CN114397294B - Preparation method of tetracycline sensor based on chitosan nanofiber membrane - Google Patents
Preparation method of tetracycline sensor based on chitosan nanofiber membrane Download PDFInfo
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- CN114397294B CN114397294B CN202210039228.6A CN202210039228A CN114397294B CN 114397294 B CN114397294 B CN 114397294B CN 202210039228 A CN202210039228 A CN 202210039228A CN 114397294 B CN114397294 B CN 114397294B
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- 229920001661 Chitosan Polymers 0.000 title claims abstract description 129
- 239000012528 membrane Substances 0.000 title claims abstract description 111
- 239000002121 nanofiber Substances 0.000 title claims abstract description 111
- 239000004098 Tetracycline Substances 0.000 title claims abstract description 43
- 235000019364 tetracycline Nutrition 0.000 title claims abstract description 43
- 150000003522 tetracyclines Chemical class 0.000 title claims abstract description 43
- 229960002180 tetracycline Drugs 0.000 title claims abstract description 41
- 229930101283 tetracycline Natural products 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000000967 suction filtration Methods 0.000 claims abstract description 43
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 20
- 230000004044 response Effects 0.000 claims abstract description 13
- 230000000007 visual effect Effects 0.000 claims abstract description 12
- 230000008859 change Effects 0.000 claims abstract description 11
- 238000011068 loading method Methods 0.000 claims abstract description 10
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- 239000012498 ultrapure water Substances 0.000 claims description 29
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 24
- 239000011888 foil Substances 0.000 claims description 24
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 21
- 238000001291 vacuum drying Methods 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 14
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- 238000002791 soaking Methods 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
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- 230000007935 neutral effect Effects 0.000 claims description 3
- 238000010008 shearing Methods 0.000 claims description 3
- 239000000523 sample Substances 0.000 abstract description 21
- 238000009987 spinning Methods 0.000 abstract description 9
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000005520 cutting process Methods 0.000 description 6
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- 239000010935 stainless steel Substances 0.000 description 6
- 239000007921 spray Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
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- 230000003115 biocidal effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 229940072172 tetracycline antibiotic Drugs 0.000 description 2
- 229940040944 tetracyclines Drugs 0.000 description 2
- 206010067484 Adverse reaction Diseases 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- 241000606161 Chlamydia Species 0.000 description 1
- 241000204031 Mycoplasma Species 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 241000606701 Rickettsia Species 0.000 description 1
- 206010072610 Skeletal dysplasia Diseases 0.000 description 1
- 206010044041 Tooth hypoplasia Diseases 0.000 description 1
- 238000010811 Ultra-Performance Liquid Chromatography-Tandem Mass Spectrometry Methods 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 230000006838 adverse reaction Effects 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008827 biological function Effects 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
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- 239000002105 nanoparticle Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
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- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
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- 238000011896 sensitive detection Methods 0.000 description 1
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
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- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
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- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6486—Measuring fluorescence of biological material, e.g. DNA, RNA, cells
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6439—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" with indicators, stains, dyes, tags, labels, marks
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Abstract
The invention relates to the field of preparation of tetracycline sensors, in particular to a preparation method of a tetracycline sensor based on a chitosan nanofiber membrane, which comprises the following steps: s1, preparing chitosan solution, and carrying out electrostatic spinning to obtain a chitosan nanofiber membrane; s2, loading metal ions which can be complexed with the tetracycline to further cause the color/fluorescence intensity change of the system on the chitosan nanofiber membrane, and finally obtaining the chitosan nanofiber membrane sensor with visual response to the tetracycline. Directly loading metal ions which can be complexed with tetracycline to further cause the change of system color/fluorescence intensity on the surface of the chitosan nanofiber membrane by a suction filtration coating method, and simply and rapidly preparing the chitosan nanofiber membrane sensor; the complicated operations of functional modification of the nanofiber membrane in advance or adding probe molecules into the electrostatic spinning solution in advance, stirring uniformly, co-spinning and the like are avoided, and the preparation process of the tetracycline nanofiber membrane sensor is simplified.
Description
Technical Field
The invention relates to the field of preparation of tetracycline sensors, in particular to a preparation method of a tetracycline sensor based on a chitosan nanofiber membrane.
Background
Tetracyclines (TCs) are a widely used class of broad-spectrum antibiotics that have good therapeutic effects on infections caused by gram-positive and negative bacteria, mycoplasma, chlamydia and rickettsia. With the deep understanding of the adverse reaction of the tetracycline antibiotics caused by the mass production of the antibiotic resistant bacteria in clinic, part of the tetracycline antibiotics gradually withdraw from the clinical application. However, TC is still in use in many countries and regions as a low cost drug, especially as a veterinary antibiotic. TC residues in animal-derived foods can enter a human body through a food chain to cause symptoms such as skeletal dysplasia, enamel hypoplasia and the like, and monitoring the TC residues has important practical significance for ensuring food safety.
Currently, methods commonly used for detecting TC residues mainly include UPLC-MS/MS, HPLC-UV, HPLC-FLD, and the like. However, the above-mentioned methods mostly require complicated equipment, cumbersome operations, and time-consuming chromatographic separation processes, resulting in low detection efficiency, and it is difficult to achieve rapid detection of TC residues. In recent years, the fluorescence/colorimetric sensing method has become a novel TC residue detection means by virtue of the advantages of short response time, high sensitivity, simplicity, easiness in use and the like. For this purpose, researchers have prepared a series of TC sensors having different structures and excellent properties, including Eu 3+ Functionalized nanoparticles, gold/silver nanoclusters, quantum dots, metal organic framework materials, and the like. However, in practical applications, these probe molecules typically need to be dispersed into the sample solution, and interact with the target, resulting in a corresponding change in the fluorescence intensity or color of the system. Although these sensors have successfully achieved rapid and sensitive detection of TC residues, they still have some non-negligible drawbacks. For example, probe molecules are susceptible to failure due to environmental changes in the solution system, inconvenient to carry, and incapable of recycling due to being separated from the sample solution. In order to solve the above shortcomings, an electrostatic spinning technology is used to prepare nanofiber membrane (NFM) sensors, which is getting more and more attention.
NFM has the advantages of high porosity, large specific surface area, stable physicochemical properties, etc. The high porosity created by the internally interconnected channels can accelerate interactions between the target and probe molecules. Moreover, a high specific surface area can provide a large number of sites for supporting probe molecules. Therefore, the development of the TC solid-phase sensor based on the NFM has wide research prospect. However, in the prior art, in order to load more probe molecules, it is necessary to perform functional modification on NFM in advance or add probe molecules into an electrospinning solution in advance, stir them uniformly, and then co-spin them. These additional operations complicate the process of preparing TC nanofiber membrane sensors. Compared with electrospun polymers such as polyacrylonitrile, polyvinyl alcohol, nylon 6 and the like, chitosan (CS) has more advantages in preparing a TC nanofiber membrane sensor.
CS is a natural polysaccharide produced by removing partial acetyl groups from chitin, and has various unique biological functions, such as biodegradability, biocompatibility, nontoxicity, antibacterial property and the like. CS NFM surface has abundant hydroxyl (-OH) and amino (-NH) 2 ). Due to the presence of these reactive functional groups, the probe molecules can react directly with CS NFM, effecting loading of the probe molecules by hydrogen bonding, chelation, or electrostatic interactions. Therefore, the CS NFM is used as a substrate material, so that the preparation process of the TC nanofiber membrane sensor can be effectively simplified.
Disclosure of Invention
In order to solve the defects in the background art, the invention aims to provide a preparation method of a tetracycline sensor based on a chitosan nanofiber membrane.
The aim of the invention can be achieved by the following technical scheme:
a method for preparing a tetracycline sensor based on chitosan nanofiber membrane, comprising the following steps:
s1, preparing chitosan solution, and carrying out electrostatic spinning to obtain a chitosan nanofiber membrane;
s2, loading metal ions which can be complexed with the tetracycline to further cause the color/fluorescence intensity change of the system on the chitosan nanofiber membrane, and finally obtaining the chitosan nanofiber membrane sensor with visual response to the tetracycline.
Further, the specific steps of S1 are as follows:
s1.1, adding chitosan and polyethylene oxide into ultrapure water containing 1% of acetic acid serving as a solvent to prepare a solution with the mass concentration of 0.01-0.05 g/mL of chitosan and the mass concentration of 0.005-0.01 g/mL of polyethylene oxide, and placing the solution into a spraying container;
s1.2, setting the high-voltage power supply voltage for providing a high-voltage electrostatic field to be 15-20 kV, setting the propulsion speed to be 0.5-1.0 mL/h, and adjusting the distance from a nozzle to an aluminum foil receiving screen to be 10-15 cm;
s1.3, collecting for 10-15 h, taking down the chitosan nanofiber membrane from the aluminum foil, and soaking the chitosan nanofiber membrane into Na with the concentration of 0.1mol/L 2 CO 3 In an aqueous solution;
s1.4, soaking for 30min, taking out the chitosan nanofiber membrane, washing the chitosan nanofiber membrane to be neutral by ultrapure water, and drying the chitosan nanofiber membrane in a vacuum drying oven at 45 ℃.
Further, the volume ratio of acetic acid to ultrapure water in the solvent in S1.1 is 1:99.
further, the chitosan in S1.1 has a deacetylation degree of 95% or more, the polyethylene oxide has a viscosity average molecular weight of 600000, and the nozzle hole diameter in the spray container is 0.4 to 0.86mm.
Further, the specific steps of S2 are as follows:
s2.1, preparing a metal ion solution capable of complexing with tetracycline to further cause the color/fluorescence intensity change of the system;
s2.2, shearing the prepared chitosan nanofiber membrane into a wafer with the diameter of 80mm, placing the wafer in a Buchner funnel, mounting the Buchner funnel on a suction filtration bottle, connecting the suction filtration bottle with a vacuum pump, and pouring a metal ion solution into the Buchner funnel for suction filtration through glass rod drainage;
s2.3, taking out the chitosan nanofiber membrane, washing the chitosan nanofiber membrane with ultrapure water, and drying the chitosan nanofiber membrane in a vacuum drying oven at 45 ℃;
further, the metal ion in S2.1 is Ca 2+ 、Zn 2+ 、Cu 2+ 、Ni 2+ 、Pb 2+ 、Cd 2+ The concentration of the metal ion solution is 0.1-0.5 mg/mL.
Further, the number of times of suction filtration in the step S2.2 is 5-10, and the volume of the metal ion solution is 20mL.
The invention has the beneficial effects that:
according to the invention, metal ions which can be complexed with the tetracycline and further cause the color/fluorescence intensity change of the system are directly loaded on the surface of the chitosan nanofiber membrane by a suction filtration coating method, so that the chitosan nanofiber membrane sensor with visual response to the tetracycline is simply and rapidly prepared; the complicated operations of functional modification of the nanofiber membrane or adding probe molecules into an electrostatic spinning solution in advance, stirring uniformly, co-spinning and the like in the existing preparation method of the tetracycline nanofiber membrane sensor are avoided, and the preparation process of the tetracycline nanofiber membrane sensor is simplified.
In addition, compared with a method for loading the probe molecules by immersing the chitosan nanofiber membrane into the probe molecule solution, the suction filtration coating method provided by the invention not only can load the probe molecules on the surface of the chitosan nanofiber membrane, but also can load the probe molecules into the chitosan nanofiber membrane by means of the suction filtration process, so that the loading amount of the probe molecules is increased.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described, and it will be obvious to those skilled in the art that other drawings can be obtained according to these drawings without inventive effort;
FIG. 1 is a schematic flow chart of the preparation method of the invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
A preparation method of a tetracycline sensor based on chitosan nanofiber membrane, as shown in fig. 1, the preparation method comprises the following steps:
s1, preparing chitosan solution, and carrying out electrostatic spinning to obtain a chitosan nanofiber membrane;
the specific steps of the S1 are as follows:
s1.1, adding chitosan and polyethylene oxide into ultrapure water containing 1% of acetic acid serving as a solvent to prepare a solution with the mass concentration of 0.01-0.05 g/mL of chitosan and the mass concentration of 0.005-0.01 g/mL of polyethylene oxide, and placing the solution into a spraying container;
s1.2, setting the high-voltage power supply voltage for providing a high-voltage electrostatic field to be 15-20 kV, setting the propulsion speed to be 0.5-1.0 mL/h, and adjusting the distance from a nozzle to an aluminum foil receiving screen to be 10-15 cm;
s1.3, collecting for 10-15 h, taking down the chitosan nanofiber membrane from the aluminum foil, and soaking the chitosan nanofiber membrane into Na with the concentration of 0.1mol/L 2 CO 3 In an aqueous solution;
s1.4, soaking for 30min, taking out the chitosan nanofiber membrane, washing the chitosan nanofiber membrane to be neutral by ultrapure water, and drying the chitosan nanofiber membrane in a vacuum drying oven at 45 ℃.
Wherein, the volume ratio of acetic acid to ultrapure water in the solvent in S1.1 is 1:99, the deacetylation degree of chitosan is more than or equal to 95%, the viscosity average molecular weight of polyethylene oxide is 600000, and the aperture of a nozzle in a spraying container is 0.4-0.86 mm.
S2, loading metal ions which can be complexed with the tetracycline to further cause the color/fluorescence intensity change of the system on the chitosan nanofiber membrane, and finally obtaining the chitosan nanofiber membrane sensor with visual response to the tetracycline.
The specific steps of S2 are as follows:
s2.1, preparing a metal ion solution capable of complexing with tetracycline to further cause the color/fluorescence intensity change of the system;
s2.2, shearing the prepared chitosan nanofiber membrane into a wafer with the diameter of 80mm, placing the wafer in a Buchner funnel, mounting the Buchner funnel on a suction filtration bottle, connecting the suction filtration bottle with a vacuum pump, and pouring a metal ion solution into the Buchner funnel for suction filtration through glass rod drainage;
s2.3, taking out the chitosan nanofiber membrane, washing the chitosan nanofiber membrane with ultrapure water, and drying the chitosan nanofiber membrane in a vacuum drying oven at 45 ℃;
wherein, the metal in S2.1 is separated fromThe son is Ca 2+ 、Zn 2+ 、Cu 2+ 、Ni 2+ 、Pb 2+ 、Cd 2+ The concentration of the metal ion solution is 0.1-0.5 mg/mL, the times of suction filtration are 5-10 times, and the volume of the metal ion solution is 20mL.
Example 1:
s1, preparing chitosan nanofiber membrane
The ultra-pure water containing 1% (v/v) acetic acid was used as a solvent, chitosan (the degree of deacetylation was 95% or more) and polyethylene oxide (average MV-600,000) were added to prepare a solution having a mass concentration of 0.01g/mL of chitosan and a mass concentration of 0.005g/mL of polyethylene oxide, and the solution was placed in a 20mL spray container, and the aperture of the nozzle was 0.86mm. The nozzle is connected with the anode of the high-voltage power supply, and the aluminum foil collecting screen is connected with the cathode of the high-voltage power supply. The spraying voltage is set to be 15kV, the distance from the stainless steel needle head to the aluminum foil receiving screen is adjusted to be 15cm, and the advancing speed of the spinning solution is 1.0mL/h. After 10h of collection, the chitosan nanofiber membrane was removed from the aluminum foil and soaked to 0.1mol/L Na 2 CO 3 Soaking in water solution for 30min, taking out chitosan nanofiber membrane, washing with ultrapure water to neutrality, and drying in vacuum drying oven at 45deg.C.
S2, preparing chitosan nanofiber membrane sensor with visual response to tetracycline
Cutting the chitosan nanofiber membrane obtained in the step S1 into a wafer with the diameter of 80mm, placing the wafer in a Buchner funnel, mounting the Buchner funnel on a suction filtration bottle, connecting the suction filtration bottle with a vacuum pump, and 20mL of CaCl 2 The solution (0.2 mg/mL) was poured into a Buchner funnel through glass rod drainage for suction filtration, and after suction filtration for 8 times, the chitosan nanofiber membrane was taken out and washed with ultrapure water, and was dried in a vacuum drying oven at 45 ℃.
Example 2:
s1, preparing chitosan nanofiber membrane
Adding chitosan (deacetylation degree is more than or equal to 95%) and polyethylene oxide (average MV-600,000) into ultrapure water containing 1% (v/v) acetic acid as solvent to prepare a solution with the mass concentration of chitosan of 0.015g/mL and the mass concentration of polyethylene oxide of 0.005g/mLThe liquid was placed in a 20mL spray container, and the orifice diameter of the nozzle was 0.86mm. The nozzle is connected with the anode of the high-voltage power supply, and the aluminum foil collecting screen is connected with the cathode of the high-voltage power supply. The spraying voltage is set to be 16kV, the distance from the stainless steel needle head to the aluminum foil receiving screen is adjusted to be 15cm, and the spinning solution propelling speed is 0.8mL/h. After 12h of collection, the chitosan nanofiber membrane was removed from the aluminum foil and soaked to 0.1mol/L Na 2 CO 3 Soaking in water solution for 30min, taking out chitosan nanofiber membrane, washing with ultrapure water to neutrality, and drying in vacuum drying oven at 45deg.C.
S2, preparing chitosan nanofiber membrane sensor with visual response to tetracycline
Cutting the chitosan nanofiber membrane obtained in the step S1 into a wafer with the diameter of 80mm, placing the wafer in a Buchner funnel, arranging the Buchner funnel on a suction filtration bottle, connecting the suction filtration bottle with a vacuum pump, and 20mL of FeCl 3 The solution (0.1 mg/mL) was poured into a Buchner funnel through glass rod drainage and suction filtration was performed, after 10 times of suction filtration, the chitosan nanofiber membrane was taken out and washed with ultrapure water, and was placed in a vacuum drying oven at 45℃for drying.
Example 3:
s1, preparing chitosan nanofiber membrane
The ultra-pure water containing 1% (v/v) acetic acid was used as a solvent, chitosan (the degree of deacetylation was 95% or more) and polyethylene oxide (average MV-600,000) were added to prepare a solution having a mass concentration of 0.04g/mL for chitosan and 0.008g/mL for polyethylene oxide, and the solution was placed in a 20mL spray container, and the aperture of the nozzle was 0.6mm. The nozzle is connected with the anode of the high-voltage power supply, and the aluminum foil collecting screen is connected with the cathode of the high-voltage power supply. The spraying voltage is set to be 18kV, the distance from the stainless steel needle head to the aluminum foil receiving screen is adjusted to be 17cm, and the spinning solution propelling speed is 0.8mL/h. After 13h of collection, the chitosan nanofiber membrane was removed from the aluminum foil and soaked to 0.1mol/L Na 2 CO 3 Soaking in water solution for 30min, taking out chitosan nanofiber membrane, washing with ultrapure water to neutrality, and drying in vacuum drying oven at 45deg.C.
S2, preparing chitosan nanofiber membrane sensor with visual response to tetracycline
Cutting the chitosan nanofiber membrane obtained in the step S1 into a wafer with the diameter of 80mm, placing the wafer in a Buchner funnel, mounting the Buchner funnel on a suction filtration bottle, connecting the suction filtration bottle with a vacuum pump, and 20mL of CuSO 4 The solution (0.5 mg/mL) was poured into a Buchner funnel through glass rod drainage for suction filtration, and after 5 times of suction filtration, the chitosan nanofiber membrane was taken out and washed with ultrapure water, and was dried in a vacuum drying oven at 45 ℃.
Example 4:
s1, preparing chitosan nanofiber membrane
The ultra-pure water containing 1% (v/v) acetic acid is used as a solvent, chitosan (the deacetylation degree is more than or equal to 95%) and polyethylene oxide (average MV-600,000) are added, a solution with the mass concentration of 0.01g/mL of chitosan and the mass concentration of 0.01g/mL of polyethylene oxide is prepared, and the solution is placed in a 20mL spraying container, and the aperture of a nozzle is 0.4mm. The nozzle is connected with the anode of the high-voltage power supply, and the aluminum foil collecting screen is connected with the cathode of the high-voltage power supply. The spraying voltage is set to be 18kV, the distance from the stainless steel needle head to the aluminum foil receiving screen is adjusted to be 18cm, and the spinning solution propelling speed is 1.0mL/h. After 15h of collection, the chitosan nanofiber membrane was removed from the aluminum foil and soaked to 0.1mol/L Na 2 CO 3 Soaking in water solution for 30min, taking out chitosan nanofiber membrane, washing with ultrapure water to neutrality, and drying in vacuum drying oven at 45deg.C.
S2, preparing chitosan nanofiber membrane sensor with visual response to tetracycline
Cutting the chitosan nanofiber membrane obtained in the step S1 into a wafer with the diameter of 80mm, placing the wafer in a Buchner funnel, mounting the Buchner funnel on a suction filtration bottle, connecting the suction filtration bottle with a vacuum pump, and 20mL of NiCl 2 The solution (0.2 mg/mL) was poured into a Buchner funnel through glass rod drainage for suction filtration, and after suction filtration for 8 times, the chitosan nanofiber membrane was taken out and washed with ultrapure water, and was dried in a vacuum drying oven at 45 ℃.
Example 5:
s1, preparing chitosan nanofiber membrane
With ultrapure water containing 1% (v/v) acetic acid as solventChitosan (with deacetylation degree of more than or equal to 95%) and polyethylene oxide (average MV-600,000) are added to prepare a solution with the mass concentration of chitosan of 0.04g/mL and the mass concentration of polyethylene oxide of 0.005g/mL, and the solution is placed in a 20mL spraying container, and the aperture of a nozzle is 0.86mm. The nozzle is connected with the anode of the high-voltage power supply, and the aluminum foil collecting screen is connected with the cathode of the high-voltage power supply. The spraying voltage is set to be 20kV, the distance from the stainless steel needle head to the aluminum foil receiving screen is adjusted to be 20cm, and the spinning solution propelling speed is 0.6mL/h. After 13h of collection, the chitosan nanofiber membrane was removed from the aluminum foil and soaked to 0.1mol/L Na 2 CO 3 Soaking in water solution for 30min, taking out chitosan nanofiber membrane, washing with ultrapure water to neutrality, and drying in vacuum drying oven at 45deg.C.
S2, preparing chitosan nanofiber membrane sensor with visual response to tetracycline
Cutting the chitosan nanofiber membrane obtained in the step S1 into a wafer with the diameter of 80mm, placing the wafer in a Buchner funnel, mounting the Buchner funnel on a suction filtration bottle, connecting the suction filtration bottle with a vacuum pump, and 20mL of ZnSO 4 The solution (0.5 mg/mL) was poured into a Buchner funnel through glass rod drainage for suction filtration, and after 6 times of suction filtration, the chitosan nanofiber membrane was taken out and washed with ultrapure water, and was dried in a vacuum drying oven at 45 ℃.
Example 6:
s1, preparing chitosan nanofiber membrane
The ultra-pure water containing 1% (v/v) acetic acid was used as a solvent, chitosan (the degree of deacetylation was 95% or more) and polyethylene oxide (average MV-600,000) were added to prepare a solution having a mass concentration of 0.05g/mL of chitosan and a mass concentration of 0.005g/mL of polyethylene oxide, and the solution was placed in a 20mL spray container, and the aperture of the nozzle was 0.6mm. The nozzle is connected with the anode of the high-voltage power supply, and the aluminum foil collecting screen is connected with the cathode of the high-voltage power supply. The spraying voltage is set to be 20kV, the distance from the stainless steel needle head to the aluminum foil receiving screen is adjusted to be 18cm, and the spinning solution propelling speed is 0.5mL/h. After 10h of collection, the chitosan nanofiber membrane was removed from the aluminum foil and soaked to 0.1mol/L Na 2 CO 3 Soaking in water solution for 30min, taking out chitosan nanofiber membrane, and treating with superbWashing with pure water to neutrality, and drying in a vacuum drying oven at 45deg.C.
S2, preparing chitosan nanofiber membrane sensor with visual response to tetracycline
Cutting the chitosan nanofiber membrane obtained in the step S1 into a wafer with the diameter of 80mm, placing the wafer in a Buchner funnel, mounting the Buchner funnel on a suction filtration bottle, connecting the suction filtration bottle with a vacuum pump, and 20mL of CdCl 2 The solution (0.3 mg/mL) was poured into a Buchner funnel through glass rod drainage for suction filtration, and after 9 times of suction filtration, the chitosan nanofiber membrane was taken out and washed with ultrapure water, and was placed in a vacuum drying oven at 45℃for drying.
To sum up:
according to the invention, metal ions which can be complexed with the tetracycline and further cause the color/fluorescence intensity change of the system are directly loaded on the surface of the chitosan nanofiber membrane by a suction filtration coating method, so that the chitosan nanofiber membrane sensor with visual response to the tetracycline is simply and rapidly prepared; the complicated operations of functional modification of the nanofiber membrane or adding probe molecules into an electrostatic spinning solution in advance, stirring uniformly, co-spinning and the like in the existing preparation method of the tetracycline nanofiber membrane sensor are avoided, and the preparation process of the tetracycline nanofiber membrane sensor is simplified. In addition, compared with a method for loading the probe molecules by immersing the chitosan nanofiber membrane into the probe molecule solution, the suction filtration coating method provided by the invention not only can load the probe molecules on the surface of the chitosan nanofiber membrane, but also can load the probe molecules into the chitosan nanofiber membrane by means of the suction filtration process, so that the loading amount of the probe molecules is increased.
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims.
Claims (5)
1. The preparation method of the tetracycline sensor based on the chitosan nanofiber membrane is characterized by comprising the following steps of:
s1, preparing chitosan solution, and carrying out electrostatic spinning to obtain a chitosan nanofiber membrane;
s2, loading metal ions which can be complexed with the tetracycline to further cause the color/fluorescence intensity change of the system on the chitosan nanofiber membrane, and finally obtaining the chitosan nanofiber membrane sensor with visual response to the tetracycline;
the specific steps of the S1 are as follows:
s1.1, adding chitosan and polyethylene oxide into ultrapure water containing 1% of acetic acid serving as a solvent to prepare a solution with the mass concentration of 0.01-0.05 g/mL of chitosan and the mass concentration of 0.005-0.01 g/mL of polyethylene oxide, and placing the solution into a spraying container;
s1.2, setting the high-voltage power supply voltage for providing a high-voltage electrostatic field to be 15-20 kV, setting the propulsion speed to be 0.5-1.0 mL/h, and adjusting the distance from a nozzle to an aluminum foil receiving screen to be 10-15 cm;
s1.3, collecting for 10-15 h, taking down the chitosan nanofiber membrane from the aluminum foil, and soaking the chitosan nanofiber membrane into Na with the concentration of 0.1mol/L 2 CO 3 In an aqueous solution;
s1.4, soaking for 30min, taking out the chitosan nanofiber membrane, washing the chitosan nanofiber membrane to be neutral by ultrapure water, and drying the chitosan nanofiber membrane in a vacuum drying oven at 45 ℃;
the specific steps of the S2 are as follows:
s2.1, preparing a metal ion solution capable of complexing with tetracycline to further cause the color/fluorescence intensity change of the system;
s2.2, shearing the prepared chitosan nanofiber membrane into a wafer with the diameter of 80mm, placing the wafer in a Buchner funnel, mounting the Buchner funnel on a suction filtration bottle, connecting the suction filtration bottle with a vacuum pump, and pouring a metal ion solution into the Buchner funnel for suction filtration through glass rod drainage;
s2.3, taking out the chitosan nanofiber membrane, washing the chitosan nanofiber membrane with ultrapure water, and drying the chitosan nanofiber membrane in a vacuum drying oven at 45 ℃.
2. The method for preparing the tetracycline sensor based on the chitosan nanofiber membrane, according to claim 1, wherein the volume ratio of acetic acid to ultrapure water in the solvent in S1.1 is 1:99.
3. the method for preparing the tetracycline sensor based on the chitosan nanofiber membrane, which is characterized in that the deacetylation degree of chitosan in S1.1 is more than or equal to 95%, the viscosity average molecular weight of polyethylene oxide is 600000, and the aperture of a nozzle in a spraying container is 0.4-0.86 mm.
4. The method for preparing a tetracycline sensor based on chitosan nanofiber membrane according to claim 3, wherein the metal ion in S2.1 is Ca 2+ 、Zn 2+ 、Cu 2+ 、Ni 2+ 、Pb 2+ 、Cd 2+ The concentration of the metal ion solution is 0.1-0.5 mg/mL.
5. The method for preparing the tetracycline sensor based on the chitosan nanofiber membrane, which is characterized in that the suction filtration time in S2.2 is 5-10 times.
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