CN110441375A - A kind of monosaccharide transistor sensor and preparation method thereof - Google Patents

A kind of monosaccharide transistor sensor and preparation method thereof Download PDF

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CN110441375A
CN110441375A CN201910610923.1A CN201910610923A CN110441375A CN 110441375 A CN110441375 A CN 110441375A CN 201910610923 A CN201910610923 A CN 201910610923A CN 110441375 A CN110441375 A CN 110441375A
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aspartame
monosaccharide
graphene oxide
semiconductor layer
modification
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周晔
吕子玉
韩素婷
王燕
周黎
王俊杰
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Shenzhen University
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/403Cells and electrode assemblies
    • G01N27/414Ion-sensitive or chemical field-effect transistors, i.e. ISFETS or CHEMFETS
    • G01N27/4145Ion-sensitive or chemical field-effect transistors, i.e. ISFETS or CHEMFETS specially adapted for biomolecules, e.g. gate electrode with immobilised receptors
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/403Cells and electrode assemblies
    • G01N27/414Ion-sensitive or chemical field-effect transistors, i.e. ISFETS or CHEMFETS
    • G01N27/4146Ion-sensitive or chemical field-effect transistors, i.e. ISFETS or CHEMFETS involving nanosized elements, e.g. nanotubes, nanowires

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  • Carbon And Carbon Compounds (AREA)

Abstract

The present invention discloses a kind of monosaccharide transistor sensor and preparation method thereof, and the monosaccharide transistor sensor includes: source electrode, drain electrode, semiconductor layer, dielectric layer, grid;The dielectric layer connects above the grid, and the semiconductor layer is connected in the dielectric layer, and the source electrode and the drain electrode are all to connect above semiconductor layer, and the source electrode is not directly contacted with the drain electrode;The semiconductor layer is the graphene oxide of Aspartame modification.The present invention is using Aspartame as monosaccharide recognition unit, graphite surface is modified using chemical means, the graphene oxide semiconductor layer of Aspartame modification is made, the difference for causing channel current by there is specific interaction force between Aspartame and different monosaccharide, the transistor sensor that can identify monosaccharide not of the same race simultaneously is realized, there are good biocompatibility and biologic applications potentiality.

Description

A kind of monosaccharide transistor sensor and preparation method thereof
Technical field
The present invention relates to transistor sensor fields more particularly to a kind of monosaccharide transistor sensor and preparation method thereof.
Background technique
There is various sugar, including monosaccharide, disaccharides, trisaccharide, oligosaccharides and polysaccharide etc. in nature.These carbohydrates are not Only it is used as the intracorporal structural material of organic life and energy matter, while the cell of the various physiology courses also in life system Identification, signal transduction, immune etc. play an important role.The accurate identification of sugar, in medicine and biologically with important Meaning, the detection of many diseases are all based on the identification of the derivative of sugar and sugar.
Sugared monosaccharide molecule is the aldehydes or ketone molecule for having multiple hydroxyls, and many kinds of, it is known that monosaccharide molecule have More than 20 kinds, difference each other is only in that the difference of hydroxyl arrangement mode.The glycosidic linkage of multiple monosaccharide combinations, there is also Branched structure, combination and connection type diversity, this greatly increase sugar and sugar derivative identification difficulty.Especially Ground, the identification of monosaccharide is basis in carbohydrate identification, and the sensor of building monosaccharide identification is conducive to open up new prospect for sugar identification, have There is important practical application value.
So far, most study is glucose sensor in monosaccharide sensor, is mainly used for wearable device, faces The detection of the concentration of glucose in fields such as bed chemical examination, food safety.The glucose of transistor types existing in the prior art passes Inductor component generates gluconic acid and hydrogen peroxide, while causing ditch by reacting after semiconductor absorption using glucose The variation of road electric current;By the monitoring changed to channel current, the detection to concentration of glucose is realized.Due to different monosaccharide point It is only merely the different isomers of hydroxyl direction between son, and glucose sensor can not distinguish knowledge for a variety of monosaccharide Not.
Therefore, the existing technology needs to be improved and developed.
Summary of the invention
The purpose of the present invention is to provide it is a kind of applied to identification monosaccharide type and monosaccharide concentration transistor sensor and Preparation method cannot be distinguished with solving glucose sensor in the prior art, identify the technical issues of various monosaccharide.
Technical scheme is as follows:
The present invention provides a kind of monosaccharide transistor sensors, comprising: source electrode, drain electrode, semiconductor layer, dielectric layer and grid; The dielectric layer connects above the grid, and the semiconductor layer is connected in the dielectric layer, the source Pole and the drain electrode all connect above semiconductor layer, and the source electrode is not contacted with the drain electrode;The semiconductor layer For the graphene oxide layer of Aspartame modification.
Preferably, the Aspartame is α type aspartoyl-phenyalanine methyl ester.
Preferably, the semiconductor layer with a thickness of 10-30 nanometers.
Preferably, the dielectric layer is silicon oxide dielectric layer, the grid is silicon gate.
The present invention also provides a kind of preparation methods of monosaccharide transistor sensor, comprising the following steps:
Step S1: the graphene oxide solution of Aspartame modification is prepared, is existed using UV-vis spectral detection graphene oxide Characteristic peak calibration at 230nm is modified with the concentration of the graphene oxide water solution of Aspartame.
Step S2: being arranged dielectric layer above grid, and the graphene oxide of Aspartame modification is added dropwise on dielectric layer Solution is annealed 10-30 hours under 80-120 degrees Celsius, and the semiconductor layer of the graphene of Aspartame modification is made;
Step S3: being deposited source electrode and drain electrode on the graphene oxide semiconductor layer of Aspartame modification, to be made described Monosaccharide transistor sensor.
The preparation method of the graphene oxide solution of Aspartame described above modification the following steps are included:
Step S11: monoxone and sodium hydroxide being added in graphene oxide water solution, reacts 3-10 hours under ultrasound condition, Obtain the graphene oxide water solution for being modified with carboxyl;
Step S12: being added 2-morpholine ethane sulfonic acid in the solution through processing of step A, EDC and NHS aqueous solution is then added and stirs It mixes, wherein the EDC is 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride, and the NHS is N- hydroxyl fourth two Acid imide;
Step S13: being added α type aspartoyl-phenyalanine methyl ester Aspartame aqueous solution in the solution handled through step B, It reacts 48-72 hours at room temperature, the graphene oxide of Aspartame modification is made.
Preferably, the mass ratio of the graphene oxide, monoxone and sodium hydroxide is 1:9-11:10-14.
Preferably, the mass ratio of the 2-morpholine ethane sulfonic acid, EDC, NHS and Aspartame is 100:11-15:7-9: 15-25。
Preferably, the Aspartame quality accounting of the graphene oxide of the Aspartame modification is 15-25%.
Temperature as the preferred annealing is 100 degrees Celsius.
The device have the advantages that are as follows:
The present invention, as monosaccharide recognition unit, is modified surface of graphene oxide using chemical means using Aspartame, The graphene oxide semiconductor layer of Aspartame modification is made, by there is specificity between Aspartame and different monosaccharide mutually Active force causes the difference of channel current, can identify the transistor sensor of monosaccharide not of the same race simultaneously, has good biofacies Capacitive and biologic applications potentiality.
Detailed description of the invention
Fig. 1 is monosaccharide transistor sensor structural schematic diagram provided by the invention;
Fig. 2 is the preparation method flow chart of monosaccharide transistor sensor provided by the invention;
Fig. 3 is the preparation method flow chart of the graphene oxide solution of Aspartame provided by the invention modification.
Specific embodiment
The present invention provides a kind of monosaccharide transistor sensor and preparation method thereof, to make the purpose of the present invention, technical solution And effect is clearer, clear, the present invention is described in more detail below.It should be appreciated that specific implementation described herein Example is used only for explaining the present invention, is not intended to limit the present invention.
Aspartame is a kind of dipeptidase derivant, by carrying out stereoselectivity interaction from different monosaccharide, is formed The intermolecular hydrogen bonding of varying strength has stereoselectivity to monosaccharide identification.However, this recognizable monosaccharide in the prior art Interaction is determined often by laboratory techniques such as fluorescence titration, nuclear-magnetism titration, and does not have the development commercially produced Prospect.There is no the sensor of different monosaccharide for identification at present, it is therefore proposed that a kind of sensor applied to identification monosaccharide and its Preparation method has important medicine and biological significance.
The preferred embodiment as shown in Figure 1 of a kind of monosaccharide transistor sensor provided by the invention, comprising: source electrode 1, leakage Pole 2, semiconductor layer 3, dielectric layer 4 and grid 5;The dielectric layer connects the semiconductor layer above the grid It connects in the dielectric layer, the source electrode and the drain electrode all connect above semiconductor layer, and the source Pole is not contacted with the drain electrode.
Specifically, for the present invention using apical grafting touch bottom-gate-type transistor structure, the source of top contact structure, drain electrode are remote From substrate, be connected directly with semiconductor layer and dielectric layer, production when can for dielectric layer modify, change semiconductor structure and Pattern, to improve the carrier mobility of device;If desired semiconductor layer is exposed in test environment without covering, for half When conductor layer optimizes test, bottom contact type structure also can be used, i.e., semiconductor layer is on source, drain electrode, and and dielectric The structure of layer contact.
The source electrode 1 is with drain electrode 2 using the good conductors such as gold, silver, copper, germanium, nickel metal material as source, drain electrode, thickness For 20-50nm, source, drain electrode material are preferably gold, and thickness is preferably 30nm.
The semiconductor layer 3 is the graphene oxide layer of Aspartame modification, and the semiconductor layer is received with a thickness of 10-30 Rice, the thickness of the semiconductor layer is preferably 20 nanometers, and the Aspartame is preferably α type aspartoyl-phenyalanine methyl ester, In the graphene oxide of the Aspartame modification mass ratio of Aspartame is 15%-25%, can according to the present invention in provide The graphene oxide preparation method preparation of Aspartame modification;Can also be had and monosaccharide using other in the semiconductor layer 3 Replace Aspartame, such as aspartic acid-tyrosine dipeptides and benzene in conjunction with the short chain of dipeptides of active force between formation specific molecular Ala-glu dipeptides.
Preferably, the α type aspartoyl-phenyalanine methyl ester can be CAS number be 22839-47-0 L-type Ah This Ba Tian.
The dielectric layer 4 is silicon oxide dielectric layer, can also be using dielectric layer materials such as epoxy resin.
The grid 5 is silicon gate, can also use metal silicide made of tungsten, titanium, cobalt or nickel and polysilicon, or Metal including tantalum, tungsten, tantalum nitride, titanium nitride is one of.
Originally a kind of preparation method that monosaccharide transistor sensor is as shown in Figure 2 is additionally provided, comprising the following steps:
Step S1: the graphene oxide solution of Aspartame modification is prepared, is existed using UV-vis spectral detection graphene oxide Characteristic peak calibration at 230nm is modified with the concentration of the graphene oxide water solution of Aspartame.
Step S2: being arranged dielectric layer above grid, and the A Siba that mass fraction is 15-25% is added dropwise on dielectric layer The graphene oxide water solution of sweet tea modification, anneals 10-30 hours under 80-120 degrees Celsius, and the oxidation of Aspartame modification is made The semiconductor layer of graphene;The property meeting for the semiconductor layer being made of after annealing 10 hours the graphene oxide of Aspartame modification It tends towards stability, to avoid annealing time is too long from causing energy waste, until mostly using 30 hours annealing times.
Step S3: being deposited source electrode and drain electrode on the graphene oxide semiconductor layer of Aspartame modification, to be made The monosaccharide transistor sensor.
Wherein, step S1 prepares the graphene oxide solution of Aspartame modification, specifically include with reference to it is as shown in Figure 3 with Lower step:
Step S11: monoxone and sodium hydroxide being added in graphene oxide water solution, reacts 3-10 hours under ultrasound condition, The hydroxyl of surface of graphene oxide is set to be converted into carboxyl, will pass through carboxyl and amino dehydrating condensation for Aspartame modification to oxygen On graphite alkene, the graphene oxide water solution for being modified with carboxyl is obtained;Reaction is conducive to graphene oxide under ultrasound condition Dispersion improves the homogeneity of Aspartame modification, and reacting 3 hours or more under ultrasound condition can be achieved this effect, to avoid The ultrasound condition lower reaction time is too long to cause energy waste, until mostly using 10 hours ultrasound condition lower reaction time.
Step S12: being added 2-morpholine ethane sulfonic acid in the solution through processing of step A, EDC and NHS aqueous solution is then added And stir 1 hour or more, wherein the EDC is 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride, the NHS For N- hydroxysuccinimide;The EDC and NHS is for being catalyzed the carboxyl that Abbas's sweet tea grafts on graphene oxide.
Step S13: α type aspartoyl-phenyalanine methyl ester Aspartame water is added in the solution handled through step B Solution reacts 48-72 hours at room temperature, the graphene oxide water solution of Aspartame modification is made.
In application monosaccharide transistor of the present invention, referring to following methods: configuring various concentration, different types of list Sugar aqueous solution impregnates channel using these solution, utilizes the situation of change of semiconductor analysis instrument detection channel current;According to being surveyed Current data corresponds to monosaccharide type, establishes the relationship between monosaccharide type and monosaccharide concentration and channel current;Utilize the crystal Tube sensor is measured the different monosaccharide of unknown concentration, is carried out according to type and concentration of the electric current measured to different monosaccharide Identification.
Below by specific embodiment, the invention will be further described.
Embodiment one
The silicon oxide dielectric layer of 100 nano thickness is equipped on 20 × 20 mm squares, 500 microns of thick silicon gates;Silicon As the grid of transistor, silica is as dielectric layer;The A Si that mass fraction is 15% is added dropwise on the silicon oxide dielectric layer It stirs 1 minute under 200 microlitres of graphene oxide solution, 3000 revs/min of Ba Tian modification, anneals 10 hours at 100 degrees Celsius, As semiconductor layer;By mask plate with the rate thermal evaporation of 0.1 angstroms per second, Jin Yuan, drain electrode, ditch are deposited on the semiconductor layer Road length and channel width are respectively 30 microns and 1000 microns.
Embodiment two
The silicon oxide dielectric layer of 100 nano thickness is equipped on 20 × 20 mm squares, 500 microns of thick silicon gates;Silicon As the grid of transistor, silica is as dielectric layer;The A Si that mass fraction is 20% is added dropwise on the silicon oxide dielectric layer It stirs 1 minute under 200 microlitres of graphene oxide solution, 3000 revs/min of Ba Tian modification, anneals 30 hours at 80 degrees Celsius, As semiconductor layer;By mask plate with the rate thermal evaporation of 0.1 angstroms per second, Jin Yuan, drain electrode, ditch are deposited on the semiconductor layer Road length and channel width are respectively 30 microns and 1000 microns.
Embodiment three
The silicon oxide dielectric layer of 100 nano thickness is equipped on 20 × 20 mm squares, 500 microns of thick silicon gates;Silicon As the grid of transistor, silica is as dielectric layer;The A Si that mass fraction is 25% is added dropwise on the silicon oxide dielectric layer It stirs 1 minute under 200 microlitres of graphene oxide solution, 3000 revs/min of Ba Tian modification, anneals 20 hours at 120 degrees Celsius, As semiconductor layer;By mask plate with the rate thermal evaporation of 0.1 angstroms per second, Jin Yuan, drain electrode, ditch are deposited on the semiconductor layer Road length and channel width are respectively 30 microns and 1000 microns.
Example IV
1 gram of monoxone and 1.2 grams of hydrogen is added in 10 milliliters of graphene oxide water solution for preparing 10 mg/mls thereto Sodium oxide molybdena, ultrasonic 5 hours adjust solution to neutrality, and filtering with ultrapure water or deionized water repeated flushing, is modified with The graphene oxide of carboxyl.Carboxyl is modified with using characteristic peak titration of the UV-vis spectral detection graphene oxide at 230nm The water-soluble concentration of graphene oxide, obtain the carboxyl modified graphene oxide water solution of 10 mg/mls;Take the carboxyl modified 10 milliliters of graphene oxide solution, 100 milligrams of 2-morpholine ethane sulfonic acid is added thereto, and adjust pH to 6, is added contains later There is 13 milligrams EDC and 8 milligram of NHS aqueous solution, stirs 1 hour at room temperature;5 milliliters, which are added, into the solution contains 20 milligrams Aspartame aqueous solution, after reacting 48 hours at room temperature, fully reacting, reaction solution is centrifuged under the conditions of 10000 revs/min, bottom Layer is the graphene oxide of Aspartame modification, and mass ratio shared by Aspartame is about 15-25%, using ultrasound and largely Ultrapure water recycles characteristic peak calibration of the UV-vis spectral detection graphene oxide at 230nm to be modified with Aspartame Graphene oxide water solution concentration.
Embodiment five
Prepare 10 mg/mls 10 milliliters of graphene oxide water solution, be added thereto 0.9 gram monoxone and 1.4 grams Sodium hydroxide, ultrasonic 5 hours adjust solution to neutrality, and filtering with ultrapure water or deionized water repeated flushing, is modified There is the graphene oxide of carboxyl.Carboxylic is modified with using characteristic peak titration of the UV-vis spectral detection graphene oxide at 230nm The water-soluble concentration of the graphene oxide of base obtains the carboxyl modified graphene oxide water solution of 10 mg/mls;The carboxyl is taken to repair 10 milliliters of the graphene oxide solution of decorations, is added 100 milligrams of 2-morpholine ethane sulfonic acid thereto, and adjusts pH to 6, is added later Containing 15 milligrams EDC and 7 milligram of NHS aqueous solution, stir 1 hour at room temperature;5 milliliters are added into the solution and contains 15 milligrams Aspartame aqueous solution, at room temperature react 72 hours after, fully reacting, reaction solution is centrifuged under the conditions of 10000 revs/min, Bottom is the graphene oxide of Aspartame modification, and mass ratio shared by Aspartame is about 15-25%, using ultrasound and largely Ultrapure water, recycle characteristic peak of the UV-vis spectral detection graphene oxide 230nm to demarcate and be modified with A Siba The concentration of the graphene oxide water solution of sweet tea.
Embodiment six
1.1 grams of monoxone and 1 gram of hydrogen is added in 10 milliliters of graphene oxide water solution for preparing 10 mg/mls thereto Sodium oxide molybdena, ultrasonic 5 hours adjust solution to neutrality, and filtering with ultrapure water or deionized water repeated flushing, is modified with The graphene oxide of carboxyl.Carboxyl is modified with using characteristic peak titration of the UV-vis spectral detection graphene oxide at 230nm The water-soluble concentration of graphene oxide, obtain the carboxyl modified graphene oxide water solution of 10 mg/mls;Take the carboxyl modified 10 milliliters of graphene oxide solution, 100 milligrams of 2-morpholine ethane sulfonic acid is added thereto, and adjust pH to 6, is added contains later There is 11 milligrams EDC and 9 milligram of NHS aqueous solution, stirs 1 hour at room temperature;5 milliliters, which are added, into the solution contains 25 milligrams Aspartame aqueous solution, after reacting 60 hours at room temperature, fully reacting, reaction solution is centrifuged under the conditions of 10000 revs/min, bottom Layer is the graphene oxide of Aspartame modification, and mass ratio shared by Aspartame is about 15-25%, using ultrasound and largely Ultrapure water recycles characteristic peak calibration of the UV-vis spectral detection graphene oxide at 230nm to be modified with Aspartame Graphene oxide water solution concentration.
It will be appreciated by persons skilled in the art that the Aspartame quality accounting for being necessary to adopt other ranges Ah In the case that this Ba Tian modifies graphene oxide, the dosage of Aspartame can be adjusted according to the actual situation, obtains target A Siba The Aspartame of saccharoid amount accounting modifies graphene oxide.
It should be understood that the application of the present invention is not limited to the above for those of ordinary skills can With improvement or transformation based on the above description, all these modifications and variations all should belong to the guarantor of appended claims of the present invention Protect range.

Claims (10)

1. a kind of monosaccharide transistor sensor characterized by comprising source electrode, drain electrode, semiconductor layer, dielectric layer and grid; The dielectric layer connects above the grid, and the semiconductor layer is connected in the dielectric layer, the source Pole and the drain electrode all connect above semiconductor layer, and the source electrode is not contacted with the drain electrode;The semiconductor layer For the graphene oxide layer of Aspartame modification.
2. monosaccharide transistor sensor according to claim 1, which is characterized in that the Aspartame is α type aspartoyl- Phenyalanine methyl ester.
3. monosaccharide transistor sensor according to claim 1, which is characterized in that the semiconductor layer with a thickness of 10-30 Nanometer.
4. monosaccharide transistor sensor according to claim 1, which is characterized in that the dielectric layer is silicon oxide dielectric layer, The grid is silicon gate.
5. a kind of preparation method of the monosaccharide transistor sensor as described in claim 1-4 is any, which is characterized in that including with Lower step:
Step S1: the graphene oxide solution of Aspartame modification is prepared;
Step S2: being arranged dielectric layer above grid, and the graphene oxide solution of Aspartame modification is added dropwise on dielectric layer, It anneals 10-30 hours under 80-120 degrees Celsius, the semiconductor layer of the graphene of Aspartame modification is made;
Step S3: being deposited source electrode and drain electrode on the graphene oxide semiconductor layer of Aspartame modification, to be made described Monosaccharide transistor sensor.
6. the preparation method of monosaccharide transistor sensor according to claim 5, which is characterized in that described to prepare Aspartame The method of the graphene oxide solution of modification the following steps are included:
Step S11: monoxone and sodium hydroxide being added in graphene oxide water solution, reacts 3-10 hours under ultrasound condition, Obtain the graphene oxide water solution for being modified with carboxyl;
Step S12: being added 2-morpholine ethane sulfonic acid in the solution through processing of step A, EDC and NHS aqueous solution is then added and stirs It mixes, wherein the EDC is 1- (3- dimethylamino-propyl) -3- ethyl-carbodiimide hydrochloride, and the NHS is N- hydroxyl fourth two Acid imide;
Step S13: it is water-soluble that α type aspartoyl-phenyalanine methyl ester Aspartame is added in the solution handled through step B Liquid reacts 48-72 hours at room temperature, the graphene oxide of Aspartame modification is made.
7. monosaccharide transistor sensor according to claim 6, which is characterized in that the graphene oxide, monoxone and hydrogen The mass ratio of sodium oxide molybdena is 1:9-11:10-14.
8. monosaccharide transistor sensor according to claim 6, which is characterized in that the 2-morpholine ethane sulfonic acid, EDC, NHS and The mass ratio of Aspartame is 100:11-15:7-9:15-25.
9. monosaccharide transistor sensor according to claim 6, which is characterized in that the graphite oxide of the Aspartame modification The Aspartame quality accounting of alkene is 15-25%.
10. the preparation method of monosaccharide transistor sensor according to claim 5, which is characterized in that the temperature of the annealing It is 100 degrees Celsius.
CN201910610923.1A 2019-07-08 2019-07-08 A kind of monosaccharide transistor sensor and preparation method thereof Pending CN110441375A (en)

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Publication number Priority date Publication date Assignee Title
CN1648661A (en) * 2005-01-21 2005-08-03 陈锐宁 Method and device for detecting sugar content in food
JP6019944B2 (en) * 2011-12-28 2016-11-02 逢坂 哲彌 Saccharide compound-immobilized semiconductor sensing device and biological substance detection method
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Publication number Priority date Publication date Assignee Title
CN1648661A (en) * 2005-01-21 2005-08-03 陈锐宁 Method and device for detecting sugar content in food
JP6019944B2 (en) * 2011-12-28 2016-11-02 逢坂 哲彌 Saccharide compound-immobilized semiconductor sensing device and biological substance detection method
CN106226377A (en) * 2016-07-06 2016-12-14 无锡盈芯半导体科技有限公司 A kind of field-effect transistor biosensor based on Graphene and preparation method thereof

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