CN100520389C - Needle biosensor based on carbon nano tube and manufacturing method thereof - Google Patents
Needle biosensor based on carbon nano tube and manufacturing method thereof Download PDFInfo
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- CN100520389C CN100520389C CNB2006100539563A CN200610053956A CN100520389C CN 100520389 C CN100520389 C CN 100520389C CN B2006100539563 A CNB2006100539563 A CN B2006100539563A CN 200610053956 A CN200610053956 A CN 200610053956A CN 100520389 C CN100520389 C CN 100520389C
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Abstract
This invention discloses one carbon nanometer needle biological sensor and its process method, which comprises hollow tube with positive electrode and negative electrode outside, wherein the hollow tube top end is set with conductive interface connected to positive and negative electrode. The invention is composed of several electrodes, wherein, the positive electrode is composed of carbon nanometer tube, conductive carbon powder, biological active subject and adhesive agent as certain proportion; the negative electrode is composed of conductive metal; the electrode is assembled to hollow tube made by biological materials to form micro needle biological sensor.
Description
Technical field
The present invention relates to the data acquisition assembly of biology, medicine detector device, relate in particular to a kind of get involved biological tissue based on needle biosensor of carbon nano-tube and preparation method thereof.
Technical background
Electrochemical sensor is to be the feature detection object with the electric signal, a kind of device of qualitative and quantitative analysis reactive material kind and concentration.Except the application of traditional field, electrochemical analysis method also is widely used for the detection of biological sample, and for example blood and urine are as a kind of means of indagation disease.When biological sample was carried out clinical analysis, the method for employing comprised chemical method, optical means, electrical method, nuclear-magnetism method etc., and electrochemical method is to develop very fast a kind of method at present.
At present, the main sampling and analyzing method that adopts on the clinical detection is with patients'blood, urinates and deliver to test center after samples such as night, tissue are taken a sample, by using large-sized analytic instrument to carry out quantitatively or detecting qualitatively.Because the uncertainty of sample time, the content of biological substance possibly can't accurately reflect the state of an illness in the sample that collects, and maybe can't reflect the trend of change of illness state.Therefore, detection method online, that work long hours is generally paid attention to.And electrochemical sensor is a kind of extraordinary means that realize this long-time online detection.
The basic comprising element of electrochemical sensor is an electrode, and the kind of the employed material of electrode is very many, but mainly is divided into two big classes: metal material and nonmetallic materials.Using maximum in the metal material is platinum and gold, is carbon/graphite and use maximum in the nonmetallic materials.Particularly in biology sensor, need bioactivator is fixed on electrode surface in a lot of the application, and therefore carbon become and use maximum electrode materials on the biology sensor owing to have electric conductivity concurrently and easy associativity.
With material with carbon element be as the greatest problem that biology sensor was faced of electrode: since the electric conductivity of carbon for metal a little less than, so the response sensitivity of sensor is lower, sensing range is less, is restricted in clinical practice.
Carbon nano-tube, a kind of material with carbon element that is found in 1991 with brand new, because conductive capability with superelevation, simultaneously the same with the conventional carbon material again, can extraordinary immobilized biological activated material (as enzyme), therefore be considered to the optimum substituent that to be the conventional carbon material, can be used for making biological sensor electrode.Simultaneously, because carbon nano-tube has the specific surface area of nano level size and super large, by the surface modification to carbon nano-tube, can fix great deal of bioactive substances, and can keep activity stabilized, so carbon nano-tube is again a kind of good biological fixnig base material.
Based on above-mentioned two characteristics of carbon nano-tube, the present invention is that electrode material is made novel needle biosensor with the carbon nano-tube, is used for imbedding hypodermis, the variation tendency of biological substance content in the long-time detection of dynamic body.
Summary of the invention
Electrochemical needle biosensor based on carbon nano-tube that the purpose of this invention is to provide biotic component content in a kind of quantitative measurment body and preparation method thereof.
It has hollow tube, is provided with positive electrode in the hollow tube, and hollow tube is provided with negative electrode outward, and the hollow tube upper end is provided with conductive interface, and is connected with negative electrode with positive electrode.
Described positive electrode with carbon nano-tube as conductive material, negative electrode with metal as conductive material.Positive electrode is bonded in hollow tube by carbon nano-tube, electrically conductive graphite powder, bioactivator and bonding agent.Negative electricity is platinum very, and the platinum layer covers the hollow tube outside surface, is compounded with biocompatibility macromolecule infiltration rete at the platinum laminar surface.The material of hollow tube is macromolecular material, glass or pottery.Very one piece of positive electricity, very parallel with one another two pieces, three pieces or four pieces of negative electricity; Very one piece of negative electricity, very parallel with one another two pieces, three pieces or four pieces of positive electricity.Bioactivator is an enzyme.Positive electrode and negative electrode mutual encapsulation are on hollow tube, and the positive electrode lead-in wire by the conductive interface end that is attached thereto, first negative electrode lead-in wire, and second negative electrode lead-in wire is connected with the external detection environment.
The method for making of carbon nano-tube needle biosensor comprises the steps:
1) with carbon nano-tube: the electrically conductive graphite powder: the enzyme freeze-dried powder evenly mixes by the mass ratio of 50:50:1 to 1:1:5;
2) in above-mentioned mixed-powder, add bonding agent, stir, behind the pulp, be pressed in the hollow tube;
3) hollow tube that filling is finished is put into vacuum sputtering equipment, forms the platinum layer in the outside surface sputter of hollow tube, and metal layer thickness is 100 nanometers to 1 millimeter;
4) conductive interface is encapsulated in an end of above-mentioned hollow tube, the positive and negative electrode on the hollow tube is connected with extension line on the conductive interface.
The present invention will solve the problem that traditional electrochemica biological sensor can't be taken into account excellent electron transport performance, catalytic performance and good bioactivator immobilization ability, the invention provides the electrochemica biological sensor that a kind of new material makes up for this reason.
Employed carbon nano-tube is through special chemical treatment among the present invention, a large amount of reactive groups has been modified on the surface, as hydroxyl, carboxyl, amino etc., can be in certain environment and enzyme molecule generation covalent bond, make the enzyme molecule be combined in carbon nano tube surface securely, form carbon nano-tube-multienzyme complex.Because the special structure of this kind compound can remain unchanged enzymatic activity for a long time.Because the insertion type biology sensor needs to keep the stable of testing result in long-time testing process, therefore this above-mentioned specific character makes biology sensor of the present invention have very excellent stability, is highly suitable for the insertion type detection system.
Because carbon nano-tube has unique apparent structure, so its electric conductivity is very excellent.Sensor of the present invention, owing to use carbon nano-tube as main conductive material, the reactivity and the preservation cycle that not only can effectively keep biological substance, and can obviously improve the conductive capability and the catalytic capability of electrode, make described sensor have better linearity sensing range and higher detection sensitivity.
When the present invention is applied to the insertion type detection, can adopt flexible biocompatible materials to make the employed hollow tube of sensor, the carbon nano-tube multienzyme complex is pressed together in the pipe as positive electrode, simultaneously platinum is formed thin layer as negative electrode with the coating or the method for sputter at the outside surface of hollow tube, make needle biosensor.This sensor has pliability, and is implantable to subcutaneous fixing, the situation of change of some biochemical parameter in the detection of dynamic body.Because the volume of sensor can be done very finely by micro-processing technology, the wound that causes during implantation is very little.
Description of drawings
Fig. 1 is based on the needle biosensor cross-sectional view of carbon nano-tube;
Fig. 2 is the D/W concentration/sensor response current graph of relation in the embodiments of the invention 3;
Fig. 3 be in the embodiments of the invention 4 24 hours concentration of glucose/sensor response current graph of relation.
Embodiment
As shown in Figure 1, the carbon nano-tube needle biosensor has hollow tube 1, is provided with positive electrode 2 in the hollow tube, and hollow tube is provided with negative electrode 3 outward, and the hollow tube upper end is provided with conductive interface 4, and is connected with negative electrode with positive electrode.
The present invention is formed by a plurality of combination of electrodes.Positive electrode with carbon nano-tube as conductive material, negative electrode with metal as conductive material.Positive electrode is mixed by a certain percentage by carbon nano-tube, electrically conductive graphite powder, bioactivator and bonding agent, is bonded in hollow tube.Negative electricity is platinum very, and the platinum layer covers the hollow tube outside surface, is compounded with biocompatibility macromolecule infiltration rete at the platinum laminar surface.The material of hollow tube is macromolecular material, glass or pottery.Positive and negative electrode is assembled in the hollow tube by the biocompatible material manufacturing and constitutes miniature needle biosensor.Above-described needle sensor can insert in the testing sample, the dynamic change of measured matter in the online test sample.
Carbon nano-tube needle biosensor of the present invention is made of at least one positive electrode and a negative electrode, and the upper end of positive electrode and negative electrode is connected with conductive interface.Described positive electrode is in the same place with the negative electrode mutual encapsulation, and is connected with the external detection environment by the conductive interface that is attached thereto, and the position of conductive interface is positioned at an end of sensor.
The employed hollow material of encapsulated electrode can be any can be by the material of machine-shaping, for example macromolecular material, glass, pottery etc.If this sensor uses in the clinical treatment field, then hollow material need be used biocompatible materials, as silicon rubber, medical superpolymer, pottery etc.
In the present invention, positive electrode is made of jointly carbon nano-tube, electrically conductive graphite powder, bioactivator and bonding agent, the shape and size of positive electrode can determine according to the shape and size of hollow material, range of size from micron to centimetre, shape can be an Any shape.
The present invention also can be: very one piece of positive electricity, very parallel with one another two pieces, three pieces or four pieces of negative electricity; Very one piece of perhaps described negative electricity, very parallel with one another two pieces, three pieces or four pieces of positive electricity.
Described positive electrode is pressed together on hollow material inside by carbon nano-tube, electrically conductive graphite powder, bioactivator and bonding agent and forms, described negative electrode is made of platinum, platinum can be coated in hollow material and form the platinum layer outward, also can be encapsulated in the hollow material.
Described bioactivator is an enzyme, and its freeze-dried powder evenly mixes with the carbon nano-tube and the dag of conduction in certain proportion, by bonding agent cohere, pressing makes positive electrode.Enzyme used in the present invention be with oxygen as reactant, hydrogen peroxide is as the enzyme that generates product, as glucose oxidase, Lactate Oxidase, cholesterol oxidase etc.
Embodiment 1:
This routine biology sensor, carbon nano-tube, electrically conductive graphite powder, glucose oxidase are mixed with 50:50:1 (mass ratio), be filled into the aciculiform hollow tube 1 interior (internal diameter 0.5mm) that glass is made after adding bonding agent, press forming 2 applies at the hollow tube outer wall by vacuum sputtering simultaneously and forms gold layer 3 as negative electrode as positive electrode.A pointed end of needle sensor is the test side, can insert subcutaneous fixing; The conductive interface 4 of the other end of sensor by special manufacturing will derive from the power detection signal of sensor and draw, and be connected with external unit by conductor wire 5,6,7, carry out signal and receive and record.
Embodiment 2
This routine biology sensor, carbon nano-tube, electrically conductive graphite powder, glucose oxidase are mixed with 1:1:5 (mass ratio), be filled in the aciculiform hollow tube of making by silicon rubber 1 (internal diameter 0.4mm) after adding bonding agent, press forming 2 applies at the hollow tube outer wall by vacuum sputtering simultaneously and forms platinum layer 3 as negative electrode as positive electrode.A pointed end of needle sensor is the test side; The conductive interface 4 of the other end of sensor by special manufacturing will derive from the power detection signal of sensor and draw, and be connected with external unit by conductor wire 5,6,7, carry out signal and receive and record.
This routine biology sensor, carbon nano-tube, electrically conductive graphite powder, glucose oxidase are mixed with 5:3:2 (mass ratio), be filled into the aciculiform hollow tube 1 interior (internal diameter 0.3mm) that polyimide is made after adding bonding agent, press forming 2 applies at the polyimide tube outer wall by vacuum sputtering simultaneously and forms platinum layer 3 as negative electrode as positive electrode.A pointed end of needle sensor is the test side, can insert subcutaneous fixing; The conductive interface 4 of the other end of sensor by special manufacturing will derive from the power detection signal of sensor and draw, and be connected with external unit by conductor wire 5,6,7, carry out signal and receive and record.
Fig. 2 be this sensor in phosphate buffer (pH7) to the current-responsive curve of concentration of glucose, the glucose solution concentration that each ladder is corresponding respectively in the curve is 0,1,5,10,15,20mmol/L, and the test duration of each concentration of glucose is 200 seconds.
Embodiment 4:
This routine biology sensor, production method and last example are similar, carbon nano-tube, electrically conductive graphite powder, glucose oxidase are mixed with 5:2:3 (mass ratio), be filled into the aciculiform hollow tube 1 interior (internal diameter 0.4mm) that polyimide is made after adding bonding agent, press forming 2 forms platinum layer 3 as negative electrode by vacuum sputtering in the sputter of polyimide tube outer wall simultaneously as positive electrode.A pointed end of needle sensor is the test side, can insert subcutaneous fixing; The conductive interface 4 of the other end of sensor by special manufacturing will derive from the power detection signal of sensor and draw, and be connected with external unit by conductor wire 5,6,7, carry out signal and receive and record.
Only, form positive electrode, two negative electrodes at two platinum layers of outside wall portions difference sputter of hollow tube.This sensor is put into the glucose solution that concentration is 5mmol/L, continuous 24 hours uninterrupted its current-responsives of test, the result is shown in Figure 3.
Claims (1)
1, a kind of method for making of carbon nano-tube needle biosensor is characterized in that, it comprises the steps:
1) with carbon nano-tube: the electrically conductive graphite powder: the enzyme freeze-dried powder evenly mixes by the mass ratio of 50:50:1 to 1:1:5;
2) in above-mentioned mixed-powder, add bonding agent, stir, behind the pulp, be pressed in the hollow tube, form positive electrode;
3) hollow tube that filling is finished is put into vacuum sputtering equipment, forms the platinum layer in the outside surface sputter of hollow tube, forms negative electrode, and metal layer thickness is 100 nanometers to 0.5 millimeter;
4) conductive interface is encapsulated in an end of above-mentioned hollow tube, the positive and negative electrode on the hollow tube is connected with extension line on the conductive interface.
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| CNB2006100539563A CN100520389C (en) | 2006-10-25 | 2006-10-25 | Needle biosensor based on carbon nano tube and manufacturing method thereof |
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| KR100996532B1 (en) * | 2008-08-22 | 2010-11-24 | 주식회사 엠아이텍 | A method for enhancing the sensitivity of biosensor based on carbon nanotube using linker and spacer |
| CN105319257A (en) * | 2015-11-05 | 2016-02-10 | 北京农业信息技术研究中心 | ABA (abscisic acid) concentration detection method based on biosensing technology |
| CN108828037B (en) * | 2018-06-26 | 2020-04-24 | 长春工业大学 | Gold nano electrode and preparation method thereof |
| CN111693444B (en) * | 2020-06-24 | 2021-09-28 | 南京大学 | Spring nanowire detector for cell mechanics detection and detection method thereof |
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| Title |
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| 碳糊电极在有机物电化学分析中的应用. 刘传根等.化学研究与应用，第17卷第4期. 2005 |
| 碳糊电极在有机物电化学分析中的应用. 刘传根等.化学研究与应用，第17卷第4期. 2005 * |
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