本文選題：殼聚糖膜　切入點(diǎn)：RGP接觸鏡　出處：《華南理工大學(xué)》2012年博士論文　論文類型：學(xué)位論文

【摘要】：殼聚糖和氟硅丙烯酸脂廣泛應(yīng)用于角膜修復(fù)材料的研究，角膜修復(fù)材料的發(fā)展對(duì)材料表面特性提出了更高的要求，但殼聚糖膜表面親水性較差，表面自由能尤其是其極性分量較低，缺乏細(xì)胞識(shí)別位點(diǎn)，不利于細(xì)胞在材料表面的黏附與增殖。氟硅丙烯酸樹(shù)脂（FSA）是新一代高透氧性硬性角膜接觸鏡材料，但材料表面憎水，不利于淚液在鏡片表面的鋪展與潤(rùn)濕；且表面非極性基團(tuán)與蛋白質(zhì)分子間的非極性相互作用容易導(dǎo)致蛋白與脂質(zhì)等在鏡片表面的黏附，影響鏡片佩戴舒適性和佩戴時(shí)間。為改善兩種角膜修復(fù)材料的表面特性，本論文在對(duì)材料表面性能進(jìn)行綜合表征的基礎(chǔ)上，采用低溫等離子體進(jìn)行表面處理和表面接枝改性，改善其表面物化特性和生物學(xué)性能。 采用角分辨XPS對(duì)殼聚糖膜表面化學(xué)基團(tuán)的空間分布進(jìn)行分析表征。結(jié)果表明，殼聚糖膜隨著在空氣中放置時(shí)間延長(zhǎng)，其表面極性基團(tuán)-OH等逐漸轉(zhuǎn)移到膜的內(nèi)部；殼聚糖膜表面N元素主要以-NH_2形式存在，其分子鏈上的-CONH_2主要伸向殼聚糖膜內(nèi)部。表面極性基團(tuán)的這種空間取向是造成殼聚糖膜表面親水性較差，表面自由能較低的主要原因。 實(shí)驗(yàn)分別采用非反應(yīng)性O(shè)2和N_2低溫等離子體對(duì)殼聚糖膜進(jìn)行表面處理。殼聚糖膜在O_2等離子體處理下，表面引入-OH、-COO、H_2N-C=O等極性基團(tuán)，表面親水性得到改善；采用O_2等離子體進(jìn)行改性的最佳工藝條件為100W下處理60s，如功率過(guò)大或處理時(shí)間過(guò)長(zhǎng)，則容易引起殼聚糖膜表面刻蝕；O2等離子體對(duì)殼聚糖膜進(jìn)行表面處理未造成明顯的表面形貌變化，但表面粗糙度有一定增加。采用N_2等離子體處理，也能改善殼聚糖膜表面親水性，但效果不如O_2明顯，采用100W等離子體功率和60s處理時(shí)間，其表面接觸角下降為65°；N_2等離子體處理可在表面引入一定量的N元素，引入的N元素主要是以O(shè)=C-NH_2的形式存在；等離子體處理后暴露于大氣中，膜表面活性自由基與空氣中的氧氣、水汽等進(jìn)行反應(yīng)，在表面引入含氧極性基團(tuán)是等離子體處理樣品表面極化的主要過(guò)程。 等離子體處理在殼聚糖膜表面引入的極性基團(tuán)會(huì)隨著時(shí)間的推移而逐漸轉(zhuǎn)移到膜的內(nèi)部，這種極性基團(tuán)的翻轉(zhuǎn)內(nèi)遷，導(dǎo)致了等離子體處理效果的時(shí)效性，其親水性逐漸下降，接觸角增大，表面自由能尤其是其極性分量逐漸下降，殼聚糖膜表面等離子體處理的時(shí)效性大約為10天。 實(shí)驗(yàn)采用Ar等離子體誘導(dǎo)接枝在殼聚糖膜表面引入聚乙二醇（PEG）分子鏈；表面接枝層厚度約10nm；PEGMA單體濃度10%、Ar等離子體功率100W、時(shí)間60s時(shí)表面接枝量最大；采用PEGMA單體比采用具有相同分子量的PEGDA單體接枝率高；將PEGMA單體接枝到殼聚糖膜表面后，其表面水接觸角下降，親水性改善，表面自由能和粗糙度增加。表面接枝殼聚糖膜具有較好的牛血清蛋白吸附特性；細(xì)胞試驗(yàn)結(jié)果表明等離子體處理和表面接枝殼聚糖膜表面的細(xì)胞黏附率高于未經(jīng)處理的殼聚糖膜，表面改性殼聚糖膜具有較好的表面細(xì)胞相容性。 采用O_2、N_2和Ar等離子體對(duì)硬性透氣性（RGP）FSA角膜接觸鏡片進(jìn)行表面處理均能極大地改善鏡片表面的親水性。等離子體處理在表面引入了含O基團(tuán)，其中表面Si-CH3發(fā)生分子鍵的斷裂，形成Si-O，硅烷轉(zhuǎn)變?yōu)橛H水性的無(wú)機(jī)硅氧基團(tuán)（Si-O），是表面親水性改善的主要原因。在等離子體處理下，表面分子中C-O發(fā)生部分?jǐn)噫I，生成O-C=O。N2等離子體處理能夠在RGP表面引入含N基團(tuán)，N元素主要是以O(shè)=C-NH_2的形式存在。等離子體處理后表面活性自由基與空氣中的氧氣反應(yīng)形成含氧基團(tuán)是表面活化的主要過(guò)程，其中表面引入的O主要是與Si結(jié)合形成Si-O。等離子體處理對(duì)RGP表面形貌的影響主要取決于等離子體功率的大小，Ar等離子體相比O2和N2等離子體對(duì)表面的刻蝕更為明顯，，等離子體處理工藝以100W和120s為宜。三種氣氛等離子體相比較，N2相比Ar和O_2等離子體較為溫和，而Ar等離子體在功率較大時(shí)，容易導(dǎo)致表面刻蝕，表面粗糙度增加，表面親水性反而下降，這與等離子體中的粒子能量大小有關(guān)。 采用Ar等離子體輔助接枝能有效地將PEGMA單體分子接枝聚合到RGP表面，所得PEGMA接枝層的厚度大約10納米；結(jié)果表明：表面接枝量大小與單體濃度有關(guān)，采用去離子水作為溶劑，PEGMA單體濃度10%時(shí)具有最大的表面接枝量，RGP表面接枝PEG后，表面親水性改善，RGP鏡片表面溶菌酶蛋白質(zhì)的吸附量減少，表面改性RGP鏡片具有較好的表面細(xì)胞相容性。 采用低溫等離子體技術(shù)對(duì)殼聚糖膜和角膜接觸鏡材料進(jìn)行表面改性，能有效改善材料表面的親水性和生物學(xué)性能，在角膜修復(fù)材料領(lǐng)域具有廣泛的應(yīng)用前景。
[Abstract]:The study of chitosan and fluorosilicone acrylate is widely used in corneal repair materials, the development of corneal repair materials put forward higher requirements on the material properties of the surface, but the surface hydrophilic chitosan film is poor, especially the surface free energy of the polar component is low, the lack of cell recognition sites, is not conducive to cell adhesion and the proliferation of material surface. Fluorosilicone acrylic resin (FSA) is a new generation of rigid gas permeable contact lens material, but the material surface hydrophobicity, is not conducive to tear in spreading and wetting the surface of the lens; and the surface of non polar groups and protein molecular interactions can lead to protein and lipid the adhesion of the surface of the lens, lens wearing comfort and wear time. For improving the surface characteristics of two kinds of corneal repair materials, this paper is based on the comprehensive characterization of surface properties of materials, with low temperature etc. Plasma modification on the surface treatment and surface grafting, improve chemical properties and biological properties of the surface.
The angular resolution of XPS on chitosan membrane surface chemical groups to analyze the spatial distribution of characterization. The results showed that the chitosan membrane with the prolonging of time in air, the surface polar groups such as -OH gradually transferred to the internal membrane; chitosan membrane surface element N mainly exists in the form of -NH_2 within the molecular chains of the -CONH_2 is mainly to the chitosan membrane. The spatial orientation of polar groups on the surface is caused by the surface hydrophilic chitosan membrane is poor, mainly due to the lower surface free energy.
The experiment used non reactive O2 and N_2 low temperature plasma on chitosan membrane surface treatment. The chitosan membrane in the O_2 plasma treatment, the surface of the introduction of -OH, -COO, H_2N-C=O and other polar groups, the surface hydrophilicity was improved; the optimum conditions were modified by O_2 plasma 100W treatment by 60s, such as power too big or too long, it is easy to cause the etching on the surface of chitosan membrane; O2 plasma surface treatment on chitosan membrane surface morphology caused no obvious change, but the surface roughness is increased by N_2 plasma treatment, can also improve the surface hydrophilicity of chitosan membrane, but the effect is not obvious as O_2, the 100W plasma power and treatment time of 60s, the surface contact angle decreased to 65 degrees; N_2 plasma treatment N element by introducing a certain amount in the surface of the N element is introduced mainly based on O= C-NH_2 The form is present. After the plasma is exposed to the atmosphere, the active free radicals on the membrane react with oxygen and water vapor in the air. The introduction of oxygen containing polar groups on the surface is the main process of the polarization of the plasma surface.
Plasma treatment groups were introduced into the chitosan membrane with the passage of time will gradually shift into the internal membrane, the migration of polar groups led to flip, ageing of plasma treatment, the hydrophilicity decreased gradually, the contact angle increases, especially the surface free energy of polar component gradually decreased, timeliness of chitosan membrane surface plasma treatment is about 10 days.
The experiment using Ar plasma induced grafting onto chitosan membrane surface with polyethylene glycol (PEG) molecular chain; surface graft thickness is about 10nm; the PEGMA monomer concentration was 10% Ar, the plasma power is 100W, the maximum amount of time of 60s surface grafting; using PEGDA monomer grafted PEGMA monomer has the same molecular weight than the rate will be high; the PEGMA monomer was grafted onto chitosan membrane surface, the surface water contact angle decreased, improve the hydrophilicity, surface free energy and surface roughness increase. Grafted chitosan has good adsorption characteristics of bovine serum protein; cell test results show that the plasma treatment and grafting of chitosan film on the surface of cell adhesion rate is higher than that without chitosan membrane treatment, surface modification of chitosan membrane surface has good compatibility with cells.
Using O_2, N_2 and Ar in plasma of rigid gas permeable contact lens (RGP) FSA surface treatment can improve the hydrophilicity of the surface of the lens greatly. The plasma processing on the surface is introduced with O group, the fracture surface of Si-CH3 molecular bond formation of Si-O silane into inorganic hydrophilic silica group the (Si-O), is the main reason for surface hydrophilicity improvement. In plasma processing, part of the bond breaking of C-O surface molecules, generated O-C=O.N2 plasma treatment can be introduced containing N group on the surface of RGP, N elements are mainly in the form of O= C-NH_2. After treatment of plasma free radical reaction of surface activity and in the air the formation of oxygen oxygen containing groups is the main process of surface activation, which is mainly introduced to the surface of the O and Si combine to form the Si-O. effect of plasma treatment on the surface morphology of RGP mainly depends on the plasma power The rate of the size of plasma etching on the surface of Ar compared to O2 and N2 plasma is more obvious, plasma processing technology in 100W and 120s as appropriate. Three kinds of atmosphere plasma compared to N2 compared to Ar and O_2 plasma and Ar plasma in moderate, power is large, easily lead to surface etching, the surface roughness increases, surface hydrophilicity decreased, which is related to the size of particle energy in the plasma.
Using Ar plasma assisted grafting can effectively PEGMA monomers grafted onto the RGP surface, the PEGMA graft layer thickness of about 10 nm; the results show that the surface graft size and monomer concentration, using deionized water as the solvent, with the largest amount of PEGMA surface grafting monomer concentration of 10%, RGP grafted after PEG, the hydrophilicity of the surface to improve the adsorption capacity of RGP, the lens surface of lysozyme protein decreased, the surface modification of RGP lens surface has good compatibility with cells.
Surface modification of chitosan membrane and contact lens material with low temperature plasma technology can effectively improve the hydrophilic and biological properties of the material surface, and has wide application prospects in the field of corneal repair materials.

【學(xué)位授予單位】：華南理工大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2012
【分類號(hào)】：R318.08

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