CN110791883B

CN110791883B - Lubricating fiber film and preparation method thereof

Info

Publication number: CN110791883B
Application number: CN201910987189.0A
Authority: CN
Inventors: 张洪玉; 王毅; 崔文国; 邓廉夫; 成梁; 王臻
Original assignee: SHANGHAI INSTITUTE OF TRAUMATOLOGY AND ORTHOPEDICS; Tsinghua University
Current assignee: SHANGHAI INSTITUTE OF TRAUMATOLOGY AND ORTHOPEDICS; Tsinghua University
Priority date: 2019-10-17
Filing date: 2019-10-17
Publication date: 2021-04-23
Anticipated expiration: 2039-10-17
Also published as: CN110791883A

Abstract

The invention relates to a lubricating fiber membrane, which is formed by interweaving fibers, wherein the fiber material for forming the fibers comprises a fiber base material and a zwitterionic polymer, the zwitterionic polymer accounts for 1-15% of the mass of the fiber base material, and the average molecular weight of the zwitterionic polymer is 10000-30000. The invention also discloses a preparation method of the lubricating fiber membrane. The lubricating fiber membrane is formed by interweaving fibers, in the fiber material forming the fibers, the zwitterionic polymer is added on the basis of the fiber base material, and the addition of the zwitterionic polymer reduces the friction coefficient of the surface of the lubricating fiber membrane, so that the cell adhesion effect can be prevented.

Description

Lubricating fiber film and preparation method thereof

Technical Field

The invention relates to the technical field of medical materials, in particular to a lubricating fiber membrane and a preparation method thereof.

Background

In recent years, biomedical membranes have been widely used in clinical diagnosis, treatment, repair, and the like because of their excellent properties, for example, bone-inducing membranes, hemodialysis membranes, tissue adhesion-preventing membranes, and the like. These medical membranes for specific purposes usually require some specific biological functions, such as bone inducing membranes which are required to promote bone cell growth and differentiation. Among them, the tissue adhesion-preventing membrane for preventing postoperative tissue adhesion is the most demanding of these membranes, and is required not only to be resistant to cell adhesion but also to be permeable to air and to permeate nutrients.

At present, electrostatic spinning is more mature to be applied to the preparation of fiber membranes. The fiber membrane prepared by electrostatic spinning has a three-dimensional micro-nano porous structure, and can ensure the characteristics of ventilation, nutrient substance permeation and the like, but the surface of the traditional degradable electrostatic spinning fiber membrane generally has a large friction coefficient, so that cells are easy to adhere, namely the traditional electrostatic spinning fiber membrane is difficult to realize cell adhesion resistance while ensuring the gas/nutrient permeation of the fiber membrane. In the traditional research, there is a technical scheme for preventing tendon tissue adhesion by loading drugs such as mitomycin and ibuprofen on a fibrous membrane, but local side effects of the drugs can slow down the repair time of tendons. Therefore, it is a great challenge to construct a lubricating fiber membrane that can achieve both gas/nutrient permeation and cell adhesion resistance without drug loading.

Disclosure of Invention

Based on this, it is necessary to provide a lubricating fiber membrane with a low surface friction coefficient, so as to ensure the characteristics of air permeability, nutrient permeation and the like, and simultaneously play a role in resisting cell adhesion.

A lubricating fiber membrane is formed by interweaving fibers, the fiber materials for forming the fibers comprise fiber base materials and zwitterionic polymers, the zwitterionic polymers account for 1% -15% of the mass of the fiber base materials, and the average molecular weight of the zwitterionic polymers is 10000-30000.

In one embodiment, the zwitterionic polymer is 10-15% by mass of the fibrous base material.

In one embodiment, the zwitterionic polymer is selected from one or more of phosphorylcholine-based polymers, sulfobetaine-based polymers, or carboxybetaine-based polymers.

In one embodiment, the zwitterionic polymer is poly 2-methacryloyloxyethyl phosphorylcholine (PMPC).

In one embodiment, the fiber matrix material is a biodegradable polymer having an average molecular weight of 60000-150000.

In one embodiment, the biodegradable polymer is selected from one or more of Polycaprolactone (PCL), polylactic acid (PLA), Polyhexenol (PVA), polyglycolic acid (PGA), Gelatin (Gelatin), and chitosan.

In one embodiment, the fibrous base material is Polycaprolactone (PCL).

In one embodiment, the lubricating fiber film comprises two surfaces, wherein at least one surface has a friction coefficient of 0.05-0.2.

A method of making a lubricating fiber membrane of any preceding claim, comprising:

mixing a fiber matrix material, a zwitterionic polymer and a solvent to prepare a spinning solution;

preparing the spinning solution into fibers through electrostatic spinning, and forming a fiber membrane; and

and drying the fiber membrane to obtain the lubricating fiber membrane.

In one embodiment, the step of forming the spinning solution into fibers by electrospinning and forming a fiber film comprises:

forming the spinning dope into a fiber by electrospinning, and

and interweaving the fibers on a conductive plane to form the fiber membrane.

In one embodiment, the conductive plane is a metal plane.

In one embodiment, the conductive plane is selected from the group consisting of aluminum foil, tin foil, and steel plate.

In one embodiment, the step of drying the fiber membrane to obtain the lubricating fiber membrane is performed under vacuum condition.

In one embodiment, the step of forming the spinning solution into fibers by electrospinning and forming a fiber film is performed under a relative humidity of 20% or more.

In one embodiment, the step of forming the spinning solution into fibers by electrospinning and forming a fiber film is performed under a relative humidity of 35% to 65%.

In one embodiment, the solvent is a fluoroalcohol organic solvent.

In one embodiment, the fluoroalcohol organic solvent is selected from Hexafluoroisopropanol (HFIP), trifluoroethanol, or a mixture thereof.

The lubricating fiber membrane provided by the embodiment of the invention is formed by interweaving fibers, in the fiber material forming the fibers, the zwitterionic polymer is added on the basis of the fiber base material, and the addition of the zwitterionic polymer reduces the friction coefficient of the surface of the lubricating fiber membrane, so that cell adhesion can be prevented, and the lubricating fiber membrane can be used as a postoperative tissue adhesion prevention membrane, for example.

Drawings

FIG. 1 is a scanning electron micrograph of each lubricating fiber film in example 1 of the present invention;

FIG. 2 is a scanning electron microscope photograph of the bottom and top surfaces of each lubricating fiber film in example 2 of the invention;

FIG. 3 is a graph comparing the percent area of smooth fibrous zones on the bottom surface of a lubricating fibrous film formed at different relative humidities in example 2 of the present invention;

FIG. 4 is a graph comparing the EDS results for the bottom and top surfaces of lubricating fiber membranes formed at different relative humidities in example 2 of the present invention;

FIG. 5 is a graph showing the results of testing the surface friction coefficients of lubricating fiber membranes at different PMPC concentrations in example 1 of the present invention;

FIG. 6 is a comparison of the friction coefficient of the bottom and top surfaces of a lubricating fiber film having a relative humidity of 65% in example 2 of the present invention with that of ice;

FIG. 7 is a graph of the coefficient of friction of the bottom and top surfaces of a lubricating fiber film having a relative humidity of 65% versus time in example 2 of the present invention;

FIG. 8 is a graph showing the results of air permeability tests of lubricating fiber films formed at different relative humidities in example 2 of the present invention;

FIG. 9 is a graph showing the results of in vitro cell studies of lubricating fiber membranes in example 1 of the present invention;

FIG. 10 is a graph showing the results of in vitro cell studies of lubricating fiber membranes in example 2 of the present invention.

Detailed Description

To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items. The average molecular weight, Mw, in the present application refers to the weight average molecular weight of the polymer.

The embodiment of the invention provides a lubricating fiber membrane, which is formed by interweaving fibers, wherein the fiber material for forming the fibers comprises a fiber base material and a zwitterionic polymer, the zwitterionic polymer accounts for 1-15% of the mass of the fiber base material, and the average molecular weight of the zwitterionic polymer is 10000-30000. Preferably, the zwitterionic polymer accounts for 10-15% of the mass of the fiber matrix material.

In the present invention, the diameter of the fibers forming the fiber membrane may be in the micrometer scale or in the nanometer scale. Preferably, the diameter of the fiber may be 1 to 10 μm; in some embodiments, the fibers may also have a diameter of 1nm to 1000 nm.

In the examples of the present invention, the concentration of the zwitterionic polymer in the lubricating fiber film refers to the mass percent of the zwitterionic polymer in the fiber matrix material. The addition of the zwitterionic polymer obviously reduces the friction coefficient of the surface of the lubricating fiber membrane while not influencing the mechanical property and the air permeability of the lubricating fiber membrane, so that the addition of the zwitterionic polymer can be predicted to reduce the adhesion of cells on the surface of the membrane. In the invention, the action mechanism of the zwitterionic polymer is that the zwitterionic polymer can strongly adsorb water molecules, so that a stable hydrated lubricating layer is formed on the surface of the lubricating fiber membrane, the friction coefficient of the surface of the lubricating fiber membrane is reduced, the surface of the lubricating fiber membrane is lubricated, and the cell adhesion prevention effect is achieved.

In the embodiment of the invention, the fibers are not loaded with medicaments, and the medicaments comprise mitomycin and ibuprofen. I.e. no drug is contained in the fibre material forming the fibres, said drug comprising mitomycin, ibuprofen.

In embodiments of the invention, the zwitterionic polymer is selected from one or more of phosphorylcholine-based polymers, sulfobetaine-based polymers, or carboxybetaine-based polymers; preferably, the zwitterionic polymer is selected from phosphorylcholine-type polymers; further preferred, the zwitterionic polymer is poly-2-methacryloyloxyethyl phosphorylcholine (PMPC).

As a main body material of the fiber, the fiber matrix material is a biodegradable polymer, and the average molecular weight of the biodegradable polymer is 60000-150000. The biodegradable polymer that can be applied in the present invention is, for example, one or more selected from Polycaprolactone (PCL), polylactic acid (PLA), Polyhexenol (PVA), polyglycolic acid (PGA), Gelatin (Gelatin), and chitosan. Preferably, the fibrous base material is Polycaprolactone (PCL) having an average molecular weight of 80000.

The embodiment of the invention also provides a preparation method of the lubricating fiber membrane, which comprises the following steps:

s100: mixing a fiber matrix material, a zwitterionic polymer and a solvent to prepare a spinning solution;

s200: preparing the spinning solution into fibers through electrostatic spinning, and forming a fiber membrane; and

s300: and drying the fiber membrane to obtain the lubricating fiber membrane.

In step S100, the solvent is a fluorinated alcohol organic solvent, preferably, the fluorinated alcohol organic solvent is selected from Hexafluoroisopropanol (HFIP), trifluoroethanol or a mixture thereof. More preferably, the fluoroalcohol organic solvent is Hexafluoroisopropanol (HFIP).

Step S200 may further include:

s210: forming the spinning dope into a fiber by electrospinning, and

s220: and interweaving the fibers on the conductive plane to form the fiber membrane.

Wherein, the step S200 is carried out under the condition that the relative humidity is more than or equal to 20 percent. Preferably, step S200 is performed under a relative humidity of 35% to 65%.

It was found experimentally that the coefficient of friction of the surface of the lubricating fiber film on the side close to the conductive plane was lower relative to the coefficient of friction of the surface on the side away from the conductive plane. And the greater this difference is with increasing ambient humidity during electrospinning. Under the condition that the concentration of the zwitterionic polymer is 10%, two surfaces of the lubricating fiber film obtained under different relative humidities are subjected to electron microscope scanning, wherein the surface of the lubricating fiber film, close to one side of the conductive plane, is a bottom surface, and the surface of the lubricating fiber film, far away from the conductive plane, is a top surface. Substantially identical interconnected porosity between the top surface and the floor at a relative humidity of 20%; as the relative humidity increases, smooth fibrous zones with disconnected pores appear on the bottom surface, the pores of the smooth fibrous zones are independent with respect to the pores of the top surface, and this phenomenon, which exists only on the bottom surface; the area of the smooth fibrous zones increases with increasing relative humidity.

The zwitterionic polymer has positively charged groups and negatively charged groups, and the positively charged groups and the negatively charged groups can strongly adsorb water molecules to form a stable hydrated lubricating layer; however, in the case of the conventional method for preparing a fiber membrane, since ultra-large-scale micropores are connected to each other between fibers, it is almost impossible to form a stable nano-hydration layer on the surface of the fibers. In the method of the embodiment of the invention, the reason why the smooth fiber area can be formed on the bottom surface of the lubricating fiber membrane is that under the condition of introducing the zwitterionic polymer, in the electrostatic spinning process, the process of depositing the spinning solution on the conductive plane (aluminum foil) is carried out under the condition of high relative humidity, the zwitterionic polymer can adsorb water molecules in the air, so that the evaporation of the solvent is slowed down, the contact of the bottom surface of the lubricating fiber membrane and the conductive plane further hinders the evaporation of the solvent in the fibers positioned at the bottom surface, so that the fibers close to the bottom surface are in a semi-molten state, so that the air holes between the bottom surface and the top surface are not communicated, the smooth fiber area can be formed, the friction coefficient of the bottom surface is obviously reduced, and the super-lubricating fiber membrane is obtained; namely, the super-lubricating fiber membrane in the embodiment of the invention is obtained under the dual-mediation effect of humidity and a zwitterionic polymer.

Preferably, in step S200, the conductive plane is an aluminum foil, a tin foil or a steel plate. It is further preferred that the conductive plane is an aluminum foil, and that a smooth aluminum foil is used as the conductive plane, which results in a higher density of deposited fibers than a porous collector, resulting in a much slower solvent evaporation rate. Thereby further promoting the fibers deposited on the aluminum foil close to the aluminum foil to pass through a semi-molten state before solidification, and forming an ice-like smooth surface (smooth fiber area) with disconnected pores on the bottom surface of the lubricating fiber film.

In a preferred embodiment, the solvent is a fluoroalcohol organic solvent. Further preferably, the fluoroalcohol organic solvent is selected from Hexafluoroisopropanol (HFIP), trifluoroethanol or a mixture thereof.

The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.

To observe the microscopic morphology of the fibers, all fibers were first sprayed with Pt for 10min with a vacuum ion sputter (EM ACE600, Leica, Germany), and then randomly scanned with a scanning electron microscope (SEM, Quanta200, FEI, Eindhoven, Netherlands) under a 15kV electron beam, and the energy spectrometer (EDS) was measured with the Scanning Electron Microscope (SEM).

Water Contact Angle (WCA) is measured by dropping 5. mu.L of deionized water onto a simple plane using an OCA-20 contact angle system (Dataphysics Instruments, Filderstadt, Germany).

Mechanical properties were measured on fiber samples using a mechanical tester (Instron 5567, Norwood, MA).

The air permeability of the fiber samples was measured using an air permeability tester (FX 3300, TEXTEST AG Zurich, Switzerland) according to EN ISO 9237 standard at 100Pa air pressure.

The rubbing test was performed by a universal material testing machine (UMT-5, Bruker Nano Inc., Germany) in a spin mode under the action of deionized water.

In vitro cell studies were performed using NIH/3T3 fibroblasts.

All data are expressed as means ± standard deviation and one-way anova was performed using SPSS 19.0 software to assess statistical differences. Significant differences were considered when p < 0.05.

Example 1

According to the proportion in the table 1, different weights of poly 2-methacryloyloxyethyl phosphorylcholine (PMPC Mw-20000) and polycaprolactone (PCL Mw-80000) are dissolved in 20mL Hexafluoroisopropanol (HFIP) to prepare spinning solutions containing PMPC with different concentrations;

preparing spinning solution containing PMPC with different concentrations into fibers (the diameter of the fibers is about 200nm in the embodiment) by electrostatic spinning, and interweaving the fibers on an aluminum foil to form a fiber membrane, wherein the electrostatic spinning process parameters are as follows: feed rate 6 ml. h^-1The distance between the needle point and the aluminum foil heat collector is 18cm, the voltage is 20kv, and the Relative Humidity (RH) is 20 percent, and the temperature is room temperature;

and separating the fiber membrane from the aluminum foil, and then drying under a vacuum condition to obtain the lubricating fiber membrane.

The sample names of the obtained lubricating fiber membranes were named as the mass percentage of PMPC relative to PCL, which was PCL, 1% PMPC, 2.5% PMPC, 5% PMPC, 10% PMPC, and 15% PMPC in this order.

TABLE 1

Sample name	PCL(g)	PMPC(g)	HFIP(mL)
				PCL	2	0	20
1％PMPC	2	0.02	20
				2.5％PMPC	2	0.05	20
5％PMPC	2	0.1	20
				10％PMPC	2	0.2	20
15％PMPC	2	0.3	20

Example 2

The same as example 1, except that the spinning solutions of 10% PMPC samples in table 1 were used, and electrostatic spinning was performed under conditions of Relative Humidity (RH) of 20%, 35%, 50%, and 65%, respectively, to obtain lubricating fiber membranes prepared at different relative humidities.

Experimental example 1 Material characteristics of lubricating fiber film

1. Scanning surface of electron microscope

Firstly, spraying various groups of lubricating fiber membranes with Pt for 10min by a vacuum ion sputtering device (EM ACE600, Leica, Germany); then, each group of lubricating fiber membranes was randomly scanned under a 15kV electron beam using a scanning electron microscope (SEM, Quanta200, FEI, Eindhoven, Netherlands); measurements were made on an energy spectrometer (EDS) using a Scanning Electron Microscope (SEM). Wherein a scanning electron microscope image of each lubricating fiber membrane in example 1 is shown in fig. 1, it can be seen from fig. 1 that the incorporation of the zwitterionic polymer PMPC does not affect the uniformity of the fibers of the lubricating fiber membranes and the morphology of the interconnections. Scanning electron micrographs of the bottom and top surfaces of each lubricating fiber film of example 2 are shown in FIG. 2, at a scale of 10 μm, and at a relative humidity of 20%, the top and ground surfaces have substantially the same interconnected porosity; as the relative humidity increases, smooth fibrous zones with disconnected pores appear on the bottom surface, the pores of the smooth fibrous zones are independent with respect to the pores of the top surface, and this phenomenon, which exists only on the bottom surface; as can be seen from fig. 2 and 3, the area of the smooth fibrous regions on the bottom surface as a percentage of the entire area of the bottom surface increases with increasing relative humidity.

2. Elemental determination

EDS (energy dispersive spectroscopy) was measured during SEM observation. Wherein the atomic percentage of the P element is shown in figure 4. As can be seen from fig. 4, the distribution of P elements is higher on the bottom surface than on the top surface.

3. Water Contact Angle (WCA)

Water Contact Angle (WCA) is measured by dropping 5. mu.L of deionized water onto a simple plane using an OCA-20 contact angle system (Dataphysics Instruments, Filderstadt, Germany). The Water Contact Angle (WCA) of the lubricating fiber membranes of 10% PMPC at different relative humidities in example 2 was determined. P <0.05, p < 0.005.

TABLE 2

In example 2, the mechanism of formation of the smooth fibrous domains on the bottom surface of the lubricating fibrous membrane surface therein is related to the slower solvent evaporation mediated by the dual RH/PMPC synergy during electrospinning. Under the condition of high relative humidity, PMPC in the rotary jet strongly adsorbs water molecules in the process of rotary jet solidification on the aluminum foil, so that the solvent is difficult to volatilize quickly. At the same time, a smooth aluminum foil would produce a higher density of deposited fibers than a porous collector, resulting in a much slower rate of solvent evaporation. The fibers finally deposited on the aluminum foil are semi-melted before solidification to form smooth fiber areas (ice-like smooth surfaces) with disconnected pores. Furthermore, it is speculated that PMPCs should be distributed more on the bottom surface, so that the bottom surface has an ultra-low coefficient of friction. Indeed, as expected, from the EDS results in fig. 4, it can be seen that the P elements from the PMPC are distributed far more on the bottom surface than on the top surface. The Water Contact Angle (WCA) results as shown in table 2 also have a similar trend due to the higher distribution of PMPCs on the bottom side, with the WCA values for the bottom side being significantly lower than the top side (p <0.005) for the 65% RH group. Thus, both EDS and WCA results demonstrate the mechanism of the "RH/PMPC dual co-mediated" technique.

Experimental example 2 Friction test

1. For each lubricating fiber film obtained in example 1, a friction test was performed in a spin mode under the action of deionized water using a universal material testing machine (UMT-5, Bruker Nano inc., Germany) under the specific test conditions: the rotating speed is 50mm min-1, the normal load is 0.5N, and the rotating radius is 3 mm. The results of testing the surface friction coefficients of the lubricating fiber membranes at different PMPC concentrations in example 1 are shown in fig. 5. It can be seen from fig. 5 that the surface friction coefficient of the lubricating fiber membrane in example 1 of the present invention gradually decreased as the concentration of PMPC increased. When the concentration of PMPC increased above 5%, the friction coefficient of the lubricating fiber membrane surface began to be significantly lower than when PMPC was added in an amount of 0% (pure PCL). When the PMPC concentration reached 10%, the friction coefficient of the lubricating fiber membrane surface was about 0.12. Then, as the concentration of PMPC increases, the friction coefficient of the lubricating fiber membrane surface no longer becomes significantly smaller.

2. The bottom and top surfaces of the lubricating fiber membranes of example 2, which had a relative humidity of 65%, were subjected to a rubbing test in a spin mode under deionized water using a universal material testing machine (UMT-5, Bruker Nano inc., Germany) under the following test conditions: the rotating speed is 50mm min-1, the normal load is 0.5N, and the rotating radius is 3 mm. The coefficient of friction was measured on ice using the same test conditions.

As shown in fig. 6, the bottom surface and the super-lubricated ice surface have the same ultra-low coefficient of friction of about 0.05, and the top surface has a coefficient of friction of about 0.15. Also, as shown in fig. 7, the friction coefficient of the bottom surface and the top surface did not change much with time during the friction test, thus indicating that the bottom surface had the same stability as the top surface. The bottom surface of the lubricating fiber film formed at a relative humidity of 65% had the largest smooth fiber area.

Experimental example 3 air permeability test

The air permeability of the 10% PMPC lubricating fiber membranes of example 2 was measured at different relative humidities using an air permeability tester (FX 3300, TEXTEST AG Zurich, Switzerland) according to EN ISO 9237 standard at 100Pa air pressure.

As a result, as shown in fig. 8, although the pores on the bottom surface of the lubricating fiber membrane in example 2 of the present invention were isolated and not communicated, the resulting lubricating fiber membrane developed still had sufficient air permeability to maintain air permeation and nutrient exchange.

Experimental example 4 in vitro cell study

NIH/3T3 fibroblasts were used for in vitro cell studies, the specific method was as follows:

placing the electro-spinning membrane with the diameter of 15mm in a 24-hole culture plate, and sterilizing for 24h by ultraviolet light. The cell suspension was then incubated at 4X 10⁴The density per well was inoculated onto the sample surface and incubated at 37 ℃ and 5% CO 2 atmosphere until characterization. Cell proliferation was measured by the method of Cell Counting Kit-8(CCK-8, Dojindo, Japan). After 1,3 and 7 days of incubation, each well was refreshed with 100 μ L of CCK-8 test solution and incubated for an additional 2 hours. The absorbance of the final solution at 450nm was then read by a microplate reader (Infinite F50, TECAN, Switzerland). Live/Dead Cell kits (Live/Dead Cell kits) (Life Tech, US) were used to assess Cell viability on electrospun membrane surfaces. After 1,3 and 7 days of culture, cells on each well were stained with 500 μ L of a combination dye consisting of 2mM calcein AM and 10mM EthD-1 for 30 minutes, and then observed on a confocal laser scanning microscope (CLSM, LSM800, ZEISS, Germany). Furthermore, the cytoskeletal arrangement on the electrospun membrane was also fluorescently stained. Briefly, cell samples were individually fixed with 4% paraformaldehyde and permeabilized with 0.1% Triton X-100(Sigma, USA) for 10 min; then, before CLSM imaging, stained with 20mg/mL phalloidin (Cytoskeleton, USA) for 30 minutes and 1mg/mL DAPI (Sigma, USA) for 5 minutes at room temperature. Cell density and cell area were calculated from CLSM images using image J software.

In vitro cell studies of the lubricating fiber membranes of example 1 and example 2 were performed using the methods described above, and the results are shown in fig. 9 and 10.

In FIG. 9, (a) is an OD value at 450nm measured by the CCK-8 method. (b) Is the average cell area counted from CLSM images. (c) Cell density counted from CLSM images. In the legend, 1%, 2.5%, 5%, 10%, and 15% represent lubricating fiber membranes made in example 1 with different concentrations of PMPC fiber material; the control group refers to a control group which was cultured and treated directly with NIH/3T3 fibroblasts without seeding the cells on any fiber membrane under the same conditions as described above.

As shown in FIG. 9, after 1,3 and 7 days of culture, NIH/3T3 fibroblasts were seeded on each of the lubricating fiber membranes in example 1, and cell adhesion and proliferation were observed. The number of cells decreased significantly starting from the 5% group, demonstrating that a relatively high PMPC content in the fibers can inhibit cell proliferation. Furthermore, over time, 10% and 15% of the cell groups almost stopped growing. The data of OD value at 450nm measured by CCK-8 as shown in FIG. 9(a) and cell density as shown in FIG. 9(c) also revealed a tendency to decrease with increasing PMPC concentration, i.e., the OD value and cell number of the 15% group were the lowest. Therefore, it was confirmed that the lubricating fiber membrane obtained by electrostatic spinning of the PCL/PMPC composite in example 1 had the effect of inhibiting cell growth.

In FIG. 10, (a) is the OD value at 450nm measured with CCK-8. (b) Is the average cell area counted from CLSM images. (c) Cell density counted from CLSM images. In the legend, 20% RH, 35% RH, 50% RH and 65% RH represent lubricating fiber films made in example 2 under different humidity conditions; the control group refers to a control group which was cultured and treated directly with NIH/3T3 fibroblasts without seeding the cells on any fiber membrane under the same conditions as described above.

As is clear from FIG. 10, after 1,3 and 7 days of culture, NIH/3T3 fibroblasts were seeded on the electrospun fiber membrane (lubricant fiber membrane) of example 2, and numbered PCL, 20% RH, 35% RH, 50% RH and 65% RH in this order. The growth of the cells was observed. As shown in fig. 10(b), the data of the cell area therein showed a downward trend with the 65% RH group being the lowest, as the relative humidity was increased. The study also found that the cell area of the 50% RH membrane and 65% RH membrane surfaces did not increase significantly over time, indicating that the 50% RH membrane and 65% RH membrane may have a durable anti-adhesion capability. The spreading of cells on the surface of the developed super-lubricious fibers is significantly inhibited due to the effect of the stable hydration layer based on the mechanism of hydration lubrication. The statistical results of the OD value at 450nm measured by CCK-8 shown in FIG. 10(a) and the cell density shown in FIG. 10(c) on days 1,3 and 7 can clearly find that the cell density of the different RH groups is obviously lower than that of the PCL group, and the cell density is in a descending trend with the increase of RH. . Furthermore, while the PCL group cells proliferated normally within 1-7 days, the cells appeared to stop proliferating at 65% RH. The results show that in example 2, the lubricating fiber membranes of the 50% RH group and the 65% RH group can reduce the number of cells on the fiber surface for a longer time, and the lubricating fiber membranes of the 50% RH group and the 65% RH group have stronger anti-cell adhesion capability.

The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.

The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims

1. A method of making a lubricating fiber film, comprising:

mixing a fiber base material, a zwitterionic polymer and a solvent to prepare a spinning solution, wherein the zwitterionic polymer accounts for 10-15% of the mass of the fiber base material, the average molecular weight of the zwitterionic polymer is 10000-30000, the zwitterionic polymer is poly (2-methacryloyloxyethyl phosphorylcholine), and the fiber base material is selected from polycaprolactone;

preparing the spinning solution into fibers by electrostatic spinning under the condition that the relative humidity is 35-65%, and interweaving on a conductive plane to form a fiber membrane; and

and drying the fiber membrane to obtain the lubricating fiber membrane, wherein the surface of the lubricating fiber membrane is provided with a hydration layer, the lubricating fiber membrane comprises two surfaces, the friction coefficient of at least one surface is 0.05-0.2, and the lubricating fiber membrane has the function of resisting cell adhesion.

2. The method of claim 1, wherein the conductive plane is a metal plane.

3. The method of claim 1, wherein the conductive plane is selected from the group consisting of aluminum foil, tin foil, and steel plate.

4. The method according to claim 1, wherein the solvent is a fluoroalcohol organic solvent.

5. The method according to claim 4, wherein the fluoroalcohol organic solvent is selected from hexafluoroisopropanol, trifluoroethanol, and a mixture thereof.

6. A lubricating fiber film produced by the method for producing a lubricating fiber film according to any one of claims 1 to 5.