CN110409014A - The nanofiber and its preparation and application that a kind of SAB and heparin are modified jointly - Google Patents

The nanofiber and its preparation and application that a kind of SAB and heparin are modified jointly Download PDF

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Publication number
CN110409014A
CN110409014A CN201910509577.8A CN201910509577A CN110409014A CN 110409014 A CN110409014 A CN 110409014A CN 201910509577 A CN201910509577 A CN 201910509577A CN 110409014 A CN110409014 A CN 110409014A
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sab
solution
msn
nanofiber
shell
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CN201910509577.8A
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Chinese (zh)
Inventor
莫秀梅
匡海珠
陆树洋
王尧
石宇
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Zhongshan Hospital Fudan University
Donghua University
National Dong Hwa University
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Zhongshan Hospital Fudan University
Donghua University
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Priority to CN201910509577.8A priority Critical patent/CN110409014A/en
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • 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
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02—Inorganic materials
    • A61L27/025—Other specific inorganic materials not covered by A61L27/04 - A61L27/12
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • 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
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/14—Macromolecular materials
    • A61L27/18—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • 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
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/14—Macromolecular materials
    • A61L27/20—Polysaccharides
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • 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
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/14—Macromolecular materials
    • A61L27/22—Polypeptides or derivatives thereof, e.g. degradation products
    • A61L27/24—Collagen
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • 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
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/507—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials for artificial blood vessels
    • 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
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • 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
    • D01F8/02—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from cellulose, cellulose derivatives, or proteins
    • 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
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • 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
    • A61L2400/00—Materials characterised by their function or physical properties
    • A61L2400/12—Nanosized materials, e.g. nanofibres, nanoparticles, nanowires, nanotubes; Nanostructured surfaces

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Transplantation (AREA)
  • Epidemiology (AREA)
  • Dermatology (AREA)
  • Animal Behavior & Ethology (AREA)
  • Medicinal Chemistry (AREA)
  • Public Health (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Biophysics (AREA)
  • Vascular Medicine (AREA)
  • Inorganic Chemistry (AREA)
  • Materials For Medical Uses (AREA)

Abstract

The nanofiber and its preparation modified jointly the present invention relates to a kind of SAB and heparin and application.The fiber includes shell and sandwich layer, and shell includes SAB-MSN and high molecular polymer, and sandwich layer includes heparin.This method comprises: prepared by SAB-MSN, and shell layer spinning solution preparation, the preparation of sandwich layer solution, nanofiber preparation.This method is simple and efficient, cheap.The nanofiber sandwich layer shell carries medicine simultaneously, can reach dual-sustained-release effect, and have good biocompatibility and blood compatibility, have fabulous application prospect in intravascular tissue engineering.

Description

The nanofiber and its preparation and application that a kind of SAB and heparin are modified jointly
Technical field
The invention belongs to artificial blood vessel's material and its preparation and application field, in particular to one kind has SAB and heparin common The nanofiber of modification and its preparation and application.
Background technique
Coronary heart disease and peripheral vascular disease have become the serious burden of human health.According to statistics, have in worldwide About 10,000,000 vascular operations, the transplanting of self and allogeneic blood vessels cannot provide enough Vascular implantation human bodies, therefore grind Study carefully artificial minute vessel clinically to have great importance.Early period needs strong after artificial minute vessel transplanting enters animal model Anticoagulant functions, prevent the generation of acute thrombus, while needing to promote the fast-growth of endothelial cell to be proliferated, and artificial small Blood vessel migration.But so far, the implantation of small-caliber vascular usually fails, after grafting vessel enters in vivo it occur frequently that Acute thrombus largely reduces the patency rate of small-caliber vascular.And there are many more artificial minute vessels due to material property The reason of, prevent manually small-caliber vascular inner wall is from quick endothelialization, so as to cause the hyperplasia of smooth muscle cell, so that Artificial small-caliber vascular restenosis, reduces patency rate.The problem of artificial blood vessel exists in clinical practice is not still filled The solution divided.
Summary of the invention
The nanofiber modified jointly technical problem to be solved by the invention is to provide a kind of SAB and heparin and its preparation And application, to overcome, generation acute thrombus and blood vessel cannot be quickly interior in small-caliber vascular implantation human body in the prior art The defect of skin.
A kind of nanofiber of the invention, the fiber include shell and sandwich layer, and the shell includes polydanshinolate- Meso-porous nano silicon and high molecular polymer, the sandwich layer include heparin.
The high molecular polymer is PLCL and collagen, PLGA/Silk, PLLA/COL or PLCL/Silk.
The mass ratio of the PLCL and collagen is 5~8:5~2.
A kind of preparation method of nanofiber of the invention, comprising:
(1) polydanshinolate SAB is dissolved in solvent, obtains the SAB solution that concentration is 1-4mg/ml, is received mesoporous Rice silicon MSN is scattered in above-mentioned SAB solution, and ultrasound stirs, and centrifugation obtains SAB-MSN, and wherein the mass ratio of SAB and MSN is 1 ~4:1~4；
(2) SAB-MSN in step (1) is dissolved in solvent, is ultrasonically treated, obtain the SAB-MSN that concentration is 1-3mg/ml High molecular polymer is dissolved in above-mentioned SAB-MSN solution, obtains shell layer spinning solution by solution；Wherein high molecular polymer with The mass ratio of SAB-MSN is 0.8~1:0.01~0.03；
(3) in a solvent by heparin dissolution, sandwich layer solution is obtained, shell layer spinning solution carries out same in the solution and step (2) Axis electrostatic spinning obtains nanofiber, and the mass fraction of heparin is 10-20% in center core layer solution.
Solvent is ethyl alcohol in the step (1)；Concentration of the MSN in SAB solution is 1-4mg/ml.
Whipping temp is room temperature, mixing time 22-26h in the step (1).
Centrifugal rotational speed is 13000 revs/min in the step (1), and centrifugation time is 30 minutes.
Solvent is HFIP in the step (2).
High molecular polymer is PLCL and collagen, PLGA/Silk, PLLA/COL or PLCL/Silk in the step (2). It can guarantee that preparation has the nanofiber of core -shell structure as internal layer.
The mass ratio of the PLCL and collagen is 5~8:5~2.
Solvent is RO water in the step (3).
The technological parameter of coaxial electrostatic spinning in the step (3) are as follows: voltage is 14~15kV, shell layer spinning solution and sandwich layer The velocity ratio of solution is 1~1.5:0.1~0.15.
A kind of application of nanofiber of the invention as intravascular stent internal layer.Such as nanofiber is as in intravascular stent Layer can be used for intravascular stent and use in revascularization.
The nanofiber with core -shell structure that the present invention is prepared by coaxial electrostatic spinning technology is carried in sandwich layer respectively There is the heparin with anti-blood effect, the SAB for promoting endothelial cell adherency and proliferation is loaded in shell.
Beneficial effect
The present invention is spun into the shell of the nanofiber with core -shell structure after loading SAB with meso-porous nano silicon particle, in this way SAB can reach a releasing effect steady in a long-term, and the SAB of release can not only promote the proliferation and migration of endothelial cell, together When can also protect and reduce endothelial cell and have damage and apoptosis caused by oxidative stress.Simultaneously in the nanometer with core -shell structure The sandwich layer of fiber is loaded with heparin, since with phenomenon of burst release, heparin initial release amount is larger, can before transplantation the phase play resist it is acute The effect of thrombus.Simultaneously in material selection, by synthetic material poly-lactic acid-caprolactone (PLCL) and natural material collagen (COL) Mixing, enhances the biocompatibility of synthetic material, is more suitable for cell in the growing multiplication of material.It is this that there is promotion endothelial cell Growing multiplication migration and the functionalized nano-fiber with good blood compatibility as blood vessel inner layer be prepared as studying it is small Calibre can improve patency rate in clinical trial and provide a kind of simply and effectively preparation thinking.
Detailed description of the invention
Fig. 1 is the schematic diagram that shell layer spinning solution of the present invention and sandwich layer solution carry out coaxial electrostatic spinning.
Fig. 2 (A) is the transmission plot that the MSN of SAB is carried in embodiment 1；It (B) is that nanofiber is in embodiment 1 in scale Transmission plot under 0.5 μm；It (C) is transmission plot of the nanofiber in the case where scale is 0.2 μm in embodiment 1.
Fig. 3 is heparin and elution profiles of the polydanshinolate SAB in 30 days in nanofiber in embodiment 1.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited Range.
Embodiment 1
(1) SAB-MSN is prepared, SAB is dissolved in ethyl alcohol at room temperature, concentration 4mg/ml, then, by meso-porous nano Silicon (MSN) is scattered in the SAB solution of preparation, and concentration 4mg/ml, ultrasound makes MSN be uniformly dispersed.SAB and MSN mixture exists After stirring 24 hours at room temperature, centrifugation obtains sediment SAB-MSN, and revolving speed is 13000 revs/min, and centrifugation time is 30 minutes.
(2) shell spinning solution is prepared, SAB-MSN in step (1) is dispersed in HFIP, concentration 2mg/ml, then It is evenly dispersed to ensure through ultrasonic vibration treatment 30 minutes, obtain SAB-MSN dispersion solution；By 0.8g PLCL and 0.2g collagen It is dissolved in the SAB-MSN dispersion solution of 10mL, obtains shell spinning solution.
(3) nanofiber is prepared, heparin is dissolved in RO water, heparin mass fraction is 15%, obtains sandwich layer solution, should Shell spinning solution uses coaxial electrostatic spinning technology to prepare shell-core nanofiber as blood vessel inner layer in solution and step (2), spins Voltage when silk is 14kV, and shell solution flow velocity is 1.0mL/h, and the flow velocity of sandwich layer solution is 0.1mL/h.Obtain with SAB and The nanofiber that heparin is modified jointly is as intravascular stent internal layer.
Fig. 2 (B) shows: nanofiber has core -shell structure.
Fig. 2 (C) shows: SAB-MSN is loaded into the shell of nanofiber, and is observed that and is inlaid in fiber surface SAB-MSN。
Fig. 3 shows: SAB slowly discharges, and does not have phenomenon of burst release.Cumulative release reaches total amount in 10 days 38%, then rate of release is slack-off, and total burst size reaches the 56% of total drugloading rate in 30 days.It is considerable in the elution profiles of heparin It observes heparin first day and releases the 36% of total amount, have apparent phenomenon of burst release, burst size then can be observed in 30 days Stablize and increases.When off-test, the cumulative release amount of heparin is up to the 68% of total amount.
Embodiment 2
According to embodiment 1, " heparin will be dissolved in RO water, heparin mass fraction is 15% " in 1 step of embodiment (3) Be changed to " heparin is dissolved in RO water, heparin mass fraction is 10% ", remaining is same as Example 1, obtain with SAB and The nanofiber that heparin is modified jointly is as intravascular stent internal layer.
Comparative example 1
(1) shell spinning solution is prepared, by 0.8g PLCL and 0.2g collagenolysis in 10mL HFIP, obtains shell spinning Silk solution.
(2) nanofiber is prepared, heparin is dissolved in RO water, the mass fraction of heparin is 15%, the solution and step (1) shell spinning solution uses coaxial electrostatic spinning technology to prepare shell-core nanofiber as blood vessel inner layer in, voltage when spinning For 14kV, shell solution flow velocity is 1.0mL/h, and the flow velocity of sandwich layer solution is 0.1mL/h.Obtain heparin modified nanofiber. The release profiles that such nanofiber carries heparin are similar with the release profiles of heparin in figure (3), have obvious initial burst phenomenon, For needing drug that is gentle, discharging for a long time, such load prescription formula is simultaneously improper.
Common coaxial electrostatic spinning technology usually only carries medicine in sandwich layer, and such load prescription formula is existing with drug initial burst As, and it is an advantage of the present invention that the shell in nanofiber is loaded with the drug adsorbed by nano-silicon, while sandwich layer is also loaded with medicine Object can not only achieve the effect that dual-sustained-release, and be loaded into shell by the drug that nano-silicon adsorbs to reach gentle, long-term Releasing effect.

Claims (9)

1. a kind of nanofiber, which is characterized in that the fiber includes shell and sandwich layer, and the shell includes salvia root polyphenol acid Salt-meso-porous nano silicon and high molecular polymer, the sandwich layer include heparin.
2. fiber according to claim 1, which is characterized in that the high molecular polymer is PLCL and collagen, PLGA/ Silk, PLLA/COL or PLCL/Silk.
3. fiber according to claim 1, which is characterized in that the mass ratio of the PLCL and collagen is 5~8:5~2.
4. a kind of preparation method of nanofiber, comprising:
(1) polydanshinolate SAB is dissolved in solvent, the SAB solution that concentration is 1-4mg/ml is obtained, by meso-porous nano silicon MSN is scattered in above-mentioned SAB solution, and ultrasound stirs, and centrifugation obtains SAB-MSN, and wherein the mass ratio of SAB and MSN is 1~4: 1~4；
(2) SAB-MSN in step (1) is dissolved in solvent, is ultrasonically treated, obtain the SAB-MSN solution that concentration is 1-3mg/ml, High molecular polymer is dissolved in above-mentioned SAB-MSN solution, shell layer spinning solution is obtained；Wherein high molecular polymer and SAB- The mass ratio of MSN is 0.8~1:0.01~0.03；
(3) in a solvent by heparin dissolution, sandwich layer solution is obtained, shell layer spinning solution in sandwich layer solution and step (2) is carried out same Axis electrostatic spinning obtains nanofiber, and the mass fraction of heparin is 10-20% in center core layer solution.
5. method according to claim 4, which is characterized in that solvent is ethyl alcohol in the step (1)；MSN is in SAB solution Concentration be 1-4mg/ml.
6. method according to claim 4, which is characterized in that whipping temp is room temperature in the step (1), and mixing time is 22-26h；Centrifugal rotational speed is 13000 revs/min, and centrifugation time is 30 minutes.
7. method according to claim 4, which is characterized in that solvent is HFIP in the step (2)；High molecular polymer is PLCL and collagen, PLGA/Silk, PLLA/COL or PLCL/Silk.
8. method according to claim 4, which is characterized in that solvent is RO water in the step (3)；Coaxial electrostatic spinning Technological parameter are as follows: voltage is 14~15kV, and the velocity ratio of shell layer spinning solution and sandwich layer solution is 1~1.5:0.1~0.15.
9. a kind of application of nanofiber as described in claim 1 as intravascular stent internal layer.
CN201910509577.8A 2019-06-13 2019-06-13 The nanofiber and its preparation and application that a kind of SAB and heparin are modified jointly Pending CN110409014A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111973313A (en) * 2019-05-06 2020-11-24 深圳市罗湖区人民医院 Small-caliber artificial blood vessel and preparation method thereof
CN115990293A (en) * 2023-01-30 2023-04-21 博裕纤维科技（苏州）有限公司 Preparation method of medical multi-layer self-supporting medicine-carrying shell-core structure nanofiber tube

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101509153A (en) * 2009-03-23 2009-08-19 东华大学 Method for producing shell-core structure medicament nano-fibre with coaxial electrostatic spinning technology
CN105233339A (en) * 2015-11-06 2016-01-13 东华大学 Preparation method of heparin and twin factor synergistically regulated P(LLA-CL)/collagen bilayer intravascular stent
CN108992711A (en) * 2018-07-06 2018-12-14 东华大学 A kind of internal layer passes through the preparation method for the double-layer artificial small-caliber vascular modified

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101509153A (en) * 2009-03-23 2009-08-19 东华大学 Method for producing shell-core structure medicament nano-fibre with coaxial electrostatic spinning technology
CN105233339A (en) * 2015-11-06 2016-01-13 东华大学 Preparation method of heparin and twin factor synergistically regulated P(LLA-CL)/collagen bilayer intravascular stent
CN105233339B (en) * 2015-11-06 2018-04-20 东华大学 A kind of preparation method of heparin and P (LLA CL)/collagen bilayer intravascular stent of twin factor coordinated regulation
CN108992711A (en) * 2018-07-06 2018-12-14 东华大学 A kind of internal layer passes through the preparation method for the double-layer artificial small-caliber vascular modified

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HAIZHU KUANG等: "A Method for Preparation of an Internal Layer of Artificial Vascular Graft Co-Modified with Salvianolic Acid B and Heparin", 《ACS APPLIED MATERIALS & INTERFACES》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111973313A (en) * 2019-05-06 2020-11-24 深圳市罗湖区人民医院 Small-caliber artificial blood vessel and preparation method thereof
CN115990293A (en) * 2023-01-30 2023-04-21 博裕纤维科技（苏州）有限公司 Preparation method of medical multi-layer self-supporting medicine-carrying shell-core structure nanofiber tube

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