Cu-Catalyzed Azide-Alkyne Reactions for Novel Dental Composite Materials

铜催化叠氮化物-炔烃反应用于新型牙科复合材料

• 批准号: 8610736
• 负责人: Christopher N Bowman
• 金额: $ 49.94万
• 依托单位: UNIVERSITY OF COLORADO
• 依托单位国家: 美国
• 财政年份: 2013
• 资助国家: 美国
• 起止时间: 2013-09-01 至 2018-08-31
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/8610736
• 关键词: Achievement; Acids; Address; Adhesions; Adhesives; Alkynes; Azides; Behavior; Binding; Characteristics; Chemistry; Composite Resins; Copper; Coupling; Dental; Dental General Practice; Dental caries; Dentistry; Development; Drug Formulations; Enzymes; Esters; Failure; Fatigue; Filler; Fracture; Gel; Glass; Goals; Grant; Growth; Hydrogen Bonding; Kinetics; Lead; Life; Mechanics; Methacrylates; Metric; Names; Nature; Oxygen; Performance; Phase; Plant Resins; Polymers; Property; Reaction; Relative (related person); Research; Sampling; Services; Side; Stress; Structure; Surface; Swelling; System; Triazoles; Urethane; Viscosity; Visible Radiation; Water; Work; base; biomaterial compatibility; composite restoration; crosslink; cycloaddition; dental adhesive; functional group; improved; mechanical behavior; meetings; monomer; next generation; novel; novel strategies; photopolymerization; polymerization; polymerization shrinkage; premature; public health relevance; restoration; restorative composite; restorative dentistry; restorative material; triethylene glycol dimethacrylate; uptake

!"#!$%$&'()*+$(,*)#$&-'.)+/)$!%,0.1+20/+.03)&+*).%$&+!04501,%)+4$%)/,$&1+ + 1644$/'+ + More than 60% of the more than one hundred million dental restorations performed each year involve the use of photopolymerizable polymeric composites. Despite their ubiquitous presence in modern dentistry, these composites suffer from significant problems that limit their applicability and utility. Based on resin chemistry developed and implemented nearly 50 years ago, the problems with these materials include issues associated with the presence of extractable, unreacted monomer following cure, degradation of the monomers and composite, polymerization shrinkage and shrinkage induced stresses, the long timeframe for polymerization, lack of toughness and other mechanical behavior of the resin material, thermal and moisture uptake by the sample following polymerization. With less than an 8 year average service life, the result of these problems is often the premature failure of composite restorations, resulting either from secondary caries or from mechanical failure within the bulk or at the interface. We propose to develop and evaluate a composite restorative system based on the now-classic "click" reaction, that is the copper catalyzed azide-alkyne (CuAAC) reaction. Its characteristics include achieving high conversion without side reactions, being robust and readily performed at ambient, and forming a product that is not readily degradable by acids, water, or enzymes. Moreover, the product of the reaction is a triazole ring structure that is capable of secondary molecular interactions (i.e., non-covalent bond formation) that enhance toughness, glass transition, and modulus of the crosslinked polymer material. Thus, this research will address the critical shortcomings of methacrylate composite systems by (i) developing a completely new approach to the resin portion of these composites that implements the CuAAC reaction in a manner that will lead to achievement of near-quantitative functional group conversions, limit extractable monomers, eliminate the potential for hydrolytic and enzymatic degradation, improve the mechanical properties through secondary molecular interactions, and dramatically reduce shrinkage and stress; (ii) combining this novel CuAAC-based resin phase with appropriately functionalized fillers to achieve the desired mechanical performance, improve fracture toughness, extend the lifetime of these restorations, and achieve enhanced dimensional stability of the composite; and (iii) analyzing the adhesion, degradation, extraction, and other long-term performance metrics for these resins and composites. The photo-induced CuAAC polymerization system is ideally suited for the next generation of dental restoratives and our goal is the development of a composite system that is compatible with current dental practices and adhesives and yet yields at least a two fold increase in the service life of these restoratives. ! !

! "#!$%$& '()*+$(,*)#$&-'.)+/)$!%, 0.1+20/+.03）&+*）.%$&+！04501，%）+4$%）/，$&1 + + 1644$/'+ + 在每年进行的一亿多例牙科检查中， 使用可光聚合的聚合物复合材料。尽管它们在现代牙科中无处不在， 复合材料存在限制其适用性和实用性的重大问题。基于树脂化学 开发和实施近50年前，这些材料的问题包括相关的问题 在固化后存在可萃取的未反应单体的情况下，单体降解， 复合材料，聚合收缩和收缩引起的应力，聚合的长时间框架， 树脂材料缺乏韧性和其它机械性能， 聚合后的样品。由于平均使用寿命不到8年，这些问题的结果是 通常复合修复体过早失效，要么是由于继发性龋齿，要么是由于 本体内或界面处的机械故障。 我们建议开发和评估一个复合修复系统的基础上，现在经典的“点击” 反应，即铜催化的叠氮化物-炔（CuAAC）反应。其特点包括实现高 没有副反应的转化，是稳健的并且在环境下容易进行，并且形成 不易被酸、水或酶降解。此外，反应的产物是三唑环 能够进行二级分子相互作用的结构（即，非共价键形成）， 交联聚合物材料的韧性、玻璃化转变和模量。因此，本研究将解决 甲基丙烯酸酯复合体系的关键缺点，（i）开发一种全新的方法， 这些复合材料的树脂部分以将导致 实现接近定量的官能团转化，限制可提取单体，消除 水解和酶降解的潜力，通过二次加工提高机械性能 分子相互作用，并显着降低收缩和应力;（ii）结合这种新的CuAAC基 具有适当官能化填料的树脂相，以实现所需的机械性能，改善 断裂韧性，延长这些膨胀的寿命，并实现增强的尺寸稳定性， 复合材料;以及（iii）分析粘附、降解、提取和其他长期性能指标 用于这些树脂和复合材料。光诱导的CuAAC聚合体系理想地适用于聚合反应。 我们的目标是开发一种复合系统， 与目前的牙科实践和粘合剂兼容，但在服务方面至少增加了两倍， 这些人的生活。 ! !