CN107817284A - Electrospun for DBPs detection fixes imitative enzyme electrode and preparation method thereof - Google Patents
Electrospun for DBPs detection fixes imitative enzyme electrode and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to water pollution detection technique field, more particularly to a kind of Electrospun for DBPs detection fixes imitative enzyme electrode and preparation method thereof, and this method comprises the following steps：By N, N' dicyclohexylcarbodiimides are mixed with Cu with cupric dimethyldithio carbamate in dimethylformamide and imitate enzyme, the polar non-proton organic solvent that imitative enzyme is added to methyl methacrylate acrylonitrile copolymer prepares spinning solution, spinning is carried out to spinning solution and obtains the glass-carbon electrode covered with electrospun fiber membrane, electrostatic spinning immobilized imitative enzyme electrode is produced after activation.The imitative enzyme electrode has processability stable, prepares simple, and effective surface area is big, the advantages that strong antijamming capability, available for micro phenols DBPs in detection drinking water.
Description
Technical field
The present invention relates to water pollution detection technique field, more particularly to a kind of Electrospun for DBPs detection is consolidated
Surely imitative enzyme electrode and preparation method thereof.
Background technology
In order to prevent the pathophorous generation of various water, generally use chloridising carries out purifying sterilizing to natural water, greatly
Ground improves the drinking water general level of the health of the mankind.However, the seventies in last century is found that the presence of Chlorination Disinfection By-products, make one
Recognize the negative effect of cholorination.Chlorination Disinfection By-products be chlorine-containing disinfectant with naturally occurring organic matter in water,
Pollutant reaction and a kind of harmful substance generated.In recent years, it is latent to confirm that DBPs has to human health for correlative study
Threatening, be especially in the presence of mutagenicity, teratogenesis, carcinogenicity, causing people to start to carry out Chlorination Disinfection By-products in water
Again examine closely and evaluate.
In a variety of Chlorination Disinfection By-products, chlorophenol is the main source of degree of smelling and genetoxic in water.Chlorophenol be chlorine with
The product of phenolic compound reaction, and the catabolite of some agricultural chemicals.When the concentration ratio of chlorine and phenol is in the range of 1~4, in chlorine
2-chlorophenol, 3- chlorophenols, 2,4- Dichlorophenols, 2,6- Dichlorophenols, 2,3,4- trichlorophenols, 2,4 can be predominantly detected out after sterilizing in water by changing,
5- trichlorophenols and 2,4,6- trichlorophenols.Wherein, 2-chlorophenol, 3- chlorophenols, 2,4- Dichlorophenols and 2,6- Dichlorophenol are that have strong thorn
Swash the compound of property smell, the organoleptic properties of water are had a great influence.And some chlorophenols such as 2,3,4- trichlorophenols and 2,4,6- trichlorines
The Ames Mutagenicities of phenol are higher.Because the growing amount of such material during cholorination is higher, it is to drinking water water
The influence of matter can not be ignored.Undoubtedly, to safeguard water safety, it is necessary to chlorophenol pollutant in drinking water and recycled water
Concentration is strictly detected.
The national standard method of measure aldehydes matter is 4-AA colorimetric method at present, and this method is more numerous and diverse, need to be to sample
Product carry out pre-distillation, and analyze speed is slow, and whole process takes about two hours, it is impossible to realizes on-line monitoring.It would therefore be highly desirable to open
Chlorophenol detection technique is to realize quick, convenient, efficient, accurate detection in the water for sending out new.Compared with traditional analysis, enzyme passes
Sensor has the characteristics that analyze speed is fast, is quick on the draw, high specificity, simple operation, is easy to miniaturization and electronic, in recent years
By the extensive concern of environmental monitoring correlative study.However, at present on being detected using phenolase sensor in actual water body
The also rare report of the research of chlorophenol pollutant.This mainly due to：
1) existing phenolase sensor detecting is limited by current-responsive and electrode conditions, can not meet low in water
The testing requirements of concentration chlorophenol；
2) actual water condition is complicated, there is that a variety of bioavailabilities are low, toxicity is high, are not easy redox environmental pollution
Thing, easily cause enzyme electrode passivation and loss of activity；
3) phenolase electrode stability is bad, reuses for several times or after preservation certain time, its current-responsive is significantly decayed.
Therefore, such as enzyme sensor is used to detect chlorophenol pollutant in actual water body, also needs further to improve its performance
And stability.Imitative enzyme is the artificial preparations similar to biology enzyme based on a kind of function that bionic concept proposes, preferably imitates enzyme
It is a kind of superiority that can show enzyme, and the non-proteinaceous molecule combination simpler than enzymatic structure, stability is high, have the bottom of to
The performances such as identification, combination and the catalysis of thing.Method of electrostatic spinning is a kind of technology for efficiently easily obtaining superfine fibre film, can be with
Nanometer is obtained to the tunica fibrosa of micron-sized similar non-woven fabrics.Electrospinning fibre membrane porosity is high, and homogeneity is good, and specific surface area is big,
Particularly biocompatibility is better than metal or metal oxide nano-material, and therefore, electro spinning nanometer fiber membrane is considered as excellent
Enzyme immobilization carrier.Therefore, the height adjustable control of electrostatic spinning technique is made full use of, by optimizing spinning condition and spinning
Formula of liquid, it is possible to achieve enzyme is imitated in the immobilization of electrospinning fibre embedding in situ.Enzyme is imitated in the immobilization being prepared has load enzyme amount height, enzyme
It is living to lose the advantages that small, stability is strong.If preparing imitative enzyme membrane electrode by electrostatic spinning technique, be advantageous to keep height to imitate enzyme activity
Property, and can exposes the active surface of imitative enzyme, it is anti-to improve adsorption concentration and imitative enzymatic of the pollutant on electrode to greatest extent
Electron transport rate during answering, it is expected to improve phenolase electrode activity and improve its detection sensitivity and stability.
The content of the invention
The present invention be in view of the above-mentioned problems in the prior art and make, it is an object of the invention to provide one kind
Electrostatic spinning immobilized imitative enzyme electrode detected for phenols DBPs in drinking water and preparation method thereof.
To achieve these goals, one kind of the first technical scheme of the invention is used for phenols DBPs inspection in drinking water
The preparation method for the electrostatic spinning immobilized imitative enzyme electrode surveyed, it is characterised in that comprise the following steps：
(1) first by N, N'- dicyclohexylcarbodiimides are with cupric dimethyldithio carbamate in dimethylformamide
Mixing, forms sticky light green solution, and 12h is incubated at 45 DEG C, adds absolute ethyl alcohol washing, is dried in vacuo at 60 DEG C
24h,
Obtain absinthe-green Cu and imitate enzyme；
(2) Methyl Methacrylate-acrylonitrile Copolymer is added in polar non-proton organic solvent, in 60 DEG C of stirrings
12h, it is completely dissolved to Methyl Methacrylate-acrylonitrile Copolymer, is configured to the metering system that mass concentration is 3%~10%
Sour methacrylate-acrylonitrile copolymer solution, add three halogen acetic acids that mass concentration is 0.1% and adjust electrical conductivity, be eventually adding quality
The Cu that concentration is 0.1%~1.0% imitates enzyme, stirs to being completely dissolved, imitative enzyme spinning solution is made；
(3) imitative enzyme spinning solution is incorporated into electric spinning device, using glass-carbon electrode as receiver board, setting spinning voltage is
20~50kV, receive distance be 15cm, rate of extrusion is 0.1~0.5mL/min, and the spinning time continues 1~2h, obtain covered with
The glass-carbon electrode of electrospun fiber membrane；
(4) glassy carbon electrode surface that will be covered with nano fibrous membrane is immersed in glutaraldehyde water solution, at 15 DEG C~35 DEG C
Vibration activation 30min, then washs 3~5 activation with the aqueous hydrogen peroxide solution that mass concentration is 1%, the electrode of activation is soaked
Enter in the potassium dihydrogen phosphate buffer solution that pH value is 3.5, preserved at 4 DEG C stand-by.
N described in step (1), mass concentration of the N'- dicyclohexylcarbodiimides in dimethylformamide are
12.5%~25%；Mass concentration of the cupric dimethyldithio carbamate in dimethylformamide is 5%~10%；
Polar non-proton organic solvent described in step (2) is acetonitrile, dimethyl sulfoxide (DMSO), 1,3- dimethyl -2- miaows
One kind of oxazoline ketone；Mass concentration of the Methyl Methacrylate-acrylonitrile Copolymer in above-mentioned solvent is 3%~10%；
Electric spinning device described in step (3) by high-voltage DC power supply, spinning head, glass-carbon electrode, infusion pump and is matched somebody with somebody
Wire, pipeline composition are covered, spinning head is connected by wire with the positive pole of high-voltage DC power supply, is connected with infusion pump by pipeline；
Glass-carbon electrode is connected with the negative pole of high-voltage DC power supply；
The aqueous solution mass concentration of glutaraldehyde described in step (4) is 2.5%~10%.
In above-mentioned building-up process, N, N'- dicyclohexylcarbodiimides are to form with cupric dimethyldithio carbamate
The Basal activity unit of imitative enzyme system.In this imitative enzyme system, Cu2+With the chelate of dimethyl dithiocarbamic acid first
By H2O2It is reduced into Cu+, and oxygen is released simultaneously, there is excessive H2O2In the presence of, then it can produce by Cu3+/ DMDS generation
The peroxide that carbamic chelate is formed with O.Now, most H2O2It has been decomposed into oxygen.It is this by peroxidating
Thing oxidability is extremely strong, phenyl ring that can be directly in attack chlorophenols, and Cu is formed with C atoms3+The connection of-C keys, in the mistake
Along with substantial amounts of electron transmission in journey, under the conditions of the steady-state field in will be expressed as obvious redox signal.
Compared with traditional biology enzyme and imitative enzyme system, dimethyl dithiocarbamic acid is to Cu2+Sequestering power it is stronger,
Property is more stable, it is not easy to is influenceed by other heavy metal ion in water.Although cupric dimethyldithio carbamate is imitated
The redox ability and biology enzyme of enzyme, being compared such as laccase has certain gap, but for chlorophenols detection, stable reproduction
Property is even more important；And the chelating body of dimethyl dithiocarbamic acid can be to Cu2+Form stable full encirclement, prevent its
In Electrospun solution or dissolution during electrode measurement；In addition, carbamic function in dimethyl dithiocarbamic acid
The suitably path as electric transmission is rolled into a ball, most of enzymatic reaction can be realized via carbamic acid structure, be effectively improved
Electronics conduction efficiency and chelating Cu2+Stability.
The general principle of electrostatic spinning is to add the spray nozzle front end of Polymer Solution or directly Polymer Solution is applied
High voltage, in the droplet surface of spray nozzle front end, electric charge because enrichment cause it is mutually exclusive.With the increase of electric field force, drop is in electricity
It is drawn into the presence of field force coniform (Taylor cones).The repulsive force of electric charge gradually strengthens, when repulsive force is more than surface
During power, liquid sprays from the front end of circular cone.Thread is in course of injection, and solvent volatilization is fiber solidifying, and finally falls and collecting dress
Put, obtain nanometer to the tunica fibrosa of micron-sized similar non-woven fabrics.Electrostatic spinning technique be traditional Electrostatic Spray Technology with
The perfect adaptation of nanosecond science and technology, new material foundation is provided for field of functional materials.Superfine fibre prepared by method of electrostatic spinning
The characteristics of be：(1) porosity is high, and homogeneity is good；(2) specific surface area is big, and surface nature is adjustable；(3) product is easy to collect and divided
From etc..It is fast that membrane material efficiency high, speed are particularly prepared with the technology, can obtain with multiple functions structure, can be used as excellent
The fiber film material of carrier.When as enzyme material is carried, mimetic enzyme catalyst can be uniformly distributed in fiber surface, have immobilized side
Just the advantages of, activity recovery is high, stability is strong, and the specific surface area of electrospun fiber membrane and hydrophobic property are advantageous to imitative enzyme bottom
Absorption and catalysis oxidation of the thing on film, be advantageous to electron transmission, and can further enhanced signal intensity.
To sum up, the electrostatic spinning immobilized imitative enzyme electricity of the present invention for being used for phenols DBPs in drinking water and detecting
Pole and preparation method thereof
Brief description of the drawings
To be illustrated more clearly that the embodiment of the present invention, below to being used in the description of specific embodiment part
To accompanying drawing be briefly described.
Fig. 1 is the scanning electron microscope image that electrostatic spinning immobilized Cu imitates enzyme electrode；
Fig. 2 is that Electrospun immobilization Cu imitates the experimental provision schematic diagram that enzyme electrode detects chlorophenol；
Wherein reference is：1st, electrostatic spinning immobilized imitative enzyme electrode；2nd, enzyme membrane reaction tank；3rd, electrochemical workstation；
4th, signal acquisition computer；5th, wire；6th, sample inputs；7th, reference inputs
Fig. 3 is that electrostatic spinning immobilized Cu imitates cyclic voltammetry curve of the enzyme electrode when detecting chlorophenol.
Embodiment
First embodiment
Include such as the electrostatic spinning immobilized imitative enzyme electrode preparation method that phenols DBPs in drinking water detects
Lower step：
First N, N'- dicyclohexylcarbodiimides are mixed with cupric dimethyldithio carbamate in dimethylformamide
Close, wherein N, the mass concentration of N'- dicyclohexylcarbodiimides is 12.5%, and the quality of cupric dimethyldithio carbamate is dense
Spend for 5%, it is well mixed to form sticky light green solution, 12h is incubated at 45 DEG C, absolute ethyl alcohol washing is added, at 60 DEG C
Lower vacuum drying 24h, obtain absinthe-green Cu and imitate enzyme；Methyl Methacrylate-acrylonitrile Copolymer is added in acetonitrile,
60 DEG C of stirring 12h, are completely dissolved to Methyl Methacrylate-acrylonitrile Copolymer, are configured to the methyl-prop that mass concentration is 3%
E pioic acid methyl ester-acrylonitrile copolymer acetonitrile solution, add three halogen acetic acids that mass concentration is 0.1% and adjust electrical conductivity, finally add
Enter the Cu that mass concentration is 0.1%% and imitate enzyme, stir to being completely dissolved, imitative enzyme spinning solution is made；Imitative enzyme spinning solution is drawn
Enter into electric spinning device, using glass-carbon electrode as receiver board, setting spinning voltage is 20kV, and it is 15cm to receive distance, extrusion speed
Rate is 0.1mL/min, and the spinning time continues 1h, obtains the glass-carbon electrode covered with nano fibrous membrane；It will be covered with nanofiber
The glassy carbon electrode surface of film is immersed in glutaraldehyde water solution, the vibration activation 30min at 15 DEG C, is then 1% with mass concentration
Aqueous hydrogen peroxide solution wash 3~5 activation, the electrode of activation is immersed in the potassium dihydrogen phosphate buffer solution that pH value is 3.5,
Preserved at 4 DEG C stand-by.
Second embodiment
Second embodiment is the variation of first embodiment, and the difference with first embodiment is N, N'- dicyclohexyl carbon
The mass concentration of diimine is 25%, and the mass concentration of cupric dimethyldithio carbamate is 10%, and aprotic, polar is organic
Solvent is dimethyl sulfoxide (DMSO), and Methyl Methacrylate-acrylonitrile Copolymer is 10%, penta 2 in the mass concentration of dimethyl sulfoxide (DMSO)
The aqueous solution mass concentration of aldehyde is 10%, and it is 1.0%, spinning voltage 50kV that the Cu added wherein, which imitates enzyme mass concentration, is squeezed
It is 0.5mL/min to go out speed, and the spinning time is 2h, and the glassy carbon electrode surface covered with nano fibrous membrane is in glutaraldehyde water solution
Activation temperature be 35 DEG C, other are identical with first embodiment, will not be described here.
3rd embodiment
3rd embodiment is the variation of first embodiment, and the difference with first embodiment is N, N'- dicyclohexyl carbon
The mass concentration of diimine is 22%, and the mass concentration of cupric dimethyldithio carbamate is 6.5%, and aprotic, polar is organic
Solvent is DMI, and Methyl Methacrylate-acrylonitrile Copolymer is in 1,3- dimethyl -2- imidazolines
Mass concentration in ketone is 5%, and the aqueous solution mass concentration of glutaraldehyde is 5%, and the Cu added wherein imitates enzyme mass concentration and is
0.3%, spinning voltage 30kV, rate of extrusion 0.2mL/min, spinning time are 1.5h, the glass covered with nano fibrous membrane
Activation temperature of the carbon electrodes in glutaraldehyde water solution is 22 DEG C, and other are identical with first embodiment, will not be described here.
Fourth embodiment
Fourth embodiment is the variation of first embodiment, and the difference with first embodiment is N, N'- dicyclohexyl carbon
The mass concentration of diimine is 17%, and the mass concentration of cupric dimethyldithio carbamate is 8%, and aprotic, polar is organic molten
Agent is DMI, and Methyl Methacrylate-acrylonitrile Copolymer is in DMI
In mass concentration be 5%, the aqueous solution mass concentration of glutaraldehyde is 5%, and the Cu added wherein imitates enzyme mass concentration and is
0.3%, spinning voltage 45kV, rate of extrusion 0.7mL/min, spinning time are 1.2h, the glass covered with nano fibrous membrane
Activation temperature of the carbon electrodes in glutaraldehyde water solution is 22 DEG C, and other are identical with first embodiment, will not be described here.
5th embodiment
The experiment for imitating Cu enzyme electrode measurement phenols DBPs is carried out in electrochemical workstation system, with naked glass carbon
Electrode, electrospun fibers membrane electrode and electrostatic spinning immobilized imitative enzyme electrode are working electrode, and saturated calomel electrode (SCE) is
Reference electrode, platinum electrode are to electrode, three-electrode system are put into supporting electrolyte solution, in CHI660D electrochemical operations
Stand and carry out cyclic voltammetry scan, study electrochemical behavior.Scanning voltage is determined according to the size of the spike potential of redox peaks
Scope, peak current scope are selected according to the size of actual measured value.
From a kind of obtained electrostatic spinning immobilized imitative enzyme electrode of embodiment to three kinds of chlorophenols dirts in the present embodiment
Dye thing has a higher current-responsive value (see Fig. 3), electrode pair 4-CP, 2,4-DCP, 2,4,6-TCP tri- kinds of chlorophenols it is minimum
Test limit is respectively 0.12 μM, 0.17 μM and 0.29 μM, and system reappearance is good.
Sixth embodiment
The electrostatic spinning immobilized imitative enzyme electrode that selection 3rd embodiment is obtained is to 4-CP, 2,4-DCP, 2,4,6-
The minimum detection limit of tri- kinds of chlorophenols of TCP is respectively 0.10 μM, 0.12 μM and 0.19 μM, and system reappearance is good.
7th embodiment
The electrostatic spinning immobilized imitative enzyme electrode that selection fourth embodiment is obtained is to 4-CP, 2,4-DCP, 2,4,6-
The minimum detection limit of tri- kinds of chlorophenols of TCP is respectively 0.25 μM, 0.13 μM and 0.06 μM, and system reappearance is good.
Above-described embodiment is only used for illustrating the spirit of the present invention, and protection scope of the present invention is not
This is confined to, to those of ordinary skill in the art, can be led to certainly according to technology contents disclosed in this specification
The mode for crossing change, displacement or modification makes other embodiments easily, and these other embodiments should all cover at this
Within the protection domain of invention.
Claims (5)
1. a kind of Electrospun for DBPs detection fixes imitative enzyme electrode and preparation method thereof, it is characterised in that including
Following steps：
1) first N, N'- dicyclohexylcarbodiimides are mixed with cupric dimethyldithio carbamate in dimethylformamide,
Sticky light green solution is formed, 12h is incubated at 45 DEG C, absolute ethyl alcohol washing is added, is dried in vacuo 24h at 60 DEG C, obtains
Enzyme is imitated to absinthe-green Cu；
2) Methyl Methacrylate-acrylonitrile Copolymer is added in polar non-proton organic solvent, 12h is stirred at 60 DEG C,
It is completely dissolved to Methyl Methacrylate-acrylonitrile Copolymer, is configured to the methyl methacrylate that mass concentration is 3%~10%
Ester-acrylonitrile copolymer solution, add three halogen acetic acids that mass concentration is 0.1% and adjust electrical conductivity, be eventually adding mass concentration
Enzyme is imitated for 0.1%~1.0% Cu, stirs to being completely dissolved, imitative enzyme spinning solution is made；
3) imitative enzyme spinning solution is incorporated into electric spinning device, using glass-carbon electrode as receiver board, set spinning voltage be 20~
50kV, it is 15cm to receive distance, and rate of extrusion is 0.1~0.5mL/min, and the spinning time continues 1~2h, obtained covered with electrospinning
The glass-carbon electrode of tunica fibrosa；
4) glassy carbon electrode surface that will be covered with nano fibrous membrane is immersed in glutaraldehyde water solution, is vibrated and is lived at 15 DEG C~35 DEG C
Change 30min, then wash 3~5 activation with the aqueous hydrogen peroxide solution that mass concentration is 1%, the electrode of activation is immersed into pH value
In 3.5 potassium dihydrogen phosphate buffer solution, to be preserved at 4 DEG C stand-by.
2. according to a kind of preparation side for being used for the imitative enzyme electrode of Electrospun fixation that DBPs detects described in claim 1
Method, it is characterised in that mass concentration of the carbodicyclo hexylimide in dimethylformamide is 12.5%~25%；Dimethyl two
Mass concentration of the thiocarbamic acid copper in dimethylformamide is 5%~10%.
3. according to a kind of preparation side for being used for the imitative enzyme electrode of Electrospun fixation that DBPs detects described in claim 1
Method, it is characterised in that described polar non-proton organic solvent is acetonitrile, dimethyl sulfoxide (DMSO), DMI
One kind；Mass concentration of the Methyl Methacrylate-acrylonitrile Copolymer in above-mentioned solvent is 3%~10%.
4. according to a kind of preparation side for being used for the imitative enzyme electrode of Electrospun fixation that DBPs detects described in claim 1
Method, it is characterised in that described electric spinning device is by high-voltage DC power supply, spinning head, glass-carbon electrode, infusion pump and matched guide
Line, pipeline are formed, and spinning head is connected by wire with the positive pole of high-voltage DC power supply, is connected with infusion pump by pipeline；Glass carbon
Electrode is connected with the negative pole of high-voltage DC power supply.
5. according to a kind of preparation side for being used for the imitative enzyme electrode of Electrospun fixation that DBPs detects described in claim 1
Method, it is characterised in that the aqueous solution mass concentration of described glutaraldehyde is 2.5%~10%.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711000121.6A CN107817284B (en) | 2017-10-24 | 2017-10-24 | The preparation method of enzyme electrode is imitated in Electrospun immobilization for disinfection by-products detection |
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|---|---|---|---|
| CN201711000121.6A CN107817284B (en) | 2017-10-24 | 2017-10-24 | The preparation method of enzyme electrode is imitated in Electrospun immobilization for disinfection by-products detection |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101285792A (en) * | 2008-05-23 | 2008-10-15 | 浙江大学 | Mediator electrochemical enzyme electrode and method for making same |
| CN101865874A (en) * | 2010-06-11 | 2010-10-20 | 东华大学 | High-sensitivity biological sensor and preparation method thereof |
| CN101915797A (en) * | 2010-07-27 | 2010-12-15 | 北京师范大学 | Method for preparing electrostatic spinning immobilized laccase electrode |
| US20110201242A1 (en) * | 2010-02-17 | 2011-08-18 | Samsung Electronics Co., Ltd. | Fiber for detecting target and use thereof |
| CN103901088A (en) * | 2014-04-17 | 2014-07-02 | 扬州大学 | Electrostatic spinning method for preparing nanofiber membrane biosensor |
-
2017
- 2017-10-24 CN CN201711000121.6A patent/CN107817284B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101285792A (en) * | 2008-05-23 | 2008-10-15 | 浙江大学 | Mediator electrochemical enzyme electrode and method for making same |
| US20110201242A1 (en) * | 2010-02-17 | 2011-08-18 | Samsung Electronics Co., Ltd. | Fiber for detecting target and use thereof |
| CN101865874A (en) * | 2010-06-11 | 2010-10-20 | 东华大学 | High-sensitivity biological sensor and preparation method thereof |
| CN101915797A (en) * | 2010-07-27 | 2010-12-15 | 北京师范大学 | Method for preparing electrostatic spinning immobilized laccase electrode |
| CN103901088A (en) * | 2014-04-17 | 2014-07-02 | 扬州大学 | Electrostatic spinning method for preparing nanofiber membrane biosensor |
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