball bonding, with the working electrode of chip, to electrode and contrast electrode, is connected with external electrode on the printed circuit board (PCB);
C-erects protruding wall with the manual package method of epoxy sealing glue around chip, all spun gold wires and chip edge are encapsulated in the protruding wall, consist of uncovered duplex measurement pond.
8. the preparation method of two-parameter compound microsensor as claimed in claim 5, it is characterized in that, described sensitive membrane preparation is three sensors that are positioned at same chip, have separately independently three electrodes: working electrode, to electrode, contrast electrode, and micro reaction pool galvanochemistry microelectrode system; The preparation sensitive membrane is electricity consumption polymerizable molecular engram technology, prepares molecular imprinted membrane in the working electrode surface original position, comprises situ cleaning, in-situ polymerization and the original position demoulding three parts.
9. such as the preparation method of claim 5 or 8 described two-parameter compound microsensors, it is characterized in that, the situ cleaning of described sensitive membrane preparation is the situ cleaning before three galvanochemistry microelectrode system surface in situ prepare molecular imprinted membrane, comprising:
(1) chip being carried out conventional chemical cleans;
(2) chip bombards 1～3min with oxonium ion to electrode surface in plasma etching machine;
(3) then, drip H in the electrochemical reaction cell on micro-electrode chip
2O
2: H
2SO
4=3: the mixed solution of 7, v/v soaks 2min;
(4) again with three electrodes: working electrode, to the connection corresponding to electrochemical workstation of electrode and contrast electrode, carry out cyclic voltammetry scanning, by the in-situ oxidation reduction reaction, reach the purpose of purification at electrode surface, this process repeats 2-3 time;
(5) last, repeatedly replace cleaning, drying dehydration with the second alcohol and water.
10. such as the preparation method of claim 5 or 8 described two-parameter compound microsensors, it is characterized in that, the in-situ polymerization of described sensitive membrane preparation comprises step:
(1) in three galvanochemistry micro reaction pools, fills with respectively the electropolymerization solution for preparing in advance;
(2) again with the working electrode of chip, to electrode, contrast electrode connection corresponding to electrochemical workstation, in-0.2V～1.0V scope, carry out polymerization with cyclic voltammetry respectively, the polymerization number of turns is 30 circles, generates non-conductive polymeric membrane;
(3) about in two galvanochemistry micro reaction pools, inject the electropolymerization solution that is mixed with the corresponding template molecule, contain respectively creatinine molecule and urea molecule, and inject the electropolymerization solution that does not contain template molecule in the middle galvanochemistry micro reaction pool.
11. the manufacture method such as claim 5 or 8 described two-parameter compound microsensors is characterized in that, the original position demoulding of described sensitive membrane preparation, to about two microsensors, wash-out is embedded in the polymeric membrane template molecule separately respectively, comprises step:
(1) for example creatinine molecule and urea molecule, first in the galvanochemistry micro reaction pool of the relatively little sensor of template molecule amount, wherein contain urea molecule, the ammonia spirit of injection 1% carries out the demoulding to be processed: soaked 12 hours, the low power ultrasound that carried out again 1 minute cleans;
(2) then change the program three times that fresh 1% ammonia spirit repeats (1) step;
(3) finally use a large amount of deionized water rinsings clean;
(4) then process another sensor electrical chemistry micro reaction pool, wherein contain the creatinine molecule, the sulfuric acid solution that injects 0.5mol/L in micro reaction pool soaked four hours;
(5) then change the program three times that fresh 0.5mol/L sulfuric acid solution repeats (4) step,
(6) finally use a large amount of deionized water rinsings clean; Embedded template molecule not in the polymeric membrane of middle microsensor is without wash-out.
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Application publication date: 20130130 |