CN106480537A - A kind of method that gelatin is grafted PLGA electrospinning fibre - Google Patents

A kind of method that gelatin is grafted PLGA electrospinning fibre Download PDF

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Publication number
CN106480537A
CN106480537A CN201611187472.8A CN201611187472A CN106480537A CN 106480537 A CN106480537 A CN 106480537A CN 201611187472 A CN201611187472 A CN 201611187472A CN 106480537 A CN106480537 A CN 106480537A
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CN
China
Prior art keywords
plga
gelatin
solution
electrospinning
drying
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CN201611187472.8A
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Chinese (zh)
Inventor
李佳
肖瑶
郑卫
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HARBIN TECHNOLOGY UNIV
Harbin University of Science and Technology
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HARBIN TECHNOLOGY UNIV
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Priority to CN201611187472.8A priority Critical patent/CN106480537A/en
Publication of CN106480537A publication Critical patent/CN106480537A/en
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    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/96Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from other synthetic polymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91Polymers modified by chemical after-treatment
    • C08G63/912Polymers modified by chemical after-treatment derived from hydroxycarboxylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08HDERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H1/00Macromolecular products derived from proteins
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D1/00Treatment of filament-forming or like material
    • D01D1/02Preparation of spinning solutions
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00Formation of filaments, threads, or the like
    • D01D5/0007Electro-spinning
    • D01D5/0015Electro-spinning characterised by the initial state of the material
    • D01D5/003Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Textile Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • Materials Engineering (AREA)
  • Artificial Filaments (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)

Abstract

The present invention is to provide a kind of method that gelatin is grafted PLGA electrospinning fibre.PLGA solution is obtained including PLGA is dissolved in solvent;After aqueous slkali reaction, drying and forming-film;Film is activated;Soak in gelatin warm water solution, dry;Being dissolved in solvent carries out the processes such as electrospinning.The present invention passes through chemical graft method, gelatin is chemically bonded on PLGA and forms polymer, then be spun into fiber by electrospinning process.The method preparation process is simple, less demanding to reaction condition, is easier to realize.The fiber obtained by the method has good mechanical property, hydrophily and biocompatibility, is with a wide range of applications in field of tissue engineering technology.

Description

A kind of method that gelatin is grafted PLGA electrospinning fibre
Technical field
The present invention relates to a kind of method that gelatin is grafted PLGA electrospinning fibre.
Background technology
The nanofiber prepared by electrospinning process has that porosity is high, specific surface area is big, fiber fine degree with equal The advantages of one property is high, draw ratio is big, is widely applied prospect so as to impart electrospun fibers, has at home and abroad caused wide General concern.
Nano fiber scaffold and the extracellular matrix prepared due to electrostatic spinning with similitude on morphosis, therefore Can be applicable in organizational project.Can be used for the polymeric material including collagen of tissue engineering bracket, PLA, gather in oneself Ester, gelatin, PGA etc., they are respectively provided with biocompatibility and degradable feature.However, these materials are applied individually to any Field of biomedical materials, due to the defect of nature, the function needed for possibly cannot realizing, for example, PLGA surface lacks There is certain difference compared with natural macromolecular in cell recognition factors and biocompatible functional group, its biocompatibility.Cause This, improves the histocompatbility of PLGA further, improves biologically active, and the application for extending which in biomedical sector is particularly weighed Will.
Chemical graft process is that occur chemistry anti-using the reactive group of material surface with the monomer being grafted or macromolecular chain Should, and then realize a kind of method of modifying of surface grafting.Using chemical graft process to material modification, between modified material and base material It is connected by chemical bond, modified material stability in the substrate, and then the performance of raising material can be improved, is being given birth to meeting which Application in terms of thing medical science.
Content of the invention
It is an object of the invention to provide a kind of method that gelatin is grafted PLGA electrospinning fibre, the fiber obtained with the method Its hydrophily and cell compatibility can be improved under conditions of PLGA mechanical property is not reduced, the method preparation process is simple, right Reaction condition is less demanding, is easier to realize, is with a wide range of applications in field of tissue engineering technology.
The object of the present invention is achieved like this:
(1)PLGA is dissolved completely in solvent, obtains the PLGA solution of homogeneous transparent;
(2)Above-mentioned solution and certain density aqueous slkali were reacted after certain time, molten with watery hydrochloric acid and distilled water flushing respectively Liquid is constant to pH value, then drying and forming-film;
(3)Above-mentioned desciccator diaphragm is immersed in activator solution, is taken out after certain time, with distilled water flushing, drying;
(4)Again above-mentioned desciccator diaphragm is transferred in certain density gelatin warm water solution and soaks, take out after certain time, with temperature steaming Distilled water rinsing, drying;
(5)Dried polymer is dissolved in solvent spinning solution is obtained, adjusting electrospinning parameters carries out electrospinning, obtain gelatin grafting PLGA electrospinning fibre.
The present invention can also include:
1st, the solvent of the dissolving PLGA is trifluoroethanol, and resulting solution concentration is 10%w/v;
2nd, the aqueous slkali is the sodium hydrate aqueous solution of 50mg/mL, and the reaction time is 1h, and drying means is:40 DEG C of vacuum are done Dry 12h;
3rd, the activator solution is N, the N of 100mg/mL '-carbonyl dimidazoles(CDI)Ethanol solution, soaking at room temperature, living The change time is 4h-8h, and drying condition is:40 DEG C of vacuum drying 2h;
4th, the concentration of the gelatin warm water solution is 50mg/mL, and temperature is 35 DEG C, and soak time is 12h-24h, temperature distillation water temperature Spend for 35 DEG C, drying means is:Room temperature in vacuo dries 24h;
5th, the solvent of the dissolving polymer is trifluoroethanol, and the electrospinning parameters are:Concentration of dope 10%w/v-16%w/v, Voltage 13-17kV, spinning flow velocity 0.3-0.5mL/h, reception are apart from 10-14cm.
Technical problem solved by the invention is to provide a kind of method that gelatin is grafted PLGA electrospinning fibre, is connect by chemistry Branch, first activates PLGA with alkali, makes PLGA produce carboxyl, then with a kind of activator CDI activated carboxyl with stronger reactivity, Carbonylic imidazole intermediate is generated, is then reacted with gelatin and gelatin grafting PLGA polymer is generated, last electrospinning obtains fiber.Use this PLGA is chemically bound together by method with gelatin, can under conditions of PLGA mechanical property is not reduced, improve its hydrophily and Cell compatibility.
Activator CDI used by the present invention has stronger chemical reactivity, is widely used as the adhesive of enzyme and protein, Antibioticses synthetic drug intermediate, especially as the bonding agent of synthesis polypeptide compound.Research discovery in recent years, CDI Have the advantages that reactivity is strong, widely applicable, course of reaction low toxicity, product purification are simple as activator.The method synthesis Nanofiber, is with a wide range of applications in field of tissue engineering technology.
Description of the drawings
In Fig. 1, a and b is respectively the FTIR spectrum that pure PLGA and gelatin are grafted PLGA polymer(FT-IR)Figure;
Fig. 2 is grafted the ESEM of PLGA electrospinning fibre for gelatin(SEM)Photo;
Fig. 3 a and Fig. 3 b is respectively the water contact angle test photo of PLGA raw material and gelatin grafting PLGA electrospinning fibre, wherein Fig. 3 a For before modified, being 111.47 ° ± 0.20 °;Fig. 3 b for modified, 85.23 ° ± 0.20 °.
Specific embodiment
The present invention is further elaborated for citing below.
PLGA is dissolved completely in trifluoroethanol, obtains PLGA solution of the concentration for 10%w/v homogeneous transparent;Will be above-mentioned Solution reacts 1h with the sodium hydrate aqueous solution of 50mg/mL, constant to pH value with watery hydrochloric acid and distilled water flushing solution respectively, and 40 DEG C vacuum drying 12h;Take out in the CDI absolute ethyl alcohol activator solution of desciccator diaphragm immersion 100mg/mL, soaking at room temperature activates 8h Afterwards, with distilled water flushing, 40 DEG C of vacuum drying 2h;Desciccator diaphragm is transferred in 35 DEG C of gelatin warm water solution of 50mg/mL and soaks Take out after 24h, with 35 DEG C of warm distilled water flushings, room temperature in vacuo dries 24h;The above-mentioned post-consumer polymer that dries is dissolved in trifluoroethanol Spinning solution of the concentration for 13%w/v is obtained, in voltage 17kV, spinning flow velocity 0.4mL/h, receives the electrospinning parameters apart from 10cm Under carry out electrospinning, obtain gelatin grafting PLGA electrospinning fibre.

Claims (6)

1. a kind of method that gelatin is grafted PLGA electrospinning fibre, is characterized in that:
(1)PLGA is dissolved completely in solvent, obtains the PLGA solution of homogeneous transparent;
(2)Above-mentioned solution and certain density aqueous slkali were reacted after certain time, molten with watery hydrochloric acid and distilled water flushing respectively Liquid is constant to pH value, then drying and forming-film;
(3)Above-mentioned desciccator diaphragm is immersed in activator solution, is taken out after certain time, with distilled water flushing, drying;
(4)Again above-mentioned desciccator diaphragm is transferred in certain density gelatin warm water solution and soaks, take out after certain time, with temperature steaming Distilled water rinsing, drying;
(5)Dried polymer is dissolved in solvent spinning solution is obtained, adjusting electrospinning parameters carries out electrospinning, obtain gelatin grafting PLGA electrospinning fibre.
2. the method that gelatin according to claim 1 is grafted PLGA electrospinning fibre, is characterized in that the dissolving PLGA's is molten Agent is trifluoroethanol, and resulting solution concentration is 10%w/v.
3. the method that gelatin according to claim 1 is grafted PLGA electrospinning fibre, is characterized in that the aqueous slkali for 50mg/ The sodium hydrate aqueous solution of mL, reaction time are 1h, and drying means is:40 DEG C of vacuum drying 12h.
4. the method that gelatin according to claim 1 is grafted PLGA electrospinning fibre, is characterized in that the activator solution is N, the N of 100mg/mL '-carbonyl dimidazoles(CDI)Ethanol solution, soaking at room temperature, soak time are 4h -8h, drying condition For:40 DEG C of vacuum drying 2h.
5. the method that gelatin according to claim 1 is grafted PLGA electrospinning fibre, is characterized in that the gelatin warm water solution Concentration be 50mg/mL, temperature is 35 DEG C, and soak time is 12h-24h, and temperature distillation coolant-temperature gage is 35 DEG C, and drying means is:Room Temperature vacuum drying 24h.
6. the method that gelatin according to claim 1 is grafted PLGA electrospinning fibre, is characterized in that the dissolving polymer Solvent is trifluoroethanol, and the electrospinning parameters are:Concentration of dope 10%w/v-16%w/v, voltage 13-17kV, spinning flow velocity 0.3-0.5mL/h, reception are apart from 10-14cm.
CN201611187472.8A 2016-12-21 2016-12-21 A kind of method that gelatin is grafted PLGA electrospinning fibre Pending CN106480537A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109183172A (en) * 2018-08-22 2019-01-11 浙江理工大学 It is a kind of to be modified anti bacteria natural silk as the preparation method of the face mask substrate material of substrate

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005023906A1 (en) * 2003-09-08 2005-03-17 Chugai Seiyaku Kabushiki Kaisha Hyaluronic acid modification product and drug carrier therefrom
CN101693024A (en) * 2009-10-20 2010-04-14 中国科学院化学研究所 Radionuclide-labelled biodegradable bioabsorbable biopolymer nano fibrous membrane, preparation process and application thereof
CN101695585A (en) * 2009-10-27 2010-04-21 吉林大学 Degradation controlled tissue engineering comea fibrous scaffold and preparation method thereof
CN102251393A (en) * 2011-05-18 2011-11-23 哈尔滨工程大学 Surface modification method of aliphatic polyester electrospun fiber by using sodium alginate and gelatin
CN102580160A (en) * 2012-02-20 2012-07-18 汪泱 Tissue engineering scaffold material of chemical bonding active material and preparation method thereof
US20150322202A1 (en) * 2012-12-21 2015-11-12 University Of Pittsburgh - Of The Commonwealth System Of Higher Education Methods of electrospinning and compositions made therefrom
CN105536057A (en) * 2016-01-12 2016-05-04 河南工程学院 Preparation method and application of polylactic acid-glycolic acid grafted RGD peptide

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005023906A1 (en) * 2003-09-08 2005-03-17 Chugai Seiyaku Kabushiki Kaisha Hyaluronic acid modification product and drug carrier therefrom
CN101693024A (en) * 2009-10-20 2010-04-14 中国科学院化学研究所 Radionuclide-labelled biodegradable bioabsorbable biopolymer nano fibrous membrane, preparation process and application thereof
CN101695585A (en) * 2009-10-27 2010-04-21 吉林大学 Degradation controlled tissue engineering comea fibrous scaffold and preparation method thereof
CN102251393A (en) * 2011-05-18 2011-11-23 哈尔滨工程大学 Surface modification method of aliphatic polyester electrospun fiber by using sodium alginate and gelatin
CN102580160A (en) * 2012-02-20 2012-07-18 汪泱 Tissue engineering scaffold material of chemical bonding active material and preparation method thereof
US20150322202A1 (en) * 2012-12-21 2015-11-12 University Of Pittsburgh - Of The Commonwealth System Of Higher Education Methods of electrospinning and compositions made therefrom
CN105536057A (en) * 2016-01-12 2016-05-04 河南工程学院 Preparation method and application of polylactic acid-glycolic acid grafted RGD peptide

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109183172A (en) * 2018-08-22 2019-01-11 浙江理工大学 It is a kind of to be modified anti bacteria natural silk as the preparation method of the face mask substrate material of substrate

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