多糖界面复合薄膜及其应用
发布时间：2019-06-13 11:33
【摘要】：多糖是在自然界中大量存在的天然高分子,价格便宜,具有独特的特性,例如亲水性、稳定、安全、无毒,生物可降解性。多糖的特殊结构和功能使之可作为改性生物医学器件表面的生物材料。由于其天然成分,它们是模拟活体细胞环境结构和生物化学特性系统的理想的构筑单元。在过去的十五年中,很多研究已经尝试通过界面复合将多糖组装于聚电解质复合膜中,例如以静电力为主要驱动力的层层组装界面复合。大多数多糖带有负电荷,因而可作为聚阴离子成分,也可经过化学改性成为聚阳离子,如氨基改性的透明质酸和季铵化的壳聚糖。然而聚阳离子多糖的种类是非常有限的,目前只有壳聚糖(甲壳素的去乙酰化形式)是可利用的且可用于制备聚电解质复合薄膜。由于其多个显著优势,包括获取途径广泛,生物相容性高,提高伤口的自愈性和和抗菌性,壳聚糖在层层组装膜中是使用最广泛的多糖。然而壳聚糖在pH大于6的水溶液中的低溶解性,限制了它在口鼻传输系统中作为吸附强化剂的使用。此外,由于壳聚糖在水溶液中的快速吸水性和高溶胀性,限制了壳聚糖薄膜在药物输运等多方面的应用。本研究的目的是使用新型带正电荷的多糖(如季铵纤维素和阳离子瓜尔豆胶)代替壳聚糖,用于构筑基于层层组装的界面复合薄膜。此外,我们研究了物理参数如pH值,离子强度和温度对阳离子多糖与天然(或合成)阴离子聚电解质之间相互作用的影响,此外还研究了多糖薄膜的吸水性,防雾,防霜行为。为了实现上述的目的,我们使用了多种表征手段对层层组装的多糖薄膜进行了研究。紫外可见光谱,光学反射仪,傅里叶红外变换光谱用于监控复合过程、膜厚度增长和金属离子与薄膜之间的相互作用。石英晶体微天平用于确定生长模式并计算聚电解质离子对的吸收质量。原子力显微镜用于观察膜的表面形态。接触角测定用于研究多糖薄膜的亲水性。通过区域抑制测试被用来揭示多糖薄膜的抗菌性。本论文的第一部分是将带相反电荷的纤维素衍生物,季铵化纤维素(QC)和羧甲基纤维素(CMC),交替沉积于硅片和石英基片来制备薄膜。研究了pH值,离子强度,温度因素对于薄膜增长和形态的影响。QC和CMC的主链由葡萄糖环组成,具有亲水性和刚性,因此QC和CMC表现出与合成的乙烯基聚电解质(如聚苯乙烯磺酸钠(PSS)和聚二烯丙基二甲基氯化铵(PDDA))不同的组装行为。随着pH值在3～5范围内增大时,QC和CMC可通过层层组装形成薄膜；而在中性pH区间,QC和CMC难以组装；当pH值高于10,QC和CMC又可通过沉积制备薄膜。QC和CMC的层层组装对离子强度非常敏感。在组装溶液中加入0.1 M的NaCl,薄膜的增长趋势急剧下降,而提高温度则可加快膜厚的增长。浸渍时间的延长有利于QC/CMC薄膜厚度的增加,而清洗时间的增加使得薄膜变薄。早期,季铵化纤维素作为阳离子多糖制备薄膜。因此,本章的目的是确定阳离子瓜尔豆胶(CGG)与酸性聚合物如：聚弱酸如羧甲基纤维素(CMC)和聚丙烯酸(PAA)基于静电作用层层组装制备薄膜的可能性,然后研究pH值,离子强度和温度对薄膜增长模式和表面形态的依赖性。随着pH值在3～4范围内的增大,CGG和聚弱酸可通过层层组装制备薄膜；然而,在中性和高的pH区间,CGG和聚弱酸很难组装。不同于合成聚电解质复合薄膜,如PSS/PDDA和PSS/PAH, CGG/CMC和CGG/PAA的层层组装对盐浓度非常敏感。在低盐浓度的情况下,离子强度促进了CGG/CMC和CGG/PAA薄膜的增长,但增加盐浓度不易于CGG/CMC薄膜的生长。在组装过程中,升高温度对CGG/聚弱酸体系的厚度增长具有较大的影响。增加浸渍时间,能够为高分子链在薄膜表面的吸附和重排提供足够的时间,有利于更多的高分子链向薄膜内部扩散,从而增加了薄膜的厚度。然而,增加清洗时间,导致薄膜中的分子链进入溶液中,从而引起薄膜厚度的降低。第四章中,我们研究了多糖薄膜的防雾和防霜性能。发现多糖薄膜具有的防雾和防霜特性,是多糖与合成聚电解质如QC/PAA, QC/PSS, CGG/PAA, CGG/PSS等层层复合薄膜所不具备的。多糖薄膜具有的这两个特殊性能是由于水分子被快速吸附到薄膜基质中引起的。聚合物的极性基团与水分子的氢键相互作用阻止了水的凝结,使多糖薄膜具有防雾和防霜性能。研究表明通过层层组装技术,多糖可用来制备具有防雾和防霜性能的光学薄膜。最后,研究了金属离子在多糖薄膜中的渗透性以及薄膜的抗菌行为。以QC和CGG为聚阳离子,CMC和PAA为聚阴离子构筑了几种类型的多糖薄膜,并且发现Cu~(2+),Fe~(2+)和Ag+能够与基质中的羧酸基团之间发生配位作用。用于CGG/PAA基质能够与Cu~(2+), Fe~(2+)和Ag+之间发生强的相互作用,因此进一步研究了它们的抗菌性。抗菌实验表明CGG/PAA-Ag+具有很好的抗菌效果。含Ag的CGG/PAA的抗菌性能是由于薄膜中的Ag+能够被释放出来与细菌发生多种形式的相互作用从而杀死细菌。因此,我们使用这些新型阳离子多糖成功构筑了具有防雾和防霜优良性能的多糖薄膜。这些功能薄膜在生物医学应用和药物输运系统等多个不同领域将具有广泛的应用前景。
[Abstract]:The polysaccharide is a large amount of natural polymer in nature, is cheap, has unique characteristics, such as hydrophilic, stable, safe, non-toxic and biodegradable. The special structure and function of the polysaccharide can be used as the biological material of the surface of the modified biomedical device. Due to their natural components, they are ideal construction units for simulating the structural and biochemical properties of living cells. In the past 15 years, many studies have attempted to assemble the polysaccharides into the polyelectrolyte complex film by interfacial compounding, for example, by a layer-by-layer assembly interface with an electrostatic force as the main driving force. Most of the polysaccharides are negatively charged, and thus can be used as polyanionic components, and can also be chemically modified to be polycations such as amino-modified hyaluronic acid and quaternary-encapsulated chitosan. However, the species of polycationic polysaccharides are very limited, and at present only the chitosan (the deethanizing form of the chitin) is available and can be used to prepare the polyelectrolyte composite film. The chitosan is the most widely used polysaccharide in the layer-by-layer assembly film due to its multiple significant advantages, including wide access, high biocompatibility, and improved self-healing and antibacterial properties of the wound. However, the low solubility of the chitosan in the aqueous solution with a pH of more than 6 limits its use as an adsorption enhancer in the oral nasal transport system. In addition, due to the rapid water absorption and high swelling property of the chitosan in the aqueous solution, the application of the chitosan film in drug delivery and the like is limited. The purpose of this study was to use a novel positively charged polysaccharide (such as quaternary cellulose and cationic guar gum) in place of chitosan to construct an interfacial composite film based on layer-by-layer assembly. In addition, we have studied the effect of physical parameters such as pH, ionic strength and temperature on the interaction between cationic polysaccharides and natural (or synthetic) anionic polyelectrolyte, and also studies the water-absorbing, antifogging and anti-frost behavior of the polysaccharide film. In order to achieve the above-mentioned objects, we used a variety of characterization methods to study the layer-by-layer polysaccharide film. The ultraviolet-visible spectrum, the optical reflection instrument and the Fourier infrared conversion spectrum are used to monitor the composite process, the growth of the film thickness and the interaction between the metal ions and the thin film. A quartz crystal microbalance is used to determine the growth pattern and to calculate the absorption mass of the polyelectrolyte ion pair. The atomic force microscope is used to observe the surface morphology of the film. The contact angle measurement was used to study the hydrophilicity of the polysaccharide film. The antimicrobial properties of the polysaccharide film are disclosed by a regional inhibition test. The first part of this paper is to prepare a thin film by alternately depositing cellulose derivatives with opposite charges, quaternary cellulose (QC) and methylcellulose (CMC) on a silicon wafer and a quartz substrate. The effects of pH, ionic strength and temperature on the growth and morphology of the film were studied. The main chain of the QC and CMC is composed of a glucose ring, with hydrophilicity and rigidity, so that QC and CMC exhibit different assembly behavior than synthetic vinyl polyelectrolytes such as sodium polystyrene sulfonate (PSS) and polydiallyl dimethyl chloride (PDDA). As the pH value increases in the range of 3 to 5, the QC and CMC can form the film by layer-by-layer assembly; in the neutral pH range, QC and CMC are difficult to assemble; and when the pH value is higher than 10, the QC and CMC can be further deposited to prepare the film. The layer-to-layer assembly of QC and CMC is very sensitive to ionic strength. Adding 0.1M of NaCl into the assembly solution, the growth trend of the film drops sharply, and the increase of the temperature can accelerate the growth of the film thickness. The elongation of the dipping time is favorable to the increase of the thickness of the QC/ CMC film, and the cleaning time is increased so that the film is thinned. In the early stage, it was used as a cationic polysaccharide to prepare the film. It is therefore an object of this chapter to determine the possibility of a cationic guar gum (CGG) and an acidic polymer such as, for example, a weak acid such as, for example, methylcellulose (CMC) and polyacrylic acid (PAA), to produce a thin film by layer-by-layer assembly, and then to study the pH, The dependence of ionic strength and temperature on the growth pattern and surface morphology of the film. As the pH value increases in the range of 3 to 4, the CGG and the weak acid can be prepared by layer-by-layer assembly; however, in the neutral and high pH sections, the CGG and the polyacids are difficult to assemble. Unlike synthetic polyelectrolyte complex films, such as PSS/ PDDA and PSS/ PAH, the layer-to-layer assembly of CGG/ CMC and CGG/ PAA is very sensitive to salt concentration. In the case of low salt concentration, the ionic strength promoted the growth of the CGG/ CMC and the CGG/ PAA film, but the increase of the salt concentration is not easy for the growth of the CGG/ CMC film. In the process of assembly, the elevated temperature has a great effect on the growth of the CGG/ polyacid system. The soaking time can be increased, and a sufficient time can be provided for the adsorption and rearrangement of the high-molecular chain on the surface of the film, so that more high-molecular chains can diffuse to the inside of the film, and the thickness of the film is increased. However, increasing the cleaning time results in the molecular chain in the film entering the solution, resulting in a reduction in the film thickness. In the fourth chapter, we study the anti-fog and anti-frost properties of the polysaccharide film. It is found that the anti-fog and anti-frost properties of the polysaccharide film are not provided by the polyelectrolytes such as QC/ PAA, QC/ PSS, CGG/ PAA, CGG/ PSS. The two special properties of the polysaccharide film are caused by the rapid adsorption of water molecules into the thin film matrix. The hydrogen bond interaction between the polar groups of the polymer and the water molecules prevents the coagulation of the water, so that the polysaccharide film has anti-fog and frost-proof properties. Studies have shown that polysaccharides can be used to prepare optical films with antifogging and anti-frost properties by layer-by-layer assembly techniques. Finally, the permeability of the metal ions in the polysaccharide film and the antibacterial behavior of the film were studied. Several types of polysaccharide films were constructed by using QC and CGG as polycations, CMC and PAA, and Cu ~ (2 +), Fe ~ (2 +) and Ag + were found to play a role in coordination with the acid groups in the matrix. The CGG/ PAA matrix can interact with Cu ~ (2 +), Fe ~ (2 +) and Ag +. The antibacterial experiment shows that the CGG/ PAA-Ag + has good antibacterial effect. The antibacterial properties of the Ag-containing CGG/ PAA are due to the fact that the Ag + in the film can be released to interact with the bacteria to kill the bacteria. Therefore, we successfully constructed a polysaccharide film with excellent anti-fog and anti-frost properties using these new cationic polysaccharides. These functional films will have a wide range of application prospects in many different fields, such as biomedical applications and drug delivery systems.
【学位授予单位】：东华大学
【学位级别】：博士
【学位授予年份】：2016
【分类号】：TB383.2;O636.1
，
本文编号：2498504
[Abstract]:The polysaccharide is a large amount of natural polymer in nature, is cheap, has unique characteristics, such as hydrophilic, stable, safe, non-toxic and biodegradable. The special structure and function of the polysaccharide can be used as the biological material of the surface of the modified biomedical device. Due to their natural components, they are ideal construction units for simulating the structural and biochemical properties of living cells. In the past 15 years, many studies have attempted to assemble the polysaccharides into the polyelectrolyte complex film by interfacial compounding, for example, by a layer-by-layer assembly interface with an electrostatic force as the main driving force. Most of the polysaccharides are negatively charged, and thus can be used as polyanionic components, and can also be chemically modified to be polycations such as amino-modified hyaluronic acid and quaternary-encapsulated chitosan. However, the species of polycationic polysaccharides are very limited, and at present only the chitosan (the deethanizing form of the chitin) is available and can be used to prepare the polyelectrolyte composite film. The chitosan is the most widely used polysaccharide in the layer-by-layer assembly film due to its multiple significant advantages, including wide access, high biocompatibility, and improved self-healing and antibacterial properties of the wound. However, the low solubility of the chitosan in the aqueous solution with a pH of more than 6 limits its use as an adsorption enhancer in the oral nasal transport system. In addition, due to the rapid water absorption and high swelling property of the chitosan in the aqueous solution, the application of the chitosan film in drug delivery and the like is limited. The purpose of this study was to use a novel positively charged polysaccharide (such as quaternary cellulose and cationic guar gum) in place of chitosan to construct an interfacial composite film based on layer-by-layer assembly. In addition, we have studied the effect of physical parameters such as pH, ionic strength and temperature on the interaction between cationic polysaccharides and natural (or synthetic) anionic polyelectrolyte, and also studies the water-absorbing, antifogging and anti-frost behavior of the polysaccharide film. In order to achieve the above-mentioned objects, we used a variety of characterization methods to study the layer-by-layer polysaccharide film. The ultraviolet-visible spectrum, the optical reflection instrument and the Fourier infrared conversion spectrum are used to monitor the composite process, the growth of the film thickness and the interaction between the metal ions and the thin film. A quartz crystal microbalance is used to determine the growth pattern and to calculate the absorption mass of the polyelectrolyte ion pair. The atomic force microscope is used to observe the surface morphology of the film. The contact angle measurement was used to study the hydrophilicity of the polysaccharide film. The antimicrobial properties of the polysaccharide film are disclosed by a regional inhibition test. The first part of this paper is to prepare a thin film by alternately depositing cellulose derivatives with opposite charges, quaternary cellulose (QC) and methylcellulose (CMC) on a silicon wafer and a quartz substrate. The effects of pH, ionic strength and temperature on the growth and morphology of the film were studied. The main chain of the QC and CMC is composed of a glucose ring, with hydrophilicity and rigidity, so that QC and CMC exhibit different assembly behavior than synthetic vinyl polyelectrolytes such as sodium polystyrene sulfonate (PSS) and polydiallyl dimethyl chloride (PDDA). As the pH value increases in the range of 3 to 5, the QC and CMC can form the film by layer-by-layer assembly; in the neutral pH range, QC and CMC are difficult to assemble; and when the pH value is higher than 10, the QC and CMC can be further deposited to prepare the film. The layer-to-layer assembly of QC and CMC is very sensitive to ionic strength. Adding 0.1M of NaCl into the assembly solution, the growth trend of the film drops sharply, and the increase of the temperature can accelerate the growth of the film thickness. The elongation of the dipping time is favorable to the increase of the thickness of the QC/ CMC film, and the cleaning time is increased so that the film is thinned. In the early stage, it was used as a cationic polysaccharide to prepare the film. It is therefore an object of this chapter to determine the possibility of a cationic guar gum (CGG) and an acidic polymer such as, for example, a weak acid such as, for example, methylcellulose (CMC) and polyacrylic acid (PAA), to produce a thin film by layer-by-layer assembly, and then to study the pH, The dependence of ionic strength and temperature on the growth pattern and surface morphology of the film. As the pH value increases in the range of 3 to 4, the CGG and the weak acid can be prepared by layer-by-layer assembly; however, in the neutral and high pH sections, the CGG and the polyacids are difficult to assemble. Unlike synthetic polyelectrolyte complex films, such as PSS/ PDDA and PSS/ PAH, the layer-to-layer assembly of CGG/ CMC and CGG/ PAA is very sensitive to salt concentration. In the case of low salt concentration, the ionic strength promoted the growth of the CGG/ CMC and the CGG/ PAA film, but the increase of the salt concentration is not easy for the growth of the CGG/ CMC film. In the process of assembly, the elevated temperature has a great effect on the growth of the CGG/ polyacid system. The soaking time can be increased, and a sufficient time can be provided for the adsorption and rearrangement of the high-molecular chain on the surface of the film, so that more high-molecular chains can diffuse to the inside of the film, and the thickness of the film is increased. However, increasing the cleaning time results in the molecular chain in the film entering the solution, resulting in a reduction in the film thickness. In the fourth chapter, we study the anti-fog and anti-frost properties of the polysaccharide film. It is found that the anti-fog and anti-frost properties of the polysaccharide film are not provided by the polyelectrolytes such as QC/ PAA, QC/ PSS, CGG/ PAA, CGG/ PSS. The two special properties of the polysaccharide film are caused by the rapid adsorption of water molecules into the thin film matrix. The hydrogen bond interaction between the polar groups of the polymer and the water molecules prevents the coagulation of the water, so that the polysaccharide film has anti-fog and frost-proof properties. Studies have shown that polysaccharides can be used to prepare optical films with antifogging and anti-frost properties by layer-by-layer assembly techniques. Finally, the permeability of the metal ions in the polysaccharide film and the antibacterial behavior of the film were studied. Several types of polysaccharide films were constructed by using QC and CGG as polycations, CMC and PAA, and Cu ~ (2 +), Fe ~ (2 +) and Ag + were found to play a role in coordination with the acid groups in the matrix. The CGG/ PAA matrix can interact with Cu ~ (2 +), Fe ~ (2 +) and Ag +. The antibacterial experiment shows that the CGG/ PAA-Ag + has good antibacterial effect. The antibacterial properties of the Ag-containing CGG/ PAA are due to the fact that the Ag + in the film can be released to interact with the bacteria to kill the bacteria. Therefore, we successfully constructed a polysaccharide film with excellent anti-fog and anti-frost properties using these new cationic polysaccharides. These functional films will have a wide range of application prospects in many different fields, such as biomedical applications and drug delivery systems.
【学位授予单位】：东华大学
【学位级别】：博士
【学位授予年份】：2016
【分类号】：TB383.2;O636.1
，
本文编号：2498504
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