CN103399059A - Au(111)-like nano-particle non-enzyme glucose sensor electrode, and preparation method and application of same - Google Patents
Au(111)-like nano-particle non-enzyme glucose sensor electrode, and preparation method and application of same Download PDFInfo
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Abstract
The invention belongs to the technical field of electrochemical sensors, and in particular relates to an Au(111)-like nano-particle modified non-enzyme glucose sensor electrode, and a preparation method and application of the same. The preparation method comprises the following steps of: firstly, wiping a conductive substrate with alcohol, then, respectively performing ultrasonic washing with acetone, isopropyl alcohol and ultrapure water, adding the conductive substrate in the mixed liquor of deionized water, ammonia water and hydrogen peroxide, heating until boiling, finally, cleaning the conductive substrate with the ultrapure water and blowing the conductive substrate to dry with nitrogen; in the electrolyte solution composed of sodium perchlorate and chloroauric acid solution, firstly, performing electrolytic deposition on the conductive substrate by means of chronoamperometry, then, further performing electrolytic deposition on the conductive substrate by means of cyclic voltammetry, and cleaning the conductive substrate with the deionized water. The non-enzyme glucose sensor electrode is very sensitive to the concentration variation of the glucose and presents better linear relation, moreover, the non-enzyme glucose sensor electrode has better selectivity to the glucose, only needs 1.5s response time to the glucose and can achieve the detection limit of 5mu moL/L.
Description
Technical field
The invention belongs to the electrochemical sensor technical field, particularly a kind Au(111) nano-particle modified glucose sensor electrode without enzyme and preparation method thereof and the application in glucose detection.
Background technology
Golden nanometer particle has unique electrical and optical properties, good catalytic activity, good bioaffinity and nonlinear optical property, can as the 26S Proteasome Structure and Function unit, construct various two dimensions or three-dimensional superlattice structure with this inorganic nano-particle, at aspects such as bioelectrochemical sensor, Optochemical sensor, electronics nano-devices, be with a wide range of applications, cause numerous scientific workers' very big interest.So far the gold nano-material of existing different-shape is produced out, as nano wire, nanometer rods, flower-like nanometer particle etc.Simultaneously, different preparation methods has also appearred, such as: ion sputtering method, etching method, electrodeposition process etc., wherein the electrodeposition process equipment needed thereby is simple, is easy to universal and suitability for industrialized production, has broad application prospects.But in real work, size and density how well to control the nano particle that generates are still a difficult problem, and the research that the electrodeposition process that utilizes timing electric current and cyclic voltammetric method to combine prepares class Au (111) gold nano grain yet there are no bibliographical information.
The analysis of glucose with detect in diabetes monitoring, treatment and control, food industry, and there is very important meaning in the field such as bioengineering.From Clark in 1962 and Lyons, reported for work and carried out monitoring glucose with enzyme electrode first, formed first generation glucose sensor, decades subsequently, a lot of scientific research personnel are devoted to the research of glucose sensor.There is enzyme sensor to be based on the specific recognition function of enzyme to substrate, have selectivity and high selectivity, yet, instability due to enzyme self, be subject to the impact of ambient temperature, humidity and pH, and immobilized enzyme may leak, so that affects stability and the serviceable life of sensor, has limited to a certain extent the range of application of such sensor.So the third generation that development has higher stability has very important realistic meaning without enzyme sensor.Enzyme-free glucose sensor is a kind ofly based on the catalytic oxidation signal of glucose molecule on relevant catalytically-active materials surface, it to be carried out to sensing device qualitative and that quantitatively detect.
But the preparation time of the enzyme-free glucose sensor that golden nanometer particles more of the prior art are modified is long, the particle diameter of golden nanometer particle is even not, selectivity is poor, the effect time is longer.
The indium tin oxide-coated glass electrode that in this patent, prepared class Au (111) golden nanometer particle is modified, in the preparation between, the aspects such as the density of gold nano grain, grain size, operation, detectability have advantage preferably.At first in the preparation aspect between, bibliographical information porous gold enzyme-free glucose sensor, its preparation time is approximately 11 hours; The gold nanotubes enzyme-free glucose sensor, its preparation time reaches 10 hours; Gold nano branch enzyme-free glucose sensor preparation time also reaches 18 hours.Patent preparation time of the present invention is about 50min (with regard to the electric potential scanning number of turns is 500 circles).By contrast, the preparation time of patent of the present invention is relatively short.With regard to the pattern and density of gold nano grain, prepared its particle diameter of golden nanometer particle of patent of the present invention is comparatively even, and comparatively even in the indium tin oxide-coated glass surface distributed.Aspect preparation section, patent of the present invention does not relate to comparatively complicated instrument and equipment, directly utilize electrochemical workstation to using indium tin oxide-coated glass as working electrode, on its surface, use electrochemical method to carry out the golden nanometer particle nucleation and growth, form the golden nanometer particle of class Au (111).Because indium tin oxide-coated glass can be realized large-scale industrial production, its cost is relatively low.Aspect detectability, its detectability of gold nanorod enzyme-free glucose sensor of bibliographical information only reaches 60 μ M; Its detectability of gold dish enzyme-free glucose sensor only reaches 10 μ M.With respect to these enzyme-free glucose sensors, its detectability of patent of the present invention reaches 5 μ M, has detection limit preferably.This shows with other compares without enzyme sensor, and the described class Au of patent of the present invention (111) nano particle enzyme-free glucose sensor has good performance, and preparation process is comparatively simple, has and applies preferably potential and marketable value preferably.
Summary of the invention
The purpose of this invention is to provide a kind Au(111) nano-particle modified glucose sensor electrode without enzyme, this electrode pair glucose has good linear response and selectivity, and the response time is very fast, and detectability is low.
Another object of the present invention is to provide a kind of above-mentioned class Au(111 for preparing) preparation method of nano-particle modified glucose sensor electrode without enzyme.
Purpose of the present invention can be achieved through the following technical solutions:
One kind Au(111) nano particle glucose sensor electrode without enzyme, it is characterized in that: the spherical class Au(111 of deposition on conductive substrates) nano particle, described class Au(111) Au (111) the crystal face proportion in nano particle is greater than 80%, and particle diameter is 40～55nm.
Described conductive substrates is a kind of in glass-carbon electrode, indium tin oxide-coated glass or gold electrode.Preferably, described conductive substrates is indium tin oxide-coated glass.
A kind of above-mentioned class Au(111) preparation method of nano particle glucose sensor electrode without enzyme, its step comprises: in the electrolytic solution of sodium perchlorate solution and chlorauric acid solution composition, first adopt chronoamperometry, on pretreated conductive substrates, carry out electro-deposition, open circuit potential from 0.04～0.9V step to-0.1～-1.0V, the time is 5～30 seconds; Use cyclic voltammetry, in the potential range of-0.08～0.8V, scanning 50～900 circles, to the further electro-deposition of conductive substrates again; The washed with de-ionized water conductive substrates.Preferably, before adopting the chronoamperometry electro-deposition, in electrolytic solution, pass into high pure nitrogen, duration of ventilation is 10～50 minutes; The open circuit potential of described chronoamperometry is from the 0.74V step to-0.8V, and the time is 10 seconds; Cyclic voltammetry is in the potential range of-0.04～0.3V, and scanning 150～800 is enclosed.
The preprocess method of described conductive substrates is: by conductive substrates first with after ethanol, use respectively again acetone, isopropyl alcohol and ultrapure water supersound washing, then be placed in the mixed liquor that deionized water, ammoniacal liquor and hydrogen peroxide form and heat and boil, finally conductive substrates is cleaned to nitrogen afterwards with ultrapure water and dry up.
The volume ratio of the deionized water in described mixed liquor, ammoniacal liquor and hydrogen peroxide is 2～10:1～3:1; The mass concentration of ammoniacal liquor is 25-28%, and the mass concentration of hydrogen peroxide is 28-32%.
Sodium perchlorate in described electrolytic solution and the mol ratio of gold chloride are 1:10
-5～10
-3.
The ratio of the amount of substance of described gold chloride and the surface area of conductive substrates is 0.005～0.05mol:1m
2.
The invention still further relates to class Au(111) application of nano particle glucose sensor electrode without enzyme in glucose detection.
Compared with prior art, beneficial effect of the present invention is:
(1) described class Au(111) gold nano grain of nano particle glucose sensor electrode without enzyme surface deposition is spherical, particle diameter is the 50nm left and right, and has a narrower particle diameter distribution width, between adjacent gold nano grain, have less nano gap, Au in the gold nano structure (111) occupation rate reaches more than 80%.
(2) described class Au(111) nano particle glucose sensor electrode without enzyme, responsive and present good linear relationship to the concentration change of glucose, and glucose is had to good selectivity, response time to glucose only has 1.5s, this glucose sensor electrode without enzyme has glucose detection characteristic preferably to glucose, under the condition of S/N=3, its detectability can reach 5 μ moL/L, has and applies preferably potential and marketable value preferably.
(3) described class Au(111) preparation method of nano particle glucose sensor electrode without enzyme is simple, and preparation time is shorter, has saved human cost and resources costs.
The accompanying drawing explanation
Fig. 1 is in embodiment 2, is deposited on the low resolution field emission scanning electron microscope figure of the gold nano grain of ITO electrode surface.
Fig. 2 is in embodiment 2, is deposited on the high-resolution field emission scanning electron microscope figure of the gold nano grain of ITO electrode surface.
Fig. 3 is in embodiment 2, be deposited on the ITO electrode surface gold nano grain X-ray powder diffraction figure.
Fig. 4 is in embodiment 2, is deposited on the X ray energy dispersive spectroscopy figure of the gold nano grain of ITO electrode surface.
Fig. 5 is in embodiment 2, is deposited on the gold nano grain of ITO electrode surface, the cyclic voltammetry curve figure of the Cys in the KOH of 0.5moL/L.
Fig. 6 is the class Au(111 that makes in embodiment 2) nano-particle modified glucose sensor electrode without enzyme, common gold electrode, the cyclic voltammetry curve comparison diagram of naked ITO electrode in the glucose solution of 10mmol/L.
Fig. 7 is the class Au(111 that makes in embodiment 2) nano-particle modified glucose sensor electrode without enzyme is to the electrochemical response comparison diagram of the glucose of variable concentrations.
Fig. 8 is the class Au(111 that makes in embodiment 2) nano-particle modified glucose sensor electrode without enzyme is to the detection graph of a relation of the glucose of variable concentrations, 8(A wherein) be the graph of a relation of current density and time, Fig. 8 (B) is the graph of a relation of current density and concentration of glucose.
Fig. 9 is the class Au(111 that makes in embodiment 2) nano-particle modified glucose sensor electrode without enzyme Ascorbic Acid (0.1mmol/L), uric acid (0.02mmol/L), the current density of glucose (1mmol/L) and the graph of a relation of time.
Figure 10 is the class Au(111 that makes in embodiment 2) the nano-particle modified current density of glucose sensor electrode without enzyme under different concentration of glucose and the graph of a relation of time.
Embodiment
Below in conjunction with embodiment, the invention will be further described:
Embodiment 1
(1), the pre-service of conductive substrates:
Tin indium oxide (ITO) electro-conductive glass is first used to ethanol, then use respectively acetone, isopropyl alcohol, ultrapure water difference ultrasonic cleaning 20 minutes.Put into again deionized water, in the mixed liquor that ammoniacal liquor (mass concentration is 25%-28%) and hydrogen peroxide (mass concentration is 30%) form, wherein the volume ratio of ionized water, ammoniacal liquor and hydrogen peroxide is 5:1:1, and heating is boiled and with ultrapure water, cleaned afterwards in 30 minutes, high pure nitrogen dries up, and is standby.
(2), the preparation of glucose sensor electrode without enzyme:
In the 40mL electrolytic solution that the gold chloride of the sodium perchlorate of 0.1mol/L and 0.0001mol/L forms, the ITO electro-conductive glass is as working electrode, and platinized platinum is to electrode, and saturated calomel electrode is contrast electrode, and the ITO electrode area is 0.4cm
2.Before deposition, can be first with high pure nitrogen air-blowing 30 minutes, remove the dissolved oxygen DO in electrolytic solution, with chronoamperometry, from open circuit potential 0.74V, jump to-0.8V, the time is 10s again, continues with cyclic voltammetry-0.04 to+0.3V potential range interscan 600 circles, the ITO electrode is carried out to further electro-deposition, washed with de-ionized water ITO electrode, be stored in deionized water, saves backup under 4 ℃.
(1), the pre-service of conductive substrates: with embodiment 1
(2), the preparation of glucose sensor electrode without enzyme:
In the 40mL electrolytic solution that the gold chloride of the sodium perchlorate of 0.1mol/L and 0.0001mol/L forms, the ITO electro-conductive glass is as working electrode, and platinized platinum is to electrode, and saturated calomel electrode is contrast electrode, and the ITO electrode area is 0.4cm
2.Before deposition, can be first with high pure nitrogen air-blowing 30 minutes, remove the dissolved oxygen DO in electrolytic solution, with chronoamperometry, from open circuit potential 0.74V, jump to-0.8V, the time is 10s again, continues with cyclic voltammetry-0.04 to+0.3V potential range interscan 500 circles, the ITO electrode is carried out to further electro-deposition, washed with de-ionized water ITO electrode, be stored in deionized water, saves backup under 4 ℃.
Fig. 1 is the low resolution field emission scanning electron microscope photo that is deposited on the gold nano grain of ITO electrode surface, in Electronic Speculum figure, can see, deposition has formed spherical gold nano grain on substrate surface, the particle diameter of this gold nano grain is the 50nm left and right, have narrower particle diameter and distribute, the particle diameter relative deviation is in 17% left and right.Fig. 2 is the high-resolution field emission scanning electron microscope photo that deposits the gold nano grain on the glucose sensor electrode without enzyme surface that makes in the present embodiment, can see and between adjacent nano particle, form less nano gap.
Fig. 3 be deposited on the ITO electrode surface gold nano grain X-ray powder diffraction figure.With standard diagram, compare, can see that except the diffraction peak of the ITO that indicates asterisk the diffraction peak of an Emission in Cubic gold (111) face is only arranged, this shows that gold nano probably has mono-crystalline structures, and be octahedral structure, from the spherical gold nano figure, also can find out.
Fig. 4 is the X ray energy dispersive spectroscopy that is deposited on the gold nano grain of ITO electrode surface, and the constituent content of the Au on surface is 1.62%, can see Na, Al, and Si, Mg, O, Ca, from substrate I TO, the peak of other materials do not occur, show that product is proof gold.
Fig. 5 is the gold nano grain that is deposited on the ITO electrode surface, the desorption of the Cys unimolecular film of its adsorption experiment in the KOH of 0.5moL/L solution, due to the energy of adsorption difference of short chain mercaptan at the different crystal faces of gold, the easier desorption of mercaptan on Au (111) face, can see that in the gold nano structure of preparation, Au (111) occupation rate reaches more than 80%.
Fig. 6 is the class Au(111 that makes in the present embodiment) nano-particle modified glucose sensor electrode without enzyme, common gold electrode, the naked cyclic voltammetry curve of ITO electrode in the glucose solution of 10mmol/L, wherein, the a curve is the electrode that makes in the present embodiment, the b curve is common gold electrode, and the c curve is the naked ITO electrode that does not have gold nano to modify.As can be seen from the figure, the ITO electrode that does not have gold nano to modify does not have the electrochemical redox peak appearance of glucose, and the sensor electrode that makes in the present embodiment demonstrates good electric catalyticing characteristic to the glucose of 10mmol/L.
Embodiment 3
(1), the pre-service of conductive substrates: with embodiment 1
(2), the preparation of glucose sensor electrode without enzyme:
In the 40mL electrolytic solution that the gold chloride of the sodium perchlorate of 0.1mol/L and 0.0001mol/L forms, the ITO electro-conductive glass is as working electrode, and platinized platinum is to electrode, and saturated calomel electrode is contrast electrode, and the ITO electrode area is 0.4cm
2.Before deposition, can be first with high pure nitrogen air-blowing 30 minutes, remove the dissolved oxygen DO in electrolytic solution, with chronoamperometry, from open circuit potential 0.74V, jump to-0.8V, the time is 10s again, continues with cyclic voltammetry-0.04 to+0.3V potential range interscan 300 circles, the ITO electrode is carried out to further electro-deposition, washed with de-ionized water ITO electrode, be stored in deionized water, saves backup under 4 ℃.
(1), the pre-service of conductive substrates: with embodiment 1
(2), the preparation of glucose sensor electrode without enzyme:
In the 40mL electrolytic solution that the gold chloride of the sodium perchlorate of 0.1mol/L and 0.0001mol/L forms, the ITO electro-conductive glass is as working electrode, and platinized platinum is to electrode, and saturated calomel electrode is contrast electrode, and the ITO electrode area is 0.4cm
2.Before deposition, can be first with high pure nitrogen air-blowing 30 minutes, remove the dissolved oxygen DO in electrolytic solution, with chronoamperometry, from open circuit potential 0.74V, jump to-0.8V, the time is 10s again, continues with cyclic voltammetry-0.04 to+0.3V potential range interscan 150 circles, the ITO electrode is carried out to further electro-deposition, washed with de-ionized water ITO electrode, be stored in deionized water, saves backup under 4 ℃.
by the class Au(111 that makes in embodiment 2) the nano particle glucose sensor electrode without enzyme is working electrode, platinized platinum is to electrode, saturated calomel electrode is contrast electrode, (be respectively: 10mmol/L containing different glucose, 9mmol/L, 8mmol/L, 7mmol/L, 6mmol/L, 5mmol/L, 3mmol/L, 1mmol/L, 600 μ mol/L, 200 μ mol/L) in the KOH solution of 0.5moL/L, detect, specifically as shown in Figure 7, the current-responsive of the enzyme-free glucose sensor that makes in embodiment 2 is along with the increase of concentration of glucose is also increasing, show the concentration change sensitivity of prepared electrode pair glucose and present good linear relationship.
by the class Au(111 that makes in embodiment 2) nano particle glucose sensor electrode without enzyme or common gold electrode be working electrode, platinized platinum is to electrode, saturated calomel electrode is contrast electrode, be placed in the KOH solution of 40mL0.5moL/L, under the current potential of 0.15V, at interval of 25s, add glucose solution, concentration change is 1mmol/L, current value while using chronoamperometry mensuration electric current to reach stable state, concrete as shown in Fig. 8 (A) and Fig. 8 (B), be respectively the i-t current curve of concentration of glucose from 0 to 10mmol/L and the linear relationship of current-responsive and different concentration of glucose, wherein, the a line is glucose sensor electrode without enzyme, the b line is common gold electrode, as can be seen from Figure, the glucose sensor electrode without enzyme that makes in the present invention and the contrast of common gold electrode, demonstrate good electrocatalysis characteristic for glucose.
by the class Au(111 that makes in embodiment 2) nano particle glucose sensor electrode without enzyme or common gold electrode be working electrode, platinized platinum is to electrode, saturated calomel electrode is contrast electrode, be placed in the KOH solution of 40mL0.5moL/L, under the current potential of 0.15V, add 1mmol/L glucose, 0.1mmol/L ascorbic acid, 0.02mmol/L uric acid, current value when measuring current reaches stable state, as shown in Figure 9, in figure, demonstrate glucose sensor electrode without enzyme Ascorbic Acid prepared by the present invention, uric acid is significantly response not, only glucose is had to obvious response, explanation has good selectivity to glucose, response time to glucose only has 1.5s.
by the class Au(111 that makes in embodiment 2) nano particle glucose sensor electrode without enzyme or common gold electrode be working electrode, platinized platinum is to electrode, saturated calomel electrode is contrast electrode, be placed in the KOH solution of 40mL0.5moL/L, under the current potential of 0.15V, add successively 5 μ moL/L, 10 μ moL/L, 10 μ moL/L, the glucose of 10 μ moL/L, test corresponding current value, specifically as shown in figure 10, as can be seen from the figure, the prepared glucose sensor electrode without enzyme of the present invention has glucose detection characteristic preferably, under the condition of S/N=3, its detectability can reach 5 μ moL/L.
The above is preferred embodiment of the present invention, but the present invention should not be confined to the disclosed content of this embodiment.So everyly do not break away from the equivalence that completes under spirit disclosed in this invention or revise, all falling into the scope of protection of the invention.
Claims (10)
1. a kind Au(111) nano particle glucose sensor electrode without enzyme, it is characterized in that: the spherical class Au(111 of deposition on conductive substrates) nano particle, described class Au(111) Au (111) the crystal face proportion in nano particle is greater than 80%, and the particle diameter diameter is 40～55nm.
2. class Au(111 according to claim 1) nano particle glucose sensor electrode without enzyme is characterized in that: described conductive substrates is a kind of in glass-carbon electrode, indium tin oxide-coated glass or gold electrode.
3. the described class Au(111 of the claim 1 or 2) preparation method of nano particle glucose sensor electrode without enzyme, its step comprises:
In the electrolytic solution that sodium perchlorate solution and chlorauric acid solution form, first adopt chronoamperometry, on pretreated conductive substrates, carry out electro-deposition, open circuit potential from 0.04～0.9V step to-0.1～-1.0V, the time is 5～30 seconds; Use cyclic voltammetry, in the potential range of-0.08～0.8V, scanning 50～900 circles, to the further electro-deposition of conductive substrates again; The washed with de-ionized water conductive substrates.
4. the class Au(111 according to claim 3) preparation method of nano particle glucose sensor electrode without enzyme, it is characterized in that, the preprocess method of described conductive substrates is: by conductive substrates first with after ethanol, use respectively again acetone, isopropyl alcohol and ultrapure water supersound washing, then be placed in the mixed liquor that deionized water, ammoniacal liquor and hydrogen peroxide form and heat and boil, finally conductive substrates is cleaned to nitrogen afterwards with ultrapure water and dry up.
5. class Au(111 according to claim 4) preparation method of nano particle glucose sensor electrode without enzyme, is characterized in that, the volume ratio of the deionized water in described mixed liquor, ammoniacal liquor and hydrogen peroxide is 2～10:1～3:1; The mass concentration of ammoniacal liquor is 25-28%, and the mass concentration of hydrogen peroxide is 28-32%.
6. class Au(111 according to claim 3) preparation method of nano particle glucose sensor electrode without enzyme, is characterized in that, the sodium perchlorate in described electrolytic solution and the mol ratio of gold chloride are 1:10
-5～10
-3.
7. class Au(111 according to claim 3) preparation method of nano particle glucose sensor electrode without enzyme, is characterized in that, the ratio of the amount of substance of described gold chloride and the surface area of conductive substrates is 0.005～0.05mol:1m
2.
8. class Au(111 according to claim 3) preparation method of nano particle glucose sensor electrode without enzyme, is characterized in that, the open circuit potential of chronoamperometry is from the 0.74V step to-0.8V, and the time is 10 seconds; Cyclic voltammetry is in the potential range of-0.04～0.3V, and scanning 150～800 is enclosed.
9. class Au(111 according to claim 3) preparation method of nano particle glucose sensor electrode without enzyme, is characterized in that, before adopting the chronoamperometry electro-deposition, in electrolytic solution, passes into high pure nitrogen, and duration of ventilation is 10～50 minutes.
10. the described class Au(111 of the claim 1 or 2) application of nano particle glucose sensor electrode without enzyme in glucose detection.
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| CN103862032A (en) * | 2014-02-26 | 2014-06-18 | 国家纳米科学中心 | Core-shell precious metal nanorod with square superlattice and self-assembly method thereof |
| CN104458699A (en) * | 2014-12-11 | 2015-03-25 | 福建出入境检验检疫局检验检疫技术中心 | Nanogold surface reinforced active substrate prepared based on chemical assembly and cyclic voltammetry |
| CN105132981A (en) * | 2015-09-18 | 2015-12-09 | 盐城工学院 | Preparation method of disorder photon zinc oxide nanowire-embedded plasma nanogold photoanode material |
| CN105355788A (en) * | 2015-11-06 | 2016-02-24 | 昆明物理研究所 | ZnO nanocrystal and organic polymer heterojunction vertical structure UV photovoltaic detector |
| CN105911128A (en) * | 2016-04-13 | 2016-08-31 | 中国石油大学(华东) | Enzyme-free glucose electrochemical sensor and application thereof |
| CN108796463A (en) * | 2018-06-29 | 2018-11-13 | 吉林大学 | A kind of compound film electrode for examination of glucose concentration, preparation method and applications |
| CN113340961A (en) * | 2021-05-17 | 2021-09-03 | 西安交通大学 | Flexible enzyme-free glucose sensor electrode and preparation method thereof |
| CN114544730A (en) * | 2022-02-15 | 2022-05-27 | 华南农业大学 | Ion sensor and preparation method and application thereof |
| CN115058690A (en) * | 2022-05-23 | 2022-09-16 | 小护士(天津)科技股份有限公司 | Manufacturing method of glucose sensor |
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| CN103862032A (en) * | 2014-02-26 | 2014-06-18 | 国家纳米科学中心 | Core-shell precious metal nanorod with square superlattice and self-assembly method thereof |
| CN103862032B (en) * | 2014-02-26 | 2016-08-03 | 国家纳米科学中心 | The nucleocapsid noble metal nano rod of four directions superlattices and self-assembling method thereof |
| CN104458699A (en) * | 2014-12-11 | 2015-03-25 | 福建出入境检验检疫局检验检疫技术中心 | Nanogold surface reinforced active substrate prepared based on chemical assembly and cyclic voltammetry |
| CN105132981A (en) * | 2015-09-18 | 2015-12-09 | 盐城工学院 | Preparation method of disorder photon zinc oxide nanowire-embedded plasma nanogold photoanode material |
| CN105355788A (en) * | 2015-11-06 | 2016-02-24 | 昆明物理研究所 | ZnO nanocrystal and organic polymer heterojunction vertical structure UV photovoltaic detector |
| CN105911128A (en) * | 2016-04-13 | 2016-08-31 | 中国石油大学(华东) | Enzyme-free glucose electrochemical sensor and application thereof |
| CN105911128B (en) * | 2016-04-13 | 2018-11-09 | 中国石油大学(华东) | A kind of enzyme-free glucose electrochemical sensor and its application |
| CN108796463A (en) * | 2018-06-29 | 2018-11-13 | 吉林大学 | A kind of compound film electrode for examination of glucose concentration, preparation method and applications |
| CN113340961A (en) * | 2021-05-17 | 2021-09-03 | 西安交通大学 | Flexible enzyme-free glucose sensor electrode and preparation method thereof |
| CN114544730A (en) * | 2022-02-15 | 2022-05-27 | 华南农业大学 | Ion sensor and preparation method and application thereof |
| CN114544730B (en) * | 2022-02-15 | 2023-09-15 | 华南农业大学 | Ion sensor and preparation method and application thereof |
| CN115058690A (en) * | 2022-05-23 | 2022-09-16 | 小护士(天津)科技股份有限公司 | Manufacturing method of glucose sensor |
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