A kind of polyaniline nano fiber film vitamin C color sensor and detection method thereof
Technical field
The present invention relates to a kind of polyaniline nano fiber film vitamin C color sensor, belong to the technical field of nano-functional material.
Background technology
Vitamin C has another name called the L-ascorbic acid, is a kind of water soluble compound, and not only complicated metabolic process such as the oxidation of wide participation body, reduction can also promote the synthetic of interior collagen of body and mucopolysaccharide, the enhancing body resistibility.Can cause scurvy symptoms such as haematogenous mechanism obstacle, anaemia, wall of micrangium permeability increase, and fragility strengthens, and is hemorrhage easily during shortage.Hence one can see that vitamin C is very close with human relation, but human body self can not synthetic vitamin C, must from food, absorb.The minimum intake of each adult every day is 30mg, but ascorbic absorption is not The more the better yet, and human body is if once take in 2500-5000mg when above, just may cause the red blood cell critical phenomenons such as haemolysis occur of breaking in a large number.In addition vitamin C bring certain trouble also can for human daily laboratory examination, as long as " oxidation-reduction reaction " process is wherein arranged, vitamin C all might be participated, and then check result is impacted.Wherein modal is influence to urinalysis.A large amount of vitamin Cs of taking in can make that urine is occulted blood, false-negative result appears in lab works such as glucose in urine and nitrite, so must detect ascorbic content.Existing vitamin C detection method mainly contains titrimetry (as 2,6-dichloroindophenol titrimetry and iodimetry), AAS, XRF and chromatography etc.These methods more or less all exist defective.For example 2, the impurity that often has except that vitamin C in the 6-dichloroindophenol titrimetry can be with 2, and 6-dichloroindophenol reduction makes the poor specificity of this titrimetry; And the iodimetric titration that is adopted among patent CN200810219725.4 test, wherein used demarcation thing arsenic trioxide then is a kind of extremely toxic substance; Adopt the experiment developing time of 2,4 dinitrophenyl hydrazine colourimetry longer, experiment interference is more, and the color of liquid to be measured itself can influence absorbance, all right simultaneously and pentose of 2,4 dinitrophenyl hydrazine, and the reaction of carbohydrates such as hexose, thus influence is measured; The high performance liquid chromatography complicated operation, instrument and equipment is expensive, thus chromatographic column is very easily polluted and is influenced test result.Thereby be badly in need of a kind of easy and simple to handle, cheap and can guarantee to test the test component of effect.
Compare with other conducting polymer composites; Polyaniline have conductivity height, doping attitude and unadulterated environmental stability good, be easy to synthesize, the monomer low cost and other advantages; Being considered to has one of conducting polymer of actual application prospect most, has received domestic and international researchist's extensive concern and research.Especially under different oxidation electric potential field and PH environment, a series of reversible change color can take place, make polyaniline also come into one's own just gradually in the color sensor research field, be expected to be used to prepare high-performance vitamin C color sensor.In addition; The polyaniline material of nanostructured is because its special nanoscale effect; And controlled galvanochemistry, optical property, caused people's very big concern in the novel nano field of functional materials, become the hot fields of nanometer technology and material science research gradually.But because the existence of benzene ring structure on the polyaniline molecule main chain; Strand has stronger rigidity and chain interphase interaction, makes that its dissolubility and film forming are poor, and corresponding processing characteristics also is affected; Existing polyaniline nano membrane material mechanical strength is low; Be difficult to form homogeneous system, use cost is high, has limited its widespread use technically.
Summary of the invention
The object of the invention provides a kind of polyaniline nano fiber film vitamin C color sensor and detection method thereof, thus solve said vitamin C detect in complex process, instrument expensive, error appears when measuring easily; Problems such as poor performance in the polyaniline nano membrane material processing, mechanical strength is low, dispersiveness is bad.
In order to achieve the above object, the invention provides a kind of preparation method of polyaniline fiber film vitamin C color sensor, it is characterized in that, may further comprise the steps:
The first step: at ambient temperature, in stirred tank, the polyaniline in eigenstate raw material is dissolved in the solvent, speed of agitator is 50-200rpm, obtains the polyaniline solutions that massfraction is 0.2%-15%;
Second step: the blending polymkeric substance is joined in the polyaniline solutions that the first step obtains, and speed of agitator is 200-1000rpm, mixes, and obtaining blending polymer quality mark is the solution of 0.5%-30%;
The 3rd step: under the condition of relative humidity 20%-60%, the flow velocity of second solution that obtains of step with 0.1-4mL/h is input on the spinning head of electrospinning device, simultaneously spinning head connected the 10-40kV power supply and carry out electrostatic spinning and prepare nano-composite fiber;
The 4th step: the 3rd nano-composite fiber that make of step deposited to obtain being deposited on the nano-composite fiber film on ITO electro-conductive glass, aluminium foil or the paperboard on ITO electro-conductive glass, aluminium foil or the paperboard; Behind the vacuum drying 1-4h, immerse the KMnO of 0.001mol/L-0.01mol/L
4In the Treatment Solution, reaction 1-5min;
The 5th step: take out the 4th and go on foot the nano-composite fiber film on ITO electro-conductive glass, aluminium foil or the paperboard that is deposited on that obtains, after distilled water drip washing, immerse in the distilled water and soak 3-15min, speed of agitator is 50-200rpm;
The 6th step: go on foot the nano-composite fiber film vacuum drying 2-4h under 40-90 ℃ of condition on ITO electro-conductive glass, aluminium foil or the paperboard that is deposited on that obtains with the 5th; After polyaniline composite nano-fiber membrane color becomes dark brown by green, make polyaniline nano fiber film vitamin C color sensor.
Preferably; Solvent in the described first step is formic acid, trifluoroacetic acid, perfluoro caprylic acid, hexafluoroisopropanol, N-Methyl pyrrolidone, N; In dinethylformamide, DMAC N,N, tetrahydrofuran, dimethyl sulfoxide (DMSO), sulfolane, dodecylbenzene sulfonic acid, sulfosalicylic acid, methenyl choloride, triethylamine, ethanol and the methylene chloride any one or two or more potpourris.
Preferably, the blending polymkeric substance in described second step is any one or two or more potpourris in nylon 6, polyvinyl butyral, polymethylmethacrylate, acetyl cellulose, ethyl cellulose, polyacrylonitrile and the PLA.
The present invention also provides the detection method of above-mentioned polyaniline fiber film vitamin C color sensor, it is characterized in that concrete steps are following:
The first step: the vitamin c solution of polyaniline nano fiber film vitamin C color sensor being got 100-500 variable concentrations point in weight concentration is 100ppb-100ppm is tested; Observe the change color of polyaniline nano fiber film vitamin C color sensor under the room temperature; Utilize fiber spectrometer to detect its reflectance spectrum; Adopt Lab color mode and RGB color mode to calculate simultaneously; According to the reflection strength value that obtains of test, and should value and its corresponding wavelength carry out integral and calculating, compare through the color standard of issuing with International Commission on Illumination (CIE); Calculate the related color change value, the relation curve of making between change color and the concentration is decided to be typical curve;
Second step: polyaniline fiber film vitamin C color sensor is put into the to be measured vitamin c solution of weight concentration in the 100ppb-100ppm scope at ambient temperature, leave standstill 5-30min, vacuum drying 2h-4h at room temperature after the taking-up; Utilize fiber spectrometer to detect its reflectance spectrum; Adopt Lab color mode and RGB color mode to calculate simultaneously, the reflection strength value that obtains according to test, and should value and its corresponding wavelength carry out integral and calculating; Through comparing with the color standard of International Commission on Illumination (CIE) promulgation; Calculate the related color change value, and compare, thereby obtain ascorbic concrete concentration value with typical curve.
The present invention compared with prior art, advantage is following:
(1) the present invention adopts the solution blending electrostatic spinning technique, has realized that the homogeneous phase of polyaniline and blending polymkeric substance is blended into fibre.Mix through polyaniline and blending component in the nano-composite fiber film of this method preparation, do not have the situation that is separated and take place.Improve the mechanical property of polyaniline nano fiber film greatly, demonstrated fabulous pliability.Polyaniline molecule is dispersed in the nano fibrous membrane uniformly, makes the tunica fibrosa colour developing evenly, and color saturation is high, helps the accurate measurement of spectral information.Mix characteristic and the different oxidation attitude changes based on the unique doping of polyaniline/take off, thereby make tunica fibrosa realize a series of reversible color change.
(2) vitamin C color sensor employing polyaniline composite nano-fiber membrane provided by the present invention is a sensing material; Specific surface area than common solid membrane improves the 1-2 one magnitude; Increased polyaniline with the interaction between the vitamin C; Having improved sensor's response speed and detection sensitivity, is 100ppb-100ppm to ascorbic sensing range.When vitamin C concentration increased in the 100ppb-100ppm scope gradually, the change color of vitamin C color sensor was followed successively by brown, purple, blueness, green.
(3) vitamin C color sensor provided by the present invention, use equipment is simple, and is cheap, do not produce objectionable impurities in the testing process, visual result, disturbing factor is few, and can detect in real time.
Embodiment
Below in conjunction with embodiment, further set forth the present invention.
Polyaniline among the embodiment 1-6 is selected the polyaniline (Mw=65000) that Co., Ltd produces among the Sigma for use; Butvar B-76 polyvinyl butyral Mw=120000, CP ethyl cellulose (Mw=44900), CDFH-NSIX20K nylon-6 (Mw=220000), the acetyl cellulose (Mw=100000) of hydroxyl 2%, CDFH-PLA1300K PLA (Mw=1323000), CDFH-PAN85K polyacrylonitrile (Mw=85250) that spinning selects for use Shanghai brilliant pure reagent company limited to produce with the blending polymkeric substance, solvent is selected acetyl 40% for use; The DW-P303-1ACD8 type that high-voltage power supply selects for use east, Tianjin civilian high-voltage power supply factory to produce; The LSP02-113 type that transfusion system selects for use Baoding LanGe constant flow pump Co., Ltd to produce.
The method of the typical curve of drawing among the embodiment 1-6 is: adopt polyaniline nano fiber film vitamin C color sensor in weight concentration is 100ppb-100ppm, the vitamin solution of 100 variable concentrations points to be tested; Utilize the fiber spectrum measuring instrument to detect its reflectance spectrum; Adopt Lab color mode and RGB color mode to calculate simultaneously; According to the reflection strength value that obtains of test, and will be worth and integral and calculating that its corresponding wavelength is carried out, compare through the color standard of issuing with International Commission on Illumination (CIE); Calculate the related color change value, the relation curve of making between change color and the concentration is decided to be typical curve.
Embodiment 1
Under 25 ℃ of conditions of room temperature; In stirred tank with the 0.02g polyaniline with rotating speed 50rpm stirring and dissolving in 9.93g formic acid and acetate mixed solvent (weight ratio is 5:1); After treating that polyaniline dissolves fully; In solution, add the 0.05g polyvinyl butyral, 200rpm stirs with rotating speed, obtains the polyaniline massfraction and be 0.2%, the polyvinyl butyral massfraction is 0.5% co-blended spinning solution.Under the condition of room temperature, humidity 30%-40%, the flow velocity of co-blended spinning solution solution with 1.5mL/h is input on the spinning head, simultaneously spinning head is connected the 20kV power supply and carry out electrostatic spinning and prepare polyaniline/polyvinyl alcohol butyral blended nanofibre; To ITO electro-conductive glass receiving trap, the distance between receiving trap and the spinning head is 10cm with spun fiber laydown; After treating that spinning is accomplished, the ITO electro-conductive glass is put into vacuum drying oven with 40 ℃ of dry 4h, can obtain green polyaniline/polyvinyl alcohol butyral blending nano-fiber membrane.The polyaniline/polyvinyl alcohol butyral blending nano-fiber membrane of green is immersed the KMnO of 0.001mol/L
4In the Treatment Solution, reaction 5min.Take out the back and use distilled water drip washing, immerse subsequently and soak 15min in the distilled water, speed of agitator is 200rpm, and under 40 ℃ of conditions vacuum drying 2h, acquisition polyaniline nano fiber film vitamin C color sensor.
Polyaniline nano fiber film vitamin C color sensor is immersed in the vitamin c solution of 100ppb reaction 60min, the change color process of color sensor experience brown-purple.Utilize fiber spectrometer to detect its reflectance spectrum; Adopt Lab color mode and RGB color mode to calculate simultaneously; According to the reflection strength value that obtains of test, and should value and its corresponding wavelength carry out integral and calculating, compare through the color standard of issuing with International Commission on Illumination (CIE); Calculate the related color change value, compare with typical curve.Corresponding typical curve can know that this ascorbic concrete concentration is 100ppb.
Embodiment 2
Under 25 ℃ of conditions of room temperature; In stirred tank with the 0.5g polyaniline with rotating speed 100rpm stirring and dissolving in 8.5g formic acid; After treating that polyaniline dissolves fully; In solution, add the 1g ethyl cellulose, 400rpm stirs with rotating speed, obtains the polyaniline massfraction and be 5%, the ethyl cellulose massfraction is 10% co-blended spinning solution.Under the condition of room temperature, humidity 50%, the flow velocity of co-blended spinning solution with 1.2mL/h is input on the spinning head, simultaneously spinning head is connected the 18kV power supply and carry out electrostatic spinning and prepare polyaniline/ethyl cellulose blended nanofibre; To the aluminium foil receiving trap, the distance between receiving trap and the spinning head is 15cm with spun fiber laydown; After treating that spinning is accomplished, aluminium foil is put into vacuum drying oven with 55 ℃ of dry 8h, can obtain green polyaniline/ethyl cellulose blending nano-fiber membrane.The polyaniline/polyvinyl alcohol butyral blending nano-fiber membrane of green is immersed the KMnO of 0.009mol/L
4In the Treatment Solution, reaction 1min.Take out the back and use distilled water drip washing, immerse subsequently and soak 15min in the distilled water, speed of agitator is 100rpm, and under 40 ℃ of conditions vacuum drying 2h, acquisition polyaniline nano fiber film vitamin C color sensor.
Polyaniline nano fiber film vitamin C color sensor is immersed in the vitamin c solution of 10ppm reaction 30min, the change color process of color sensor experience brown-purple.Utilize fiber spectrometer to detect its reflectance spectrum; Adopt Lab color mode and RGB color mode to calculate simultaneously; According to the reflection strength value that obtains of test, and should value and its corresponding wavelength carry out integral and calculating, compare through the color standard of issuing with International Commission on Illumination (CIE); Calculate the related color change value, compare with typical curve.Corresponding typical curve can know that this ascorbic concrete concentration is 10ppm.
Embodiment 3
Under 25 ℃ of conditions of room temperature; In stirred tank with the 1.5g polyaniline with rotating speed 200rpm stirring and dissolving in 7g formic acid and acetate mixed solvent (mass ratio is 10:1); After treating that polyaniline dissolves fully; In solution, add 1.5g nylon 6,500rpm stirs with rotating speed, obtains the polyaniline massfraction and be 15%, nylon 6 massfractions are 15% co-blended spinning solution.Under the condition of room temperature, humidity 30%-40%, the flow velocity of co-blended spinning solution with 0.4mL/h is input on the spinning head, simultaneously spinning head is connected the 30kV power supply and carry out electrostatic spinning and prepare polyaniline/nylon 6 blended nanofibres; To the paperboard receiving trap, the distance between receiving trap and the spinning head is 16cm with spun fiber laydown; After treating that spinning is accomplished, paperboard is put into vacuum drying oven with 55 ℃ of dry 6h, can obtain green polyaniline/nylon 6 blending nano-fiber membranes.The polyaniline/polyvinyl alcohol butyral blending nano-fiber membrane of green is immersed the KMnO of 0.01mol/L
4In the Treatment Solution, reaction 5min.Take out the back and use distilled water drip washing, immerse subsequently and soak 5min in the distilled water, speed of agitator is 200rpm, and under 40 ℃ of conditions vacuum drying 2h, acquisition polyaniline nano fiber film vitamin C color sensor.
Polyaniline nano fiber film vitamin C color sensor is immersed in the vitamin c solution of 100ppm reaction 30min, the change color process of color sensor experience brown-purple.Utilize fiber spectrometer to detect its reflectance spectrum; Adopt Lab color mode and RGB color mode to calculate simultaneously; According to the reflection strength value that obtains of test, and should value and its corresponding wavelength carry out integral and calculating, compare through the color standard of issuing with International Commission on Illumination (CIE); Calculate the related color change value, compare with typical curve.Corresponding typical curve can know that this ascorbic concrete concentration is 100ppm.
Embodiment 4
Under 25 ℃ of conditions of room temperature; In stirred tank with the 0.5g polyaniline with rotating speed 100rpm stirring and dissolving in 8.5g formic acid and trifluoroacetic acid mixed solvent (mass ratio is 8:1); After treating that polyaniline dissolves fully; In solution, add the 1g acetyl cellulose, 600rpm stirs with rotating speed, obtains the polyaniline massfraction and be 5%, the acetyl cellulose massfraction is 10% co-blended spinning solution.Under the condition of room temperature, humidity 40%-50%, the flow velocity of co-blended spinning solution with 4mL/h is input on the spinning head, simultaneously spinning head is connected the 10kV power supply and carry out electrostatic spinning and prepare polyaniline/acetyl cellulose blend nanofiber; To the aluminium foil receiving trap, the distance between receiving trap and the spinning head is 15cm with spun fiber laydown; After treating that spinning is accomplished, aluminium foil is put into vacuum drying oven with 40 ℃ of dry 8h, can obtain green polyaniline/acetyl cellulose blend nano fibrous membrane.Polyaniline/acetyl cellulose blend the nano fibrous membrane of green is immersed the KMnO of 0.006mol/L
4In the Treatment Solution, reaction 1min.Take out the back and use distilled water drip washing, immerse subsequently and soak 5min in the distilled water, speed of agitator is 50-200rpm, and under 40 ℃ of conditions vacuum drying 2h, acquisition polyaniline nano fiber film vitamin C color sensor.
Polyaniline nano fiber film vitamin C color sensor is immersed in the vitamin c solution of 1ppm reaction 60min, the change color process of color sensor experience brown-purple.Utilize fiber spectrometer to detect its reflectance spectrum; Adopt Lab color mode and RGB color mode to calculate simultaneously; According to the reflection strength value that obtains of test, and should value and its corresponding wavelength carry out integral and calculating, compare through the color standard of issuing with International Commission on Illumination (CIE); Calculate the related color change value, compare with typical curve.Corresponding typical curve can know that this ascorbic concrete concentration is 1ppm.
Embodiment 5
Under 25 ℃ of conditions of room temperature; In stirred tank with the 0.4g polyaniline with rotating speed 100rpm stirring and dissolving in 8.6g formic acid and hexafluoroisopropanol mixed solvent (mass ratio is 4:1); After treating that polyaniline dissolves fully; In solution, add the 1g PLA, 500rpm stirs with rotating speed, obtains the polyaniline massfraction and be 4%, the PLA massfraction is 10% co-blended spinning solution.Under the condition of room temperature, humidity 40%-50%, the flow velocity of co-blended spinning solution with 2mL/h is input on the spinning head, simultaneously spinning head is connected the 25kV power supply and carry out electrostatic spinning and prepare polyaniline/polylactic acid blend nanofiber; Receiving trap is the ITO electro-conductive glass, and the distance between electro-conductive glass and the spinning head is 30cm; After treating that spinning is accomplished, the ITO electro-conductive glass is put into vacuum drying oven with 25 ℃ of dry 4h, vacuum drying 2h under 40 ℃ of conditions promptly obtains the polyaniline composite nano-fiber membrane subsequently.Polyaniline/polylactic acid blend the nano fibrous membrane of green is immersed the KMnO of 0.01mol/L
4In the Treatment Solution, reaction 4min.Take out the back and use distilled water drip washing, immerse subsequently and soak 13min in the distilled water, speed of agitator is 200rpm, and under 40 ℃ of conditions vacuum drying 2h, acquisition polyaniline nano fiber film vitamin C color sensor.
Polyaniline nano fiber film vitamin C color sensor is immersed in the vitamin c solution of 10ppm reaction 60min, the change color process of color sensor experience brown-purple.Utilize fiber spectrometer to detect its reflectance spectrum; Adopt Lab color mode and RGB color mode to calculate simultaneously; According to the reflection strength value that obtains of test, and should value and its corresponding wavelength carry out integral and calculating, compare through the color standard of issuing with International Commission on Illumination (CIE); Calculate the related color change value, compare with typical curve.Corresponding typical curve can know that this ascorbic concrete concentration is 10ppm.
Embodiment 6
Under 25 ℃ of conditions of room temperature; In stirred tank with the 0.4g polyaniline with rotating speed 100rpm stirring and dissolving in 8.1g formic acid and N-methyl pyrrolidone mixed solvent (mass ratio is 7:1); After treating that polyaniline dissolves fully; It is fine in solution, to add the 1g polypropylene, and 600rpm stirs with rotating speed, obtains the polyaniline massfraction and be 4%, the fine massfraction of polypropylene is 10% co-blended spinning solution.Under the condition of room temperature, humidity 35%-50%, the flow velocity of co-blended spinning solution with 2mL/h is input on the spinning head, simultaneously spinning head is connected the 20kV power supply and carry out electrostatic spinning and prepare the fine blended nanofibre of polyaniline/polypropylene; Receiving trap is the ITO electro-conductive glass, and the distance between electro-conductive glass and the spinning head is 15cm; After treating that spinning is accomplished, the ITO electro-conductive glass is put into vacuum drying oven with 25 ℃ of dry 4h, vacuum drying 2h under 40 ℃ of conditions promptly obtains the polyaniline composite nano-fiber membrane subsequently.Polyaniline/polylactic acid blend the nano fibrous membrane of green is immersed the KMnO of 0.01mol/L
4In the Treatment Solution, reaction 5min.Take out the back and use distilled water drip washing, immerse subsequently and soak 5min in the distilled water, speed of agitator is 200rpm, and under 40 ℃ of conditions vacuum drying 2h, acquisition polyaniline nano fiber film vitamin C color sensor.
Polyaniline nano fiber film vitamin C color sensor is immersed in the vitamin c solution of 40ppm reaction 30min, the change color process of color sensor experience brown-purple.Utilize fiber spectrometer to detect its reflectance spectrum; Adopt Lab color mode and RGB color mode to calculate simultaneously; According to the reflection strength value that obtains of test, and should value and its corresponding wavelength carry out integral and calculating, compare through the color standard of issuing with International Commission on Illumination (CIE); Calculate the related color change value, compare with typical curve.Corresponding typical curve can know that this ascorbic concrete concentration is 40ppm.