CN112358595A - Operation suture line with antibacterial and shape memory functions and preparation method thereof - Google Patents
Operation suture line with antibacterial and shape memory functions and preparation method thereof Download PDFInfo
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- CN112358595A CN112358595A CN202011157938.6A CN202011157938A CN112358595A CN 112358595 A CN112358595 A CN 112358595A CN 202011157938 A CN202011157938 A CN 202011157938A CN 112358595 A CN112358595 A CN 112358595A
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- surgical suture
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
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- A61L17/00—Materials for surgical sutures or for ligaturing blood vessels ; Materials for prostheses or catheters
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- A—HUMAN NECESSITIES
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- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L17/00—Materials for surgical sutures or for ligaturing blood vessels ; Materials for prostheses or catheters
- A61L17/005—Materials for surgical sutures or for ligaturing blood vessels ; Materials for prostheses or catheters containing a biologically active substance, e.g. a medicament or a biocide
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- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L17/00—Materials for surgical sutures or for ligaturing blood vessels ; Materials for prostheses or catheters
- A61L17/06—At least partially resorbable materials
- A61L17/10—At least partially resorbable materials containing macromolecular materials
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- C—CHEMISTRY; METALLURGY
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
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- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
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- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
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- A61L2300/20—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials
- A61L2300/204—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing organic materials with nitrogen-containing functional groups, e.g. aminoxides, nitriles, guanidines
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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Abstract
The invention relates to an operation suture line with antibacterial and shape memory functions and a preparation method thereof. In particular to shape memory polyurethane, the structure of which is shown in formula I. The invention also provides an antibacterial shape memory surgical suture which is prepared from the shape memory polyurethane and antibacterial drugs serving as raw materials by a spinning processIn (1). The surgical suture has good biocompatibility and excellent shape memory function, can effectively avoid wound mechanical traction necrosis caused in the process of furling the surgical suture after an operation (especially an operation with a deep organ and a narrow operation visual field) is finished, and reduces the risk of wound infection; meanwhile, the operation difficulty can be reduced, and the operation time can be shortened. In addition, the surgical suture provided by the invention has obvious inhibition effect on gram-negative bacteria and gram-positive bacteria, can obviously reduce the infection risk of the surgical site, obviously improves the healing capacity of the wound after suture, and has wide application prospect.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to an operation suture line with antibacterial and shape memory functions and a preparation method thereof.
Background
The surgical suture line is a special line used for wound ligation suture hemostasis and tissue suture in surgical operations. They can be classified into two categories according to their biodegradability: non-absorbable threads and absorbable threads. The former has the characteristics of high tensile strength, easy disinfection and sterilization and low tissue reaction, but can not be degraded in vivo, so that stitches need to be removed after suturing, secondary pain and infection are easily caused, and scars are left; the latter can be degraded into soluble products in vivo, absorbed by human body and gradually excreted out of body, thereby relieving pain of patients. An ideal absorbable suture material for clinical use should meet the following conditions: the suture knot has the advantages of universality, sterility, no electrolysis, no surface tension, no allergy, no carcinogenicity, easiness in operation, no harm to bacterial growth, capability of ensuring the safety of the suture knot without abrasion or cutting during knotting, capability of resisting the contraction in tissues, capability of being absorbed by the tissues after the suture is achieved, and slight reaction.
Biodegradable polyurethane materials have received much attention in the preparation of absorbable surgical sutures due to their excellent mechanical properties, good hemocompatibility, histocompatibility and biodegradability.
However, the surgical suture used at present has some problems, such as the process of folding the surgical suture after the operation (especially the operation of deep organs and operation with narrow visual field) is completed, which easily causes the mechanical traction and necrosis of the wound and increases the probability of wound infection. And for wounds which are susceptible to infection and difficult to care after operation, the existing most of operation sutures still have higher infection risk after being sutured, and are not beneficial to wound healing. In addition, due to abuse of antibiotics, a large amount of drug-resistant bacteria are generated, so that the inhibition effect of many existing surgical sutures on bacteria at wounds is poor, and the recovery of the wounds is not facilitated.
Therefore, it is very important to develop a new absorbable surgical suture which can effectively inhibit bacteria, reduce the infection risk of wounds and promote wound healing, and meanwhile, the suture can be automatically and slowly furled after the operation is completed.
Disclosure of Invention
The invention aims to provide shape memory polyurethane, and an operation suture line with antibacterial and shape memory functions prepared from the shape memory polyurethane.
The invention provides shape memory polyurethane, which has a structure shown in a formula I:
furthermore, the shape memory polyurethane is prepared by taking hydroxyl-terminated polycaprolactone, diphenylmethane diisocyanate and butanediol as raw materials;
wherein, the mol ratio of the hydroxyl-terminated polycaprolactone to the diphenylmethane diisocyanate to the butanediol is preferably 1: (7-13): (36-42), more preferably 1: 12.2: 41.3
And/or, the molecular weight of the hydroxyl-terminated polycaprolactone is preferably 2000-.
The invention also provides a preparation method of the shape memory polyurethane, which comprises the following steps: (1) reacting hydroxyl-terminated polycaprolactone with diphenylmethane diisocyanate; (2) adding butanediol into the system obtained in the step (1) for reaction to obtain the butanediol-containing catalyst;
preferably, in the step (1), the reaction is carried out under the protection of inert gas, the reaction temperature is 80-90 ℃, and the reaction time is 1-3 hours; in the step (2), the reaction is carried out under the protection of inert gas, the reaction temperature is 70-90 ℃, and the reaction time is 20-30 hours;
more preferably, in the step (1), the reaction temperature is 85 ℃ and the reaction time is 2 hours; in the step (2), the reaction temperature is 80 ℃, and the reaction time is 24 hours.
The invention also provides a shape memory surgical suture which is prepared from the shape memory polyurethane serving as a raw material.
The invention also provides an antibacterial shape memory surgical suture which is prepared from the shape memory polyurethane and antibacterial drugs.
Further, the antibacterial drug is one or two of polyhexamethylene biguanide hydrochloride and berberine hydrochloride.
Further, the antibacterial agent is polyhexamethylene biguanide hydrochloride, and the concentration ratio of the shape memory polyurethane to the antibacterial agent in the raw materials is 25: (20-40), preferably 25: 40;
or, the antibacterial drug is berberine hydrochloride, and the concentration ratio of the shape memory polyurethane to the antibacterial drug in the raw materials is 20: (3-6), preferably 20: 6.
The invention also provides a preparation method of the shape memory surgical suture or the shape memory surgical suture with antibacterial property, which is characterized in that: the method is a wet spinning process and comprises the following steps:
(a) dissolving the raw materials in an organic solvent to obtain a spinning solution; the raw materials are the shape memory polyurethane, or the raw materials are the shape memory polyurethane and berberine hydrochloride;
(b) carrying out wet spinning on the spinning solution, and then solidifying in a coagulating bath to obtain spinning fibers; the coagulating bath is water;
(c) stretching and drying the spinning fiber to obtain the fiber;
or, the method is a wet spinning process, comprising the steps of:
(a') dissolving the shape memory polyurethane in an organic solvent to obtain a spinning solution;
(b') carrying out wet spinning on the spinning solution, and then solidifying in a coagulating bath to obtain spinning fibers; the coagulating bath is an aqueous solution of polyhexamethylene biguanide hydrochloride;
and (c') stretching and drying the spinning fiber to obtain the fiber.
Further, the organic solvent of step (a) or step (a') is dimethylacetamide; and/or, the temperature of the wet spinning in the step (b) or the step (b') is 20-30 ℃, preferably 25 ℃, and the solidification temperature is 20-30 ℃, preferably 25 ℃; and/or, the stretching temperature of the step (c) or the step (c') is 20-30 ℃, preferably 25 ℃;
and/or, the concentration of the shape memory polyurethane in the spinning solution in the step (a) is 20-25% mg/mL, preferably 20% mg/mL, and the concentration of the berberine hydrochloride is 3-6% mg/mL, preferably 3% mg/mL; the concentration of the shape memory polyurethane in the spinning solution in the step (a ') is 20-25% mg/mL, preferably 25% mg/mL, and the concentration of the polyhexamethylene biguanide hydrochloride in the step (b') is 20-40% mg/mL, preferably 40% mg/mL.
The invention also provides the application of the shape memory polyurethane in preparing the shape memory surgical suture or the shape memory surgical suture with antibacterial property.
The shape memory polyurethane SMPU provided by the invention can automatically recover to an initial shape within the temperature range of the body temperature of a human body, has excellent shape memory function and mechanical property, and can be used for preparing an operation suture with the shape memory function.
The shape memory surgical suture provided by the invention has good biocompatibility and an excellent shape memory function, the triggering of the shape memory function mainly depends on the change of temperature, and the shape memory surgical suture has obvious advantages in wound suture, particularly in wound suture of deep organs and narrow surgical visual field.
The principle of utilizing the shape memory surgical suture line to suture wounds is as follows: before suturing, the surgical suture is heated to about 50 ℃, stretched to a required length, and then rapidly cooled to about 25 ℃ to fix the stretched length. And (3) suturing the wound under the stretched stable length, after the suturing is finished, heating the surgical suture line to the temperature, recovering to the initial length again, and gradually furling the wound to close the wound. By adopting the shape memory surgical suture line to suture wounds, the mechanical traction and necrosis of the wounds caused in the process of folding the surgical suture line after the operation (especially the operation of deep organs and narrow operation visual field) is completed can be effectively avoided, and the infection risk of the wounds is reduced; meanwhile, the operation difficulty can be reduced, and the operation time can be shortened.
In addition, the surgical suture with antibacterial performance provided by the invention has an obvious inhibiting effect on gram-negative bacteria (such as escherichia coli) and gram-positive bacteria (such as staphylococcus aureus), can obviously reduce the infection risk of a surgical site, and can obviously improve the healing capacity of a wound after suturing. The surgical suture provided by the invention can be used for suturing common clean wounds, is more suitable for suturing wounds with high infection risk and difficult postoperative care, and has wide application prospect.
The shape memory surgical suture line provided by the invention is simple in preparation method, mild in condition and suitable for expanded production.
Obviously, many modifications, substitutions, and variations are possible in light of the above teachings of the invention, without departing from the basic technical spirit of the invention, as defined by the following claims.
The present invention will be described in further detail with reference to the following examples. This should not be understood as limiting the scope of the above-described subject matter of the present invention to the following examples. All the technologies realized based on the above contents of the present invention belong to the scope of the present invention.
Drawings
FIG. 1 is a synthesis scheme of a shape memory polyurethane SMPU of the present invention.
Fig. 2 is a picture of a shape memory surgical suture SP-3 product having antimicrobial properties according to the present invention.
Fig. 3 is a picture of the shape memory surgical suture BP-1 product having antibacterial properties according to the present invention.
FIG. 4 shows the surface topography of shape memory surgical sutures BP-0, BP-1, BP-2.
FIG. 5 DSC test results (A) and breaking strength (B) of shape memory surgical sutures BP-0, BP-1, BP-2.
FIG. 6 is the result of in vitro test of shape memory performance of the shape memory surgical suture BP-1 having antibacterial properties according to the present invention.
FIG. 7 is a result of in vivo testing of shape memory properties of the shape memory surgical suture BP-1 having antibacterial properties according to the present invention.
FIG. 8 shows the surface topography of shape memory surgical sutures SP-0, SP-1, SP-2, SP-3.
FIG. 9 DSC test results (A) and breaking strength (B) of shape memory surgical sutures SP-0, SP-1, SP-2, SP-3.
FIG. 10 shape memory performance test procedure (A) and test result (B) of shape memory surgical sutures SP-0, SP-1, SP-2, SP-3.
FIG. 11 shows the in vitro antibacterial effect of the suture prepared from SMPU and BCH of the shape memory polyurethane of the present invention.
FIG. 12 shows the in vitro antibacterial effect of the suture prepared from SMPU and PHMB according to the present invention.
FIG. 13 shows the in vivo antibacterial effect of the suture prepared from SMPU and BCH of the shape memory polyurethane according to the present invention, wherein: g I denotes BP-0 surgical suture without berberine, not inoculated with bacterial group; g II represents BP-1 surgical suture without inoculation of bacterial group; g III represents a BP-0 surgical suture without berberine, inoculated with a bacterial group; g IV represents BP-1 operation suture line, inoculation bacterial group.
FIG. 14 shows the in vivo antibacterial effect of the suture prepared from SMPU and PHMB according to the present invention, wherein: group I represents SP-0 surgical suture, no bacterial Group inoculated; group II represents SP-3 surgical suture, not inoculated with bacterial Group; group III represents SP-0 surgical suture, bacterial intervention Group; group IV represents SP-3 surgical suture, bacterial intervention Group.
FIG. 15 shows the results of the biocompatibility test of the shape memory surgical sutures BP-0, BP-1.
Detailed Description
The raw materials and equipment used in the invention are known products and are obtained by purchasing commercial products.
Wherein, the polyhexamethylene biguanide hydrochloride (PHMB) is purchased from chemical reagent factories of metropolis department, and the molecular weight is 1100-1800; hydroxyl terminated polycaprolactone (OH-PCL-OH) was purchased from Perstop/Sigma Aldrich and had a molecular weight of 4000.
EXAMPLE 1 Synthesis of the shape memory polyurethane SMPU of the invention
According to the route shown in FIG. 1, the shape memory polyurethane SMPU of the invention is obtained. The method comprises the following specific steps:
adding hydroxyl-terminated polycaprolactone (OH-PCL-OH, molecular weight 4000) into a reaction bottle, dehydrating at 85 ℃, vacuumizing, protecting with argon, adding diphenylmethane diisocyanate (MDI) dehydrated at 85 ℃, stirring and reacting at 85 ℃ for 2 hours, adding Butanediol (BDO), quickly pouring the system into a preheated polytetrafluoroethylene mold, and curing and reacting in an oven at 80 ℃ for 24 hours to obtain the shape memory polyurethane SMPU.
The molar ratio of OH-PCL-OH, MDI and BDO is 1: 12.2: 41.3.
example 2 preparation of shape memory surgical suture SP-1 having antibacterial Properties according to the present invention
The shape memory polyurethane SMPU prepared in example 1 is added with dimethyl acetamide (DMAc) and stirred to be dissolved, so as to obtain a uniform SMPU solution with the SMPU concentration of 25% mg/mL, and 40mL of spinning solution is obtained.
The spinning solution was wet-spun at 25 ℃ by a wet spinning apparatus, and coagulated in a 40L coagulating bath (aqueous solution of PHMB at a concentration of 20% mg/mL) at 25 ℃ to obtain a spun fiber. The wet spinning apparatus was comprised of a 20mL syringe and a pump-driven needle (0.51 mm inner diameter) with a dope flow rate of 2.00 mm/min.
The obtained spinning fiber passes through a drawing roller (the drawing temperature is 25 ℃), a drying roller and finally is collected on a rotating mandrel to obtain the shape memory surgical suture SP-1 with antibacterial performance.
Example 3 preparation of shape memory surgical suture SP-2 having antibacterial Properties according to the present invention
The concentration of PHMB in the coagulation bath in example 2 was changed to 30% mg/mL, and the remaining raw materials and preparation process were the same as those in example 2, thereby preparing the shape memory surgical suture SP-2 having antibacterial properties according to the present invention.
Example 4 preparation of shape memory surgical suture SP-3 having antibacterial Properties according to the present invention
The concentration of PHMB in the coagulation bath in example 2 was changed to 40% mg/mL, and the remaining raw materials and preparation process were the same as those in example 2, thereby preparing the shape memory surgical suture SP-3 having antibacterial properties according to the present invention. The product picture is shown in fig. 2.
Example 5 preparation of the shape memory surgical suture SP-0 of the present invention
The concentration of PHMB in the coagulation bath in example 2 was modified to 0% mg/mL (i.e., PHMB was not contained), and the remaining raw materials and preparation process were the same as those in example 2, to obtain a shape memory surgical suture SP-0 of the present invention.
Example 6 preparation of the shape memory surgical suture BP-1 having antibacterial Properties of the present invention
The shape memory polyurethane SMPU prepared in example 1 is added with dimethyl acetamide (DMAc) and stirred to dissolve, so as to obtain a uniform SMPU solution with the SMPU concentration of 20% mg/mL. Then berberine hydrochloride (BCH) is added into the SMPU solution to obtain 40mL of spinning solution, wherein the concentration of the BCH in the spinning solution is 3% mg/mL.
The spinning solution was wet-spun at 25 ℃ by a wet spinning apparatus and coagulated in 40L of a coagulation bath (water) at 25 ℃ to obtain a spun fiber. The wet spinning apparatus was comprised of a 20mL syringe and a pump-driven needle (0.51 mm inner diameter) with a dope flow rate of 2.00 mm/min.
The obtained spinning fiber passes through a drawing roller (the drawing temperature is 25 ℃), a drying roller and finally is collected on a rotating mandrel to obtain the shape memory surgical suture BP-1 with antibacterial performance. The product picture is shown in fig. 3.
Example 7 preparation of shape memory surgical suture BP-2 having antibacterial Properties of the present invention
The concentration of BCH in the spinning solution of the embodiment 6 is modified to be 6% mg/mL, and the rest of raw materials and the preparation process are the same as those of the embodiment 6, so that the shape memory surgical suture BP-2 with antibacterial performance is prepared.
Example 8 preparation of shape memory surgical suture BP-0 of the invention
The concentration of BCH in the spinning solution of example 6 was modified to 0% mg/mL (i.e., BCH was not included), and the remaining raw materials and preparation process were the same as those of example 6, to prepare a shape memory surgical suture BP-0 of the present invention.
The beneficial effects of the present invention are demonstrated by the following experimental examples.
Experimental example 1: the BCH-added shape memory surgical suture line has the characteristics of drug loading, morphology and mechanical property
1. Experimental methods
(1) And (3) testing the drug loading capacity: each of the shape memory surgical suture and the shape memory surgical suture having antibacterial property was prepared according to the method of example, and during the spinning, the amount of the spinning liquid was calculated by weighing, and the absorbance value of the coagulation bath after spinning was measured with an ultraviolet spectrophotometer. According to the standard curve of the berberine, the content of the berberine leaked into the coagulation bath is calculated, and the actual drug-loading rate of the berberine in the fiber is calculated.
(2) The surface morphology and cross-sectional morphology of the gold-plated fibers were observed by Scanning Electron Microscopy (SEM).
(3) The mechanical properties of the fibers are tested by an electronic single yarn strength tester, the clamping distance is 50mm, the stretching speed is 100mm/min, and the fracture threshold is 85%. Differential Scanning Calorimetry (DSC) determines thermodynamic and kinetic parameters of a sample.
2. Results of the experiment
TABLE 1 results of characteristic test of each surgical suture to which BCH is added
The drug loading results are shown in table 1. It can be seen that the drug loading was higher for BP-1 compared to BP-2.
The scanning electron microscope result is shown in FIG. 4, which shows that the fiber surface of BP-0 is almost smooth, and the fiber gaps of BP-1 and BP-2 are gradually increased along with the increase of berberine concentration.
From the DSC curve (FIG. 5A), it can be seen that the melting point (T) is shown after adding berberinem) The influence of the three types of the prepared surgical suture lines is not obvious, and the T of the three types of the prepared surgical suture lines are BP-0, BP-1 and BP-2mAll are close to body temperature.
FIG. 5B shows typical tensile curves for BP-0, BP-1, and BP-2 surgical sutures. It can be seen that the content of berberine in the surgical suture has a significant influence on the mechanical properties, i.e. with the increase of berberine content in the surgical suture, the fracture strength and elongation of the surgical suture are both reduced, and the instability of the surgical suture is gradually enhanced.
Experimental example 2: the shape memory performance of the operation suture line added with BCH is tested
1. Experimental methods
A. In vitro experiments
(1) Taking an original length L0A 6cm fiberVitamin, pre-heated in an oven at 50 ℃ for 5 minutes. (2) Stretching the length of the film to 12cm at room temperature to obtain a deformed length L1. (3) Measuring its fixed length L at room temperature while waiting for its cooling2. (4) Heating again, and measuring its recovery length L3To evaluate the shape memory properties of the fibers.
B. In vivo experiments
(1) The initial length of BP-1 suture was first stretched twice and held at 50 ℃ for 10 minutes and then cooled at room temperature (approximately 25 ℃) until ready for use. (2) Three mice were randomly selected for general anesthesia and an incision of about 2cm length was made on the back with a scalpel. (3) The wound was then sutured more loosely with BP-1 suture. (4) The shape memory effect of BP-1 sutures was activated when the local temperature of the suture was raised from near body temperature to 41 ℃ with an electric hair dryer. This process roughly simulates the temperature change process of the wound site after trauma. (5) Images of the same wound at different temperatures were recorded from vertical and lateral shots.
2. Results of the experiment
The shape memory test results of the surgical suture BP-1 of the present invention are shown in FIGS. 6 and 7. It can be seen that the surgical suture line added with berberine hydrochloride has good shape memory characteristics in vivo and in vitro. The surgical suture prepared by the invention has excellent shape memory function.
The drug loading capacity, the mechanical property and the shape memory function of the surgery suture added with the BCH are comprehensively considered, and BP-1 is taken as the optimal selection of the surgery suture.
Experimental example 3: the PHMB is added, and the medicine-carrying amount, the appearance structure and the mechanical property of the shape memory operation suture line are represented
1. Experimental methods
(1) The surface and cross-sectional morphology of the SP-0, SP-1, SP-2 and SP-3 surgical sutures prepared in the examples were observed by scanning electron microscopy to determine the diameter of the suture.
(2) The melting temperature of the surgical suture was measured by DSC, and the mechanical properties of the surgical suture were measured by a single yarn strength tester.
(3) Lyophilized liquid was extracted by liquid nitrogen extraction of SP-1, SP-2 and SP-3 per unit mass, and the drug-loading amount (mg/g) of PHMB in the suture was calculated using the ultraviolet absorption of the lyophilized liquid at 230 nm.
2. Results of the experiment
Table 2 results of characteristic test of each surgical suture to which PHMB was added
As can be seen from the cross-sectional morphology of FIG. 8, there are a large number of pores in the internal structure of the surgical suture, and the fiber diameter increases with the addition of PHMB, but the effect of the change in concentration of PHMB on the fiber cross-section is not significant.
As can be seen from the DSC curves (FIG. 9A) of the surgical sutures, the melting points (T) of the four surgical suturesm) Close, remaining near body temperature, indicating that loading PHMB did not alter the crystalline behavior of the PCL segment.
As seen in fig. 9B, the surgical suture loaded with PHMB had better mechanical properties than the surgical suture without PHMB added.
Experimental example 4: shape memory performance characterization of PHMB-added shape memory surgical suture
1. Experimental methods
In vitro shape memory test: stretching the surgical suture with original length of 8cm to a stretching deformation length of 16cm, fixing, heating in a 50 deg.C oven for 5min, rapidly transferring to-20 deg.C oven, cooling for 1h, and releasing the fixation to obtain the fixed deformation length. The surgical suture with the fixed deformation length is then heated at 41 ℃ for 5min to obtain the recovered deformation length. The fixed deformation rate (R) of the fiber was calculated using the following formulaf) And recovery of deformation rate (R)r)：
Rf＝(L2-L0)/(L1-L0)×100％ (1)
Rr＝(L1-L3)/(L1-L0)×100％ (2)
Wherein L is0、L1、L2And L3The original length, the tensile deformation length, the fixed deformation length, and the recovered deformation length are respectively expressed.
2. Results of the experiment
FIG. 10 shows the shape memory performance testing process and results of a surgical suture, which is a classic thermal one-way shape memory process, including three main steps: heating and stretching, cooling and fixing, and heating again for recovery. According to RfAnd RrAs can be seen from the calculation results, the four operation sutures all have good RfAnd Rr, RfAnd RrRespectively 85% -95%; based on this, it can be seen that the shape memory performance of the surgical suture increased with increasing PHMB concentration, with the SP-3 shape memory performance being the best in the samples tested in the present invention.
The drug loading capacity, the mechanical property and the shape memory property of the surgical suture line are comprehensively considered, and SP-3 is used as the optimal selection of the surgical suture line.
Experimental example 5: antibacterial property test of shape memory surgical suture with antibacterial property
1. Experimental methods
Preparation of Luria-Bertani (LB) liquid Medium: 200mL of deionized water was added with 2.0g of NaCl, 2.0g of tryptone and 1.0g of yeast extract powder, heated and stirred, and sterilized at 115 ℃ for 20 minutes. Preparation of LB solid Medium: adding 4.0g of NaCl, 4.0g of tryptone, 2.0g of yeast extract powder and 8.0g of agar powder into 400mL of deionized water, heating and stirring, sterilizing at the high temperature of 115 ℃ for 20 minutes, and pouring into a sterile culture dish when the temperature is cooled to 60 ℃.
Experimental bacteria: gram-negative escherichia coli (e.coli) and gram-positive staphylococcus aureus (s.aureus) were selected as representative bacteria.
(1) In vitro antibacterial experiments:
a. the experimental steps of the sample to be tested is the operation suture line added with BCH: (1) the two strains were cultured in Luria-Bertani (LB) medium at 37 ℃ for 12 hours, and the stock suspension was diluted to 1X 10 with PBS buffer at pH 7.05～5×105CFU/ml; (2) 20mg of BP-0, BP-1 and BP-2 fibers were placed at a height of 1.5m, respectivelyl PBS, then adding 1.0ml of diluted bacterial suspension into the test bottle and culturing for 12 h; (3) diluting the co-cultured bacterial suspension into various concentrations, measuring the number of bacteria, coating 100ml of bacterial suspension on an LB agar plate, and incubating overnight at 37 ℃; (4) the number of colonies on the LB agar plate was observed and counted. Blank control is a bacterial suspension without fiber.
b. The experimental steps of the PHMB-added operation suture line are as follows: the two strains were cultured in LB liquid medium at 37 ℃ respectively. Mu.l of overnight-cultured suspension of escherichia coli (e.coli) and staphylococcus aureus (s.aureus) was diluted with PBS buffer having pH of 7.4 to obtain 5mL of diluted bacterial solution (about 10 mL)4CFU/mL). SP-0, SP-1, SP-2 and SP-3 surgical sutures were each 35mg, and were placed in a diluted bacterial solution and cultured at 37 ℃ for 24 hours. After 24h, 100. mu.L of the suspension was removed and evenly spread on solid agar medium. Subsequently, the plates were incubated overnight at 37 ℃ and then the growth of the bacteria was observed and photographed.
(2) In vivo antibacterial experiments:
a. the experimental steps of the sample to be tested is the operation suture line added with BCH: (1) the surgical suture was stretched to twice the original length and held at 50 ℃ for 5 minutes, and then cooled at room temperature (25 ℃. + -. 2 ℃) until ready for use. (2) Mice were anesthetized by intraperitoneal injection with 3% sodium pentobarbital at a dose of 1 ml/kg. (3) The hair of the experimental mouse was carefully shaved with an electric razor and then the unclothed mouse hair was thoroughly removed with depilatory cream. (4) Sequentially applying iodophor and alcohol solution for skin disinfection. (5) Each mouse was made a 1.5cm long incision along the central axis of the dorsal trunk using a scalpel, the depth of the wound penetrating the entire skin. (6) BP-0 or BP-1 surgical suture prepared in example was threaded on a surgical needle, and wound was sutured by continuous suturing. (7) Mice were randomized into 4 groups: group I (wounds were closed with BP-0, wounds were not inoculated with bacteria); group II (wounds were closed with BP-1, wounds were not inoculated with bacteria); group III (wounds were closed with BP-0 prior to bacterial inoculation); group IV (wounds were closed with BP-1 prior to bacterial inoculation). For groups III and IV, the incision site was treated by applying 10. mu.l of Staphylococcus aureus suspension (1X 10)8) And (5) performing inoculation infection. For I and II, the same volume (10. mu.l) of physiological saline was used as a blank. (8) General image data of wounds were taken with a Canon IXUS230HS camera, Japan, while infrared thermographic data was acquired with a FLIR-T62101 infrared camera.
b. The experimental steps of the PHMB-added operation suture line are as follows: 4 groups of mice were anesthetized, 6 per group, and then the back hair was shaved, depilated with depilatory cream, and washed with povidone iodine. A full-thickness longitudinal skin incision 1.5cm long was made in the back of the mouse. Each group of skin incisions were quickly closed with a different suture: group I: SP-0 suture group, wound is not inoculated with bacteria; and (II) group: SP-3 suture group, wound is not inoculated with bacteria; group III: SP-0 suture plus bacterial intervention group; group IV: SP-3 suture + bacterial intervention group. The groups I and II do not undergo bacterial infection operation, and the skin suture of the mice in the groups III and IV is applied at a concentration of 1 × 1075 mu L of CFU/mL golden yellow staphylococcus culture solution is used for shooting the wound surface by a digital camera and a thermal infrared imager every 1 day.
2. Results of the experiment
The results of in vitro antibacterial experiments are shown in fig. 11 and 12, and it can be seen that the surgical suture containing berberine and polyhexamethylene biguanide hydrochloride obviously inhibits the growth and reproduction of bacteria in the culture dish, and has good in vitro antibacterial ability. The description shows that (1) the surgical suture prepared by taking the shape memory polyurethane SMPU and the BCH as raw materials can effectively inhibit the growth of staphylococcus aureus (S.aureus) and escherichia coli (E.coli), and particularly, when the concentration ratio of the SMPU to the BCH in the raw material spinning solution is 20: 3, the inhibition effect of the obtained operation suture BP-1 on bacteria is obviously improved; (2) the surgical suture prepared by taking the shape memory polyurethane SMPU and PHMB as raw materials can also effectively inhibit the growth of staphylococcus aureus (S.aureus) and escherichia coli (E.coli), and particularly, when the concentration ratio of the SMPU to the PHMB in the raw material spinning solution is 25:40, the inhibition effect of the obtained surgical suture SP-3 on bacteria is obviously improved.
The results of in vivo antibacterial experiments are shown in fig. 13 and fig. 14, and it can be seen that the surgical suture containing berberine and polyhexamethylene biguanide hydrochloride significantly promotes the healing process of infected wound, and has good in vivo antibacterial ability. The surgical suture prepared by taking the shape memory polyurethane SMPU and the BCH as raw materials can effectively inhibit the infection of staphylococcus aureus (S.aureus) on mouse wounds and promote wound healing, and particularly, when the concentration ratio of the SMPU to the BCH in the raw material spinning solution is 20: 3, the anti-infection and healing capabilities of the obtained surgical suture BP-1 on the wound are obviously improved; (2) the surgical suture prepared by taking the shape memory polyurethane SMPU and PHMB as raw materials can also effectively inhibit infection of staphylococcus aureus (S.aureus) on mouse wounds and promote wound healing, and particularly, when the concentration ratio of the SMPU to the PHMB in the raw material spinning solution is 25:40, the anti-infection and healing capacity of the obtained surgical suture SP-3 on the wounds is remarkably improved.
Experimental example 6: biocompatibility test of the shape memory surgical suture having antibacterial property of the present invention
1. Experimental methods
(1) Randomly selecting three mice to carry out in-vivo biocompatibility experiments; (2) the mice were anesthetized by intraperitoneal injection of 3% sodium pentobarbital at a dose of 1 ml/kg; (3) after anesthesia, skin preparation and iodophor disinfection are carried out on the buttocks on the two sides of the mouse; (4) measuring a 3cm long BP-1 suture line, and implanting the suture line into the left gluteus of the mouse; in order to avoid the movement of the suture, a surgical knot needs to be made to fix the suture to the gluteus muscles; (5) implanting the right gluteus of the mouse into a control group by using a BP-0 suture line; (6) on day 3 and 7 post-surgery, 1 mouse was sacrificed each and the tissue biocompatibility of the suture was observed with H & E staining.
2. Results of the experiment
As shown in fig. 15, both surgical sutures were surrounded by a large number of inflammatory cells at day 3 after the surgical suture was implanted, indicating that the fibers as foreign substances stimulate the surrounding tissues to generate a more severe inflammatory reaction at the early stage of suture implantation regardless of the amount of berberine hydrochloride contained in the surgical suture. However, as the implantation time was gradually increased, the inflammatory reaction of BP-1 was almost disappeared by day 7, and the result showed that berberine hydrochloride had a certain anti-inflammatory effect. The shape memory surgical suture with antibacterial performance prepared by the invention is basically free from cytotoxicity and has good biocompatibility.
In summary, the present invention provides a shape memory polyurethane SMPU that can automatically return to an original shape within a temperature range of a human body temperature. The shape memory surgical suture line is prepared by wet spinning and taking the shape memory polyurethane SMPU as a raw material, has a special shape memory function, has an excellent closing effect on ligation hemostasis and suturing in minimally invasive surgeries such as endoscopic and laparoscopic surgeries, can effectively avoid mechanical wound traction necrosis caused in the process of furling the surgical suture line after the surgeries are finished, and reduces the risk of wound infection; meanwhile, the operation difficulty can be reduced, and the operation time can be shortened. The shape memory surgical suture with antibacterial property is further prepared by taking the shape memory polyurethane SMPU and antibacterial drugs as raw materials, and the surgical suture has obvious inhibition effect on gram-negative bacteria (such as escherichia coli) and gram-positive bacteria (such as staphylococcus aureus), can obviously reduce the infection risk of a surgical site, and obviously improves the healing capacity of a wound after suturing. The surgical suture provided by the invention can be used for suturing common clean wounds, is more suitable for suturing wounds with high infection risk and difficult postoperative care, and has wide application prospect.
Claims (10)
1. A shape memory polyurethane characterized by: the structure of the shape memory polyurethane is shown as formula I:
2. shape memory polyurethane according to claim 1, characterized in that: the shape memory polyurethane is prepared by taking hydroxyl-terminated polycaprolactone, diphenylmethane diisocyanate and butanediol as raw materials;
wherein, the mol ratio of the hydroxyl-terminated polycaprolactone to the diphenylmethane diisocyanate to the butanediol is preferably 1: (7-13): (36-42), more preferably 1: 12.2: 41.3
And/or, the molecular weight of the hydroxyl-terminated polycaprolactone is preferably 2000-.
3. A method for preparing a shape memory polyurethane according to any one of claims 1-2, characterized in that: the method comprises the following steps: (1) reacting hydroxyl-terminated polycaprolactone with diphenylmethane diisocyanate; (2) adding butanediol into the system obtained in the step (1) for reaction to obtain the butanediol-containing catalyst;
preferably, in the step (1), the reaction is carried out under the protection of inert gas, the reaction temperature is 80-90 ℃, and the reaction time is 1-3 hours; in the step (2), the reaction is carried out under the protection of inert gas, the reaction temperature is 70-90 ℃, and the reaction time is 20-30 hours;
more preferably, in the step (1), the reaction temperature is 85 ℃ and the reaction time is 2 hours; in the step (2), the reaction temperature is 80 ℃, and the reaction time is 24 hours.
4. A shape memory surgical suture, characterized by: the shape memory surgical suture is prepared by using the shape memory polyurethane of any one of claims 1-2 as a raw material.
5. A shape memory surgical suture having antimicrobial properties, characterized by: the shape memory surgical suture with antibacterial property is prepared by taking the shape memory polyurethane as claimed in any one of claims 1-2 and antibacterial drugs as raw materials.
6. Shape memory surgical suture having antibacterial properties, according to claim 5, characterized in that: the antibacterial drug is one or two of polyhexamethylene biguanide hydrochloride and berberine hydrochloride.
7. A shape memory surgical suture having antimicrobial properties according to claim 6, wherein: the antibacterial agent is polyhexamethylene biguanide hydrochloride, and the concentration ratio of the shape memory polyurethane to the antibacterial agent in the raw materials is 25: (20-40), preferably 25: 40;
or, the antibacterial drug is berberine hydrochloride, and the concentration ratio of the shape memory polyurethane to the antibacterial drug in the raw materials is 20: (3-6), preferably 20: 6.
8. A method for preparing the shape memory surgical suture described in claim 4 or the shape memory surgical suture having antibacterial property described in any one of claims 5 to 7, characterized in that: the method is a wet spinning process and comprises the following steps:
(a) dissolving the raw materials in an organic solvent to obtain a spinning solution; the raw material is the shape memory polyurethane of any one of claims 1 to 2, or the raw material is the shape memory polyurethane of any one of claims 1 to 2 and berberine hydrochloride;
(b) carrying out wet spinning on the spinning solution, and then solidifying in a coagulating bath to obtain spinning fibers; the coagulating bath is water;
(c) stretching and drying the spinning fiber to obtain the fiber;
or, the method is a wet spinning process, comprising the steps of:
(a') dissolving the shape memory polyurethane according to any one of claims 1 to 2 in an organic solvent to obtain a spinning dope;
(b') carrying out wet spinning on the spinning solution, and then solidifying in a coagulating bath to obtain spinning fibers; the coagulating bath is an aqueous solution of polyhexamethylene biguanide hydrochloride;
and (c') stretching and drying the spinning fiber to obtain the fiber.
9. The method of claim 8, wherein: the organic solvent of step (a) or step (a') is dimethylacetamide; and/or, the temperature of the wet spinning in the step (b) or the step (b') is 20-30 ℃, preferably 25 ℃, and the solidification temperature is 20-30 ℃, preferably 25 ℃; and/or, the stretching temperature of the step (c) or the step (c') is 20-30 ℃, preferably 25 ℃;
and/or, the concentration of the shape memory polyurethane in the spinning solution in the step (a) is 20-25% mg/mL, preferably 20% mg/mL, and the concentration of the berberine hydrochloride is 3-6% mg/mL, preferably 3% mg/mL; the concentration of the shape memory polyurethane in the spinning solution in the step (a ') is 20-25% mg/mL, preferably 25% mg/mL, and the concentration of the polyhexamethylene biguanide hydrochloride in the step (b') is 20-40% mg/mL, preferably 40% mg/mL.
10. Use of the shape memory polyurethane of any one of claims 1 to 2 for the preparation of the shape memory surgical suture of claim 4 or the shape memory surgical suture with antibacterial properties of any one of claims 5 to 7.
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