多糖界面復(fù)合薄膜及其應(yīng)用
發(fā)布時(shí)間：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,價(jià)格便宜,具有獨(dú)特的特性,例如親水性、穩(wěn)定、安全、無毒,生物可降解性。多糖的特殊結(jié)構(gòu)和功能使之可作為改性生物醫(yī)學(xué)器件表面的生物材料。由于其天然成分,它們是模擬活體細(xì)胞環(huán)境結(jié)構(gòu)和生物化學(xué)特性系統(tǒng)的理想的構(gòu)筑單元。在過去的十五年中,很多研究已經(jīng)嘗試通過界面復(fù)合將多糖組裝于聚電解質(zhì)復(fù)合膜中,例如以靜電力為主要驅(qū)動(dòng)力的層層組裝界面復(fù)合。大多數(shù)多糖帶有負(fù)電荷,因而可作為聚陰離子成分,也可經(jīng)過化學(xué)改性成為聚陽離子,如氨基改性的透明質(zhì)酸和季銨化的殼聚糖。然而聚陽離子多糖的種類是非常有限的,目前只有殼聚糖(甲殼素的去乙酰化形式)是可利用的且可用于制備聚電解質(zhì)復(fù)合薄膜。由于其多個(gè)顯著優(yōu)勢,包括獲取途徑廣泛,生物相容性高,提高傷口的自愈性和和抗菌性,殼聚糖在層層組裝膜中是使用最廣泛的多糖。然而殼聚糖在pH大于6的水溶液中的低溶解性,限制了它在口鼻傳輸系統(tǒng)中作為吸附強(qiáng)化劑的使用。此外,由于殼聚糖在水溶液中的快速吸水性和高溶脹性,限制了殼聚糖薄膜在藥物輸運(yùn)等多方面的應(yīng)用。本研究的目的是使用新型帶正電荷的多糖(如季銨纖維素和陽離子瓜爾豆膠)代替殼聚糖,用于構(gòu)筑基于層層組裝的界面復(fù)合薄膜。此外,我們研究了物理參數(shù)如pH值,離子強(qiáng)度和溫度對陽離子多糖與天然(或合成)陰離子聚電解質(zhì)之間相互作用的影響,此外還研究了多糖薄膜的吸水性,防霧,防霜行為。為了實(shí)現(xiàn)上述的目的,我們使用了多種表征手段對層層組裝的多糖薄膜進(jìn)行了研究。紫外可見光譜,光學(xué)反射儀,傅里葉紅外變換光譜用于監(jiān)控復(fù)合過程、膜厚度增長和金屬離子與薄膜之間的相互作用。石英晶體微天平用于確定生長模式并計(jì)算聚電解質(zhì)離子對的吸收質(zhì)量。原子力顯微鏡用于觀察膜的表面形態(tài)。接觸角測定用于研究多糖薄膜的親水性。通過區(qū)域抑制測試被用來揭示多糖薄膜的抗菌性。本論文的第一部分是將帶相反電荷的纖維素衍生物,季銨化纖維素(QC)和羧甲基纖維素(CMC),交替沉積于硅片和石英基片來制備薄膜。研究了pH值,離子強(qiáng)度,溫度因素對于薄膜增長和形態(tài)的影響。QC和CMC的主鏈由葡萄糖環(huán)組成,具有親水性和剛性,因此QC和CMC表現(xiàn)出與合成的乙烯基聚電解質(zhì)(如聚苯乙烯磺酸鈉(PSS)和聚二烯丙基二甲基氯化銨(PDDA))不同的組裝行為。隨著pH值在3～5范圍內(nèi)增大時(shí),QC和CMC可通過層層組裝形成薄膜；而在中性pH區(qū)間,QC和CMC難以組裝；當(dāng)pH值高于10,QC和CMC又可通過沉積制備薄膜。QC和CMC的層層組裝對離子強(qiáng)度非常敏感。在組裝溶液中加入0.1 M的NaCl,薄膜的增長趨勢急劇下降,而提高溫度則可加快膜厚的增長。浸漬時(shí)間的延長有利于QC/CMC薄膜厚度的增加,而清洗時(shí)間的增加使得薄膜變薄。早期,季銨化纖維素作為陽離子多糖制備薄膜。因此,本章的目的是確定陽離子瓜爾豆膠(CGG)與酸性聚合物如：聚弱酸如羧甲基纖維素(CMC)和聚丙烯酸(PAA)基于靜電作用層層組裝制備薄膜的可能性,然后研究pH值,離子強(qiáng)度和溫度對薄膜增長模式和表面形態(tài)的依賴性。隨著pH值在3～4范圍內(nèi)的增大,CGG和聚弱酸可通過層層組裝制備薄膜；然而,在中性和高的pH區(qū)間,CGG和聚弱酸很難組裝。不同于合成聚電解質(zhì)復(fù)合薄膜,如PSS/PDDA和PSS/PAH, CGG/CMC和CGG/PAA的層層組裝對鹽濃度非常敏感。在低鹽濃度的情況下,離子強(qiáng)度促進(jìn)了CGG/CMC和CGG/PAA薄膜的增長,但增加鹽濃度不易于CGG/CMC薄膜的生長。在組裝過程中,升高溫度對CGG/聚弱酸體系的厚度增長具有較大的影響。增加浸漬時(shí)間,能夠?yàn)楦叻肿渔溤诒∧け砻娴奈胶椭嘏盘峁┳銐虻臅r(shí)間,有利于更多的高分子鏈向薄膜內(nèi)部擴(kuò)散,從而增加了薄膜的厚度。然而,增加清洗時(shí)間,導(dǎo)致薄膜中的分子鏈進(jìn)入溶液中,從而引起薄膜厚度的降低。第四章中,我們研究了多糖薄膜的防霧和防霜性能。發(fā)現(xiàn)多糖薄膜具有的防霧和防霜特性,是多糖與合成聚電解質(zhì)如QC/PAA, QC/PSS, CGG/PAA, CGG/PSS等層層復(fù)合薄膜所不具備的。多糖薄膜具有的這兩個(gè)特殊性能是由于水分子被快速吸附到薄膜基質(zhì)中引起的。聚合物的極性基團(tuán)與水分子的氫鍵相互作用阻止了水的凝結(jié),使多糖薄膜具有防霧和防霜性能。研究表明通過層層組裝技術(shù),多糖可用來制備具有防霧和防霜性能的光學(xué)薄膜。最后,研究了金屬離子在多糖薄膜中的滲透性以及薄膜的抗菌行為。以QC和CGG為聚陽離子,CMC和PAA為聚陰離子構(gòu)筑了幾種類型的多糖薄膜,并且發(fā)現(xiàn)Cu~(2+),Fe~(2+)和Ag+能夠與基質(zhì)中的羧酸基團(tuán)之間發(fā)生配位作用。用于CGG/PAA基質(zhì)能夠與Cu~(2+), Fe~(2+)和Ag+之間發(fā)生強(qiáng)的相互作用,因此進(jìn)一步研究了它們的抗菌性�？咕鷮�(shí)驗(yàn)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+能夠被釋放出來與細(xì)菌發(fā)生多種形式的相互作用從而殺死細(xì)菌。因此,我們使用這些新型陽離子多糖成功構(gòu)筑了具有防霧和防霜優(yōu)良性能的多糖薄膜。這些功能薄膜在生物醫(yī)學(xué)應(yīng)用和藥物輸運(yùn)系統(tǒng)等多個(gè)不同領(lǐng)域?qū)⒕哂袕V泛的應(yīng)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.
【學(xué)位授予單位】：東華大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2016
【分類號(hào)】：TB383.2;O636.1
，
本文編號(hào)：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.
【學(xué)位授予單位】：東華大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2016
【分類號(hào)】：TB383.2;O636.1
，
本文編號(hào)：2498504
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