CN115058036A - 一种交联聚谷氨酸复合凝胶膜及其制备方法和应用 - Google Patents

一种交联聚谷氨酸复合凝胶膜及其制备方法和应用 Download PDF

Info

Publication number
CN115058036A
CN115058036A CN202210722015.3A CN202210722015A CN115058036A CN 115058036 A CN115058036 A CN 115058036A CN 202210722015 A CN202210722015 A CN 202210722015A CN 115058036 A CN115058036 A CN 115058036A
Authority
CN
China
Prior art keywords
polyglutamic acid
composite gel
crosslinked
aqueous solution
acid composite
Prior art date
Legal status (The legal status 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 status listed.)
Pending
Application number
CN202210722015.3A
Other languages
English (en)
Inventor
曾戎
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kangjian Bionics Qingyuan Technology Co ltd
Original Assignee
Kangjian Bionics Qingyuan Technology Co ltd
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 Kangjian Bionics Qingyuan Technology Co ltd filed Critical Kangjian Bionics Qingyuan Technology Co ltd
Priority to CN202210722015.3A priority Critical patent/CN115058036A/zh
Publication of CN115058036A publication Critical patent/CN115058036A/zh
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/33—Heterocyclic compounds
    • A61K31/335—Heterocyclic compounds having oxygen as the only ring hetero atom, e.g. fungichromin
    • A61K31/35—Heterocyclic compounds having oxygen as the only ring hetero atom, e.g. fungichromin having six-membered rings with one oxygen as the only ring hetero atom
    • A61K31/352—Heterocyclic compounds having oxygen as the only ring hetero atom, e.g. fungichromin having six-membered rings with one oxygen as the only ring hetero atom condensed with carbocyclic rings, e.g. methantheline 
    • A61K31/353—3,4-Dihydrobenzopyrans, e.g. chroman, catechin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/74—Synthetic polymeric materials
    • A61K31/785—Polymers containing nitrogen
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/02—Inorganic compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04—Dispersions; Emulsions
    • A61K8/042—Gels
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/27—Zinc; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/4973—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with oxygen as the only hetero atom
    • A61K8/498—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with oxygen as the only hetero atom having 6-membered rings or their condensed derivatives, e.g. coumarin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/88—Polyamides
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/06—Ointments; Bases therefor; Other semi-solid forms, e.g. creams, sticks, gels
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P29/00—Non-central analgesic, antipyretic or antiinflammatory agents, e.g. antirheumatic agents; Non-steroidal antiinflammatory drugs [NSAID]
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
    • A61P31/02—Local antiseptics
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/005—Antimicrobial preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/075—Macromolecular gels
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/28—Treatment by wave energy or particle radiation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0014—Use of organic additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0014—Use of organic additives
    • C08J9/0023—Use of organic additives containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0066—Use of inorganic compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0095—Mixtures of at least two compounding ingredients belonging to different one-dot groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1545—Six-membered rings

Landscapes

  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Epidemiology (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Birds (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Dermatology (AREA)
  • Manufacturing & Machinery (AREA)
  • Oncology (AREA)
  • Communicable Diseases (AREA)
  • Pain & Pain Management (AREA)
  • Rheumatology (AREA)
  • Emergency Medicine (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

本发明公开了一种交联聚谷氨酸复合凝胶膜的制备方法，包括以下步骤：将聚谷氨酸溶于去离子水中制得聚谷氨酸水溶液，再将聚谷氨酸水溶液倒入可被高能射线穿透的成膜模具中，并进行除氧、密封；使用高能射线对成膜模具内聚谷氨酸水溶液进行辐照，使之交联为聚谷氨酸凝胶；将聚谷氨酸凝胶连同含表没食子儿茶素没食子酸酯和金属盐的缓冲水溶液加入到聚四氟乙烯内衬反应釜中进行水热反应，反应后再经过洗涤，制得交联聚谷氨酸复合凝胶膜。本发明的交联聚谷氨酸复合凝胶膜制备条件绿色环保、工艺简单，可改善单一辐照交联聚谷氨酸凝胶的力学性能，并赋予其抗菌、抗炎等多种生物活性，拓展其在医疗及化妆品领域的应用。

Description

一种交联聚谷氨酸复合凝胶膜及其制备方法和应用
技术领域
本发明属于生物医用材料技术领域，特别涉及一种交联聚谷氨酸复合凝胶膜及其制备方法和应用。
背景技术
聚谷氨酸(PGA)是一种由D-谷氨酸或L-谷氨酸通过α-氨基和γ-羧基形成γ-酰胺键结合而成的阴离子聚合物。聚谷氨酸具有生物相容性好、水溶性好、可降解、可食用、无毒、保湿等诸多优点，这使得聚谷氨酸及其衍生物在食品、化妆品、医药和农业等领域具有广阔的应用前景。特别是，聚谷氨酸可通过物理方法或化学方法交联获得具有三维网络结构的水凝胶，表现出优良的溶胀性能和保水性能。与传统的化学交联相比，通过60Coγ-射线或电子束辐照交联得到的水凝胶具有安全环保，不引入其他产物且操作简便等优点，但通过辐照形成的单一化学键交联模式往往导致其力学性能不佳，限制了其应用。
发明内容
为克服现有技术的不足及存在的问题，本发明提供一种交联聚谷氨酸复合凝胶膜及其制备方法和应用，可改善单一辐照交联聚谷氨酸凝胶的力学性能，并赋予其抗菌、抗炎等多种生物活性。
本发明提供一种交联聚谷氨酸复合凝胶膜的制备方法，包括以下步骤：步骤S01、将聚谷氨酸溶于去离子水中制得聚谷氨酸水溶液，再将聚谷氨酸水溶液倒入可被高能射线穿透的成膜模具中，并进行除氧、密封；步骤S02、使用高能射线对成膜模具内聚谷氨酸水溶液进行辐照，使之交联为聚谷氨酸凝胶；步骤S03、将聚谷氨酸凝胶连同含表没食子儿茶素没食子酸酯和金属盐的缓冲水溶液加入到聚四氟乙烯内衬反应釜中进行水热反应，反应后再经过洗涤，制得交联聚谷氨酸复合凝胶膜。
优选的，所述聚谷氨酸水溶液的浓度为质量体积分数5％～15％，所述成膜模具的厚度为0.1～0.3mm。
优选的，所述步骤S01中的除氧方式为抽真空并通入惰性气体除氧，惰性气体为氮气或氩气。
优选的，所述高能射线为60Co-γ射线或电子束，辐照剂量为20KGy～100KGy。
优选的，所述步骤S03中的水热反应的温度为50～120℃，反应时间为0.5～24h。
优选的，所述含表没食子儿茶素没食子酸酯和金属盐的缓冲水溶液的制备方法为，将表没食子儿茶素没食子酸酯和金属盐加入到三羟甲基氨基甲烷缓冲液中，配制出含表没食子儿茶素没食子酸酯和金属盐的缓冲水溶液。
优选的，所述三羟甲基氨基甲烷缓冲液的PH值为6.0～9.0，金属盐为钙盐、锌盐、锶盐和铁盐的一种或几种，金属盐的摩尔浓度为0.5～5mol/L，表没食子儿茶素没食子酸酯的质量浓度为0.5～10g/L。
优选的，所述步骤S03中的洗涤方法为，将反应后物质浸泡于去离子水、生理盐水或磷酸缓冲盐溶液中，置于37℃恒温摇床中震荡4h，再放入去离子水中平衡，除去未反应的杂质。
本发明还提供一种交联聚谷氨酸复合凝胶膜，该交联聚谷氨酸复合凝胶膜通过上述制备方法制备而成。
本发明还提供一种交联聚谷氨酸复合凝胶膜的应用，通过上述制备方法制备的交联聚谷氨酸复合凝胶膜应用于化妆品和医疗领域。
由于表没食子酸儿茶素没食子酸酯(EGCG)是绿茶茶多酚的主要组成成分，具有抗菌、抗病毒、抗氧化及抗炎等多种活性，并能吸收紫外线辐射和清除自由基，其多酚羟基还可通过氢键或金属离子络合与生物大分子互作。因此，应用EGCG与金属离子可在辐照交联聚谷氨酸凝胶中形成的次级网络结构，改善其力学性能，并赋予其多种生物活性，拓展其用途。
本发明的交联聚谷氨酸复合凝胶膜制备条件绿色环保、工艺简单，可改善单一辐照交联聚谷氨酸凝胶的力学性能，并赋予其抗菌、抗炎等多种生物活性，拓展其在医疗及化妆品领域的应用。
附图说明
图1是实施例一中交联聚谷氨酸复合凝胶膜冷冻干燥的扫描电子显微镜图；
图2是实施例七中交联聚谷氨酸复合凝胶膜的细胞相容性测试结果；
图3是实施例八中交联聚谷氨酸复合凝胶膜的模量测试结果；
图4是实施例九中交联聚谷氨酸复合凝胶膜抗菌性测试结果；
图5是实施例十中交联聚谷氨酸复合凝胶膜抗炎性测试结果。
具体实施方式
为了便于本领域技术人员的理解，以下结合附图和具体实施例对本发明作进一步详细描述。
实施例一
交联聚谷氨酸复合凝胶膜的制备：
取0.5g聚谷氨酸(γ-PGA)溶于10mL去离子水中，搅拌均匀后，制得聚谷氨酸水溶液，将该聚谷氨酸水溶液倒入厚度为0.1mm的可被高能射线穿透的成膜模具中，抽真空并通入氮气除氧，并密封。然后使用辐照剂量为20KGy的60Co-γ射线照射使之交联为聚谷氨酸凝胶。
将表没食子儿茶素没食子酸酯(EGCG)和锌盐(也可以是钙盐、锶盐和铁盐的一种或几种)加入到pH为8.5的三羟甲基氨基甲烷缓冲液(Tris缓冲液)中，配制出质量浓度为0.5g/L的EGCG和摩尔浓度为0.5mol/L的锌盐的混合溶液，即为含EGCG和金属盐的缓冲水溶液。
将上述制得的聚谷氨酸凝胶及含EGCG和金属盐的缓冲水溶液一起加到聚四氟乙烯内衬反应釜中进行水热反应，水热反应温度50℃，反应时间0.5h，得到复合凝胶膜。
将上述复合凝胶膜浸泡在磷酸缓冲盐溶液(PBS缓冲液)中，置于37℃恒温摇床中震荡4h，最后在去离子水中平衡三天，除去未反应的杂质，最终得到交联聚谷氨酸复合凝胶膜。将交联聚谷氨酸复合凝胶膜冷冻干燥后通过扫描电镜观察表面形貌，如图1所示。
实施例二
交联聚谷氨酸复合凝胶膜的制备：
取1.5g聚谷氨酸(γ-PGA)溶于10mL去离子水中，搅拌均匀后，制得聚谷氨酸水溶液，将该聚谷氨酸水溶液倒入厚度为3mm的可被高能射线穿透的成膜模具中，抽真空并通入氩气除氧，并密封。然后使用辐照剂量为100KGy的60Co-γ射线照射使之交联为聚谷氨酸凝胶。
将表没食子儿茶素没食子酸酯(EGCG)和钙盐(也可以是锌盐、锶盐和铁盐的一种或几种)加入到pH为9.0的三羟甲基氨基甲烷缓冲液(Tris缓冲液)中，配制出质量浓度为10g/L的EGCG和摩尔浓度为5mol/L的钙盐的混合溶液，即为含EGCG和金属盐的缓冲水溶液。
将上述制得的聚谷氨酸凝胶及含EGCG和金属盐的缓冲水溶液一起加到聚四氟乙烯内衬反应釜中进行水热反应，水热反应温度120℃，反应时间24h，得到复合凝胶膜。
将上述复合凝胶膜浸泡在生理盐水中，置于37℃恒温摇床中震荡4h，最后在去离子水中平衡三天，除去未反应的杂质，最终得到交联聚谷氨酸复合凝胶膜。
实施例三
交联聚谷氨酸复合凝胶膜的制备：
取1g聚谷氨酸(γ-PGA)溶于10mL去离子水中，搅拌均匀后，制得聚谷氨酸水溶液，将该聚谷氨酸水溶液倒入厚度为1.6mm的可被高能射线穿透的成膜模具中，抽真空并通入氮气除氧，并密封。然后使用辐照剂量为60KGy的电子束照射使之交联为聚谷氨酸凝胶。
将表没食子儿茶素没食子酸酯(EGCG)和锶盐(也可以是钙盐、锌盐和铁盐的一种或几种)加入到pH为7.5的三羟甲基氨基甲烷缓冲液(Tris缓冲液)中，配制出质量浓度为5g/L的EGCG和摩尔浓度为2.5mol/L的锶盐的混合溶液，即为含EGCG和金属盐的缓冲水溶液。
将上述制得的聚谷氨酸凝胶及含EGCG和金属盐的缓冲水溶液一起加到聚四氟乙烯内衬反应釜中进行水热反应，水热反应温度80℃，反应时间12h，得到复合凝胶膜。
将上述复合凝胶膜浸泡在去离子水中，置于37℃恒温摇床中震荡4h，最后在去离子水中平衡三天，除去未反应的杂质，最终得到交联聚谷氨酸复合凝胶膜。
实施例四
交联聚谷氨酸复合凝胶膜的制备：
取0.5g聚谷氨酸(γ-PGA)溶于10mL去离子水中，搅拌均匀后，制得聚谷氨酸水溶液，将该聚谷氨酸水溶液倒入厚度为0.1mm的可被高能射线穿透的成膜模具中，抽真空并通入氩气除氧，并密封。然后使用辐照剂量为20KGy的电子束照射使之交联为聚谷氨酸凝胶。
将表没食子儿茶素没食子酸酯(EGCG)和铁盐(也可以是钙盐、锶盐和锌盐的一种或几种)加入到pH为6.0的三羟甲基氨基甲烷缓冲液(Tris缓冲液)中，配制出质量浓度为0.5g/L的EGCG和摩尔浓度为0.5mol/L的铁盐的混合溶液，即为含EGCG和金属盐的缓冲水溶液。
将上述制得的聚谷氨酸凝胶及含EGCG和金属盐的缓冲水溶液一起加到聚四氟乙烯内衬反应釜中进行水热反应，水热反应温度50℃，反应时间0.5h，得到复合凝胶膜。
将上述复合凝胶膜浸泡在磷酸缓冲盐溶液(PBS缓冲液)中，置于37℃恒温摇床中震荡4h，最后在去离子水中平衡三天，除去未反应的杂质，最终得到交联聚谷氨酸复合凝胶膜。
实施例五
交联聚谷氨酸复合凝胶膜的制备：
取1.5g聚谷氨酸(γ-PGA)溶于10mL去离子水中，搅拌均匀后，制得聚谷氨酸水溶液，将该聚谷氨酸水溶液倒入厚度为0.3mm的可被高能射线穿透的成膜模具中，抽真空并通入氮气除氧，并密封。然后使用辐照剂量为100KGy的60Co-γ射线照射使之交联为聚谷氨酸凝胶。
将表没食子儿茶素没食子酸酯(EGCG)和锌盐(也可以是钙盐、锶盐和铁盐的一种或几种)加入到pH为6.0的三羟甲基氨基甲烷缓冲液(Tris缓冲液)中，配制出质量浓度为10g/L的EGCG和摩尔浓度为5mol/L的锌盐的混合溶液，即为含EGCG和金属盐的缓冲水溶液。
将上述制得的聚谷氨酸凝胶及含EGCG和金属盐的缓冲水溶液一起加到聚四氟乙烯内衬反应釜中进行水热反应，水热反应温度120℃，反应时间24h，得到复合凝胶膜。
将上述复合凝胶膜浸泡在磷酸缓冲盐溶液(PBS缓冲液)中，置于37℃恒温摇床中震荡4h，最后在去离子水中平衡三天，除去未反应的杂质，最终得到交联聚谷氨酸复合凝胶膜。
实施例六
交联聚谷氨酸复合凝胶膜的制备：
取1.5g聚谷氨酸(γ-PGA)溶于10mL去离子水中，搅拌均匀后，制得聚谷氨酸水溶液，将该聚谷氨酸水溶液倒入厚度为0.1mm的可被高能射线穿透的成膜模具中，抽真空并通入氮气除氧，并密封。然后使用辐照剂量为20KGy的电子束照射使之交联为聚谷氨酸凝胶。
将表没食子儿茶素没食子酸酯(EGCG)和锌盐(也可以是钙盐、锶盐和铁盐的一种或几种)加入到pH为8.0的三羟甲基氨基甲烷缓冲液(Tris缓冲液)中，配制出质量浓度为10g/L的EGCG和摩尔浓度为0.5mol/L的锌盐的混合溶液，即为含EGCG和金属盐的缓冲水溶液。
将上述制得的聚谷氨酸凝胶及含EGCG和金属盐的缓冲水溶液一起加到聚四氟乙烯内衬反应釜中进行水热反应，水热反应温度50℃，反应时间24h，得到复合凝胶膜。
将上述复合凝胶膜浸泡在生理盐水中，置于37℃恒温摇床中震荡4h，最后在去离子水中平衡三天，除去未反应的杂质，最终得到交联聚谷氨酸复合凝胶膜。
实施例七
交联聚谷氨酸复合凝胶膜的模量测试：将聚乙醇酸(PGA)水凝胶和实施例一(或者为实施例二至六)所制得的交联聚谷氨酸复合凝胶制备成直经为1.2cm，高为5cm的圆柱形水凝胶，采用电子万能试验机对其进行压缩性能测试，压缩速率为2mm/min，压缩强度如图2所示。可以看到，改性后的水凝胶的压缩强度得到显著的增强。
实施例八
交联聚谷氨酸复合凝胶膜的细胞相容性：将PGA水凝胶和实施例一(或者为实施例二至六)所制得的交联聚谷氨酸复合凝胶膜浸泡在pH值为7.4的PBS溶液中，达到溶胀平衡后浸泡在新鲜的培养基中24h，获取其浸提液并将该浸提液用孔径为0.2μm的注射式过滤器过滤灭菌，在96孔板中每孔5×104个L929细胞种板，37℃培养24h，移除培养基，加入灭菌后的浸提液，37℃培养24h，移除培养基，PBS缓冲液清洗3次，加入100μL的CCK-8，37℃孵育1h，测定450nm波长的吸光值，计算相对活性。如图3所示，所制备的交联聚谷氨酸复合凝胶膜具有良好的细胞相容性。
实施例九
交联聚谷氨酸复合凝胶膜的抗菌性：将PGA水凝胶和实施例一(或者为实施例二至六)所制得的交联聚谷氨酸复合凝胶膜分别浸泡在pH值为7.4的PBS溶液中，达到溶胀平衡后浸入细菌悬浮液中(金黄色葡萄球菌二代ATCC 29213，S.aureus，1×108CFU/mL)，在恒温振动培养箱中培养4h(37℃，200rpm)。然后将细菌悬浮液稀释至浓度为1×106CFU/mL，从稀释过的菌液中取200-400个细菌，将其涂在浓度为5％LB琼脂培养皿上，37℃孵育12h。通过统计计算菌落抗菌率。如图4所示，交联聚谷氨酸复合凝胶膜的抗菌性能较为显著。
实施例十
交联聚谷氨酸复合凝胶膜的抗炎性：通过基因表达(qPCR)检测巨噬细胞炎症因子TNF-α的表达。将灭菌过的PGA水凝胶和实施例一(或者为实施例二至六)所制得的交联聚谷氨酸复合凝胶膜置于12孔板种。将培养的M1型巨噬细胞在12孔板铺板(1×104个/孔)，放置37℃培养箱培养4天。去除培养基收集细胞，PBS清洗1次，提取总RNA并进行逆转录，最后进行实时荧光定量PCR。如图5所示，对于M1型巨噬细胞，加入交联聚谷氨酸复合凝胶膜后，炎症因子的表达得到了明显的抑制。故交联聚谷氨酸复合凝胶膜有明显的抗炎性。
上述实施例为本发明的较佳的实现方式，并非是对本发明的限定，在不脱离本发明的发明构思的前提下，任何显而易见的替换均在本发明的保护范围之内。

Claims (10)

1.一种交联聚谷氨酸复合凝胶膜的制备方法，包括以下步骤：
步骤S01、将聚谷氨酸溶于去离子水中制得聚谷氨酸水溶液，再将聚谷氨酸水溶液倒入可被高能射线穿透的成膜模具中，并进行除氧、密封；
步骤S02、使用高能射线对成膜模具内聚谷氨酸水溶液进行辐照，使之交联为聚谷氨酸凝胶；
步骤S03、将聚谷氨酸凝胶连同含表没食子儿茶素没食子酸酯和金属盐的缓冲水溶液加入到聚四氟乙烯内衬反应釜中进行水热反应，反应后再经过洗涤，制得交联聚谷氨酸复合凝胶膜。
2.根据权利要求1所述的交联聚谷氨酸复合凝胶膜的制备方法，其特征在于：所述聚谷氨酸水溶液的浓度为质量体积分数5％～15％，所述成膜模具的厚度为0.1～0.3mm。
3.根据权利要求2所述的交联聚谷氨酸复合凝胶膜的制备方法，其特征在于：所述步骤S01中的除氧方式为抽真空并通入惰性气体除氧，惰性气体为氮气或氩气。
4.根据权利要求3所述的交联聚谷氨酸复合凝胶膜的制备方法，其特征在于：所述高能射线为60Co-γ射线或电子束，辐照剂量为20KGy～100KGy。
5.根据权利要求4所述的交联聚谷氨酸复合凝胶膜的制备方法，其特征在于：所述步骤S03中的水热反应的温度为50～120℃，反应时间为0.5～24h。
6.根据权利要求5所述的交联聚谷氨酸复合凝胶膜的制备方法，其特征在于：所述含表没食子儿茶素没食子酸酯和金属盐的缓冲水溶液的制备方法为，将表没食子儿茶素没食子酸酯和金属盐加入到三羟甲基氨基甲烷缓冲液中，配制出含表没食子儿茶素没食子酸酯和金属盐的缓冲水溶液。
7.根据权利要求6所述的交联聚谷氨酸复合凝胶膜的制备方法，其特征在于：所述三羟甲基氨基甲烷缓冲液的PH值为6.0～9.0，金属盐为钙盐、锌盐、锶盐和铁盐的一种或几种，金属盐的摩尔浓度为0.5～5mol/L，表没食子儿茶素没食子酸酯的质量浓度为0.5～10g/L。
8.根据权利要求7所述的交联聚谷氨酸复合凝胶膜及其制备方法和应用，其特征在于：所述步骤S03中的洗涤方法为，将反应后物质浸泡于去离子水、生理盐水或磷酸缓冲盐溶液中，置于37℃恒温摇床中震荡4h，再放入去离子水中平衡，除去未反应的杂质。
9.一种通过权利要求1-8中任一项所述制备方法制备的交联聚谷氨酸复合凝胶膜。
10.一种通过权利要求1-8中任一项所述制备方法制备的交联聚谷氨酸复合凝胶膜应用于化妆品和医疗领域。
CN202210722015.3A 2022-06-17 2022-06-17 一种交联聚谷氨酸复合凝胶膜及其制备方法和应用 Pending CN115058036A (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210722015.3A CN115058036A (zh) 2022-06-17 2022-06-17 一种交联聚谷氨酸复合凝胶膜及其制备方法和应用

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210722015.3A CN115058036A (zh) 2022-06-17 2022-06-17 一种交联聚谷氨酸复合凝胶膜及其制备方法和应用

Publications (1)

Publication Number Publication Date
CN115058036A true CN115058036A (zh) 2022-09-16

Family

ID=83201451

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210722015.3A Pending CN115058036A (zh) 2022-06-17 2022-06-17 一种交联聚谷氨酸复合凝胶膜及其制备方法和应用

Country Status (1)

Country Link
CN (1) CN115058036A (zh)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020120242A1 (en) * 2000-12-22 2002-08-29 Tyrrell David John Absorbent articles with hydrophilic compositions containing botanicals
EP2249884A2 (en) * 2007-11-05 2010-11-17 Technion Research & Development Foundation Ltd. Adhering bandage and methods of applying the same
CN102093582A (zh) * 2011-01-04 2011-06-15 上海大学 一种辐射交联水凝胶的制备方法
CN112316204A (zh) * 2020-11-13 2021-02-05 四川大学 一种金属多酚胶原蛋白膜材料、其制备方法及应用
CN113817326A (zh) * 2021-07-01 2021-12-21 广东省科学院健康医学研究所 一种多功能儿茶酚水凝胶敷料及其制备方法和应用
CN113842508A (zh) * 2021-09-18 2021-12-28 暨南大学 一种抗菌仿生涂层及其制备方法与应用
CN115671377A (zh) * 2022-10-21 2023-02-03 南方医科大学 多酚本体改性氧化锌及其制备方法和应用

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020120242A1 (en) * 2000-12-22 2002-08-29 Tyrrell David John Absorbent articles with hydrophilic compositions containing botanicals
EP2249884A2 (en) * 2007-11-05 2010-11-17 Technion Research & Development Foundation Ltd. Adhering bandage and methods of applying the same
CN102093582A (zh) * 2011-01-04 2011-06-15 上海大学 一种辐射交联水凝胶的制备方法
CN112316204A (zh) * 2020-11-13 2021-02-05 四川大学 一种金属多酚胶原蛋白膜材料、其制备方法及应用
CN113817326A (zh) * 2021-07-01 2021-12-21 广东省科学院健康医学研究所 一种多功能儿茶酚水凝胶敷料及其制备方法和应用
CN113842508A (zh) * 2021-09-18 2021-12-28 暨南大学 一种抗菌仿生涂层及其制备方法与应用
CN115671377A (zh) * 2022-10-21 2023-02-03 南方医科大学 多酚本体改性氧化锌及其制备方法和应用

Similar Documents

Publication Publication Date Title
da Cruz et al. Poly (vinyl alcohol)/cationic tannin blend films with antioxidant and antimicrobial activities
CN111154149A (zh) 一种水凝胶及其制备方法与敷料
CN101509025A (zh) 细菌纤维素复合材料的制备方法
US7041505B2 (en) Carrier for cell culture
Fan et al. Preparation and characterization of antibacterial polyvinyl alcohol/chitosan sponge and potential applied for wound dressing
Wang et al. Enzyme-induced dual-network ε-poly-L-lysine-based hydrogels with robust self-healing and antibacterial performance
CN113842508B (zh) 一种抗菌仿生涂层及其制备方法与应用
Kai et al. Preparation, characterization, and cytotoxicity evaluation of zinc oxide–bacterial cellulose–chitosan hydrogels for antibacterial dressing
CN104587516B (zh) 一种透明的可降解细菌纤维素再生膜及其制备方法和应用
CN112029037B (zh) 一种高强度可降解的抗菌水凝胶及其制备方法
Hsieh et al. Characterization and cell culture of a grafted chitosan scaffold for tissue engineering
Liu et al. Crosslinking of collagen using a controlled molecular weight bio-crosslinker: β-cyclodextrin polyrotaxane multi-aldehydes
CN115058036A (zh) 一种交联聚谷氨酸复合凝胶膜及其制备方法和应用
Cao et al. Biocompatible, ionic‐strength‐sensitive, double‐network hydrogel based on chitosan and an oligo (trimethylene carbonate)–poly (ethylene glycol)–oligo (trimethylene carbonate) triblock copolymer
Casimiro et al. Characterisation of gamma irradiated chitosan/pHEMA membranes for biomedical purposes
CN110669168A (zh) 修饰剂、其制备方法、使用方法以及医用材料
Sakthivel et al. Investigation on pH-switchable (itaconic acid/ethylene glycol/acrylic acid) based polymeric biocompatible hydrogel
CN113265032A (zh) 一种聚丙烯酰胺修饰的温敏共聚物的制备方法及其应用
CN107616960B (zh) 生物杀菌洗手液及其生产工艺
CN114874479B (zh) 一种海绵状大孔水凝胶的制备方法及在抗菌中的应用
CN114573833B (zh) 一种用于细胞三维培养的peg-rgd多肽水凝胶材料及其制备方法与应用
US7022523B2 (en) Carrier for cell culture
Sakai et al. Development of porous alginate-based scaffolds covalently cross-linked through a peroxidase-catalyzed reaction
CN114395141A (zh) 一种高强度丝蛋白纳米纤维水凝胶的制备方法
US20180057614A1 (en) Depolymerisation of alginic acid

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination