CN105738447B - A kind of preparation method and application of electrochemistry chloramphenicol biology sensor - Google Patents
A kind of preparation method and application of electrochemistry chloramphenicol biology sensor Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of electrochemistry chloramphenicol biology sensor.Belong to Nano-function thin films and biosensor technology field.The method comprises the steps of firstly, preparing a kind of New Two Dimensional nano composite material Mn TiO2/g‑C3N4Good biocompatibility and big specific surface area using the material, chloramphenicol antibody in load, then the crosslinked action horseradish peroxidase of glutaraldehyde is passed through, when being detected, because horseradish peroxidase can be with catalyzing hydrogen peroxide, produce electrochemical signals, antibody is recycled to be combined the influence to electron transport ability with the specific quantification of antigen, so that current strength accordingly reduces, the electrochemica biological sensor that low cost, high sensitivity, specificity are good, detection is quick, prepare simple detection chloramphenicol has finally been made.
Description
Technical field
The present invention relates to a kind of preparation method of electrochemistry chloramphenicol biology sensor.Belong to Nano-function thin films with
Biosensor technology field.
Background technology
Chloramphenicol is the antibiotic as caused by Venezuela Streptothrix, belongs to biocidal property broad-spectrum antibiotic, makes frequently as veterinary drug
With.But human body reacts more more sensitive than animal to chloramphenicol, and the drug-metabolizing function of particularly infant is not perfect, chloramphenicol
It is exceeded to cause fatal " gray syndrome " to react, the alpastic anemia of people can be also caused when serious.
At present, the method for detecting chloramphenicol mainly has chromatography, mass spectrography etc..Such method instrument is valuable, complex operation,
Laboratory personnel could be detected after needing professional training.Therefore, R＆D costs are low, detection is fast, high sensitivity, high specificity
Chloramphenicol sensor is significant.
Electrochemica biological sensor due to its high sensitivity, specificity it is good, easy to operate the advantages that be widely used in facing
The fields such as bed diagnosis, Pharmaceutical Analysis, environmental monitoring.More, its key is wherein studied with unmarked electrochemical immunosensor especially
Technology be to improve modified electrode to the fixed amount of antibody and to testing the signal response speed and size of bottom liquid.Titanium dioxide is
A kind of photocatalyst material being most widely used, simultaneously because good biocompatibility, is also commonly used as electrode matrix material.By
More high miller index surfaces can be exposed in sheet-like titanium dioxide nanomaterial, there is higher catalytic activity, titanium dioxide is received
Rice piece has than nano-particle preferably application prospect, and the research for titanium dioxide nanoplate also receives much concern.But dioxy
The sensitivity that change titanium poorly conductive also limit the electrochemical sensor built by single titanium dioxide nano material is not universal high,
It is unfavorable for practical application.Modification or compound special nano material, on the one hand add electrode ratio on semiconductor nano material
Surface area, strengthen electrodes conduct ability, on the other hand the two can produce concerted catalysis effect, and bigger enhancing is to hydrogen peroxide
Solution H2O2Catalytic response speed and current responsing signal size, greatly improve detection sensitivity.Therefore, design, prepare height
Effect, stable titanium dioxide nanoplate and its trim are the key technologies for preparing electrochemical sensor.
The content of the invention
Prepare that simple, high sensitivity, detection be quick, electrochemistry chlorine of high specificity it is an object of the invention to provide a kind of
The preparation method of mycin biology sensor, prepared sensor, quick, Sensitive Detection available for chloramphenicol.Based on this mesh
, the method comprises the steps of firstly, preparing a kind of New Two Dimensional nano composite material, i.e. additive Mn titanium dioxide nanoplate In-situ reaction nitrogen
Change carbon two-dimensional nano composite Mn-TiO2/g-C3N4, good biocompatibility and big specific surface area using the material,
Chloramphenicol antibody in load, horseradish peroxidase is then fixed by the crosslinked action of glutaraldehyde, when being detected, due to
Horseradish peroxidase can produce electrochemical signals with catalyzing hydrogen peroxide, recycle the specific quantification knot of antibody and antigen
Close the influence to electron transport ability so that current strength accordingly reduces, and finally realizes using unmarked electrochemical method
Detect the structure of the biology sensor of chloramphenicol.
The technical solution adopted by the present invention is as follows：
1. a kind of preparation method of electrochemistry salbutamol sensor, described electrochemistry salbutamol sensor is by work
Make electrode, FeMn-TiO2/g-C3N4, salbutamol antibody, bovine serum albumin(BSA), glutaraldehyde, horseradish peroxidase composition；Institute
The FeMn-TiO stated2/g-C3N4For iron and the titanium dioxide nanoplate In-situ reaction carbonitride two-dimensional nano of manganese bimetallic codope
Composite；
Characterized in that, described preparation method includes following preparation process：
a. FeMn-TiO2/g-C3N4Preparation；
B. the preparation of electrochemistry salbutamol sensor；
Wherein, step a prepares FeMn-TiO2/g-C3N4Concretely comprise the following steps：
First, 0.8 mmol molysite and 0.8 ~ 1.2 mmol manganese salts is taken to be added in 5 mL butyl titanates, whipping process
In, 0.5 ~ 0.8 mL hydrofluoric acid is slowly added to, is reacted in a kettle at 160 ~ 200 DEG C 18 ~ 24 hours, after being cooled to room temperature,
With ultra-pure water and absolute ethyl alcohol centrifuge washing three times after, be dried in vacuo at 50 DEG C；Secondly, the dried solids of 150 ~ 250 mg are taken
Mixed with 400 mg melamines, and grind into powder；Then, the powder of grinding is put into Muffle furnace, programming rate is 1 ~ 3
DEG C/min, calcined 0.5 ~ 5 hour at 480 ~ 560 DEG C；Finally, the powder after calcining is cooled to room temperature, that is, FeMn- is made
TiO2/g-C3N4；
Described molysite is selected from one of following：Ferric sulfate, iron chloride, ferric nitrate；
Described manganese salt is selected from one of following：Manganese sulfate, manganese chloride, manganese nitrate；
Step b prepares concretely comprising the following steps for electrochemistry salbutamol sensor：
（1）Using glass-carbon electrode as working electrode, in the μ L of electrode surface drop coating 8 ~ 12 FeMn-TiO2/g-C3N4Colloidal sol, room
Dried under temperature；
（2）By step（1）In obtained electrode cushioning liquid PBS, continue in the μ L of electrode surface drop coating 8 ~ 12
10 μ g/mL salbutamol antibody-solutions, preserve in 4 DEG C of refrigerators and dry；
（3）By step（2）In obtained electrode PBS, it is 100 to continue in the μ L concentration of electrode surface drop coating 8 ~ 12
μ g/mL bovine serum albumin solution, preserve in 4 DEG C of refrigerators and dry；
（4）By step（3）In obtained electrode PBS, the glutaraldehyde continued in the μ L of electrode surface drop coating 2 ~ 4 is molten
Liquid, preserve in 4 DEG C of refrigerators and dry；
（5）By step（4）In obtained electrode PBS, it is 20 μ to continue in the μ L concentration of electrode surface drop coating 6 ~ 10
G/mL horseradish peroxidase solution, preserve in 4 DEG C of refrigerators and dry；
（6）By step（5）In obtained electrode PBS, preserved in 4 DEG C of refrigerators after drying, that is, electrification be made
Learn salbutamol sensor；
Described FeMn-TiO2/g-C3N4Colloidal sol is by 50 mg FeMn-TiO2/g-C3N4It is ultrapure that powder is dissolved in 10 mL
In water, and the obtained hydrosol after 30 min of ultrasound；
Described PBS is 10mmol/L phosphate buffer solution, and the pH value of described phosphate buffer solution is 7.4；
Described glutaraldehyde solution is the glutaraldehyde water solution that volume ratio is 2.5%.
2. the application of the electrochemistry salbutamol sensor prepared by preparation method of the present invention, it is characterised in that
Including following applying step：
A. standard liquid is prepared：Prepare the salbutamol standard liquid of one group of various concentrations including blank standard specimen；
B. working electrode is modified：By the electrochemistry salbutamol sensor prepared by preparation method as described in the present invention
For working electrode, the salbutamol standard liquid for the various concentrations prepared in step a is distinguished into drop coating to working electrode surface, 4
Preserved in DEG C refrigerator；
C. working curve is drawn：Using saturated calomel electrode as reference electrode, platinum electrode is used as to electrode, with step b
The working electrode composition three-electrode system modified, connects electrochemical workstation, successively adds 15 mL PBS in a cell
With the mol/L of 20 μ L 5 H2O2；By the working electrode of chronoamperometry detection assembling to H2O2Response；Blank standard specimen
Response current is designated asI 0, the response current of the salbutamol standard liquid containing various concentrations is denoted asI i, the difference of response current reduction
It is worth for ΔI = I 0-I i, ΔIWith the mass concentration of salbutamol standard liquidCBetween it is linear, draw ΔI-CWork
Curve；
D. the detection of salbutamol：The salbutamol standard liquid in step a is replaced with testing sample, according to step b and
Method in c is detected, the difference DELTA reduced according to response currentIAnd working curve, obtain salbutamol in testing sample
Content.
The useful achievement of the present invention
（1）Electrochemistry chloramphenicol biology sensor of the present invention is prepared simply, easy to operate, is realized to sample
Quickly, sensitive, high selectivity detection, and cost is low, can be applied to portable inspectiont, has market development prospect；
（2）The present invention is prepared for New-type matrix material Mn-TiO first2/g-C3N4, because manganese is on titanium dioxide nanoplate
Growth in situ and fully contacted with titanium dioxide nanoplate, using manganese metal surface plasma body act on, effectively increase
Semiconductor substrate electron transmission ability and catalytic activity, although it is bigger and mesoporous to solve titanium dioxide nanoplate specific surface area
Characteristic is applied to electrochemical-based material, but the technical problem that electro-chemical activity is not high and current signal is unstable；While by
In carbonitride g-C3N4Good electric conductivity, along with titanium dioxide nanoplate is fully dispersed thereon, greatly increase
Electron transmission ability, solve titanium dioxide nanoplate poorly conductive and current responsing signal it is weak and be unfavorable for prepare electrochemistry pass
The technical problem of sensor, therefore, effective preparation of the material, there is important scientific meaning and application value；
（3）The present invention is first by Mn-TiO2/g-C3N4Applied in the preparation of electrochemica biological sensor, significantly improve
The strength and stability of current signal, substantially increase the detection sensitivity of electrochemical sensor so that electrochemical biosensor
Device realizes the application in real work；The application of the material, be also associated biomolecule sensor, as optical electro-chemistry sensor,
Electrochemiluminescsensor sensor etc. provides Technical Reference, has extensive potential use value.
Embodiment
The Mn-TiO of embodiment 12/g-C3N4Preparation
First, take 0.8 mmol manganese salts to be added in 5 mL butyl titanates, in whipping process, be slowly added to 0.5 mL hydrogen
Fluoric acid, react in a kettle 24 hours, after being cooled to room temperature at 160 DEG C, with ultra-pure water and absolute ethyl alcohol centrifuge washing three times
Afterwards, it is dried in vacuo at 50 DEG C；Secondly, the dried solids of 150 mg are taken to be mixed with 400 mg melamines, and pulverize
End；Then, the powder of grinding is put into Muffle furnace, programming rate is 1 DEG C/min, is calcined 5 hours at 480 DEG C；Finally,
Powder after calcining is cooled to room temperature, that is, Mn-TiO is made2/g-C3N4；
Described manganese salt is manganese sulfate.
The Mn-TiO of embodiment 22/g-C3N4Preparation
First, take 1.0 mmol manganese salts to be added in 5 mL butyl titanates, in whipping process, be slowly added to 0.6 mL hydrogen
Fluoric acid, react in a kettle 21 hours, after being cooled to room temperature at 180 DEG C, with ultra-pure water and absolute ethyl alcohol centrifuge washing three times
Afterwards, it is dried in vacuo at 50 DEG C；Secondly, the dried solids of 200 mg are taken to be mixed with 400 mg melamines, and pulverize
End；Then, the powder of grinding is put into Muffle furnace, programming rate is 2 DEG C/min, is calcined 2 hours at 520 DEG C；Finally,
Powder after calcining is cooled to room temperature, that is, Mn-TiO is made2/g-C3N4；
Described manganese salt is manganese chloride.
The Mn-TiO of embodiment 32/g-C3N4Preparation
First, take 1.2 mmol manganese salts to be added in 5 mL butyl titanates, in whipping process, be slowly added to 0.8 mL hydrogen
Fluoric acid, react in a kettle 18 hours, after being cooled to room temperature at 200 DEG C, with ultra-pure water and absolute ethyl alcohol centrifuge washing three
After secondary, it is dried in vacuo at 50 DEG C；Secondly, the dried solids of 250 mg are taken to be mixed with 400 mg melamines, and pulverize
End；Then, the powder of grinding is put into Muffle furnace, programming rate is 3 DEG C/min, is calcined 0.5 hour at 560 DEG C；Most
Afterwards, the powder after calcining is cooled to room temperature, that is, Mn-TiO is made2/g-C3N4；
Described manganese salt is manganese nitrate.
The preparation method of the electrochemistry chloramphenicol biology sensor of embodiment 4
（1）Using a width of 1 cm, a length of 4 cm glass-carbon electrode as working electrode, in the μ L of electrode surface drop coating 8 Mn-
TiO2/g-C3N4Colloidal sol, dry at room temperature；
（2）By step（1）In obtained electrode cushioning liquid PBS, continue in the μ of 8 μ L of electrode surface drop coating 10
G/mL chloramphenicol antibody solution, preserve in 4 DEG C of refrigerators and dry；
（3）By step（2）In obtained electrode PBS, it is 100 μ to continue in the μ L concentration of electrode surface drop coating 8
G/mL bovine serum albumin solution, preserve in 4 DEG C of refrigerators and dry；
（4）By step（3）In obtained electrode PBS, the glutaraldehyde continued in the μ L of electrode surface drop coating 2 is molten
Liquid, preserve in 4 DEG C of refrigerators and dry；
（5）By step（4）In obtained electrode PBS, it is 20 μ g/ to continue in the μ L concentration of electrode surface drop coating 6
ML horseradish peroxidase solution, preserve in 4 DEG C of refrigerators and dry；
（6）By step（5）In obtained electrode PBS, preserved in 4 DEG C of refrigerators after drying, that is, electrification be made
Learn chloramphenicol biology sensor；
Described Mn-TiO2/g-C3N4Colloidal sol is by 50 mg Mn-TiO2/g-C3N4Powder is dissolved in 10 mL ultra-pure waters
In, and the obtained hydrosol after 30 min of ultrasound；
Described PBS is 10mmol/L phosphate buffer solution, and the pH value of described phosphate buffer solution is 7.4；
Described glutaraldehyde solution is the glutaraldehyde water solution that volume ratio is 2.5%.
The preparation method of the electrochemistry chloramphenicol biology sensor of embodiment 5
（1）Using a width of 1 cm, a length of 4 cm glass-carbon electrode as working electrode, in the μ L of electrode surface drop coating 10 Mn-
TiO2/g-C3N4Colloidal sol, dry at room temperature；
（2）By step（1）In obtained electrode cushioning liquid PBS, continue in the μ L 10 of electrode surface drop coating 10
μ g/mL chloramphenicol antibody solution, preserve in 4 DEG C of refrigerators and dry；
（3）By step（2）In obtained electrode PBS, it is 100 μ to continue in the μ L concentration of electrode surface drop coating 10
G/mL bovine serum albumin solution, preserve in 4 DEG C of refrigerators and dry；
（4）By step（3）In obtained electrode PBS, the glutaraldehyde continued in the μ L of electrode surface drop coating 3 is molten
Liquid, preserve in 4 DEG C of refrigerators and dry；
（5）By step（4）In obtained electrode PBS, it is 20 μ g/ to continue in the μ L concentration of electrode surface drop coating 8
ML horseradish peroxidase solution, preserve in 4 DEG C of refrigerators and dry；
（6）By step（5）In obtained electrode PBS, preserved in 4 DEG C of refrigerators after drying, that is, electrification be made
Learn chloramphenicol biology sensor；
Described Mn-TiO2/g-C3N4Colloidal sol is by 50 mg Mn-TiO2/g-C3N4Powder is dissolved in 10 mL ultra-pure waters
In, and the obtained hydrosol after 30 min of ultrasound；
Described PBS is 10 mmol/L phosphate buffer solution, and the pH value of described phosphate buffer solution is 7.4；
Described glutaraldehyde solution is the glutaraldehyde water solution that volume ratio is 2.5%.
The preparation method of the electrochemistry chloramphenicol biology sensor of embodiment 6
（1）Using a width of 1 cm, a length of 4 cm glass-carbon electrode as working electrode, in the μ L of electrode surface drop coating 12 Mn-
TiO2/g-C3N4Colloidal sol, dry at room temperature；
（2）By step（1）In obtained electrode cushioning liquid PBS, continue in the μ L 10 of electrode surface drop coating 12
μ g/mL chloramphenicol antibody solution, preserve in 4 DEG C of refrigerators and dry；
（3）By step（2）In obtained electrode PBS, it is 100 μ to continue in the μ L concentration of electrode surface drop coating 12
G/mL bovine serum albumin solution, preserve in 4 DEG C of refrigerators and dry；
（4）By step（3）In obtained electrode PBS, the glutaraldehyde continued in the μ L of electrode surface drop coating 4 is molten
Liquid, preserve in 4 DEG C of refrigerators and dry；
（5）By step（4）In obtained electrode PBS, it is 20 μ g/ to continue in the μ L concentration of electrode surface drop coating 10
ML horseradish peroxidase solution, preserve in 4 DEG C of refrigerators and dry；
（6）By step（5）In obtained electrode PBS, preserved in 4 DEG C of refrigerators after drying, that is, electrification be made
Learn chloramphenicol biology sensor；
Described Mn-TiO2/g-C3N4Colloidal sol is by 50 mg Mn-TiO2/g-C3N4Powder is dissolved in 10 mL ultra-pure waters
In, and the obtained hydrosol after 30 min of ultrasound；
Described PBS is 10 mmol/L phosphate buffer solution, and the pH value of described phosphate buffer solution is 7.4；
Described glutaraldehyde solution is the glutaraldehyde water solution that volume ratio is 2.5%.
Electrochemistry chloramphenicol biology sensor prepared by the embodiment 1 ~ 6 of embodiment 7, applied to the detection of chloramphenicol, step
It is rapid as follows：
（1）Standard liquid is prepared：Prepare the chloramphenicol standard liquid of one group of various concentrations including blank standard specimen；
（2）Working electrode is modified：By the electrochemistry chloramphenicol bio-sensing prepared by preparation method as described in the present invention
Device is working electrode, by step（1）The chloramphenicol standard liquids of the various concentrations of middle preparation distinguishes drop coating to working electrode surface,
Preserved in 4 DEG C of refrigerators；
（3）Working curve is drawn：Using saturated calomel electrode as reference electrode, platinum electrode is used as to electrode, with step b
The working electrode composition three-electrode system modified, connects electrochemical workstation, successively adds 15 mL PBS in a cell
With the mol/L of 20 μ L 5 H2O2；By the working electrode of chronoamperometry detection assembling to H2O2Response；Blank standard specimen
Response current is designated asI 0, the response current of the chloramphenicol standard liquid containing various concentrations is denoted asI i, the difference of response current reduction
For ΔI = I 0-I i, ΔIWith the mass concentration of chloramphenicol standard liquidCBetween it is linear, draw ΔI-CWorking curve；
The linear detection range of chloramphenicol is：0.009 ~ 200 ng/mL, detection are limited to：3.0 pg/mL；
（4）The detection of chloramphenicol：Step is replaced with testing sample（1）In chloramphenicol standard liquid, according to step（2）With
（3）In method detected, according to response current reduce difference DELTAIAnd working curve, obtain chloramphenicol in testing sample
Content.
Claims (2)
1. a kind of preparation method of electrochemistry chloramphenicol biology sensor, described electrochemistry chloramphenicol biology sensor is by working
Electrode, Mn-TiO2/g-C3N4, chloramphenicol antibody, bovine serum albumin(BSA), glutaraldehyde, horseradish peroxidase composition；Described
Mn-TiO2/g-C3N4For additive Mn titanium dioxide nanoplate In-situ reaction carbonitride two-dimensional nano composite；
Characterized in that, described preparation method includes following preparation process：
a. Mn-TiO2/g-C3N4Preparation；
B. the preparation of electrochemistry chloramphenicol biology sensor；
Wherein, step a prepares Mn-TiO2/g-C3N4Concretely comprise the following steps：
First, take 0.8 ~ 1.2 mmol manganese salts to be added in 5 mL butyl titanates, in whipping process, be slowly added to 0.5 ~ 0.8
ML hydrofluoric acid, react in a kettle 18 ~ 24 hours, after being cooled to room temperature at 160 ~ 200 DEG C, with ultra-pure water and absolute ethyl alcohol
Centrifuge washing three times after, be dried in vacuo at 50 DEG C；Secondly, the dried solids of 150 ~ 250 mg are taken to be mixed with 400mg melamines
Close, and grind into powder；Then, the powder of grinding is put into Muffle furnace, programming rate is 1 ~ 3 DEG C/min, 480 ~ 560
Calcined 0.5 ~ 5 hour at DEG C；Finally, the powder after calcining is cooled to room temperature, that is, Mn-TiO is made2/g-C3N4；
Described manganese salt is selected from one of following：Manganese sulfate, manganese chloride, manganese nitrate；
Step b prepares concretely comprising the following steps for electrochemistry chloramphenicol biology sensor：
（1）Using glass-carbon electrode as working electrode, in the μ L of electrode surface drop coating 8 ~ 12 Mn-TiO2/g-C3N4Colloidal sol, dry in the air at room temperature
It is dry；
（2）By step（1）In obtained electrode cushioning liquid PBS, continue in the μ of 8 ~ 12 μ L of electrode surface drop coating 10
G/mL chloramphenicol antibody solution, preserve in 4 DEG C of refrigerators and dry；
（3）By step（2）In obtained electrode PBS, it is 100 μ g/ to continue in the μ L concentration of electrode surface drop coating 8 ~ 12
ML bovine serum albumin solution, preserve in 4 DEG C of refrigerators and dry；
（4）By step（3）In obtained electrode PBS, continue the glutaraldehyde solution in the μ L of electrode surface drop coating 2 ~ 4,4
Preserve and dry in DEG C refrigerator；
（5）By step（4）In obtained electrode PBS, it is 20 μ g/mL to continue in the μ L concentration of electrode surface drop coating 6 ~ 10
Horseradish peroxidase solution, preserve in 4 DEG C of refrigerators and dry；
（6）By step（5）In obtained electrode PBS, preserved in 4 DEG C of refrigerators after drying, that is, electrochemistry chlorine be made
Mycin biology sensor；
Described Mn-TiO2/g-C3N4Colloidal sol is by 50 mg Mn-TiO2/g-C3N4Powder is dissolved in 10 mL ultra-pure waters, and
The obtained hydrosol after 30 min of ultrasound；
Described PBS is 10mmol/L phosphate buffer solution, and the pH value of described phosphate buffer solution is 7.4；
Described glutaraldehyde solution is the glutaraldehyde water solution that volume ratio is 2.5%.
2. the application of the electrochemistry chloramphenicol biology sensor prepared by preparation method as claimed in claim 1, its feature exist
In, including following applying step：
A. standard liquid is prepared：Prepare the chloramphenicol standard liquid of one group of various concentrations including blank standard specimen；
B. working electrode is modified：By the electrochemistry chloramphenicol biology sensor prepared by preparation method as claimed in claim 1
For working electrode, the chloramphenicol standard liquid for the various concentrations prepared in step a is distinguished into drop coating to working electrode surface, 4 DEG C
Preserved in refrigerator；
C. working curve is drawn：It is used as saturated calomel electrode as reference electrode, platinum electrode to electrode, is repaiied with step b
The working electrode composition three-electrode system adornd, connects electrochemical workstation, successively adds 15 mL PBS and 20 in a cell
The mol/L of μ L 5 H2O2；By the working electrode of chronoamperometry detection assembling to H2O2Response；The response electricity of blank standard specimen
Stream is designated asI 0, the response current of the chloramphenicol standard liquid containing various concentrations is denoted asI i, the difference that response current reduces is ΔI
= I 0-I i, ΔIWith the mass concentration of chloramphenicol standard liquidCBetween it is linear, draw ΔI-CWorking curve；
D. the detection of chloramphenicol：The chloramphenicol standard liquid in step a is replaced with testing sample, according to the side in step b and c
Method is detected, the difference DELTA reduced according to response currentIAnd working curve, obtain the content of chloramphenicol in testing sample.
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| CN107576714B (en) * | 2017-09-05 | 2019-06-04 | 济南大学 | A kind of preparation method and application of graphite phase carbon nitride@MOF nanocrystal |
| CN108845010A (en) * | 2018-06-25 | 2018-11-20 | 上海健康医学院 | Ionic liquid auxiliary synthesis of carbon/molybdenum disulfide and graphene oxide composite material are for detecting chloramphenicol |
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