CN1766599A - Nano biologic enzyme electrode - Google Patents
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- CN1766599A CN1766599A CN 200510030082 CN200510030082A CN1766599A CN 1766599 A CN1766599 A CN 1766599A CN 200510030082 CN200510030082 CN 200510030082 CN 200510030082 A CN200510030082 A CN 200510030082A CN 1766599 A CN1766599 A CN 1766599A
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Abstract
The invention relates to a nanometer biology enzyme electrode which is formed by the tree-sharp macromolecular packaging mental nanometer and enzyme self-assembling. The nanometer particle is packaged inside the tree-sharp macromolecular to keep better activity; the electrode surface forms multi-foil layer with better scattering character and nanometer mental particle which can abridge the respond time and improve the sensing ability of the enzyme sensor. It can make super sensitive nanometer biology enzyme electrode by choosing different enzyme oxide needed by different applied.
Description
Technical field
The present invention relates to the used biochemical electrode of methods analyst material, particularly a kind of overdelicate nano biologic enzyme electrode that contains the nano-metal particle enhancing, and its preparation method by the test electrochemical variable.
Background technology
Biology sensor all has important purposes because it has that volume is little, precision is high, sensitivity is good and is convenient to advantage such as on-site measurement at aspects such as clinical diagnosis, Industry Control, food and Pharmaceutical Analysis, bio-pharmaceutical exploitation, environmental analysis, military field, biotechnology and biochips.As utilize the glucose biological sensor of glucose oxidase assembling, can be used for measuring the sugar part in people's blood sugar, industrial waste water, fermentation or the beverage.But the biologic enzyme electrode that biology sensors such as at present commercially available glucose, cholesterol are used exists, and background current is big, response characteristic is poor, be subject to the influence of oxygen concentration in the environment and be subject to many shortcomings such as electroactive material interference, has limited its practical application.In recent years, people attempt nano metal particles or nano metal composite particle etc. is incorporated in the enzyme electrode of biology sensor, utilize the specific surface area of metal nanoparticle big, the surfactivity center is many, surface reaction activity is high, catalytic efficiency is high, high adsorption capacity, and excellent properties such as good conductivity, improve electron transport between stability, catalytic activity and the enzyme of enzyme and the electrode, thereby increase substantially the current-responsive sensitivity of electrode.
Chinese patent CN 1427074A (2003) Granted publication a kind of complex enzyme function sensitive membrane and method for making and purposes that contains hydrophilic nano-platinum particle and hydrophobic silicon dioxide granules.It is with nano particle and oxidase aqueous solution, and then is dispersed in the high-molecular gel, spreads upon the composite sensitive film that electrode surface makes nano particle and glucose oxidase, and the susceptibility of current-responsive has been improved tens times.Weak point is to fail to solve the problem of easily reuniting between nano particle, and reunion then can cause the enzyme after the immobilization overlapping each other, and the effective active surface area descends, thereby has limited the abundant raising of enzyme membrane susceptibility.
In order to obtain the uniform nano particle of monodispersed particle diameter, selecting suitable template and stabilizing agent in preparation process for use is a kind of effective method.The size homogeneous of dendrimer, its big I is controlled by the algebraically of growth, and therefore yardstick is a kind of good template of preparation nano particle in the scope of several nanometers.In recent years, the people such as Crooks of the U.S. adopted a kind of novel be the method that template prepares monodispersed transition metal nano-cluster with dendrimer.Specific practice is: utilize the inner earlier amino and transition metal ion complexing of dendrimer polyamide-amide (PAMAM), transition metal is captured in the dendrimer, add excessive reductive agent again metallic ion is reduced into zero-valent metal, can generate the nano metal bunch of tree-like macromolecule encapsulation, particle diameter is generally in 5nm.But nano-metal particle/dendrimer compound that the encapsulation back generates is used as the catalyzer of organic synthesis, does not relate to biologic enzyme electrode.
Simultaneously, dendrimer itself also is a kind of nano particle, and it is assembled on the sensor, also can improve the sensitivity of sensor to a certain extent.European patent EP 1278061 A1 (2001) disclose a kind of by chemical sensor that nano particle/the dendrimer compound constitutes.Amine dendrimer by functionalization between nano particle connects and is netted and arranges, and the amine dendrimer branch can be used as the selectivity door, can effectively absorb the molecule of analyte, improves the sensitivity of sensor.And the functional group of tree-like macromolecule surface enrichment also provides possibility for the chemo-selective of sensor.But in this invention, nano particle is to be present between dendrimer, and the cluster particle diameter is big, and this invention does not simultaneously relate to enzyme biologic sensor yet.
Summary of the invention
In order to solve problems of the prior art, the present invention proposes the nano biologic enzyme electrode of a kind of amine dendrimer package metals nano particle and enzyme self assembly formation multilayer film sensing interface; And open its preparation method.
Technical scheme of the present invention is:
Nano biologic enzyme electrode of the present invention is a kind of biology sensor that contains the multilayer film sensing interface that is formed by self assembly by dendrimer package metals nano particle/enzyme, it is characterized in that, described nano biologic enzyme electrode comprises electrode, be adsorbed on electrode surface, inside is packaged with the multilayer sensing membrane that the dendrimer of metal nanoparticle and enzyme form.
Said electrode comprises the electrode of carbon, platinum, silver or gold;
Said dendrimer is meant the high molecular polymer of the different algebraically with dendritic structure, can comprise the 1-7 polyamide-amide in generation (PAMAM), the polypropylene imines (PPI) in 1-7 generation, and only is the PAMAM in 5 generations.
Said nano-metal particle is meant transition metal, as copper, and platinum, palladium, gold, monometallic nano particle or their potpourri duplex metal nano granules such as silver.Nano particle is encapsulated in the cavity of dendrimer inside, and particle diameter is at 0.5～5nm.Every gram dendrimer contains the nano-metal particle (molecular weight of 1 gram G5.0 dendrimer is 18000, with the ratio of the amount of metal be 1: 25～1: 40) of 1.3～2.2mmol.
Said enzyme is selected one or more in glucose oxidase, Lactate Oxidase, horseradish hydrogen peroxidase, cholesterol oxidase, xanthine oxidase, acetylcholinesterase, the organophosphor hydrolytic enzyme for use.
The multilayer sensing membrane that the metal nanoparticle of said dendrimer encapsulation and enzyme form is to be that the dendrimer that is packaged with nano-metal particle alternately constitutes sequence layer by one deck enzyme one deck.ABABAB for example, wherein A is an enzyme, B is the dendrimer that is packaged with nano-metal particle.The sequence number of plies is unrestricted, and effective adsorbance of enzyme successively increases to improve the sensitivity of sensor, regulates so the sensitivity of sensor can be controlled the assembling number of plies.Also can select two kinds of different types of enzymes for use,, make up the sequence layer that has of ABCBAB for example according to identical method, A wherein, C is an enzyme, B is the dendrimer that is packaged with nano-metal particle.Or and the like, generate different arrange sequence layer arranged.The method of film forming is to utilize the static self-assembling technique, leans on the electrostatic attraction film forming between layer and the layer.The CONTROL PROCESS condition, make the metal nanoparticle of dendrimer encapsulation have different electric charges with oxidase, as being 6.8 at solution environmental in the pH value, glucose oxidase generally is electronegative, and metal nanoparticle/dendrimer compound then is positively charged.
The preparation method of above-mentioned hypersensitive nano biologic enzyme electrode comprises the steps:
1) preparation of the dendrimer of different algebraically:
The big molecule of method synthesizing tree-like is dispersed in employing, hocket by Michael addition reaction and amidation process by ethylenediamine and methyl acrylate as the tree-like macromolecule PAMAM of polyamide-amide, whenever finish once complete Michael addition reaction and amidation process, then dendrimer increases a generation.
The PAMAM (being initially ethylenediamine) in whole generation is dissolved with absolute methanol, and after the logical nitrogen deoxygenation, under-40 ℃～0 ℃, preferably-30 ℃, the dropwise addition of acrylic acid methyl esters reacts after 12～96 hours decompression distillation, obtain colourless or faint yellow pulpous state viscous fluid, promptly obtain the dendrimer PAMAM in half generation.
Ethylenediamine is dissolved with absolute methanol, and logical nitrogen deoxygenation under-40 ℃～0 ℃, preferably-30 ℃, drips half for PAMAM solution.Behind the low-temp reaction 12～96 hours, system is risen to room temperature, continue reaction after 12～96 hours, its decompression distillation (adding the entrainer of several normal butyl alcohols) as excessive ethylenediamine, obtain colourless or faint yellow pulpous state viscous fluid, promptly obtain the dendrimer PAMAM in whole generation.
2) encapsulation of nanometer monometallic particle in the dendrimer:
The aqueous solution of the dendrimer (as PAMAM) that step 1) is obtained, concentration is 0.5～50 μ M, with the aqueous solution that contains certain density metallic ion (as copper), concentration is 1 * 10
-6～5 * 10
-1M, 0.1M preferably mixes by certain stoichiometric proportion (1: 12～64), uses weak acid, and as citric acid, the pH value of regulator solution is at 3～5, makes the amido complexing of metallic ion and dendrimer inside.Add excessive reductive agent again, as hydrazine hydrate, sodium borohydride etc., concentration is 0.1～0.5M, 0.3M preferably, and the ionizable metal salt in the reduction dendrimer can make encapsulation so that the dendrimer compound of nano zero-valence metal to be arranged.The particle diameter of dendrimer is generally several nanometers, is encapsulated in the particle diameter of the particle diameter of the zero-valent metal in the dendrimer less than dendrimer, also is several nanometers therefore.The particle diameter of the Pt nanoparticle of the PAMAM encapsulation in general four generations is at 0.5～4nm.
The packaging technology of bimetal granule is substantially with this step in the dendrimer, just the metal ion solution that will mix with dendrimer changes the mixed solution of thermometal ion into, as the bivalent ions mixed solution of platinum and palladium, encapsulate through complexing, reduction step again.The interionic stoichiometric proportion of thermometal is 1: 0.1～10, preferably 1: 3.
3) preparation of the multilayer sensing membrane of the metal nanoparticle of dendrimer encapsulation and enzyme formation:
The preparation of the multilayer sensing membrane that the metal nanoparticle of dendrimer encapsulation and enzyme form is to carry out on carbon, platinum, gold or silver-colored electrode.First end portion with aluminium powder polishing platinum electrode, after the mixed liquor heating with 1: 3 nitric acid of volume ratio and hydrochloric acid, the cleaning electrode surface, be placed on ethanol again, the mixed solution ultrasonic cleaning electrode of acetone and chloroform is used the distilled water ultrasonic irrigation, clean electrode surface subsequently, with metal electrode in the aqueous solution of 2% potassium hydroxide ultrasonic 20 minutes, make negative charge on the surface of metal electrode band again.
Adsorb the metal nanoparticle of dendrimer encapsulation and the process of the multilayer sensing membrane that enzyme forms at electrode surface:
I) with step 2) the dendrimer compound that is packaged with nano metal that obtains is mixed with aqueous solution, the nano metal complex concentration is 2mg/mL, enzyme is dissolved in the damping fluid of 0.1M, concentration adjustment obtains being packaged with the dendrimer compound water solution A and the oxidase aqueous solution B of nano metal at 5～10mg/mL.
Ii) the platinum electrode solution after the cleaning vertically is immersed in the water solution A of the dendrimer compound that is packaged with nano metal, the height of aqueous solution must be higher than the clean surface place of electrode.Adsorb 5～60min under the room temperature, preferably 10～30min forms the dendrimer complexes membrane that one deck is packaged with nano metal in platinum electrode surface.Then platinum electrode is carefully taken out from adsorption liquid, wash 3～5 times nitrogen repeatedly with deionized water and dry up.
Iii) with step I i) in the existing one deck in the surface that obtains platinum electrode of being packaged with the dendrimer complexes membrane of nano metal be inserted into again in the oxidase solution B, and ii) ensuing set by step operation is carried out once again.The oxidasic amount that is used to adsorb must be greater than the amount in a unimolecular layer of dendrimer complexes membrane surface adsorption that is packaged with nano metal.
Iv) step I is obtained platinum electrode in ii) and be inserted in the solution A again, and ii) ensuing set by step operation is carried out once again.So circulation repeatedly obtains the nano biologic enzyme electrode that surface-assembled has the multilayer sensing membrane that metal nanoparticle and enzyme by the dendrimer encapsulation form.
4) overdelicate nano biologic enzyme electrode is used for enzyme biologic sensor
Contain metal nanoparticle and the enzyme that dendrimer encapsulates with the surface that step 3) obtains, as glucose oxidase, the platinum electrode of the multilayer sensing membrane that forms is a working electrode, platinum electrode is to electrode, Ag/AgCl electrode or mercurous chloride electrode are as contrast electrode, the constitutive enzyme biology sensor is as the glucose oxidase enzyme biologic sensor.It is 6～7 phosphate buffered solution that three electrodes of enzyme biologic sensor are placed the pH value, measures its response current value, corresponding to the detected components concentration of response, as concentration of glucose, makes the electrode current response curve.
Advantage of the present invention and effect
The above-mentioned nano biologic enzyme electrode that makes has following characteristics: (1) has selected for use structural integrity, the uniform nanoscale dendrimer of particle diameter to prepare the zeroth order nano-metal particle as template, and the nanoparticle size that obtains is more even, and monodispersity can be better; Nano particle still keeps its activity because steric effect is encapsulated in dendrimer inside simultaneously; And the branch of dendrimer can be used as the selectivity door, and micromolecule still can be near packed nano particle; (2) the feasible surface modification that has encapsulated the compound of nano-metal particle of the functional group of dendrimer surface enrichment reaches more simple with being connected of other materials; (3) contain good dispersion in platinum electrode surface formation, particle diameter is at the multilayer film of the nano-metal particle of 0.5～5nm, the assembling of nano-metal particle and enzyme is arranged in order, the macro quanta tunnel effect of nano particle, response time can be shortened, improve the sensitivity of enzyme sensor, make the response current of enzyme sensor become order of magnitude ground to improve; And can widen the range of linearity that biology sensor is measured; (4) the multilayer sensing membrane immobilised enzymes that forms by the metal nanoparticle and the enzyme of dendrimer encapsulation of the method preparation of adopting the static self assembly, can improve the amount that is immobilized enzyme in the biologic enzyme electrode by increasing the assembling number of plies, prolonged biologic enzyme electrode serviceable life, enzyme membrane is put 0～4 ℃ in refrigerator and can be preserved more than 1 year;
(5) when the multilayer sensing membrane that platinum electrode surface preparation is formed by the metal nanoparticle and the enzyme of dendrimer encapsulation, can select different types of oxidase for use, make diversified overdelicate nano biologic enzyme electrode according to different application demands.
Embodiment
Further illustrate content of the present invention below in conjunction with embodiment, but these embodiment do not limit protection scope of the present invention.
Embodiment 1
Step (1) is dissolved in the 20g ethylenediamine in the 100mL methyl alcohol, stirs, and logical nitrogen 15min drips the methyl acrylate of 1.36mol with constant flow pump under-30 ℃, and low temperature is down behind the reaction 48h, temperature is raised to room temperature (20 ℃) allows its slaking 48h.After reacting completely, be lower than 45 ℃, solvent methanol and excessive methyl acrylate are removed in decompression distillation under the 0.1MPa, obtain 0.5G PAMAM.
With above-mentioned 25mmol-0.5G PAMAM is dissolved in the 100mL methyl alcohol, drips with constant flow pump to contain in the ethylenediamine methanol solution of 200mmol, behind the 48h low-temp reaction, adds the 48h room temperature reaction again.After same question response is complete, be lower than 45 ℃, decompression distillation under the 0.1MPa adds simultaneously and removes after normal butyl alcohol and ethylenediamine are formed azeotropic mixture, obtains 1G PAMAM.
Repeat above-mentioned building-up process, can obtain half generation of the different algebraically from 0.5G to 7G or whole for the PAMAM dendrimer.
5 generation dendrimer PAMAM of step (1) preparation are mixed with the aqueous solution of 50 μ M, use weak acid, as citric acid, the pH value of regulator solution is 5.Measuring 20mL 5 generation PAMAM dendrimer aqueous solution pours in the small beaker of 50mL.
It is the K of 0.1M that step (2) adds concentration
2PtCl
4Aqueous solution, dendrimer PAMAM and K
2PtCl
4Mol ratio be 1: 30.Stir, reaction is 72 hours under the room temperature.
Step (3) adds the K that compares again
2PtCl
420 times of amounts excessive, concentration is the reductive agent NaBH of 0.3M
4Aqueous solution, the pH value to 8 of the hydrochloric acid conditioning solution of usefulness 0.1M is reduced into the zeroth order nano particle with complexing metallic ion in dendrimer.Reduction reaction takes place rapidly, then solution is poured in the bag filter, and dialysis is 24 hours in a large amount of water environments, therebetween through repeatedly changing water.Obtain the compound that inside has encapsulated the dendrimer PAMAM of nano-metal particle.This compound is mixed with the aqueous solution of 2mg/mL, is placed in the small beaker of 50mL.
Step (4) vertically is immersed in the platinum electrode solution after the cleaning in the 50mL small beaker of the glucose oxidase solution that 5mg/mL is housed, and the height of solution must be higher than the clean surface place of electrode.Adsorb 30min under the room temperature, form the film of one deck glucose oxidase in platinum electrode surface.Then platinum electrode is carefully taken out from adsorption liquid, wash repeatedly 3～5 times with phosphate buffer.
Step (5) has the platinum electrode insertion of one deck glucose oxidase film to contain in steps in the aqueous solution of the dendrimer compound that is packaged with nano metal that obtains in (3) on the surface that obtains in the step (4), and (4) ensuing operation is carried out once more set by step, and adsorption time is 20min.
Constantly repeating step (4), (5) obtain the nano biologic enzyme electrodes that surface-assembled has three multiple layer the sensing membrane that metal nanoparticle and enzyme by the dendrimer encapsulation form at last.
The metal Pt nano particle of dendrimer encapsulation is contained on the surface that step (6) will obtain and the platinum electrode of the multilayer sensing membrane that glucose oxidase forms is a working electrode, platinum electrode is to electrode, the Ag/AgCl electrode is formed the glucose oxidase enzyme biologic sensor as contrast electrode.It is 6～7 phosphate buffered solution that three electrodes of enzyme biologic sensor are placed the pH value, and sweep speed is 50mV/S, and voltage is 0.6,25 ℃ of experimental temperatures.When concentration of glucose was 1mM in the end liquid, the sensitivity of electrode was 450 μ A/mMcm
2, improved 750 times than the sensitivity of the blank enzyme electrode that strengthens, in being the scope of 5 μ M～7.5mM, glucose solution concentration is linear change, and the response time is in 5 seconds.
Embodiment 2
With volume ratio is the K of 3: 1 0.1M
2PtCl
4K with 0.1M
2PdCl
4Mixed solution replaces the K of the 0.1M in embodiment 1 step (2)
2PtCl
4Aqueous solution repeats each step among the embodiment 1, obtains the surface at last and contains the thermometal Pt/Pd nano particle of dendrimer encapsulation and the platinum electrode of the multilayer sensing membrane that glucose oxidase forms, and be used for the detection of glucose oxidase sensor.Under identical process conditions, record when concentration of glucose is 1mM in the end liquid, the sensitivity of electrode is 720 μ A/mMcm
2, improved 1200 times than the sensitivity of the blank enzyme electrode that strengthens.
Embodiment 3
With the glucose oxidase in hydrogen peroxidase replacement embodiment 1 step (4), with the glucose in the hydrogen peroxide replacement end liquid, repeat each step among the embodiment 1, obtain the surface at last and contain the monometallic Pt nano particle of dendrimer encapsulation and the platinum electrode of the multilayer sensing membrane that hydrogen peroxidase forms, and be used for the detection of hydrogen peroxide.Under identical process conditions, record when concentration of hydrogen peroxide is 1mM in the end liquid, the sensitivity of electrode is 480 μ A/mMcm
2, than sensitivity (the 1.1 μ A/mMcm of the blank enzyme electrode that strengthens
2) improved 430 times.
Comparative Examples
Get the glucose oxidase solution 5mg/mL of identical unit of activity and same amount, utilizing weight percent concentration is that 10% glutaraldehyde 2mL carries out crosslinking Treatment, spreads upon clean platinum electrode surface, is used for the detection of glucose.Under identical process conditions, sensitivity only is 0.6 μ A/mMcm
2
Claims (5)
1, a kind of nano biologic enzyme electrode is characterized in that, described nano biologic enzyme electrode comprises electrode, and be adsorbed on electrode surface, inside is packaged with the multilayer sensing membrane that the dendrimer of metal nanoparticle and enzyme form;
Said electrode comprises a kind of in carbon, platinum, silver, the gold electrode;
Said dendrimer is meant the high molecular polymer of the different algebraically with dendritic structure, comprises the 1-7 polyamide-amide in generation (PAMAM), the polypropylene imines (PPI) in 1-7 generation;
Said nano-metal particle refers to monometallic nano particle in the transition metal or their potpourri duplex metal nano granule, nano particle is encapsulated in the cavity of dendrimer inside, particle diameter is at 0.5-5nm, and every gram dendrimer contains the nano-metal particle of 0.1-0.5 μ mol;
Said enzyme is selected one or more in glucose oxidase, Lactate Oxidase, horseradish hydrogen peroxidase, cholesterol oxidase, xanthine oxidase, acetylcholinesterase, the organophosphor hydrolytic enzyme for use.
2, nano biologic enzyme electrode as claimed in claim 1 is characterized in that, said multilayer sensing membrane is to be packaged with the sequence layer that the dendrimer of nano-metal particle alternately constitutes by one deck enzyme and one deck, and its sequence number of plies is unrestricted.
3, nano biologic enzyme electrode as claimed in claim 2 is characterized in that, the enzyme of said formation multilayer sensing membrane is a single enzyme.
4, nano biologic enzyme electrode as claimed in claim 2 is characterized in that, the enzyme of said formation multilayer sensing membrane is more than one enzyme.
5, nano biologic enzyme electrode as claimed in claim 1 is characterized in that, said dendrimer is the polyamide-amide in 5 generations.
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| CN101004404B (en) * | 2007-01-25 | 2010-08-25 | 上海师范大学 | Electrode modified by chloride, oxide enzyme capable of catalyzing organic reaction in high effect |
| CN101178375B (en) * | 2007-12-10 | 2010-12-08 | 杨星群 | Manufacturing method of biology enzymic electrode used for detecting pesticide residue |
| CN102231449A (en) * | 2011-04-21 | 2011-11-02 | 华东理工大学 | Photoelectrochemical biofuel cell based on quantum dot, titanium dioxide and enzyme, and preparation method thereof |
| CN102944549A (en) * | 2012-11-23 | 2013-02-27 | 清华大学 | Electrogenerated chemiluminescence bacterium sensing method and multi-functional probe |
| CN103263437A (en) * | 2013-05-03 | 2013-08-28 | 华东师范大学 | Tree-type high-molecular polyamide-amine wrapped platinum nanometer particles, its preparation method and applications |
| CN103954660A (en) * | 2014-04-14 | 2014-07-30 | 华南理工大学 | Enzyme biosensor for detecting cholesterol as well as preparation method and application of biosensor |
| CN105102972A (en) * | 2013-01-11 | 2015-11-25 | 东北大学 | Saliva glucose monitoring system |
| CN105334254A (en) * | 2015-12-05 | 2016-02-17 | 桂林理工大学 | Preparation method for glucose oxidase electrode based on enzymatic reduction of chloroauric acid |
| CN108303456A (en) * | 2018-01-02 | 2018-07-20 | 武汉市农业科学院 | A kind of garden stuff pesticide residue rapid detection method |
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| KR100379248B1 (en) * | 2000-12-04 | 2003-04-08 | 한국과학기술연구원 | Inorganic-organic hybrid polymers composed of nano-particles on the surface using dendrimers and Fabrication Method Thereof |
| DE60144014D1 (en) * | 2001-07-19 | 2011-03-24 | Max Planck Gesellschaft | Chemical sensors made from nanoparticle-dendrimer composite materials |
| KR100549104B1 (en) * | 2003-06-05 | 2006-02-06 | 한국과학기술원 | Method for fabricating a bionanoarray with sub-10 nanometer feature size |
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| CN101004404B (en) * | 2007-01-25 | 2010-08-25 | 上海师范大学 | Electrode modified by chloride, oxide enzyme capable of catalyzing organic reaction in high effect |
| CN101178375B (en) * | 2007-12-10 | 2010-12-08 | 杨星群 | Manufacturing method of biology enzymic electrode used for detecting pesticide residue |
| CN102231449A (en) * | 2011-04-21 | 2011-11-02 | 华东理工大学 | Photoelectrochemical biofuel cell based on quantum dot, titanium dioxide and enzyme, and preparation method thereof |
| CN102944549A (en) * | 2012-11-23 | 2013-02-27 | 清华大学 | Electrogenerated chemiluminescence bacterium sensing method and multi-functional probe |
| CN102944549B (en) * | 2012-11-23 | 2015-04-15 | 清华大学 | Electrogenerated chemiluminescence bacterium sensing method and multi-functional probe |
| CN111044591A (en) * | 2013-01-11 | 2020-04-21 | 东北大学 | Saliva glucose monitoring system |
| CN105102972A (en) * | 2013-01-11 | 2015-11-25 | 东北大学 | Saliva glucose monitoring system |
| US10732139B2 (en) | 2013-01-11 | 2020-08-04 | Northeastern University | Saliva glucose monitoring system |
| CN103263437A (en) * | 2013-05-03 | 2013-08-28 | 华东师范大学 | Tree-type high-molecular polyamide-amine wrapped platinum nanometer particles, its preparation method and applications |
| CN103954660A (en) * | 2014-04-14 | 2014-07-30 | 华南理工大学 | Enzyme biosensor for detecting cholesterol as well as preparation method and application of biosensor |
| CN103954660B (en) * | 2014-04-14 | 2016-06-22 | 华南理工大学 | Enzyme biologic sensor of a kind of cholesterol detection and preparation method thereof and application |
| CN105334254A (en) * | 2015-12-05 | 2016-02-17 | 桂林理工大学 | Preparation method for glucose oxidase electrode based on enzymatic reduction of chloroauric acid |
| CN105334254B (en) * | 2015-12-05 | 2018-04-10 | 桂林理工大学 | A kind of glucose oxidase electrode preparation method based on enzymatic reduction gold chloride |
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