CN110528112B - A kind of antibacterial temperature control micro-nano fiber and preparation method thereof - Google Patents
A kind of antibacterial temperature control micro-nano fiber and preparation method thereof Download PDFInfo
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 110
- 239000002121 nanofiber Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 51
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- 108050004290 Cecropin Proteins 0.000 claims abstract description 34
- 239000003910 polypeptide antibiotic agent Substances 0.000 claims abstract description 28
- 102000003425 Tyrosinase Human genes 0.000 claims abstract description 25
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- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 20
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims abstract description 20
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- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 19
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 75
- 239000007864 aqueous solution Substances 0.000 claims description 41
- 238000002156 mixing Methods 0.000 claims description 35
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 34
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
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- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
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Abstract
本发明提供了一种抗菌性温控微纳米纤维及其制备方法，属于纤维材料技术领域。本发明利用酪氨酸酶和天蚕素抗菌肽对本身就具有抗菌性的丝胶蛋白进行接枝，进一步提高了丝胶蛋白的抗菌性。而且，改性丝胶蛋白溶液与N‑异丙基丙烯酰胺、N,N‑亚甲基双丙烯酰胺、过硫酸铵、N,N,N,N‑四甲基乙二胺和醋酸混合，经自由基聚合，得到了具备温敏性的凝胶；此外，本发明调节微流体纺丝的流量为10～40μL/s，纺丝速率为10～90rad/min，提高了微纳米纤维比表面积，改善了纤维纳米效应，提高了微纳米纤维的抗菌性能。实施例数据表明：本发明提供的抗菌性温控微纳米纤维具有较好的抗菌性，抑菌率最高可达到99.99％以上。
The invention provides an antibacterial temperature-controlled micro-nano fiber and a preparation method thereof, belonging to the technical field of fiber materials. The invention utilizes tyrosinase and cecropin antibacterial peptide to graft sericin which itself has antibacterial properties, and further improves the antibacterial properties of sericin. Furthermore, the modified sericin solution was mixed with N-isopropylacrylamide, N,N-methylenebisacrylamide, ammonium persulfate, N,N,N,N-tetramethylethylenediamine and acetic acid, After radical polymerization, a temperature-sensitive gel is obtained; in addition, the present invention adjusts the flow rate of microfluid spinning to be 10-40 μL/s, and the spinning rate is 10-90 rad/min, which improves the specific surface area of micro-nano fibers. , improving the fiber nano-effect and improving the antibacterial properties of micro-nano fibers. The data of the examples show that the antibacterial temperature-controlled micro-nano fibers provided by the present invention have good antibacterial properties, and the highest antibacterial rate can reach more than 99.99%.
Description
Technical Field
The invention relates to the technical field of fiber materials, in particular to an antibacterial temperature-control micro-nanofiber and a preparation method thereof.
Background
The micro-nano fiber has a microstructure similar to that of a natural extracellular matrix, and is widely applied to various fields of biomedical research, and particularly, the oriented and ordered antibacterial micro-nano fiber is very important to be applied to the aspects of nervous systems, blood vessels, muscles, artificial extracellular matrices and the like.
Patent CN 201810607084 discloses an antibacterial nanofiber and a preparation method thereof, the invention prepares the nanofiber by a physical and chemical technical means, and antibacterial treatment is carried out on the nanofiber by adopting an antibacterial agent loading mode to prepare the nanofiber. However, the nano-fiber is disordered and the antibacterial property of the micro-nano-fiber is not discussed. Patent CN 201611108902.2 and patent CN 201611109738.7 respectively disclose a temperature-sensitive antibacterial nanofiber and a preparation method thereof, and a temperature-sensitive antibacterial fabric and a preparation method thereof, the nanofiber and the fabric thereof prepared by the electrostatic spinning technology have excellent antibacterial property and heat sensitivity, but the antibacterial rate of the nanofiber to escherichia coli and staphylococcus aureus is lower than 90%, and the nanofiber is disordered, so that the application field of the antibacterial micro nanofiber is limited.
Patent 201810675512.6 discloses an electrostatic spinning method for preparing ordered fibers, and Matthews et al (Biomacromolecules,2002,3,232-. Theron et al (Nanotechnology,2001, 12(3): 384-. Li et al (Advanced Materials,2004,16(4): 361-. The prior art prepares the directional nanofiber, but the energy consumption is large, the operation is difficult, the order of the micro-nanofiber is poor, and the intelligent responsiveness of the fiber is not involved.
Disclosure of Invention
In view of the above, the present invention is directed to an antibacterial temperature-controlled micro-nanofiber and a preparation method thereof, and the antibacterial temperature-controlled micro-nanofiber provided by the present invention has excellent directionality, simple preparation method, low energy consumption, and excellent antibacterial property.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides an antibacterial temperature-control micro-nanofiber, which is obtained by microfluid spinning antibacterial temperature-sensitive hydrogel and a polyethylene oxide aqueous solution; the antibacterial thermosensitive hydrogel is prepared by performing free radical polymerization on a modified sericin protein solution, N-isopropyl acrylamide, N, N-methylene bisacrylamide, ammonium persulfate, N, N-tetramethyl ethylenediamine and acetic acid; the modified sericin solution is prepared from a sericin aqueous solution, tyrosinase and cecropin antibacterial peptide through an enzymatic oxidation reaction;
the jet flow of the microfluid spinning is 10-40 mu L/s, and the spinning speed is 10-90 rad/min.
Preferably, the temperature of the microfluid spinning is 25-40 ℃.
Preferably, the translation speed of the microfluid spinning is 10-30 mm/s, and the translation distance is 10-30 cm.
Preferably, the preparation method of the modified sericin solution comprises the following steps:
under the protection of oxygen, mixing a sericin aqueous solution with tyrosinase, and carrying out an enzymatic oxidation reaction to obtain a sericin quinone solution;
and mixing the sericin quinone solution with cecropin antibacterial peptide to obtain the modified sericin protein solution.
Preferably, the concentration of the sericin aqueous solution is 10-20 wt%; the dosage of the tyrosinase is 2000-4500U/g; the mass ratio of the cecropin antibacterial peptide to the sericin is 3500-4000 microgram: 9-20 g.
Preferably, the dosage ratio of the modified sericin solution to the N-isopropylacrylamide is 1.0-3.0 mL: 0.5 to 1.0 g.
Preferably, the dosage ratio of the modified sericin solution to the N, N-methylene bisacrylamide is 1.0-3.0 mL: 0.03-0.05 g.
Preferably, the volume ratio of the modified sericin solution to N, N, N, N-tetramethylethylenediamine is 1.0-3.0: 1.0 to 6.0.
Preferably, the dosage ratio of the modified sericin solution to ammonium persulfate is 1.0-3.0 mL: 0.04-0.06 g.
The invention also provides a preparation method of the antibacterial temperature-control micro-nano fiber, which comprises the following steps:
mixing a sericin aqueous solution, tyrosinase and cecropin antibacterial peptide, and carrying out enzyme catalytic oxidation reaction to obtain a modified sericin solution;
mixing the modified sericin protein solution, N-isopropyl acrylamide, N, N-methylene bisacrylamide, ammonium persulfate, N, N-tetramethyl ethylenediamine and acetic acid, and carrying out free radical polymerization reaction to obtain an antibacterial temperature-sensitive hydrogel;
and mixing the antibacterial temperature-sensitive hydrogel with a polyethylene oxide aqueous solution, and performing microfluid spinning to obtain the antibacterial temperature-controlled micro-nanofiber.
The invention provides an antibacterial temperature-control micro-nanofiber, which is obtained by microfluid spinning antibacterial temperature-sensitive hydrogel and a polyethylene oxide aqueous solution; the antibacterial thermosensitive hydrogel is prepared by performing free radical polymerization on a modified sericin protein solution, N-isopropyl acrylamide, N, N-methylene bisacrylamide, ammonium persulfate, N, N-tetramethyl ethylenediamine and acetic acid; the modified sericin solution is prepared from a sericin aqueous solution, tyrosinase and cecropin antibacterial peptide through an enzymatic oxidation reaction; the jet flow of the microfluid spinning is 10-40 mu L/s, and the spinning speed is 10-90 rad/min.
According to the invention, the sericin with antibacterial property is grafted by using the tyrosinase and cecropin antibacterial peptide, so that the antibacterial property of the sericin is further improved; and the tyrosinase and cecropin antibacterial peptide are biological materials, are non-toxic and environment-friendly, have good compatibility with sericin, and can be well dispersed in a sericin solution to improve the antibacterial property of the sericin. In addition, the modified sericin solution is mixed with N-isopropylacrylamide, N, N-methylenebisacrylamide, ammonium persulfate, N, N, N-tetramethylethylenediamine and acetic acid, and gel with temperature sensitivity is obtained through free radical polymerization; in addition, the micro-nanofiber spinning flow is adjusted to be 10-40 mu L/s, the spinning speed is 10-90 rad/min, the specific surface area of the micro-nanofiber is increased, the fiber nano effect is improved, and the antibacterial performance of the micro-nanofiber is further improved. The data of the examples show that: the antibacterial temperature-control micro-nano fiber provided by the invention has better antibacterial property, and the highest antibacterial rate can reach more than 99.99%.
The invention also provides a preparation method of the antibacterial temperature-controlled micro-nano fiber, which is characterized in that sericin is subjected to graft modification to improve the antibacterial property of the sericin; then mixing the gel with a raw material with temperature sensitivity, obtaining gel with temperature sensitivity and antibacterial property through free radical polymerization, and obtaining the orderly-arranged micro-nano fibers by combining a microfluid spinning technology. The micro-nano fiber prepared by the method has excellent antibacterial property and temperature sensitivity; and the used raw materials are nontoxic and environment-friendly, and the method is simple to operate and low in energy consumption.
Drawings
FIG. 1 is a picture of the antibacterial temperature-controlled micro-nano parallel fiber obtained in example 1;
FIG. 2 is a contact angle diagram of the antibacterial temperature-controlled micro-nano parallel fiber obtained in example 1 at 20 ℃ and 42 ℃ for 7 s;
FIG. 3 is a DSC curve chart of the antibacterial temperature-controlled micro-nano parallel fibers obtained in examples 1-5.
Detailed Description
The invention provides an antibacterial temperature-control micro-nanofiber, which is obtained by microfluid spinning antibacterial temperature-sensitive hydrogel and a polyethylene oxide aqueous solution; the antibacterial thermosensitive hydrogel is prepared by performing free radical polymerization on a modified sericin protein solution, N-isopropyl acrylamide, N, N-methylene bisacrylamide, ammonium persulfate, N, N-tetramethyl ethylenediamine and acetic acid; the modified sericin solution is prepared from a sericin aqueous solution, tyrosinase and cecropin antibacterial peptide through an enzymatic oxidation reaction; the jet flow of the microfluid spinning is 10-40 mu L/s, and the spinning speed is 10-90 rad/min.
The antibacterial temperature-control micro-nano fiber is obtained by microfluid spinning of antibacterial temperature-sensitive hydrogel and polyethylene oxide aqueous solution.
In the invention, the injection flow rate of the microfluid spinning is 10-40 muL/s, preferably 15-35 muL/s, and further preferably 20-30 muL/s; the micro-fluid spinning speed is 10-90 rad/min, preferably 20-70 rad/min, further preferably 30-60 rad/min, and more preferably 40-50 rad/min. According to the invention, the injection flow of microfluid spinning is controlled to be 10-40 mu L/s, the spinning speed is 10-90 rad/min, the specific surface area of the micro-nanofiber is increased, the fiber nano effect is improved, and the antibacterial property of the micro-nanofiber is further improved.
In the invention, the temperature of the microfluid spinning is preferably 25-40 ℃, and more preferably 30-35 ℃.
In the invention, the translation speed of the microfluid spinning is preferably 10-30 mm/s, more preferably 15-25 mm/s, and more preferably 20 mm/s; the translation distance of the microfluid spinning is preferably 10-30 cm, more preferably 15-25 cm, and even more preferably 20 cm. According to the invention, the translation speed of the microfluid spinning is controlled to be 10-30 mm/s, and the translation distance is controlled to be 10-30 cm, so that the orientation of the micro-nano fibers is improved, and the orientation order of the micro-nano fibers is improved.
The raw materials for preparing the antibacterial temperature-control micro-nano fibers comprise polyethylene oxide aqueous solution. In the invention, the mass percentage of the polyethylene oxide aqueous solution is preferably 8-20%, and more preferably 10%; the relative molecular weight of the polyethylene oxide is preferably 40-60 kDa.
The raw materials for preparing the antibacterial temperature-controlled micro-nano fibers comprise antibacterial temperature-sensitive hydrogel. In the invention, the antibacterial thermosensitive hydrogel is prepared from a modified sericin protein solution, N-isopropylacrylamide, N, N-methylenebisacrylamide, ammonium persulfate, N, N-tetramethylethylenediamine and acetic acid through a free radical polymerization reaction.
In the present invention, the preparation method of the modified sericin solution preferably comprises the steps of:
under the protection of oxygen, mixing a sericin aqueous solution with tyrosinase, and carrying out an enzymatic oxidation reaction to obtain a sericin quinone solution;
and mixing the sericin quinone solution with cecropin antibacterial peptide to obtain the modified sericin protein solution.
In the invention, under the protection of oxygen, sericin aqueous solution and tyrosinase are mixed to carry out enzyme catalytic oxidation reaction, thus obtaining sericin quinone solution.
In the invention, the concentration of the sericin aqueous solution is preferably 10-20 wt%, more preferably 12-18 wt%, and still more preferably 14-16 wt%; the dosage of the tyrosinase is preferably 2000-4500U/g, more preferably 2500-4000U/g, and more preferably 3000-3500U/g.
In the invention, the temperature of the enzyme catalytic oxidation reaction is preferably 25-60 ℃, more preferably 30-50 ℃, and more preferably 35-40 ℃; the time of the enzymatic oxidation reaction is preferably 30-120 min; the enzymatic oxidation reaction is preferably carried out under stirring.
After obtaining the sericin quinone solution, the modified sericin quinone solution is obtained by mixing the sericin quinone solution with cecropin antibacterial peptide.
In the invention, the mass ratio of the cecropin antibacterial peptide to the sericin is preferably 3500-4000 mu g: 9-20 g, more preferably 3500-4000 μ g: 12-18 g, more preferably 3500-4000 μ g: 14-16 g. In the invention, the cecropin antibacterial peptide is preferably added into the catalytic reaction solution in the form of cecropin antibacterial peptide aqueous solution, and the concentration of the cecropin antibacterial peptide aqueous solution is preferably 3500-4000 mu g/mL; the dosage of the cecropin antibacterial peptide aqueous solution is not particularly limited, as long as the dosage of the cecropin antibacterial peptide and the concentration of the sericin aqueous solution meet the requirement. In the present invention, the temperature, time and conditions for mixing the sericin quinone solution and cecropin are preferably the same as those of the enzyme-catalyzed oxidation reaction, and thus, the detailed description thereof is omitted.
The phenolic hydroxyl in the sericin is catalyzed and oxidized into quinone by tyrosinase to form a sericin quinone solution; quinone in the sericin quinone solution and-NH in cecropin antibacterial peptide2A complex series of reactions occur, forming complex crosslinks. Through this reaction, cecropin antimicrobial peptide was successfully grafted onto the sericin molecule.
In the invention, the dosage ratio of the modified sericin solution to N-isopropylacrylamide is preferably 1.0-3.0 mL: 0.5 to 1.0g, more preferably 1.5 to 2.5 mL: 0.5 to 1.0g, more preferably 2.0 mL: 0.5-1.0 g; the preferable dosage ratio of the modified sericin solution to the N, N-methylene bisacrylamide is 1.0-3.0 mL: 0.03 to 0.05g, more preferably 1.5 to 2.5 mL: 0.03-0.05 g, more preferably 2.0 mL: 0.03-0.05 g.
In the invention, the volume ratio of the modified sericin solution to N, N, N, N-tetramethylethylenediamine is preferably 1.0-3.0: 1.0 to 6.0, and more preferably 1.5 to 2.5: 1.0 to 6.0, more preferably 2.0: 1.0 to 6.0; the preferable dosage ratio of the modified sericin solution to the ammonium persulfate is 1.0-3.0 mL: 0.04-0.06 g, more preferably 1.5-2.5 mL: 0.04-0.06 g, more preferably 2.0 mL: 0.04-0.06 g.
In the invention, the mass concentration of acetic acid is preferably 2%, and the volume ratio of the modified sericin solution to the acetic acid is preferably 1-3: 10, more preferably 1.5 to 2.5: 10, more preferably 2.0: 10.
in the invention, the specific process of the preparation method of the antibacterial thermosensitive hydrogel is preferably as follows:
mixing N-isopropylacrylamide and N, N-methylene bisacrylamide acetic acid to obtain a primary mixed solution; and under the condition of stirring, adding the modified sericin solution, ammonium persulfate and N, N, N, N-tetramethylethylenediamine into the primary mixed solution to perform free radical polymerization reaction.
In the invention, the temperature of the free radical polymerization reaction is preferably 50-60 ℃, and the time is preferably 4-6 h; the free-radical polymerization is preferably carried out under nitrogen protection.
In the invention, the volume ratio of the antibacterial temperature-sensitive hydrogel to the polyethylene oxide aqueous solution is preferably 1-5: 5.
the invention also provides a preparation method of the antibacterial temperature-control nanofiber, which comprises the following steps:
mixing a sericin aqueous solution, tyrosinase and cecropin antibacterial peptide, and carrying out enzyme catalytic oxidation reaction to obtain a modified sericin solution;
mixing the modified sericin protein solution, N-isopropyl acrylamide, N, N-methylene bisacrylamide, ammonium persulfate, N, N-tetramethyl ethylenediamine and acetic acid, and carrying out free radical polymerization reaction to obtain an antibacterial temperature-sensitive hydrogel;
and mixing the antibacterial temperature-sensitive hydrogel and a polyethylene oxide aqueous solution, and performing microfluid spinning to obtain the antibacterial temperature-controlled micro-nano fiber.
In the invention, parameters related to the preparation method of the antibacterial temperature-controlled micro-nano fiber are consistent with those related to the technical scheme, and are not described herein again.
The antibacterial temperature-controlled micro-nano fiber and the preparation method thereof provided by the present invention are described in detail with reference to the following examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Preparation of modified sericin solution
Under the conditions of oxygen protection and 25 ℃, carrying out catalytic oxidation reaction on 90mL of 10 mass percent sericin aqueous solution and tyrosinase (2000U/g) for 30min, adding 1mL of cecropin antibacterial peptide with the concentration of 3500 mu g/mL after the reaction is finished, mixing, and stirring under certain conditions to obtain the modified sericin solution.
Preparation of the spinning dope
Under the protection of nitrogen, 1mL of the modified sericin solution, 0.5g N-isopropyl acrylamide, 0.04g N, N-methylene bisacrylamide, 0.05g of ammonium persulfate and 2.0mL of N, N, N-tetramethyl ethylenediamine are mixed with 10mL of 2% acetic acid, and free radical polymerization reaction is carried out for 4h at 60 ℃ to obtain the antibacterial temperature-sensitive hydrogel.
Mixing the antibacterial temperature-sensitive hydrogel and 10% by mass of polyethylene oxide (relative molecular mass of 40kDa) aqueous solution according to a volume ratio of 1: 5, mixing, and stirring at normal temperature to be uniform to obtain spinning solution;
preparation of antibacterial temperature-control micro-nano parallel fiber
Spinning the spinning solution under the microfluid spinning conditions that the spinning injection flow is 10 mu L/s, the spinning speed is 10rad/min, the spinning temperature is 25 ℃, the spinning translation speed is 10mm/s and the spinning translation distance is 10cm to prepare the antibacterial temperature-controlled micro-nano parallel fiber.
Fig. 1 shows a picture of the antibacterial temperature-controlled micro-nano parallel fiber obtained in this embodiment, as shown in fig. 1: the embodiment can obtain micro-nano parallel fibers with uniform diameters.
FIG. 2 shows a contact angle picture of the antibacterial temperature-controlled micro-nano parallel fiber obtained in the embodiment at 20 ℃, 42 ℃ and 7s, which can be seen from FIG. 2; the antibacterial temperature-control micro-nano parallel fiber obtained by the embodiment has a good temperature-sensitive effect, and the contact angle of the micro-nano parallel fiber is gradually increased along with the rise of the external temperature, so that the micro-nano parallel fiber is gradually changed from hydrophilicity to hydrophobicity.
Example 2
Preparation of modified sericin solution
Under the conditions of oxygen protection and 35 ℃ of temperature, carrying out catalytic oxidation reaction on 90mL of 15% sericin aqueous solution by mass percentage and tyrosinase (3000U/g) for 45min, adding 1mL of cecropin antibacterial peptide with the concentration of 3600 mu g/mL after the reaction is finished, mixing, and stirring under certain conditions to obtain the modified sericin solution.
Preparation of spinning dope
Under the protection of nitrogen, 1mL of the modified sericin solution, 0.5g N-isopropylacrylamide, 0.04g N, N-methylenebisacrylamide, 0.05g of ammonium persulfate and 2.0mLN, N, N, N-tetramethylethylenediamine and 10mL of 2% acetic acid are mixed for free radical polymerization to obtain the antibacterial temperature-sensitive hydrogel.
Mixing the antibacterial temperature-sensitive hydrogel and a 10% polyethylene oxide (relative molecular mass of 40kDa) aqueous solution according to a volume ratio of 2: 5, mixing, and stirring at normal temperature to be uniform to obtain spinning solution;
preparation of antibacterial temperature-control micro-nano parallel fiber
Spinning the spinning solution under the microfluid spinning conditions that the spinning injection flow is 15 mu L/s, the spinning speed is 30rad/min, the spinning temperature is 30 ℃, the spinning translation speed is 15mm/s and the spinning translation distance is 15cm to prepare the antibacterial temperature-controlled micro-nano parallel fiber.
Example 3
Preparation of modified sericin solution
Under the conditions of oxygen protection and 45 ℃ of temperature, 90mL of sericin aqueous solution with the mass percentage of 20% and tyrosinase (4500U/g) are subjected to enzyme catalytic oxidation reaction for 60min, 1mL of Cecropin with the concentration of 3700 mu g/mL is added and mixed after the reaction is finished, and the modified sericin solution is obtained by stirring under certain conditions.
Preparation of the spinning dope
Under the protection of nitrogen, 1mL of the modified sericin solution, 0.5g N-isopropylacrylamide, 0.04g N, N-methylenebisacrylamide, 0.05g of ammonium persulfate and 2.0mLN, N, N, N-tetramethylethylenediamine and 10mL of 2% acetic acid are mixed for free radical polymerization to obtain the antibacterial temperature-sensitive hydrogel.
Mixing the antibacterial temperature-sensitive hydrogel and a 10% polyethylene oxide (relative molecular mass of 40kDa) aqueous solution according to a volume ratio of 3: 5, mixing, and stirring at normal temperature to be uniform to obtain spinning solution;
preparation of antibacterial temperature-control micro-nano parallel fiber
Spinning the spinning solution under the microfluid spinning conditions that the spinning injection flow is 20 mu L/s, the spinning speed is 50rad/min, the spinning temperature is 35 ℃, the spinning translation speed is 20mm/s and the spinning translation distance is 20cm to prepare the antibacterial temperature-controlled micro-nano parallel fiber.
Example 4
Preparation of modified sericin solution
Under the conditions of oxygen protection and 55 ℃, carrying out enzymatic oxidation reaction on 90mL of 15 mass percent sericin aqueous solution and tyrosinase (4000U/g) for 90min, adding 1mL of Cecropin antibacterial peptide (Cecropin) with the concentration of 3800 mu g/mL after the reaction is finished, mixing, and stirring under certain conditions to obtain the modified sericin solution.
Preparation of the spinning dope
Under the protection of nitrogen, 1mL of the modified sericin solution, 0.5g N-isopropylacrylamide, 0.04g N, N-methylenebisacrylamide, 0.05g of ammonium persulfate and 2.0mLN, N, N, N-tetramethylethylenediamine and 10mL of 2% acetic acid are mixed for free radical polymerization to obtain the antibacterial temperature-sensitive hydrogel.
Mixing the antibacterial temperature-sensitive hydrogel with 10% of polyethylene oxide (relative molecular mass is 60kDa) aqueous solution according to a volume ratio of 4: 5, mixing, and stirring at normal temperature to be uniform to obtain spinning solution;
preparation of antibacterial temperature-control micro-nano parallel fiber
Spinning the spinning solution under the microfluid spinning conditions that the spinning injection flow is 30 mu L/s, the spinning speed is 70rad/min, the spinning temperature is 25 ℃, the spinning translation speed is 25mm/s and the spinning translation distance is 25cm to prepare the antibacterial temperature-controlled micro-nano parallel fiber.
Example 5
Preparation of modified sericin solution
Under the conditions of oxygen protection and 60 ℃ temperature, carrying out catalytic oxidation reaction on 90mL of 20 mass percent sericin aqueous solution and tyrosinase (4500U/g) for 120min, adding 1mL of Cecropin (Cecropin) with the concentration of 4000 mu g/mL after the reaction is finished, mixing, and stirring under certain conditions to obtain the modified sericin solution.
Preparation of the spinning dope
Under the protection of nitrogen, 1mL of the modified sericin solution, 0.5g N-isopropylacrylamide, 0.04g N, N-methylenebisacrylamide, 0.05g of ammonium persulfate and 2.0mLN, N, N, N-tetramethylethylenediamine and 10mL of 2% acetic acid are mixed for free radical polymerization to obtain the antibacterial temperature-sensitive hydrogel.
Mixing the antibacterial temperature-sensitive hydrogel and 10% by mass of polyethylene oxide (relative molecular mass is 60kDa) aqueous solution according to a volume ratio of 5: 5, mixing, and stirring at normal temperature to be uniform to obtain spinning solution;
preparation of antibacterial temperature-control micro-nano parallel fiber
Spinning the spinning solution under the microfluid spinning conditions that the spinning injection flow is 40 muL/s, the spinning speed is 90rad/min, the spinning temperature is 40 ℃, the spinning translation speed is 30mm/s and the spinning translation distance is 30cm to prepare the antibacterial temperature-controlled micro-nano parallel fiber.
Comparative example 1
As in example 1, the only difference is that the parameters of the microfluid spinning are: the spinning jet flow is 50 muL/s, the spinning speed is 10rad/min, the spinning temperature is 25 ℃, the spinning translation speed is 10mm/s, and the spinning translation distance is 10 cm.
Comparative example 2
Similar to example 1, the only difference is that the parameters of the microfluid spinning are: the spinning jet flow is 10 muL/s, the spinning speed is 120rad/min, the spinning temperature is 25 ℃, the spinning translation speed is 10mm/s, and the spinning translation distance is 10 cm.
FIG. 3 is a DSC curve of the antibacterial temperature-controlled micro-nano parallel fibers obtained in examples 1-5, and it can be seen from FIG. 3 that: in the embodiments 1-5, the phase transition temperature of the temperature-sensitive micro-nano parallel fibers changes when the modified sericin solution is increased, and the phase transition temperature is reduced along with the increase of the mass fraction of the modified sericin.
The invention also detects the antibacterial performance of the samples obtained in the examples 1-5 and the comparative examples 1-2, and the specific detection process is as follows:
the antibacterial temperature-control nanofiber membrane disclosed by the invention is characterized in that escherichia coli and staphylococcus aureus are selected as test strains, an oscillating flask method is adopted for quantitative test to represent the antibacterial effect of the antibacterial temperature-control nanofiber membrane, and the test is carried out by combining the oscillating flask method in American standard ASTM E2149.
The samples of examples 1 to 5 and comparative examples 1 to 2 were cut into 0.5X 0.5cm2And (3) blocking, wherein the total mass of the sample is 0.75g, and sterilizing for 15min at the temperature of 121 ℃ under the condition of 103kPa for later use.
Placing the antibacterial temperature-controlled micro-nano parallel fiber membrane into a 250mL triangular flask, and respectively adding 70mL of LPBS solution (pH is approximately equal to 7.2) and 5mL of strain with the concentration of 1 × 105～4×105cfu/mL of the bacterial suspension, then under the condition of the action temperature of 25 ℃, shaking at 300r/min for 2min, adding 5mL of prepared inoculation bacterial liquid into each of the flasks of examples 1-5 and the blank group by using a suction pipe, covering a bottle cap, then placing the flasks on a reciprocating oscillator, and oscillating at 24 ℃ and 150r/min for 18 h.
The formula of the bacteriostatic rate is as follows:
x: the bacteriostasis rate;
a: inoculating bacteria to the standard blank sample, and culturing for 18h to obtain the viable bacteria concentration in the flask;
b: the concentration of viable bacteria in the flask after the antibacterial sample is inoculated with bacteria and cultured for 18 h.
The results of the bacteriostatic ratio test are shown in table 1.
TABLE 1 results of the bacteriostatic test for examples 1-5 and blank groups
As can be seen from table 1: the antibacterial temperature-control micro-nano parallel fiber membrane has better antibacterial property, and the highest antibacterial rate can reach more than 99.99%.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (14)
1. The antibacterial temperature-control micro-nano fiber is characterized by being obtained by microfluid spinning antibacterial temperature-sensitive hydrogel and a polyethylene oxide aqueous solution; the antibacterial thermosensitive hydrogel is prepared by performing free radical polymerization on a modified sericin protein solution, N-isopropyl acrylamide, N, N-methylene bisacrylamide, ammonium persulfate, N, N-tetramethyl ethylenediamine and acetic acid; the modified sericin solution is prepared from a sericin aqueous solution, tyrosinase and cecropin antibacterial peptide through an enzymatic oxidation reaction;
the jet flow of the microfluid spinning is 10-40 mu L/s, and the spinning speed is 10-90 rad/min;
the temperature of the microfluid spinning is 25-40 ℃;
the translation speed of the microfluid spinning is 10-30 mm/s, and the translation distance is 10-30 cm.
2. The antibacterial temperature-controlled micro-nano fiber according to claim 1, wherein the preparation method of the modified sericin solution comprises the following steps:
under the protection of oxygen, mixing a sericin aqueous solution with tyrosinase, and carrying out an enzymatic oxidation reaction to obtain a sericin quinone solution;
and mixing the sericin quinone solution with cecropin antibacterial peptide to obtain the modified sericin protein solution.
3. The antibacterial temperature-control micro-nano fiber according to claim 2, wherein the concentration of the sericin aqueous solution is 10-20 wt%; the dosage of the tyrosinase is 2000-4500U/g; the mass ratio of the cecropin antibacterial peptide to the sericin is 3500-4000 microgram: 9-20 g.
4. The antibacterial temperature-control micro-nano fiber according to claim 1, 2 or 3, wherein the dosage ratio of the modified sericin solution to N-isopropylacrylamide is 1.0-3.0 mL: 0.5 to 1.0 g.
5. The antibacterial temperature-control micro-nano fiber according to claim 1, 2 or 3, wherein the dosage ratio of the modified sericin solution to N, N-methylenebisacrylamide is 1.0-3.0 mL: 0.03-0.05 g.
6. The antibacterial temperature-control micro-nano fiber according to claim 1, 2 or 3, wherein the volume ratio of the modified sericin solution to N, N, N, N-tetramethylethylenediamine is 1.0-3.0: 1.0 to 6.0.
7. The antibacterial temperature-control micro-nano fiber according to claim 1, 2 or 3, wherein the use amount ratio of the modified sericin solution to ammonium persulfate is 1.0-3.0 mL: 0.04-0.06 g.
8. A preparation method of antibacterial temperature-control micro-nano fibers is characterized by comprising the following steps:
mixing a sericin aqueous solution, tyrosinase and cecropin antibacterial peptide, and carrying out enzyme catalytic oxidation reaction to obtain a modified sericin solution;
mixing the modified sericin protein solution, N-isopropyl acrylamide, N, N-methylene bisacrylamide, ammonium persulfate, N, N-tetramethyl ethylenediamine and acetic acid, and carrying out free radical polymerization reaction to obtain an antibacterial temperature-sensitive hydrogel;
mixing the antibacterial temperature-sensitive hydrogel with a polyethylene oxide aqueous solution, and performing microfluid spinning to obtain the antibacterial temperature-controlled micro-nanofiber;
the jet flow of the microfluid spinning is 10-40 mu L/s, and the spinning speed is 10-90 rad/min;
the temperature of the microfluid spinning is 25-40 ℃;
the translation speed of the microfluid spinning is 10-30 mm/s, and the translation distance is 10-30 cm.
9. The method according to claim 8, wherein the method for preparing the modified sericin solution comprises the steps of:
under the protection of oxygen, mixing a sericin aqueous solution with tyrosinase, and carrying out an enzymatic oxidation reaction to obtain a sericin quinone solution;
and mixing the sericin quinone solution with cecropin antibacterial peptide to obtain the modified sericin protein solution.
10. The preparation method according to claim 9, wherein the concentration of the sericin aqueous solution is 10 to 20 wt%; the dosage of the tyrosinase is 2000-4500U/g; the mass ratio of the cecropin antibacterial peptide to the sericin is 3500-4000 microgram: 9-20 g.
11. The preparation method according to claim 8, 9 or 10, wherein the dosage ratio of the modified sericin solution to N-isopropylacrylamide is 1.0-3.0 mL: 0.5 to 1.0 g.
12. The preparation method according to claim 8, 9 or 10, wherein the dosage ratio of the modified sericin solution to the N, N-methylenebisacrylamide is 1.0-3.0 mL: 0.03-0.05 g.
13. The method according to claim 8, 9 or 10, wherein the volume ratio of the modified sericin solution to N, N, N, N-tetramethylethylenediamine is 1.0-3.0: 1.0 to 6.0.
14. The preparation method according to claim 8, 9 or 10, wherein the dosage ratio of the modified sericin solution to ammonium persulfate is 1.0-3.0 mL: 0.04-0.06 g.
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