WO2009049565A2 - Procédé de production de nanofibres - Google Patents

Procédé de production de nanofibres Download PDF

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Publication number
WO2009049565A2
WO2009049565A2 PCT/CZ2008/000124 CZ2008000124W WO2009049565A2 WO 2009049565 A2 WO2009049565 A2 WO 2009049565A2 CZ 2008000124 W CZ2008000124 W CZ 2008000124W WO 2009049565 A2 WO2009049565 A2 WO 2009049565A2
Authority
WO
WIPO (PCT)
Prior art keywords
spinning
biopolymer
nanofibres
chitosan
electrode
Prior art date
Application number
PCT/CZ2008/000124
Other languages
English (en)
Other versions
WO2009049565A3 (fr
Inventor
Jana Svobodova
Original Assignee
Elmarco, S.R.O.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Elmarco, S.R.O. filed Critical Elmarco, S.R.O.
Priority to CN2008801225306A priority Critical patent/CN101903568A/zh
Priority to MX2010004085A priority patent/MX2010004085A/es
Priority to BRPI0818424 priority patent/BRPI0818424A2/pt
Priority to CA2702368A priority patent/CA2702368A1/fr
Priority to US12/738,164 priority patent/US20100244331A1/en
Priority to AU2008314287A priority patent/AU2008314287A1/en
Priority to JP2010529224A priority patent/JP2011500980A/ja
Publication of WO2009049565A2 publication Critical patent/WO2009049565A2/fr
Publication of WO2009049565A3 publication Critical patent/WO2009049565A3/fr
Priority to IL205093A priority patent/IL205093A0/en

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Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
    • D01D5/0038—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion the fibre formed by solvent evaporation, i.e. dry electro-spinning
    • 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
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
    • A61L15/28—Polysaccharides or their derivatives
    • 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
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42—Use of materials characterised by their function or physical properties
    • A61L15/425—Porous materials, e.g. foams or sponges
    • 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
    • D01F4/00—Monocomponent artificial filaments or the like of proteins; Manufacture thereof
    • 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
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • 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

Definitions

  • the invention relates to method for production of nanofibres through electrostatic spinning of polymer matrices prepared upon biopolymers of chitosan or collagen.
  • the invention relates to fabric comprising at least one layer of nanofibres produced through electrostatic spinning of biopolymer of chitosan or collagen.
  • Biopolymers feature a number of unique properties thanks to which they are suitable for application in medicine, first of all thanks to its biocompatibility and nontoxicity. Important is their application e.g. for production of bandages and plasters, but also for implants and antiadhesive mats, where they expressively decrease the risk of occurrence of postoperative adhesions between the tissues, further in dental medicine, cosmetics and surgery plastic for filling of dermatic or bone defects. Some of the biopolymers are biodegradable, that means decomposable e.g. by action of enzymes.
  • the nanofibrous materials of biopolymers are of a high porosity as well as of a specific surface, are penetrable for oxygen but not penetrable for microbes, at the same time they preserve all above mentioned properties of the used biopolymers.
  • Biopolymer nanofibres are suitable e.g. for healing of burns, when they ensure an optimum humidity at healing and simultaneous removal of exudate from the wound, further for the bandage materials, plasters, etc.
  • chitosan is the polycationic polysaccharide composed of ⁇ - (1 ⁇ 4) 2-acetamido-2-deoxy-D-glucopyranosic and 2-amino-2-deoxy-D-glucopyranosic units.
  • chitin is the polycationic polysaccharide composed of ⁇ - (1 ⁇ 4) 2-acetamido-2-deoxy-D-glucopyranosic and 2-amino-2-deoxy-D-glucopyranosic units.
  • alkaline deacetylation the source of which are the shellfish, e.g. the shells, mussels, crabs and crayfish, it is also contained in tectrices of insect and also in mushrooms.
  • Chitosan is biodecomposable, biocompatible, thanks to positive charge at physiological pH it is bioadhesive, which is a great advantage in healing of wounds, it has hemostatic effects, thus stops bleeding, it has also antibacterial effects.
  • it is contained in most of the reduction diets.
  • it is directly designated for application in medicine, e.g. for the already mentioned plasters and bandages, but also for the antiadhesive mats into the body or in dental medicine for filling to stop bleeding. It is also used in biotechnologies for purification of waste waters or liquids, e.g. beer, wine or milk.
  • chitosan Most types of chitosan are insoluble in water, but soluble in organic acids with pH of solution lower than 5. Most frequently are as solvent used the acetic acid, lactic acid, malic acid, oxalic acid, etc.
  • the method of electrostatic spinning is used.
  • the nanofibres from chitosan are produced by means of spinning devices with needle or jet spinning electrode.
  • WO2007093805A1 discloses production of composite fibres from chitosan and alginate, where the maximum content of chitosan reaches 80%, whereas the chitosan fibres coat the surface of alginate fibres. Due to the diameter of fibres, which is 50 ⁇ m , these fibres are not nanofibres.
  • WO2006133118A1 generally deals with biopolymers in a nanofibrous form, where alternate the nanofibrous layers of polymer soluble in water and insoluble in water. Diameters of produced nanofibres are in the range of 1 to 25000 nm, which is not the nano dimension any more.
  • KR100652469B deals with antibacterial nanofibres, which are made of chitosan in mixture with polyethylene terephthalate.
  • the trifluorethanol hexafluoroisopropanol or trifluoroacetic acid is used.
  • Another Korean patent deals with production of nanofibres of chitin or chitosan upon usage of jets as the spinning electrodes.
  • solvents the N- methylmorpholineoxid, hexafuoro-2-propanol or hexafluoroacetone hydrate and formic acid are used.
  • WO2006048829 patent deals with new derivates of chitin in a nanofibrous form for application in medicine, mainly for application to protect skin and as hypodermic fillings.
  • the used biopolymers are oxychitin, chitin of glycolate, chitin of hyaluronate. Also here is for production of nanofibres used the needle spinning electrode.
  • WO03042251A1 patent discloses production of composites containing chitosan in the form of nanodimensional fibres for the purpose of increasing the activity and solubility mostly for usage in cosmetic. Nevertheless the length of produced nanofibres is considerably limited and it varies in the range of 5 to 200 nm, while their diameter is in the range of 5 to 30 nm, which corresponds rather to the size of nanoparticles than the nanofibres.
  • Another patent KR1020050048360AA deals with production of nanofibrous nonwoven fabric for tissue engineering, where for production of nanofibres the natural polymer from the group of chitosan, collagen, alginic acid and synthetic polymer is used, e.g. homopolymer of lactic acid, copolymer of lactic acid and of gluconic acid, homopolymer of gluconic acid and their mixtures, while the ratio of natural and synthetic polymer is 4:1 to 1:4.
  • the natural polymer from the group of chitosan, collagen, alginic acid and synthetic polymer is used, e.g. homopolymer of lactic acid, copolymer of lactic acid and of gluconic acid, homopolymer of gluconic acid and their mixtures, while the ratio of natural and synthetic polymer is 4:1 to 1:4.
  • Bin Duan Joint of Biomaterial Science, Polymer Edition, Vol.
  • N.Bhattarai Biomaterials, vol.26, lss.31 , 2005, p.6176-6184
  • N.Bhattarai deals with production of nanofibres from the mixture of chitosanPEO in maximum ratio 90:10, where as solvent non-ionic tenside Triton X-100TM is used.
  • As a spinning electrode the syringe is used and the applied voltage is 20 to 25 kV and distance of electrodes is 17 to 20 cm.
  • As a co-solvent dimethylsulfoxide is added.
  • X.Geng et. al.. deals with spinning of chitosan in concentrated acetic acid (Biomaterials, Vol. 26,2005, p.5427 - 5432).
  • Another possible method for production of nanofibres from chitosan is spinning of chitosan solution with addition of polyvinyl alcohol, like Lei Li and his group (Carbohydrate Polymers, Vol.62, 2006, p.142 - 158) deals with.
  • the original solution is composed of mixture PVA/chitosan in ratio 83/17 (w/w) in 2% acetic acid, while the achieved diameter of nanofibres is 20 to 100 nm. Then PVA is removed from nanofibres through leaching in NaOH.
  • collagen Another in medicine mostly used biopolymers is collagen which is applicable especially at healing of burns, as implants, for artificial dermal fillings, artificial skin, artificial cartilages, vertebras, etc.
  • Collagen is contained e.g. in skin, vascular walls, cartilages, ligament.
  • In medicine are used primarily the types I 1 II and III.
  • Collagen is formed of three polypeptides creating the ⁇ -helix with regularly repeating amino acids Gly-Pro-Hyp. It is insoluble in water and soluble in a few of solvents, out of which the mostly used is hexafluoroisopropanol. Through chemical or thermal degradation the gelatine is obtained.
  • CN 1944724 is a patent that deals with production of composites of chitosan and collagen.
  • a solvent the hexafluoroisopropanol and trifluoracetic acid or their mixture are used.
  • One of publications which deals with spinning of collagen of type I is article of J.A.Matthews (Biomacromolecules,
  • WO2006068421A1 discloses production of nanofibrres which are formed of polyhydroxyalkanoate, collagen or gelatine.
  • the spinning electrode applied for production of these nanofibres is nozzle or needle, and diameter of nanofibres varies in the range of 50 to 2000 nm. It is apparent from the mentioned patents or publications, that there is not known any method of continual production of nanofibres of biopolymers, especially of chitosan or collagen.
  • the electrostatic spinning from needles, which form the spinning electrode is interrupted after the drop of polymer solution is consumed.
  • the goal of this invention is to suggest the method for production of nanofibres of biopolymers through electrostatic spinning, which would remedy the disadvantages of the background art.
  • the goal of the invention has been achieved by production method of nanofibres through electrostatic spinning of polymer matrices prepared upon on biopolymers of chitosan or collagen according to the invention, whose principle consists in that, the biopolymer is before spinning dissolved as clean or in mixture with auxiliary non-toxic polymer in solvent system, which contains an organic or inorganic acid, selected from the group of acetic acid in concentration from 30 % to 90 % of weight, lactic acid, malic acid, thhydrogen-phosphoric acid and their mixtures, and this solution is brought into electrostatic field between the spinning electrode and collecting electrode, while the produced biopolymer nanofibres comprise more than 90 % of weight of biopolymer in dry mass.
  • auxiliary non-toxic polymer in solvent system which contains an organic or inorganic acid, selected from the group of acetic acid in concentration from 30 % to 90 % of weight, lactic acid, malic acid, thhydrogen-phosphoric acid and their mixtures
  • biopolymer nanofibres comprisen more than 95 % of biopolymer in the dry mass.
  • Constant quality results at spinning are achieved if the solvent system comprises the acetic acid.
  • the solvent system comprises the acetic acid.
  • chitosan of molecular weight lower than 150 kDa is before spinning dissolved in acetic acid of concentration higher than 50 % wt. together with auxiliary nontoxic polymer PEO.
  • the fibres of chitosan may be produced also without addition of PEO, as it is shown in the claim 5.
  • PEO poly(ethylene glycol)
  • the constant good spinning results are achieved, if the biopolymer solution in electric electrostatic field for spinning is positioned on surface of the active zone of spinning mean of the spinning electrode.
  • biopolymer solution is delivered to electrostatic field for spinning through surface of the spinning electrode.
  • the spinning electrode is with advantage formed of a rotating spinning electrode of an oblong shape, which by section of its perimeter extends into the biopolymer solution.
  • such spinning electrode comprises a couple of faces made of electrically non-conductive material, between which are positioned the spinning members created of wire, which are equally distributed around perimeter, parallel with axis of rotation and mutually electrically conductive connected.
  • biopolymer solution in electrostatic field for spinning is situated on surface of the active spinning zone of the spinning means.
  • Active spinning zone of the cord during spinning has a stable position towards the collecting electrode and biopolymer solution to the active spinning zone of the cord is delivered by applying or by a motion of the cord in direction of its length.
  • Chitosan is dissolved solitary or in mixture with auxiliary nontoxic polymer, especially the one soluble in water, which is in ideal case biocompatible and biodegradable.
  • the example is polyvinylalcohol, polyethylene oxide or polyvinylpyrrolidone.
  • Chitosan is used in the concentration of 5 - 25 wt. % in dependence on the solvent system, which is formed of organic or inorganic acid, especially the acetic acid, while concentration of acetic acid is higher than 30 % and lower than 90%. Further the lactic acid, malic acid and trihydrogen phosphoric acid or their mixtures may be used.
  • the ratio of chitosan and of the auxiliary polymer is higher than 90:10 to the dry mass of nanofibres.
  • reticulate agents e.g. dialdehydes, dicarboxylic acids, genipin, trisodium citrate.
  • the process depends on molecular weight of chitosan, grade of deacetylation, concentration, or viscosity, surface tension, temperature and humidity of surroundings and parameters of technology, like rotation and type of electrode, distance between electrodes and applied voltage.
  • the device for electrostatic spinning of polymer solutions comprising the spinning electrode, which comprises the rotatably mounted spinning means extending by a portion of its perimeter into the biopolymer solution being present in the reservoir.
  • the rotatable spinning means due to its rotation carries out the biopolymer solution into electrostatic field of a high intensity, which is created by difference of potentials between the spinning electrode and against it arranged collecting electrode, while the section of surface of the rotating spinning means positioned against the collecting electrode represents the active spinning zone of the spinning means.
  • the biopolymer solution is to be found in electrostatic field on surface of the active spinning zone of the spinning means of the spinning electrode.
  • the rotatable spinning means may be performed for example according to the CZ patent 294274 or according to CZ PV 2006-545 or CZ PV 2007-485.
  • Collagen of the type I underwent spinning from its solution in diluted acetic acid, so that halogen solvents, which may cause problems in medicine applications, were not used.
  • the residua of acetic acid may be removed by a short term warming of the nanofibrous material.
  • the nanofibres of collagen may be reticulated by the same means as chitosan. Achieved weight ratio of colagenu and auxiliary polymer is higher than 90:10.
  • the applied voltage of 6 to 7 kV/cm.
  • Advantage of the described technology is a high content of biopolymer in nanofibres and a large range of surface density of nanofibres, which is 0,05 to
  • the produced nanofibres of chitosan may have diameter of 10 to 250 nm, the nanofibres of collagen 10 to 200 nm. In all cases a long term continual spinning process has been achieved.
  • Example 1 Chitosan of a low molecular weight (lower than 15OkDa, with viscosity
  • Example 2 Before spinning, collagen is dissolved in solvent system comprising the acetic acid 87,5 % of weight, the auxiliary polymer (PEO or PVA) soluble in water (concentration of 1-3%) at temperature to 35°C, humidity to 60% and this solution is brought into electrostatic field between the spinning electrode and collecting electrode.
  • solvent system comprising the acetic acid 87,5 % of weight, the auxiliary polymer (PEO or PVA) soluble in water (concentration of 1-3%) at temperature to 35°C, humidity to 60% and this solution is brought into electrostatic field between the spinning electrode and collecting electrode.
  • solvent system comprising the acetic acid 87,5 % of weight, the auxiliary polymer (PEO or PVA) soluble in water (concentration of 1-3%) at temperature to 35°C, humidity to 60% and this solution is brought into electrostatic field between the spinning electrode and collecting electrode.
  • PEO or PVA auxiliary polymer
  • the chitosan as well as collagen nanofibres provide a large possibilities of application, first of all in medicine, and thanks to possibility of nearly any surface density of nanofibres they may be applicable also as substrateless materials, antiadhesive mats, plasters, implants and fillings of undesired bone or dermal defects. Chitosan thanks to hemostatic effects may be used at operation or in dental medicine to stop bleeding along reduction of economic costs and simultaneous speeding of wound healing.
  • Colagen nanofibres will surely find their application solitary as replacement of damaged ligaments, tendons and cartilages or at injury of backbone, e.g. the intervertebral plate, or also for coating of implants, which reduces the negative immunity response of organism after introduction of a foreign element into the body.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Textile Engineering (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Veterinary Medicine (AREA)
  • Hematology (AREA)
  • Materials Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Mechanical Engineering (AREA)
  • Artificial Filaments (AREA)
  • Materials For Medical Uses (AREA)
  • Nonwoven Fabrics (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)

Abstract

L'invention concerne un procédé de production de nanofibres par filage électrostatique de matrices polymères préparées sur des biopolymères de chitosane ou de collagène. Avant le filage, le biopolymère est dissous sous forme pure ou en mélange avec un polymère non toxique auxiliaire dans un système de solvants renfermant un acide organique ou inorganique choisi dans le groupe constitué par l'acide acétique en concentration comprise entre 30% et 90% en poids, l'acide lactique, l'acide malique, l'acide trihydrogène-phosphorique et leurs mélanges, cette solution étant acheminée dans un champ électrostatique entre l'électrode de filage et l'électrode de collecte, les nanofibres biopolymères produites comprenant plus de 90% en poids de biopolymère en masse sèche.
PCT/CZ2008/000124 2007-10-15 2008-10-15 Procédé de production de nanofibres WO2009049565A2 (fr)

Priority Applications (8)

Application Number Priority Date Filing Date Title
CN2008801225306A CN101903568A (zh) 2007-10-15 2008-10-15 纳米纤维的制备方法
MX2010004085A MX2010004085A (es) 2007-10-15 2008-10-15 Metodo para la produccion de nanofibras.
BRPI0818424 BRPI0818424A2 (pt) 2007-10-15 2008-10-15 Método para produzir de nanofibras, e, pano
CA2702368A CA2702368A1 (fr) 2007-10-15 2008-10-15 Procede de production de nanofibres
US12/738,164 US20100244331A1 (en) 2007-10-15 2008-10-15 Method for Production of Nanofibres
AU2008314287A AU2008314287A1 (en) 2007-10-15 2008-10-15 Method for production of nanofibres
JP2010529224A JP2011500980A (ja) 2007-10-15 2008-10-15 ナノ繊維の製造方法
IL205093A IL205093A0 (en) 2007-10-15 2010-04-14 Method for production of nanofibres

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CZPV2007-716 2007-10-15
CZ20070716A CZ2007716A3 (cs) 2007-10-15 2007-10-15 Zpusob výroby nanovláken

Publications (2)

Publication Number Publication Date
WO2009049565A2 true WO2009049565A2 (fr) 2009-04-23
WO2009049565A3 WO2009049565A3 (fr) 2010-02-25

Family

ID=40567834

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CZ2008/000124 WO2009049565A2 (fr) 2007-10-15 2008-10-15 Procédé de production de nanofibres

Country Status (12)

Country Link
US (1) US20100244331A1 (fr)
JP (1) JP2011500980A (fr)
CN (1) CN101903568A (fr)
AU (1) AU2008314287A1 (fr)
BR (1) BRPI0818424A2 (fr)
CA (1) CA2702368A1 (fr)
CZ (1) CZ2007716A3 (fr)
IL (1) IL205093A0 (fr)
MX (1) MX2010004085A (fr)
PH (1) PH12010500803A1 (fr)
TW (1) TW200925342A (fr)
WO (1) WO2009049565A2 (fr)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011077958A1 (fr) * 2009-12-25 2011-06-30 東洋紡績株式会社 Agrégats de fibres de collagène et processus pour leur production
WO2011151225A1 (fr) * 2010-06-04 2011-12-08 Universite De Liege Echafaudages biomimétiques de chitosane et procédés de préparation associés
WO2012091636A2 (fr) * 2010-12-30 2012-07-05 Федеральное Государственное Бюджетное Образовательное Учреждение Высшего Профессионального Образования "Саратовский Государственный Университет Имени Н.Г. Чернышевского" Tissu biopolymérique, composition d'une solution de formation destinée à sa préparation, procédé de préparation d'une solution de formation, tissu à usage biomédical, procédé de sa modification, pansement biologique et procédé de traitement de plaies
RU2487701C2 (ru) * 2011-07-26 2013-07-20 Общество с ограниченной ответственностью "Инмед" Раствор для получения материала на основе хитозана, способ получения гемостатического материала из этого раствора (варианты) и медицинское изделие с использованием волокон на основе хитозана
WO2016120622A1 (fr) * 2015-01-27 2016-08-04 Medtrade Products Limited Composition pour pansements
US20170258959A1 (en) * 2013-05-30 2017-09-14 Medtrade Products Limited Degradable haemostat composition
EP3311854A1 (fr) * 2016-10-20 2018-04-25 Ústav Struktury A Mechaniky Hornin AV CR, V.V.I. Couche nanocomposite à base de nanofibres de collagène et son procédé de préparation
US10434212B2 (en) 2013-05-30 2019-10-08 Medtrade Products Limited Degradable haemostat composition
WO2020169486A1 (fr) 2019-02-22 2020-08-27 Hahn-Schickard-Gesellschaft für angewandte Forschung e.V. Procédé de production d'un couche composite, unité électrochimique et utilisation de la couche composite
US10973691B2 (en) 2015-01-27 2021-04-13 Medtrade Products Limited Composition for a wound dressing
US11013827B2 (en) 2016-04-30 2021-05-25 Bvw Holding Ag Microstructured haptotaxic implant

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JP5453690B2 (ja) * 2010-06-18 2014-03-26 国立大学法人東京工業大学 コラーゲン・キトサン複合繊維状多孔体及びその製造方法
CN102877147A (zh) * 2012-09-24 2013-01-16 四川大学 胶原蛋白水溶液静电纺丝制备纳米纤维的方法
CZ304564B6 (cs) * 2013-02-12 2014-07-09 Univerzita Pardubice Způsob přípravy vláken z chitin/chitosan-glukanového komplexu, vlákna a kryt rány
CN104007040B (zh) * 2014-06-05 2016-05-18 广州纺织服装研究院有限公司 一种检测覆盖型胶原改性纤维织物中胶原含量的方法
CN105401232B (zh) * 2015-11-02 2017-09-29 浙江纺织服装科技有限公司 一种生物敷料用复合微纳米纤维膜的制备方法
CN105350105A (zh) * 2015-11-30 2016-02-24 莫程 一种苹果醋纤维及其制备方法
CN105839407B (zh) * 2016-04-19 2018-05-08 东南大学 一种医用高分子材料纳米纤维的表面生物功能化方法
TWI731967B (zh) * 2016-04-30 2021-07-01 瑞士商Ｂｖｗ控股公司 微結構化趨觸植入物
CN108404213B (zh) * 2018-05-14 2023-05-09 上海交通大学医学院附属第九人民医院 一种利用三维打印和静电纺丝技术制备肌腱支架方法
CN111455496A (zh) * 2019-01-20 2020-07-28 泽塔纳米科技（苏州）有限公司 一种抗菌的可生物降解的纳米纤维及其制备方法
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US20100244331A1 (en) 2010-09-30
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