CN116474153B - A skin ulcer care film based on bamboo fiber-low eutectic solvent-gelatin - Google Patents
A skin ulcer care film based on bamboo fiber-low eutectic solvent-gelatin Download PDFInfo
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Classifications
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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
- 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
- A61L15/40—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing ingredients of undetermined constitution or reaction products thereof, e.g. plant or animal extracts
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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
- 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
- A61L15/20—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing organic materials
-
- 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
- A61L15/32—Proteins, polypeptides; Degradation products or derivatives thereof, e.g. albumin, collagen, fibrin, gelatin
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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
- 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
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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
- 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
- A61L15/44—Medicaments
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
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- Engineering & Computer Science (AREA)
- Animal Behavior & Ethology (AREA)
- Hematology (AREA)
- Public Health (AREA)
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Abstract
Description
技术领域Technical Field
本发明属于医疗器械/医用敷料技术领域,尤其涉及到一种具有多种功能的复合组分抗溃疡皮肤护理贴膜及其制备方法。The invention belongs to the technical field of medical devices/medical dressings, and in particular relates to a composite component anti-ulcer skin care film with multiple functions and a preparation method thereof.
背景技术Background Art
皮肤是人体面积最大的器官,其主要功能是防止细菌、病毒侵蚀机体,调节体温以及排出汗液等。皮肤溃疡是外科常见病、多发病,往往由物理、化学因素直接作用于组织或者微生物感染引起。小面积的溃疡较容易自愈,但是大面积的皮肤溃疡则往往以长期不能愈合为临床特征,从而影响到肌体的正常功能。相关组织会出现不同程度的缺损液化乃至感染坏死,伴随痒痛、溃破、渗出甚至出血等症状,易迁延不愈或反复发作,给病人带来极大的痛苦和不便,严重影响工作与生活质量;因此已成为临床医疗上长期存在的难题之一,而目前可供选择的功能较为全面的大面积护理敷料非常有限。The skin is the largest organ in the human body, and its main functions are to prevent bacteria and viruses from invading the body, regulate body temperature, and discharge sweat. Skin ulcers are common and frequently occurring surgical diseases, often caused by physical and chemical factors acting directly on tissues or microbial infections. Small-area ulcers are easier to heal on their own, but large-area skin ulcers are often characterized by long-term inability to heal, thus affecting the normal function of the body. The relevant tissues will have varying degrees of defects, liquefaction, and even infection and necrosis, accompanied by symptoms such as itching, pain, ulceration, exudation, and even bleeding. They are prone to protracted healing or recurrence, causing great pain and inconvenience to patients, and seriously affecting their work and quality of life. Therefore, it has become one of the long-standing problems in clinical medicine, and the currently available large-area nursing dressings with more comprehensive functions are very limited.
近年来越来越多的天然产物被发现具有抗溃疡、抗炎、抑制细菌生长以及提高免疫力等一系列的作用,相关的制剂和敷料已在临床上得到了很好的应用。同时可再生的生物质资源越来越受到重视,如基于木质纤维素的新材料正被普遍关注和研究开发。竹作为我国一种常见的经济作物,种植面积与产量巨大,在本领域也体现出越来越多的医用及药用价值。民间疗法中将竹茎去皮后研成粉末直接涂敷于溃疡面(厚约2~3mm,无菌纱布覆盖并以胶布固定)上用于治疗(中国民间疗法,1999,000(005):47)。而竹茎含有的竹纤维(毛竹中平均含量约为 22.7%)具有天然的吸湿、透气和抗菌性,作为内衣等纺织品材质使用时不会对皮肤产生任何过敏行为。这些特性在临床上对于治疗体表溃疡具有十分重要的意义,同时也为开发更多不同的抗溃疡外用敷料提供了基础。In recent years, more and more natural products have been found to have a series of effects such as anti-ulcer, anti-inflammatory, inhibiting bacterial growth and improving immunity. Related preparations and dressings have been well applied in clinical practice. At the same time, renewable biomass resources are increasingly valued. For example, new materials based on wood cellulose are widely concerned and researched and developed. Bamboo is a common economic crop in my country with a huge planting area and output. It also shows more and more medical and medicinal value in this field. In folk therapy, bamboo stems are peeled and ground into powder and directly applied to the ulcer surface (about 2-3 mm thick, covered with sterile gauze and fixed with adhesive tape) for treatment (Chinese Folk Therapy, 1999, 000 (005): 47). The bamboo fiber contained in bamboo stems (the average content in moso bamboo is about 22.7%) has natural moisture absorption, breathability and antibacterial properties. When used as a textile material such as underwear, it will not cause any allergic behavior to the skin. These characteristics are of great significance in the treatment of surface ulcers in the clinic, and also provide a basis for the development of more different anti-ulcer topical dressings.
低共熔溶剂(Deep Eutectic Solvent,DES)是由氢键供体(HBD)与氢键受体(HBA)按照一定摩尔比组合而成的新型多用途绿色溶剂,在室温下以液态形式存在,目前在医药领域的应用正处于起步阶段。由于其具有的独特理化性质,已被发现能够溶解以纤维素为代表的多种难溶性大分子,加上良好的生物相容性以及促进传递和渗透的特性,使其在外用透皮吸收的应用方向上具有较大潜力(Proc Natl Acad Sci USA,2014,111(37):13313-13318.)。Deep eutectic solvent (DES) is a new multi-purpose green solvent composed of hydrogen bond donor (HBD) and hydrogen bond acceptor (HBA) in a certain molar ratio. It exists in liquid form at room temperature and is currently in its infancy in the field of medicine. Due to its unique physical and chemical properties, it has been found to be able to dissolve a variety of poorly soluble macromolecules represented by cellulose. In addition, it has good biocompatibility and the ability to promote transmission and penetration, making it have great potential in the application direction of external transdermal absorption (Proc Natl Acad Sci USA, 2014, 111 (37): 13313-13318.).
明胶是胶原蛋白的部分水解产物。其来源广泛,具有易于成型的三维网络结构,与人体具有很好的生物相容性,还具有止血的功效,因而是一种良好的成膜材料。但其因溶于水后强度低、脆性大,一经溶胀后强度和弹性模量会迅速降低,这一不足极大的限制了它的应用。而植物纤维的引入往往能使明胶柔韧性和强度明显增强,同时两者具有很好的相容性和稳定性,具有共混复合作为医药材料基质的潜力。Gelatin is a partial hydrolysis product of collagen. It is widely available, has a three-dimensional network structure that is easy to form, has good biocompatibility with the human body, and has the effect of stopping bleeding, so it is a good film-forming material. However, it has low strength and high brittleness after being dissolved in water. Once swollen, its strength and elastic modulus will decrease rapidly, which greatly limits its application. The introduction of plant fibers can often significantly enhance the flexibility and strength of gelatin. At the same time, the two have good compatibility and stability, and have the potential to be blended and compounded as a matrix for medical materials.
尽管竹类资源非常丰富,但也有很多来自不同竹相关产业的加工副产物需要得到有效利用。如建材和家具行业的竹粉可作为竹纤维的重要来源,废弃竹段热解生成的竹炭具有多孔结构和较高的孔隙度,其吸附能力强,具有抑菌、止血促凝的功效(科技导报,2010(16):113-117)。而竹叶中的叶绿素的结构与血红素极其相似,不仅对皮肤组织有再生的作用,也具有消炎和促进创面愈合的作用(东北农业大学学报,2009,40(12):130-134)。将这两种物质用于治疗皮肤溃疡及损伤,可开发出更多新的医用护理材料,能够为临床治疗该类疾病提供更多选择。Although bamboo resources are very abundant, there are also many processing by-products from different bamboo-related industries that need to be effectively utilized. For example, bamboo powder in the building materials and furniture industries can be used as an important source of bamboo fiber. Bamboo charcoal generated by pyrolysis of discarded bamboo segments has a porous structure and high porosity. It has strong adsorption capacity and has antibacterial, hemostatic and coagulation effects (Science and Technology Review, 2010(16):113-117). The structure of chlorophyll in bamboo leaves is extremely similar to hemoglobin. It not only has a regenerative effect on skin tissue, but also has anti-inflammatory and wound healing effects (Journal of Northeast Agricultural University, 2009, 40(12):130-134). Using these two substances to treat skin ulcers and injuries can develop more new medical care materials and provide more options for clinical treatment of such diseases.
目前已有部分用于治疗溃疡类型疾病的敷料,其中针对口腔溃疡居多,体表皮肤溃疡贴膜极少;同时存在配方与工艺较为复杂、功能有限、需具备特殊设备、明胶易失水硬化等主要问题。本发明提供一种以低共熔溶剂、竹纤维和明胶作为主要成分的复合膜及其制备方法.其配方新颖、制备简单、功能全面,易于规模化生产,同时解决了材质易失水硬化的问题,提高了创面接触的舒适度和透气性;不仅提高了复合膜的强度、功能性及治疗效果,而且实现了竹资源的高价值开发和多重利用。At present, there are some dressings for treating ulcer-type diseases, most of which are for oral ulcers, and very few are for skin ulcers on the body surface; at the same time, there are major problems such as complex formula and process, limited functions, special equipment required, and gelatin easy to lose water and harden. The present invention provides a composite film with low eutectic solvent, bamboo fiber and gelatin as main components and a preparation method thereof. It has a novel formula, simple preparation, comprehensive functions, and is easy to mass produce. At the same time, it solves the problem of easy dehydration and hardening of the material, and improves the comfort and air permeability of the wound contact; it not only improves the strength, functionality and therapeutic effect of the composite film, but also realizes the high-value development and multiple utilization of bamboo resources.
发明内容Summary of the invention
本发明的目的是提供一种多种功能的复合组分抗溃疡皮肤护理贴膜的制备方法,所涉及的基础组分包含低共熔溶剂、竹纤维和明胶;所涉及的制备工艺简单,复合膜功能全面、性质稳定,制备时无需使用特殊设备,具有较好的开发和应用前景。通过物理方式使用明胶将低共熔溶剂和竹纤维的混合物以透明状薄膜形式复合,极大拓展了现有绿色溶剂在医药材料领域中的应用。制备环节中各组分良好的理化特性体现出了明显的组合优势,竹纤维-低共熔溶剂-明胶复合膜整体性状、功能集成性及机械强度均优于同等条件下制得的竹纤维-明胶复合材料,并可方便地添加竹叶绿素及竹炭等功能物在抗溃疡应用中发挥协同作用。复合膜外观平滑且均匀性良好;同时便于切分,且易于实现规模化制备。使用时弹性及粘附性强,热稳定性、透气性能以及吸湿、保湿性能良好,同时也体现出可作为药物释放载体的特点。The purpose of the present invention is to provide a method for preparing a composite anti-ulcer skin care film with multiple functions, wherein the basic components involved include a low eutectic solvent, bamboo fiber and gelatin; the preparation process involved is simple, the composite film has comprehensive functions and stable properties, no special equipment is required during preparation, and the film has good development and application prospects. The mixture of the low eutectic solvent and bamboo fiber is compounded in the form of a transparent film using gelatin in a physical manner, which greatly expands the application of existing green solvents in the field of pharmaceutical materials. The good physical and chemical properties of each component in the preparation process reflect obvious combination advantages, and the overall properties, functional integration and mechanical strength of the bamboo fiber-low eutectic solvent-gelatin composite film are better than those of the bamboo fiber-gelatin composite material prepared under the same conditions, and functional materials such as bamboo chlorophyll and bamboo charcoal can be conveniently added to play a synergistic role in anti-ulcer applications. The composite film has a smooth appearance and good uniformity; it is also easy to cut and easy to achieve large-scale preparation. It has strong elasticity and adhesion during use, good thermal stability, air permeability, and moisture absorption and moisture retention properties, and also reflects the characteristics of being able to be used as a drug release carrier.
技术方案:为了实现上述目的,提出了一种复合型多功能皮肤溃疡护理贴膜的制备方法:Technical solution: In order to achieve the above purpose, a preparation method of a composite multifunctional skin ulcer care film is proposed:
本发明所述一种复合型多功能皮肤溃疡护理贴膜,其特征在于:所用低共熔溶剂作为竹纤维溶剂、成膜助剂以及促渗透剂,包括但不限于氯化胆碱-乙二醇(1:2)、氯化胆碱-1,2-丙二醇(1:2)或氯化胆碱-甘油(1:2)中的一种。The composite multifunctional skin ulcer care film of the present invention is characterized in that the low eutectic solvent used as the bamboo fiber solvent, film-forming aid and penetration promoter includes but is not limited to one of choline chloride-ethylene glycol (1:2), choline chloride-1,2-propylene glycol (1:2) or choline chloride-glycerol (1:2).
上述一种复合型多功能皮肤溃疡护理贴膜制备方法,其特征在于:所用膜材料为竹纤维。The method for preparing the composite multifunctional skin ulcer care film is characterized in that the film material used is bamboo fiber.
上述一种复合型多功能皮肤溃疡护理贴膜制备方法,其特征在于:所用成膜剂为明胶。The method for preparing the composite multifunctional skin ulcer care film is characterized in that the film-forming agent used is gelatin.
具体制备步骤如下:The specific preparation steps are as follows:
(1)将竹纤维:低共熔溶剂=1:10~1:15的质量比混合,110℃加热1~2小时形成均相溶液;再加入5~25倍竹纤维质量的明胶饱和水溶液,80℃搅拌0.5~1 小时制得膜浆;(1) Mix bamboo fiber and low eutectic solvent in a mass ratio of 1:10 to 1:15, heat at 110° C. for 1 to 2 hours to form a homogeneous solution; then add a saturated gelatin aqueous solution of 5 to 25 times the mass of the bamboo fiber, stir at 80° C. for 0.5 to 1 hour to prepare a membrane slurry;
(2)当需加入功能物时,在此步按照功能物:膜浆=5:100~15:100的质量比加入叶绿素或竹炭后,室温下充分搅拌使之分散均匀;(2) When a functional substance is to be added, chlorophyll or bamboo charcoal is added in a mass ratio of functional substance to membrane slurry of 5:100 to 15:100, and then stirred at room temperature to be evenly dispersed;
步骤(2)中所述功能物包含但不限于竹叶绿素以及竹炭;The functional substance in step (2) includes but is not limited to bamboo chlorophyll and bamboo charcoal;
(3)将(1)或(2)中形成的均匀混合体系于真空条件下不断蒸发除去水分直至重量不再减少;(3) continuously evaporating the uniformly mixed system formed in (1) or (2) under vacuum conditions to remove water until the weight stops decreasing;
(4)消泡:在真空干燥环境中进行减压脱泡处理;(4) Defoaming: decompression and degassing treatment in a vacuum drying environment;
(5)涂膜:把全部膜浆倾倒在光滑洁净的玻璃平面上,待其自然延流并控制形成1~2mm厚膜;(5) Film coating: Pour all the film slurry onto a smooth and clean glass surface, wait for it to flow naturally and control the film to form a 1-2 mm thick film;
(6)静置与启膜:将制得贴膜自然静置24~48小时,完全固化后揭膜;(6) Standing and removing the film: Let the prepared film stand naturally for 24 to 48 hours, and remove the film after it is completely cured;
(7)分装:将制得贴膜切成一定规格,紫外灯照射60min灭菌消毒后,分装并密封保存。(7) Packaging: Cut the prepared film into certain sizes, sterilize it under ultraviolet light for 60 minutes, and then pack it and seal it for storage.
上述一种复合型多功能皮肤溃疡护理贴膜制备方法,膜的厚度范围包含但不限于1~2mm;对于所制得膜的厚度,可以根据实际需要通过控制膜浆体积进行调整。例如,所得到的膜厚度可以为1.0mm、1.2mm、1.4mm、1.8mm、 2.0mm等。In the above-mentioned composite multifunctional skin ulcer care film preparation method, the film thickness range includes but is not limited to 1 to 2 mm; the thickness of the prepared film can be adjusted by controlling the film slurry volume according to actual needs. For example, the obtained film thickness can be 1.0 mm, 1.2 mm, 1.4 mm, 1.8 mm, 2.0 mm, etc.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
为了更完整地说明本发明具体实施例的技术方案,下面将对实施例中所需附图进行简单的说明。所描述的附图仅仅是本发明的一部分实施例,对于本领域的技术人员,应能够根据这些附图获得实施例其它的附图。其中:In order to more completely illustrate the technical solution of the specific embodiment of the present invention, the following briefly describes the drawings required in the embodiment. The drawings described are only part of the embodiment of the present invention. For those skilled in the art, it should be possible to obtain other drawings of the embodiment based on these drawings. Among them:
图1为本发明中的竹纤维-低共熔溶剂-明胶复合膜(未添加功能物)的基膜外观;FIG1 is an appearance of a base film of a bamboo fiber-deep eutectic solvent-gelatin composite film (without adding functional substances) in the present invention;
图2为本发明中的竹纤维-低共熔溶剂-明胶复合膜的光学显微镜图像;FIG2 is an optical microscope image of the bamboo fiber-deep eutectic solvent-gelatin composite film of the present invention;
图3为本发明中的竹纤维-低共熔溶剂-明胶复合膜的原子力显微相图(左) 及其三维图(右);FIG3 is an atomic force microscopic phase diagram (left) and a three-dimensional diagram (right) of the bamboo fiber-deep eutectic solvent-gelatin composite film of the present invention;
图4为本发明中的竹纤维-低共熔溶剂-明胶复合膜的扫描电镜正视图;FIG4 is a front view of a scanning electron microscope of a bamboo fiber-deep eutectic solvent-gelatin composite film of the present invention;
图5为本发明中的竹纤维-低共熔溶剂-明胶复合膜的红外光谱(FT-IR) 图(a为竹叶绿素;b为竹炭;c为添加竹叶绿素的复合膜;d为添加竹炭的复合膜);FIG5 is an infrared spectrum (FT-IR) diagram of the bamboo fiber-deep eutectic solvent-gelatin composite film of the present invention (a is bamboo chlorophyll; b is bamboo charcoal; c is a composite film with bamboo chlorophyll added; d is a composite film with bamboo charcoal added);
图6为本发明中的竹纤维-低共熔溶剂-明胶复合膜的透气性实验(a为凝胶贴膜与漏斗紧密贴合的状态;b为透气性实验装置整体图;c为空气流穿过贴膜后在水中产生气泡的现象);FIG6 is an air permeability experiment of the bamboo fiber-deep eutectic solvent-gelatin composite film of the present invention (a is a state where the gel film is tightly fitted to the funnel; b is an overall diagram of the air permeability experimental device; c is a phenomenon in which bubbles are generated in water after air flows through the film);
图7为本发明中的竹纤维-低共熔溶剂-明胶复合膜吸湿与保湿实验结果(a 与b分别为湿度43%和81%环境下的吸湿曲线;c为湿度0%环境下的保湿曲线)。FIG. 7 shows the moisture absorption and moisture retention test results of the bamboo fiber-deep eutectic solvent-gelatin composite film of the present invention (a and b are moisture absorption curves under humidity of 43% and 81% respectively; c is the moisture retention curve under humidity of 0%).
具体实施方式DETAILED DESCRIPTION
下面是对本发明进行的详细说明。虽然显示了本发明的具体实施例,然而应当理解,可以以各种形式实现本发明而不应被这里阐述的实施例所限制。相反,提供这些实施例是为了能够更透彻地理解本发明,并且能够将本发明的范围完整的传达给本领域的技术人员。The following is a detailed description of the present invention. Although specific embodiments of the present invention are shown, it should be understood that the present invention can be implemented in various forms and should not be limited by the embodiments set forth herein. On the contrary, these embodiments are provided to enable a more thorough understanding of the present invention and to fully convey the scope of the present invention to those skilled in the art.
本说明书以及权利要求书并不以用词的差异作为区分组分的方式,而是通过组分在功能上的差异作为区分的准则。在本申请中所提及的“包含”或“包括”为开放式用语,故应解释成“包含但不限于”。说明书后续描述的实施例为本发明的较佳实施方式,并且以说明书的一般准则为目的,并非用以限定本发明的范围。This specification and claims do not use differences in terms as a way to distinguish components, but use differences in the functions of the components as the criteria for distinction. The "include" or "comprising" mentioned in this application is an open-ended term and should be interpreted as "including but not limited to". The embodiments described in the subsequent description are preferred embodiments of the present invention and are based on the general principles of the specification and are not intended to limit the scope of the present invention.
实施例1Example 1
称取0.3g竹纤维与3.0g低共熔溶剂混合,110℃加热1小时形成均相溶液;再加入7.5g明胶饱和水溶液,80℃搅拌0.5小时得到膜浆;所述竹纤维与低共熔溶剂的质量比为1:10,所述明胶饱和水溶液与竹纤维粉的质量比为25:1;Weigh 0.3g of bamboo fiber and 3.0g of low eutectic solvent, mix them, heat at 110°C for 1 hour to form a homogeneous solution; then add 7.5g of saturated gelatin aqueous solution, stir at 80°C for 0.5 hour to obtain a membrane slurry; the mass ratio of the bamboo fiber to the low eutectic solvent is 1:10, and the mass ratio of the saturated gelatin aqueous solution to the bamboo fiber powder is 25:1;
将膜浆于真空条件下不断蒸发除去水分直至重量不再减少,随后将其进行减压脱泡处理;The membrane slurry is continuously evaporated to remove water under vacuum conditions until the weight stops decreasing, and then subjected to a decompression degassing treatment;
把脱泡后的膜浆倾倒在光滑洁净的玻璃平面上,待其自然延流。自然静置24小时并完全固化后揭膜,可得竹纤维-低共熔溶剂-明胶复合膜;经紫外灯照射60min灭菌消毒后,冲切、分装并密封保存。Pour the degassed membrane slurry onto a smooth and clean glass surface and wait for it to flow naturally. After standing naturally for 24 hours and completely solidifying, peel off the membrane to obtain a bamboo fiber-low eutectic solvent-gelatin composite membrane; after sterilization by ultraviolet light for 60 minutes, punch, package and seal for storage.
实施例2Example 2
称取0.1g竹纤维与1.5g低共熔溶剂混合,110℃加热1小时形成均相溶液;再加入2.0g明胶饱和水溶液,80℃搅拌1小时得到膜浆;所述竹纤维与低共熔溶剂的质量比为1:15,所述明胶饱和水溶液与竹纤维粉的质量比为25:1;Weigh 0.1g of bamboo fiber and 1.5g of a low eutectic solvent, mix them, and heat them at 110°C for 1 hour to form a homogeneous solution; then add 2.0g of a saturated aqueous solution of gelatin, and stir at 80°C for 1 hour to obtain a membrane slurry; the mass ratio of the bamboo fiber to the low eutectic solvent is 1:15, and the mass ratio of the saturated aqueous solution of gelatin to the bamboo fiber powder is 25:1;
将膜浆于真空条件下不断蒸发除去水分直至重量不再减少,随后将其进行减压脱泡处理;The membrane slurry is continuously evaporated to remove water under vacuum conditions until the weight stops decreasing, and then subjected to a decompression degassing treatment;
把脱泡后的膜浆倾倒在光滑洁净的玻璃平面上,待其自然延流。自然静置24小时并完全固化后揭膜,可得竹纤维-低共熔溶剂-明胶复合膜;经紫外灯照射60min灭菌消毒后,冲切、分装并密封保存。Pour the degassed membrane slurry onto a smooth and clean glass surface and wait for it to flow naturally. After standing naturally for 24 hours and completely solidifying, peel off the membrane to obtain a bamboo fiber-low eutectic solvent-gelatin composite membrane; after sterilization by ultraviolet light for 60 minutes, punch, package and seal for storage.
实施例3Example 3
称取0.4g竹纤维与5.0g低共熔溶剂混合,110℃加热1小时形成均相溶液;再加入2.5g明胶饱和水溶液,80℃搅拌1小时得到膜浆;所述竹纤维与低共熔溶剂的质量比为1:12.5,所述明胶饱和水溶液与竹纤维粉的质量比为6.25:1;Weigh 0.4 g of bamboo fiber and 5.0 g of a low eutectic solvent, mix them, and heat them at 110° C. for 1 hour to form a homogeneous solution; then add 2.5 g of a saturated gelatin aqueous solution, and stir at 80° C. for 1 hour to obtain a membrane slurry; the mass ratio of the bamboo fiber to the low eutectic solvent is 1:12.5, and the mass ratio of the saturated gelatin aqueous solution to the bamboo fiber powder is 6.25:1;
将膜浆于真空条件下不断蒸发除去水分直至重量不再减少,随后将其进行减压脱泡处理;The membrane slurry is continuously evaporated to remove water under vacuum conditions until the weight stops decreasing, and then subjected to a decompression degassing treatment;
把脱泡后的膜浆倾倒在光滑洁净的玻璃平面上,待其自然延流。自然静置24小时并完全固化后揭膜,可得竹纤维-低共熔溶剂-明胶复合膜;经紫外灯照射60min灭菌消毒后,冲切、分装并密封保存。Pour the degassed membrane slurry onto a smooth and clean glass surface and wait for it to flow naturally. After standing naturally for 24 hours and completely solidifying, peel off the membrane to obtain a bamboo fiber-low eutectic solvent-gelatin composite membrane; after sterilization by ultraviolet light for 60 minutes, punch, package and seal for storage.
实施例4Example 4
称取0.5g竹纤维与6.0g低共熔溶剂混合,110℃加热1小时形成均相溶液;再加入10.0g明胶饱和水溶液,80℃搅拌1小时得到膜浆;所述竹纤维与低共熔溶剂的质量比为1:12,所述明胶饱和水溶液与竹纤维粉的质量比为20:1;Weigh 0.5 g of bamboo fiber and 6.0 g of a low eutectic solvent, mix them, and heat them at 110° C. for 1 hour to form a homogeneous solution; then add 10.0 g of a saturated gelatin aqueous solution, and stir at 80° C. for 1 hour to obtain a membrane slurry; the mass ratio of the bamboo fiber to the low eutectic solvent is 1:12, and the mass ratio of the saturated gelatin aqueous solution to the bamboo fiber powder is 20:1;
将膜浆于真空条件下不断蒸发除去水分直至重量不再减少,随后将其进行减压脱泡处理;The membrane slurry is continuously evaporated to remove water under vacuum conditions until the weight stops decreasing, and then subjected to a decompression degassing treatment;
把脱泡后的膜浆倾倒在光滑洁净的玻璃平面上,待其自然延流。自然静置24小时并完全固化后揭膜,可得竹纤维-低共熔溶剂-明胶复合膜;经紫外灯照射60min灭菌消毒后,冲切、分装并密封保存。Pour the degassed membrane slurry onto a smooth and clean glass surface and wait for it to flow naturally. After standing naturally for 24 hours and completely solidifying, peel off the membrane to obtain a bamboo fiber-low eutectic solvent-gelatin composite membrane; after sterilization by ultraviolet light for 60 minutes, punch, package and seal for storage.
实施例5Example 5
称取0.2g竹纤维与2.8g低共熔溶剂混合,110℃加热1小时形成均相溶液;再加入3.0g明胶饱和水溶液,80℃搅拌1小时得到膜浆;所述竹纤维与低共熔溶剂的质量比为1:14,所述明胶饱和水溶液与竹纤维粉的质量比为15:1;Weigh 0.2g of bamboo fiber and 2.8g of low eutectic solvent, mix them, heat at 110°C for 1 hour to form a homogeneous solution; then add 3.0g of saturated gelatin aqueous solution, stir at 80°C for 1 hour to obtain a membrane slurry; the mass ratio of the bamboo fiber to the low eutectic solvent is 1:14, and the mass ratio of the saturated gelatin aqueous solution to the bamboo fiber powder is 15:1;
将膜浆于真空条件下不断蒸发除去水分直至重量不再减少,随后将其进行减压脱泡处理;The membrane slurry is continuously evaporated to remove water under vacuum conditions until the weight stops decreasing, and then subjected to a decompression degassing treatment;
把脱泡后的膜浆倾倒在光滑洁净的玻璃平面上,待其自然延流。自然静置24小时并完全固化后揭膜,可得竹纤维-低共熔溶剂-明胶复合膜;经紫外灯照射60min灭菌消毒后,冲切、分装并密封保存。Pour the degassed membrane slurry onto a smooth and clean glass surface and wait for it to flow naturally. After standing naturally for 24 hours and completely solidifying, peel off the membrane to obtain a bamboo fiber-low eutectic solvent-gelatin composite membrane; after sterilization by ultraviolet light for 60 minutes, punch, package and seal for storage.
实施例6Example 6
称取0.4g竹纤维与5.6g低共熔溶剂混合,110℃加热1小时形成均相溶液A;再加入3.0g明胶饱和水溶液,80℃搅拌0.5小时得到膜浆;所述竹纤维与低共熔溶剂的质量比为1:14,所述明胶饱和水溶液与竹纤维粉的质量比为7.5:1;Weigh 0.4 g of bamboo fiber and 5.6 g of a low eutectic solvent, mix them, and heat them at 110° C. for 1 hour to form a homogeneous solution A; then add 3.0 g of a saturated gelatin aqueous solution, and stir at 80° C. for 0.5 hour to obtain a membrane slurry; the mass ratio of the bamboo fiber to the low eutectic solvent is 1:14, and the mass ratio of the saturated gelatin aqueous solution to the bamboo fiber powder is 7.5:1;
将膜浆于真空条件下不断蒸发除去水分直至重量不再减少,随后将其进行减压脱泡处理;The membrane slurry is continuously evaporated to remove water under vacuum conditions until the weight stops decreasing, and then subjected to a decompression degassing treatment;
把脱泡后的膜浆倾倒在光滑洁净的玻璃平面上,待其自然延流。自然静置24小时并完全固化后揭膜,可得竹纤维-低共熔溶剂-明胶复合膜;经紫外灯照射60min灭菌消毒后,冲切、分装并密封保存。Pour the degassed membrane slurry onto a smooth and clean glass surface and wait for it to flow naturally. After standing naturally for 24 hours and completely solidifying, peel off the membrane to obtain a bamboo fiber-low eutectic solvent-gelatin composite membrane; after sterilization by ultraviolet light for 60 minutes, punch, package and seal for storage.
实施例7Example 7
称取0.4g竹纤维与5.2g低共熔溶剂混合,110℃加热1小时形成均相溶液;再加入3.5g明胶饱和水溶液,80℃搅拌1小时得到膜浆;所述竹纤维与低共熔溶剂的质量比为1:13,所述明胶饱和水溶液与竹纤维粉的质量比为8.75:1;Weigh 0.4 g of bamboo fiber and 5.2 g of a low eutectic solvent, mix them, and heat them at 110° C. for 1 hour to form a homogeneous solution; then add 3.5 g of a saturated gelatin aqueous solution, and stir at 80° C. for 1 hour to obtain a membrane slurry; the mass ratio of the bamboo fiber to the low eutectic solvent is 1:13, and the mass ratio of the saturated gelatin aqueous solution to the bamboo fiber powder is 8.75:1;
将膜浆于真空条件下不断蒸发除去水分直至重量不再减少,随后将其进行减压脱泡处理;The membrane slurry is continuously evaporated to remove water under vacuum conditions until the weight stops decreasing, and then subjected to a decompression degassing treatment;
把脱泡后的膜浆倾倒在光滑洁净的玻璃平面上,待其自然延流。自然静置24小时并完全固化后揭膜,可得竹纤维-低共熔溶剂-明胶复合膜;经紫外灯照射60min灭菌消毒后,冲切、分装并密封保存。Pour the degassed membrane slurry onto a smooth and clean glass surface and wait for it to flow naturally. After standing naturally for 24 hours and completely solidifying, peel off the membrane to obtain a bamboo fiber-low eutectic solvent-gelatin composite membrane; after sterilization by ultraviolet light for 60 minutes, punch, package and seal for storage.
实施例8Example 8
称取0.4g竹纤维与4.4g低共熔溶剂混合,110℃加热1小时形成均相溶液;再加入10.0g明胶饱和水溶液,80℃搅拌1小时得到膜浆;所述竹纤维与低共熔溶剂的质量比为1:11,所述明胶饱和水溶液与竹纤维粉的质量比为25:1;Weigh 0.4 g of bamboo fiber and 4.4 g of a low eutectic solvent, mix them, and heat them at 110° C. for 1 hour to form a homogeneous solution; then add 10.0 g of a saturated gelatin aqueous solution, and stir at 80° C. for 1 hour to obtain a membrane slurry; the mass ratio of the bamboo fiber to the low eutectic solvent is 1:11, and the mass ratio of the saturated gelatin aqueous solution to the bamboo fiber powder is 25:1;
将膜浆于真空条件下不断蒸发除去水分直至重量不再减少;The membrane slurry is continuously evaporated under vacuum conditions to remove water until the weight stops decreasing;
按照竹叶绿素:膜浆=15:100的质量比称取竹叶绿素,加入至除去水分后的膜浆中,在室温下充分搅拌使之分散均匀,随后进行减压脱泡处理;Bamboo chlorophyll was weighed according to the mass ratio of bamboo chlorophyll: film slurry = 15:100, added to the film slurry after water removal, fully stirred at room temperature to make it evenly dispersed, and then decompressed and degassed;
把脱泡后的膜浆倾倒在光滑洁净的玻璃平面上,待其自然延流。自然静置24小时并完全固化后揭膜,可得负载竹叶绿素的竹纤维-低共熔溶剂-明胶复合膜;经紫外灯照射60min灭菌消毒后,冲切、分装并密封保存。Pour the degassed membrane slurry onto a smooth and clean glass surface and wait for it to flow naturally. After standing naturally for 24 hours and completely solidifying, peel off the membrane to obtain a bamboo fiber-low eutectic solvent-gelatin composite membrane loaded with bamboo chlorophyll; after sterilization by ultraviolet light for 60 minutes, punch, package and seal for storage.
实施例9Embodiment 9
称取0.8g竹纤维与10.0g低共熔溶剂混合,110℃加热1.5小时形成均相溶液;再加入4.8g明胶饱和水溶液,80℃搅拌1小时得到膜浆;所述竹纤维与低共熔溶剂的质量比为1:12.5,所述明胶饱和水溶液与竹纤维粉的质量比为6:1;Weigh 0.8g of bamboo fiber and 10.0g of low eutectic solvent, mix them, heat at 110°C for 1.5 hours to form a homogeneous solution; then add 4.8g of saturated gelatin aqueous solution, stir at 80°C for 1 hour to obtain a membrane slurry; the mass ratio of the bamboo fiber to the low eutectic solvent is 1:12.5, and the mass ratio of the saturated gelatin aqueous solution to the bamboo fiber powder is 6:1;
将膜浆于真空条件下不断蒸发除去水分直至重量不再减少,随后将其进行减压脱泡处理;The membrane slurry is continuously evaporated to remove water under vacuum conditions until the weight stops decreasing, and then subjected to a decompression degassing treatment;
按照竹炭:膜浆=10:100的质量比称取竹叶绿素,加入至除去水分后的膜浆中,在室温下充分搅拌使之分散均匀,随后进行减压脱泡处理;Bamboo chlorophyll was weighed according to the mass ratio of bamboo charcoal: film pulp = 10:100, added to the film pulp after water removal, fully stirred at room temperature to make it evenly dispersed, and then decompressed and degassed;
把脱泡后的膜浆倾倒在光滑洁净的玻璃平面上,待其自然延流。自然静置24小时并完全固化后揭膜,可得负载竹炭的竹纤维-低共熔溶剂-明胶复合膜;经紫外灯照射60min灭菌消毒后,冲切、分装并密封保存。Pour the degassed membrane slurry onto a smooth and clean glass surface and wait for it to flow naturally. After standing naturally for 24 hours and completely solidifying, peel off the membrane to obtain a bamboo fiber-low eutectic solvent-gelatin composite membrane loaded with bamboo charcoal; after sterilization by ultraviolet light irradiation for 60 minutes, punch, package and seal for storage.
对实施例8~9制备的负载功能物的竹纤维-低共熔溶剂-明胶复合膜进行了红外光谱的测试。The functional material-loaded bamboo fiber-deep eutectic solvent-gelatin composite films prepared in Examples 8 to 9 were tested by infrared spectroscopy.
红外测试结果见附图5。下面对红外测试结果进行简单的分析:The infrared test results are shown in Figure 5. The following is a brief analysis of the infrared test results:
上图为竹叶绿素(a)和负载竹叶绿素的明胶膜(c)的FT-IR谱图,下图为竹炭(b)和负载竹炭的明胶膜(d)的FT-IR谱图。在叶绿素谱图的典型信号中,1600和1276cm-1附近的吸收峰由卟啉环上的C=C耦合振动以及C-N的伸缩振动产生,添加了叶绿素的复合膜谱图中在对应波数处也出现了相关信号,表明竹叶绿素已被成功负载。同样地,在竹炭谱图的典型特征信号中,1650和1176 cm-1附近出现的吸收峰分别由芳环骨架振动和C-O伸缩振动产生,添加了竹炭的复合膜谱图对应波数处也可以观察到有关信号,表明该膜已成功负载竹炭。The upper figure shows the FT-IR spectra of bamboo chlorophyll (a) and gelatin film loaded with bamboo chlorophyll (c), and the lower figure shows the FT-IR spectra of bamboo charcoal (b) and gelatin film loaded with bamboo charcoal (d). In the typical signals of the chlorophyll spectrum, the absorption peaks near 1600 and 1276 cm -1 are generated by the C=C coupling vibration on the porphyrin ring and the stretching vibration of CN. In the spectrum of the composite film with chlorophyll added, relevant signals also appear at the corresponding wavenumbers, indicating that bamboo chlorophyll has been successfully loaded. Similarly, in the typical characteristic signals of the bamboo charcoal spectrum, the absorption peaks near 1650 and 1176 cm -1 are generated by the vibration of the aromatic ring skeleton and the stretching vibration of CO, respectively. Relevant signals can also be observed at the corresponding wavenumbers of the composite film spectrum with bamboo charcoal added, indicating that the membrane has been successfully loaded with bamboo charcoal.
对实施例8~9制备的负载功能物的竹纤维-低共熔溶剂-明胶复合膜进行了透气性测试。基于国家标准GB/T228192008和GBT7755.1-2018搭建了相应的简易装置,通过观察空气流经过贴膜后在装置尾端的液层中是否产生气泡来判断其有无透气性,具体结果见附图6。The air permeability of the bamboo fiber-deep eutectic solvent-gelatin composite membrane loaded with functional substances prepared in Examples 8 to 9 was tested. A corresponding simple device was built based on the national standards GB/T228192008 and GBT7755.1-2018, and the air permeability was judged by observing whether bubbles were generated in the liquid layer at the tail end of the device after the air flow passed through the film. The specific results are shown in Figure 6.
对实施例8~9制备的负载功能物的竹纤维-低共熔溶剂-明胶复合膜进行了吸湿与保湿的性能测试。结果见附图7,具体操作如下:The moisture absorption and moisture retention performance of the bamboo fiber-deep eutectic solvent-gelatin composite film loaded with functional substances prepared in Examples 8 to 9 were tested. The results are shown in Figure 7. The specific operation is as follows:
吸湿实验:准确称量0.5g复合膜并放入直径为4cm的广口称量瓶,然后将其置于装有碳酸钾饱和水溶液(根据需要来控制相对湿度)的干燥器内,整体温度恒定在20℃。吸湿率计算式为Ra=100*(Wn-Wo)/Wo;其中,Wo和Wn分别为放置48h前后复合膜的质量。Moisture absorption experiment: 0.5g of the composite film was accurately weighed and placed in a wide-mouth weighing bottle with a diameter of 4cm, and then placed in a desiccator filled with a saturated aqueous solution of potassium carbonate (relative humidity was controlled as needed), with the overall temperature kept constant at 20°C. The moisture absorption rate was calculated as Ra = 100*( Wn - Wo )/ Wo ; where Wo and Wn were the masses of the composite film before and after 48h of placement.
保湿实验:准确称取0.5g含10%水分的复合膜并放入直径为4cm的广口称量瓶,然后将其置于预先装有硅胶的干燥器内,整体温度恒定在20℃。保湿率(Rh%)计算式为Rh%=100*Hn/Ho;其中,Ho、Hn为放置48h前后复合膜中水分的质量。Moisture retention experiment: 0.5g of composite film containing 10% water was accurately weighed and placed in a wide-mouth weighing bottle with a diameter of 4cm, and then placed in a desiccator pre-filled with silica gel, with the overall temperature kept constant at 20°C. The moisture retention rate (Rh%) was calculated as Rh% = 100* Hn / H0 ; where H0 and Hn are the mass of water in the composite film before and after 48h.
对实施例1~9所述的竹纤维-低共熔溶剂-明胶复合膜进行了整体性状和粘附力比较。粘附力测试具体操作为:The overall properties and adhesion of the bamboo fiber-deep eutectic solvent-gelatin composite films described in Examples 1 to 9 were compared. The specific operation of the adhesion test is as follows:
取两块热塑性弹性体合成橡胶(1cm*3cm,重约5g),一块连接到天平一侧的托盘下端,另一块则固定于天平底座上。然后将贴膜(1cm*3cm)置于两块橡胶之间,用50g砝码紧压5秒(符合常见贴剂按压时长)后移去该砝码;进而在天平的另一侧托盘上不断增添砝码以加大重力,以5秒内上、下两块橡胶分离为标准,所加砝码质量用于衡量贴膜的粘附力。测试结果如表1所示。Take two pieces of thermoplastic elastomer synthetic rubber (1cm*3cm, weighing about 5g), one of which is connected to the lower end of the tray on one side of the balance, and the other is fixed to the base of the balance. Then place the film (1cm*3cm) between the two pieces of rubber, press it tightly with a 50g weight for 5 seconds (in line with the pressing time of common patches), and then remove the weight; then continue to add weights to the tray on the other side of the balance to increase the gravity, and use the separation of the upper and lower pieces of rubber within 5 seconds as the standard. The mass of the added weight is used to measure the adhesion of the film. The test results are shown in Table 1.
表1,不同实施例所得竹纤维-低共熔溶剂-明胶复合膜整体性质和粘附力比较结果:Table 1, comparison results of overall properties and adhesion of bamboo fiber-deep eutectic solvent-gelatin composite films obtained in different embodiments:
对实施例8所制备的添加了竹叶绿素的竹纤维-低共熔溶剂-明胶复合膜进行了叶绿素积累渗透量测定,测试条件与结果如表2所示。The chlorophyll accumulation permeability of the bamboo fiber-low eutectic solvent-gelatin composite film added with bamboo chlorophyll prepared in Example 8 was measured. The test conditions and results are shown in Table 2.
表2,负载竹叶绿素的竹纤维-低共熔溶剂-明胶复合膜经聚二甲基硅氧烷 (PDMS)膜积累渗透量测定的条件与结果:Table 2, conditions and results of the measurement of the accumulated permeation amount of the bamboo fiber-deep eutectic solvent-gelatin composite membrane loaded with bamboo chlorophyll through the polydimethylsiloxane (PDMS) membrane:
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