摘要
聚甲基丙烯酸甲酯(PMMA)树脂材料具有成本低、容易加工和生物相容性好等特点，因而广泛应用于牙科医学上。义齿基托是人工义齿的重要组成部分，主要由PMMA树脂制成。研究表明，佩戴义齿会改变口腔内的微生态平衡，一些微生物，例如白色念珠菌和变形链球菌，会粘附在树脂材料表面并大量增殖，导致义齿性口炎和继发龋等口腔疾病。传统的义齿清洁方法存在着抗菌时间短、操作繁琐、容易破坏义齿表面形貌等缺点，不能完全满足临床上的应用。因此赋予基托树脂抗菌性成为口腔医学的重要研究课题。
众所周知，银具有很高的抗菌活性和广谱的抗菌性，因此被广泛应用在各种抗菌材料中。与传统的有机物抗菌剂相比，载银无机抗菌剂具有更高的安全性、持久性和耐热性。介孔二氧化硅材料由于其良好的生物相容性，形貌多样性以及易修饰性，在作为银载体方面具有很大的应用潜力。通常情况下，载银抗菌剂被直接掺杂到树脂材料中，但是只有靠近树脂表面的抗菌剂才能起到抗菌作用，而树脂内部的抗菌剂完全起不到抗菌作用，造成了一定的浪费，而且过多的抗菌剂还可能影响树脂的机械性能。因此，使用含银的抗菌涂层是一个更经济有效的办法。
本论文的主旨是设计和制备可应用于义齿基托表面的抗菌涂层。我们在载银抗菌剂的制备和杂化涂层的设计上进行了一些有意义的探索。我们制备了几种不同的载银介孔二氧化硅微球作为抗菌剂，分别掺杂到我们设计的一种有机无机杂化涂料中，制备成了抗菌涂层。
在本论文第一章，我们简要介绍了义齿基托及其使用中的问题，简单回顾了一下抗菌剂和抗菌涂层的发展情况，简单的介绍了介孔材料及其在载银方面的应用，并提出了本论文的设计思想及主要内容。
在本论文第二章，我们设计合成了一种由聚合物涂料和杂化硅溶胶混合制成的杂化涂料。聚合物涂料由甲基丙烯酸缩水甘油酯(GMA)、丙烯酸(AA)和甲基丙烯酸甲酯(MMA)三种单体共聚而成；杂化硅溶胶由缩水甘油醚基丙基三甲氧基硅烷(KH560)和正硅酸乙酯(TEOS)共水解缩合制得。聚合物作为有机组分可以为提高涂层与基底的附着力，硅溶胶作为无机组分可以高涂层的硬度。同时聚合物链和硅溶胶网络上都含有环氧基团，利用环氧基团的交联反应，形成有机无机互穿网络结构，可以进一步提高涂层的硬度。我们制备了一系列具有不同有机无机组分质量比值的杂化涂层，并表征了涂层的刮伤硬度、附着力和抗破裂性等性能。我们发现，当增加硅溶胶中TEOS的使用量以及增加杂化涂层中的硅溶胶含量时，涂层的硬度有所上升，但相应的附着力和抗破裂性有所下降。综合考虑，我们选择了KH560/TEOS摩尔比为2/5，有机无机组分质量比为9/1的杂化涂层。该涂层的硬度达到了4H，附着力和抗破裂性等级最高。同时，为了提高树脂材料的固位力，我们还尝试对涂层表面进行亲水化处理。利用六亚甲基二异氰酸酯与羟基的反应，在涂层表面接枝了不同分子量的PEG。通过红外光谱和接触角测试，证明我们成功在涂层表面接枝了PEG分子。PEG接枝前涂层亲水角为64°，PEG-1000和PEG-2000接枝后的涂层的亲水角分别为46°和35°。
在本论文的第三章，我们先制备了具有介孔结构的纯二氧化硅微球，并探索了硅源加入方式、催化剂种类、催化剂用量以及水醇质量比等因素对微球粒径和形貌的影响。我们发现采用分批加入硅源和采用氨水做催化剂，有助于避免微球的团聚；增大催化剂的用量和降低水醇比能够使微球粒径变大，但是容易导致团聚发生。最终我们制备了粒径为400nm、分散性好的介孔二氧化硅微球，然后将氯化银负载到微球上，并将载银微球作为抗菌剂添加到有机无机杂化涂层中，制备了抗菌涂层。结果表明制得的无机涂层具有良好的抗菌性，当抗菌剂在涂层中固含量达到2%时，涂层抑菌率达到了99%以上。同时抗菌涂层的硬度达到4H，附着力等级在测试中达到最高等级。
在本论文的第四章，我们制备了氨基、巯基和磺酸基修饰的介孔二氧化硅微球作为银的载体，探索了有机基团种类以及基团负载量对微球结构以及载银量的影响。巯基修饰的介孔微球具有更规则的孔道结构和更高的载银量，但是银离子的释放率较低。磺酸根修饰的介孔微球具有较高的载银量，同时也具备很高的银离子释放率。通过测试针对白色念珠菌的最小杀菌浓度，将具有最高的杀菌活性的载银硅球作为抗菌剂以不同的浓度掺杂到第二章制备的杂化涂层中。由此制备的抗菌涂层具有很高的抗菌活性、较高的硬度、良好的附着力。当抗菌剂在涂层中固含量达到2%时，抑菌率达到100%，涂层硬度为4H，附着力在测试中为最高等级。
在本论文的第五章，我们采用具有空心介孔结构的硅铝氧化物微球作为氯化银的载体。空心微球上的载银量达到29.7wt%。我们将氯化银负载的空心球以不同的浓度掺杂到杂化涂层中，得到的涂层具有良好的抗菌效果，当载银空心球在涂层中固含量达到2%时，抑菌率达到100%。同时涂层还具有最高级别的附着力和较高的硬度4H。
综上，我们制备的杂化抗菌涂层具有较高的抗菌活性、较高的硬度，对PMMA基底具有良好的附着力，因此在义齿基托上具有很大的应用潜力。
Poly(methyl methacrylate) based resins are widely used in dentistry due to theproperties of low cost, easy processing and good biocompatibility. As an importantpart of artificial denture, the denture base is mainly made of PMMA resin. However,the research results revealed that the wearing of denture could break the ecologicalbalance of the oral cavity. Then some microorganisms such as Candida albicans andStreptococcus mutans would accumulate and grow on the PMMA resin basedappliances and cause oral diseases such as denture stomatitis and secondary caries.The traditional cleaning methods have the disadvantages of short antibiosis time,tedious handling and damaging the surface of the resin. Therefore, improving theantimicrobial activity of the denture materials becomes one of the most importantresearch areas in dentistry.
It is well known that silver is widely used in antibacterial materials because of itshigh antibacterial activity and broad antibacterial spectrum. Silver loaded inorganicantibacterial agents are superior in the aspects of safety, durability and heat resistance,compared with the conventional organic antibacterial materials. Ordered mesoporoussilica possesses the advantages of large specific surface area, diversity of morphology,easy functionalization and good biocompatibility, which makes it a good candidate forthe silver carrier material. Commonly, the antibacterial agents are directly doped in thepolymer resin. However, most of the inner antibacterial agents may not play anyantibacterial effect at all. Besides, the excess using of antibacterial agents may affectthe mechanical properties of the resin. According to what has been mentioned above,the using of antibacterial coatings is a preferable strategy for improving the antibacterial activity of the denture base.
In this dissertation, we aim at the design and preparation of antibacterial coatingsthat can be used on denture base. Several kinds of silver loaded mesoporous silicaspheres have been prepared and doped in a designed hybrid coating as antibacterialagents to fabricate antibacterial coatings.
In chapter1, we made a brief introduction of denture base and the problemsgenerated when using it. Then we reviewed the development and classification ofantibacterial agents, antibacterial coatings and mesoporous materials.
In chapter2, we prepared a hybrid coating by mixing a polymer coating solutionand a hybrid silica sol. The polymer coating solution was prepared byco-polymerization of glycidyl methacrylate (GMA), acrylic acid (AA) and methylmethacrylate (MMA). The hybrid silica sol was prepared by co-hydrolysis andco-condensation of γ-glycidyloxypropyltrimethoxysilane (KH560) and tetraethylorthosilicate (TEOS). The polymer could increase the adhesion while the silica solcould increase the hardness of the hybrid coatings. Besides, the epoxy groups on thepolymer chain and silica sol could form linking structure, which could further increasethe hardness of the coatings. A series of hybrid coatings with differentorganic/inorganic component weight ratio were prepared and the hardness, adhesionand resistance to rupture of the coatings were tested. As the amount of TEOS and thesilica sol component increased, the hardness of the coatings increased while theadhesion and resistance of rupture both decreased. Considering the balance of theproperties, we chose the hybrid coating with the KH560/TEOS molar ratio of2/5andthe organic/inorganic components weight ratio of9/1. The hardness of the coatingreached4H and the adhesion reached the highest level according to the test method.On the other hand, to increase the retention force of the resin, we have successfullygrafted PEG molecular on the hybrid coating surface through the reaction between theisocyanate group of HDI and the hydroxyl group of PEG, which was proved by FTIRspectroscopy and water contact angle test. The contact angle of original hybrid coatingis64°. After PEG-1000and PEG-2000were grafted, the contact angle decreased to46°and35°respectively.
In chapter3, we prepared pure mesoporous pure silica spheres and studied theinfluence of the factors including the adding method of precursor, the type and theamount of catalysis and the mass ratio of water/ethanol on the size and morphology of the silica spheres. We found that the using of ammonia as catalyst and adding theprecursor by several times are helpful to avoid the formation of aggregation.Increasing the amount of ammonia and the mass ratio of ethanol/water could increasethe size of the silica spheres. Finally, the silica spheres with the size of400nm andgood dispersity were prepared and loaded with AgCl, and then dispersed in the hybridcoating to fabricate antibacterial coatings. The coatings showed high antibacterialactivity. When the weight ratio of the silica spheres reached2%, the reduction rate ofthe fungus was higher than99%. The hardness of the coatings reached4H and theadhesion reached the best level according to the test method.
In chapter4, the amino, thiol and sulfonic group functionalized mesoporous silicaspheres were prepared and used as silver carrier. We studied the influence of the typeand amount of organic groups on the structure of the silica spheres and the loadingamount of silver. We found that the thiol-functionalized silica spheres possess moreordered mesopores, higher silver loading amount, but a much lower releasing rate ofsilver ions. The sulfonic group functionalized silica spheres possess a high loadingamount and a high releasing rate of silver ions at the same time. The samples showedthe highest antibacterial activity in the MBC test on Candida albicans were doped inthe hybrid coating with different weight ratio. The as prepared coatings exhibited highantibacterial activity, high hardness and good adhesion to the substrates. The reductionrate of the fungus reached100%when the weight ratio of antibacterial agent reached2%in the coating. The hardness of the coatings reached4H and the adhesion reachedthe best level according to the test method.
In chapter5, hollow mesoporous aluminosilica spheres were prepared byalkaline etching method and loaded with silver chloride to used as antibacterial agent.The hollow mesoporous aluminosilica spheres possess radially oriented orderedmesopores and a high loading amount of AgCl (2.75mmol/g). Then the AgCl loadedhollow mesoporous aluminosilica spheres were doped in the hybrid coating withdifferent weight ratio to fabricate antibacterial coatings. The antibacterial activity ofthe coatings was tested against the fungus Candida albicans. As the doping amountincreased to2wt%, the reduction rate of the fungus reached100%. The hardness ofthe coating reached4H and the adhesion reached the best level according to the testmethod.
To sum up, all the hybrid antibacterial coatings exhibited high antibacterial activity, high hardness and good adhesion to the PMMA substrate. Thus the coatingsshowed a great potential in the application in denture base.
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