新型可聚合季铵盐及其在牙科抗菌高分子材料中的应用研究
|
摘要
研究开发具有抗菌功能的树脂基牙科材料是口腔科学中一个长期的发展目标,而常用的牙科树脂单体均没有抗菌活性。季铵盐是一种高效广谱的有机抗菌剂,具有低毒、性能稳定、低腐蚀等特点,并表现出长期的生物学效应。将季铵盐型抗菌单体引入于牙科修复材料高分子体系中,赋予牙科材料有效、持久的抗菌性能,必将对龋病及其它继发细菌感染性口腔疾病的防治产生深远影响。本论文的主要内容包括：
设计、合成了交联和非交联型两类可聚合季铵盐类单体,傅立叶红外光谱(FT-IR)和核磁共振波谱(1H-NMR)对产物结构进行了表征。利用在口腔修复医学临床中通用的光固化方法,在树脂基牙科材料中共聚引入季铵盐抗菌单体,制备具有抗菌性能的高分子树脂基牙科修复材料。考察树脂体系中光引发剂、助引发剂等工艺条件对聚合反应的影响,确定了共聚的最佳反应条件。加入交联型抗菌单体的树脂体系双键转化率比非交联单体高17%左右,有利于降低单体的残余,显著提高使用安全性。
考察了系列季铵盐单体对常见口腔病菌的最低抑菌浓度(MIC)及最小杀菌浓度(MBC)。选择三种抗菌性较强的单体考察对主要口腔致病菌—变形链球菌的杀菌动力学。利用噻唑蓝比色法(MTT法)测试了MAE-DB和MAE-HB单体的细胞毒性。DMAE-CB、MAE-DB和MAE-HB表现出较强的杀菌性；DMAE-CB在浓度19.2μg／mL(4*MBC)与菌液混合培养10min后,杀菌率可达100%；4*MBC的MAE-DB与变形链球菌接触10min后没有活菌存在；4*MBC的MAE-HB与变形链球菌接触30min后没有活菌存在。MAE-DB和MAE-HB对人牙龈成纤维细胞的半数致死浓度为5μg／mL-10μg／mL,与树脂基质Bis-GMA(4.79gg／mL)的细胞毒性相当。
研究了抗菌共聚树脂材料的物理化学特性。修复树脂的硬度随着单体加入量的增加而增大,而加入交联型抗菌单体的树脂硬度更高。所有树脂材料的吸水性均≤40μg／mm3。使用激光共焦扫描显微镜(CLSM)和扫描电子显微镜(SEM)初步研究了共聚改性树脂的抗菌特性。材料通过破坏变形链球菌生物膜的完整性及对生物膜内菌体的活性产生抑制而发挥接触抗菌活性；并对菌体有直接的破裂作用。
The development of resinous materials with antibacterial activity, which are more and more widely used in the dental clinic for replacement, has long been the goal of oral science. Unfortunately, the monomers which were usually used as dental materials don't have antibacterial ability. Quaternary ammonium salts(QAS) not only exhibt good bactericidal properties, but slao have some advantages over other antibacterial agents, including low toxicity, greater stability, low corrosivity and extended residence time of biological activity. In order to provide resin composites with inhibitory properties against subsequent recurrent caries and other oral diseases, the dental maerials with long-lasting antibacterial ability were prepared by immobilization of an antibacterial component in the resin matrix.
In this thesis, two series of polymerizable QAS were synthesized and characterized by infrared spectroscopy(IR) and nuclear magnetic resonance(1H-NMR). The resin-based restoratives with antibacterial activity were prepared by ultraviolet(UV) induced photopolymerization, which was usually used in stomatology. The factors, such as initiating agent, coinitiator, which affect free-radical copolymerization, were studied and optimized. The degree of double bond conversion of resin system incomporated with crosslinking antibanterial monomer was 17% higher than the ones which containg non-cross linking monomer. It will be helpful for improving the mechanical properties of resin and reducing the residual monomer.
To evaluate the bactericidal activity of the QAS monomers against oral pathogenic bacterium, the minimum inhibitory concentration(MIC) and the minimum bactericidal concentration(MBC) for several species and time-kill kinetics against Streptococcus mutans were determined. The cytotoxicity was measured by MTT method. DMAE-CB、MAE-DB and MAE-HB showed strong antibacterial activity. Time-kill curve showed that all cells were killed by 10min contact with 19.2μg/mL of DMAE-CB. MAE-DB gave 100% killing rate at 4*MBC against Streptococcus mutans within 10min, while all cells were killed after contact with MAE-HB for 30min. The concentration which caused 50% toxocity(ID50) of MAE-DB and MAE-HB for human gingival fibroblasts lies between 5-10μg/mL, which was similar with that of Bis-GMA, the usual dental matrix monomer.
The chemical and physical properties of experimental resin specimens containing antibacterial monomers were investigated. Surface hardness of restorative resins raised with the increase of the monomer mass, while the antibacterial resins modified with crosslinked monomer have higher hardness than the ones with usual monomer. Water sorptions of all dental restorative resins were less than 40μg/mm3. The antibanterial activity of an copolymerization adhesive resin was investigated by confocal laser scanning microscope(CLSM) and scanning electron microscope(SEM). The modified dental materials could exert contact antibacterial activity via exerting detrimental effects on the growth and membrane integrity of S. mutans.
设计、合成了交联和非交联型两类可聚合季铵盐类单体,傅立叶红外光谱(FT-IR)和核磁共振波谱(1H-NMR)对产物结构进行了表征。利用在口腔修复医学临床中通用的光固化方法,在树脂基牙科材料中共聚引入季铵盐抗菌单体,制备具有抗菌性能的高分子树脂基牙科修复材料。考察树脂体系中光引发剂、助引发剂等工艺条件对聚合反应的影响,确定了共聚的最佳反应条件。加入交联型抗菌单体的树脂体系双键转化率比非交联单体高17%左右,有利于降低单体的残余,显著提高使用安全性。
考察了系列季铵盐单体对常见口腔病菌的最低抑菌浓度(MIC)及最小杀菌浓度(MBC)。选择三种抗菌性较强的单体考察对主要口腔致病菌—变形链球菌的杀菌动力学。利用噻唑蓝比色法(MTT法)测试了MAE-DB和MAE-HB单体的细胞毒性。DMAE-CB、MAE-DB和MAE-HB表现出较强的杀菌性；DMAE-CB在浓度19.2μg／mL(4*MBC)与菌液混合培养10min后,杀菌率可达100%；4*MBC的MAE-DB与变形链球菌接触10min后没有活菌存在；4*MBC的MAE-HB与变形链球菌接触30min后没有活菌存在。MAE-DB和MAE-HB对人牙龈成纤维细胞的半数致死浓度为5μg／mL-10μg／mL,与树脂基质Bis-GMA(4.79gg／mL)的细胞毒性相当。
研究了抗菌共聚树脂材料的物理化学特性。修复树脂的硬度随着单体加入量的增加而增大,而加入交联型抗菌单体的树脂硬度更高。所有树脂材料的吸水性均≤40μg／mm3。使用激光共焦扫描显微镜(CLSM)和扫描电子显微镜(SEM)初步研究了共聚改性树脂的抗菌特性。材料通过破坏变形链球菌生物膜的完整性及对生物膜内菌体的活性产生抑制而发挥接触抗菌活性；并对菌体有直接的破裂作用。
The development of resinous materials with antibacterial activity, which are more and more widely used in the dental clinic for replacement, has long been the goal of oral science. Unfortunately, the monomers which were usually used as dental materials don't have antibacterial ability. Quaternary ammonium salts(QAS) not only exhibt good bactericidal properties, but slao have some advantages over other antibacterial agents, including low toxicity, greater stability, low corrosivity and extended residence time of biological activity. In order to provide resin composites with inhibitory properties against subsequent recurrent caries and other oral diseases, the dental maerials with long-lasting antibacterial ability were prepared by immobilization of an antibacterial component in the resin matrix.
In this thesis, two series of polymerizable QAS were synthesized and characterized by infrared spectroscopy(IR) and nuclear magnetic resonance(1H-NMR). The resin-based restoratives with antibacterial activity were prepared by ultraviolet(UV) induced photopolymerization, which was usually used in stomatology. The factors, such as initiating agent, coinitiator, which affect free-radical copolymerization, were studied and optimized. The degree of double bond conversion of resin system incomporated with crosslinking antibanterial monomer was 17% higher than the ones which containg non-cross linking monomer. It will be helpful for improving the mechanical properties of resin and reducing the residual monomer.
To evaluate the bactericidal activity of the QAS monomers against oral pathogenic bacterium, the minimum inhibitory concentration(MIC) and the minimum bactericidal concentration(MBC) for several species and time-kill kinetics against Streptococcus mutans were determined. The cytotoxicity was measured by MTT method. DMAE-CB、MAE-DB and MAE-HB showed strong antibacterial activity. Time-kill curve showed that all cells were killed by 10min contact with 19.2μg/mL of DMAE-CB. MAE-DB gave 100% killing rate at 4*MBC against Streptococcus mutans within 10min, while all cells were killed after contact with MAE-HB for 30min. The concentration which caused 50% toxocity(ID50) of MAE-DB and MAE-HB for human gingival fibroblasts lies between 5-10μg/mL, which was similar with that of Bis-GMA, the usual dental matrix monomer.
The chemical and physical properties of experimental resin specimens containing antibacterial monomers were investigated. Surface hardness of restorative resins raised with the increase of the monomer mass, while the antibacterial resins modified with crosslinked monomer have higher hardness than the ones with usual monomer. Water sorptions of all dental restorative resins were less than 40μg/mm3. The antibanterial activity of an copolymerization adhesive resin was investigated by confocal laser scanning microscope(CLSM) and scanning electron microscope(SEM). The modified dental materials could exert contact antibacterial activity via exerting detrimental effects on the growth and membrane integrity of S. mutans.
引文
[1]樊明文.牙体牙髓病学[M].北京：人民卫生出版社.2001,1-3
[2]陈治清.口腔生物材料学[M].北京：化学工业出版社.2004,1-2
[3]Jedrychowski J R, Caputo A A, Kerper S. Antibacterial and mechanical properties of restorative materials combined with chlorhexidines[J]. J Oral Rehabil,1983,10(4): 373-381
[4]Takemura K, Sakamoto Y, Staninec M, et al. Antibacterial activity of a bis-GMA based composite resin and antibacterial effect of chlorhexidine incorporation[J]. Jpn J Conserv Dent,1983,26(7):540-547
[5]Imazato S. Antibacterial properties of resin composites and dentin bonding systems[J]. Dent Mater,2003,19(6):449-457
[6]张林祺,高勃,杨聚才等.三种无机抗菌剂对常见牙体牙周致病菌的抗菌效果[J].现代口腔医学杂志,2007,21(1)：13-15
[7]张听,高保娇,朱勇等.季铵化聚乙烯亚胺的抗菌性能研究[J].高分子学报,2007,7：627-631
[8]Imazato S, Torii M, Tsuchitani Y, et al.Immobilization of an antibacterial component in composite resin. Dentistry in Japan,1993,30:63-68
[9]Imazato S, Torii M, Tsuchitani Y, et al. Incorporation of bacterial inhibitor into resin composite[J]. Journal of Dental Research,1994,73(8):1437-1443
[10]Imazato S, McCabe J F. Influence of incorporation of antibacterial monomer on curing behavior of a dental resin composite[J]. Journal of Dental Research,1994,73(15): 1641-1645
[11]Imazato S, Russell R R B, McCabe J F. Antibacterial activity of MDPB polymer incorporated in dental resin[J]. Journal of Dental Research,1995,23(3):177-181
[12]Imazato S, Tarumi H, Kato S, et al. Water sorption and colour stability of composites containing the antibacterial monomer MDPB[J]. Journal of Dental Research,1999, 27(4):279-283
[13]Imazato S, Kinomoto Y, Tarumi H, et al. Antibacterial activity and bonding characteristics of adhesive resin containing antibacterial monomer MDPB[J]. Dental Materials,2003,19(4):313-319
[14]Imazato S. Antibacterial properties of resin composites and dentin bonding systems[J]. Dental Materials,2003,19(6):449-457
[15]张朝武.应用广泛的季铵盐类消毒剂[J].现代预防医学,2006,33(5)：855-857
[16]佟会,邱树毅.季铵盐类抗菌剂及其应用研究进展[J].贵州化工,2006,31(5)：1-7
[17]孙洪,夏英,陈莉,等.国内外抗菌剂的研究现状及发展趋势[J].塑料工业,2006,34(9)：1-4
[18]Franklin T J, Snow G A. Biochemistry of antimicrobial action[M]. London:Chapman and hall,1981,32-33
[19]王蕊欣,高保娇.聚(4-乙烯基吡啶季铵盐-丙烯酰胺)的抗菌性能与机理研究[J].高等学校化学学报,2005,26(9)：1774-1776
[20]Koji T, Kan M,Yoshiharu L. Synthesis of α, α'-diaminocarboxylic acids [J]. Bulletin of the Chemical Society of Japan,1960,33:1529-1532
[21]郑静,周飞,张威.两种含羟基双季铵盐杀菌剂的合成与固定化[J].日用化学工业,2007,37(2)：92-96
[22]孙记夫,李秋小,李运玲.双癸基甲基羟乙基氯化铵的合成与杀菌性能[J].精细化工,2008,25(6)：565-275
[23]周娟,马云,屈撑囤,等.甲硝唑双季铵盐的合成与杀菌性能研究.西安石油大学学报(自然科学版),2009(5)：10-13
[24]Joerg C, Alexander M. Polymer surface derivatized with poly(vinyl-N-hexylpyridinium) kill airborne and waterborne bacteria[J]. Biotechnol Bioeng,2002,79(4):465-468
[25]Lin J, Qiu S Y, Klibanov A M. Bactercidal properties of flat surfaces and nanoparticles derivatized with alkylated polyethylenimines[J]. Biotechnol Prog,2002,18(5):1082
[26]Lin J, Qiu S Y, Klibanov A M. Mecheanism of bactericidal and fungicidal activities of textiles covalently modified weth alkylated polyethylenimine[M]. Wiley Periodicals, Inc, 2003
[27]Nudel R, Janauer G E, Schrier E E, et al. Water insoluble disinfectant composition:US, 4349646[P],1980
[28]Lewis K, Alexander M, Klibanov. Surpassing nature:rational design of sterile-surface materials. Trends in Biotechnology,2005,23 (7):343-348
[29]Sauvel G, Dupond S, Znierski, et al. Biocidal Polymers Activeby Contact Ⅴ:Synthesis of Polysiloxanes with Biocidal Activity[J]. J Apply Polym Sci,2000, (75):1005-1012
[30]张葵花,谭绍早,刘应亮.季铵盐改性蒙脱土的抗菌活性及抗菌机理[J].硅酸盐学报,2006,34(1)：87-92
[31]周轩榕,卢滇楠,邢晓东等.表面接枝季铵盐型高分子材料抗菌过程的特性研究[J].高等学校化学学报,2003,24(6)：1131-1135
[32]张昌辉,谢瑜,徐旋.抗菌剂的研究进展.化工进展,2007,26(9)：1237-1241
[33]Ayfer B, Dizman B, ElasriMO, et al. Synthesis and antibacterial activities of new quaternary ammonium monomers [J]. DesMonomers Polym,2005,8(5):437-451
[34]Scherzer T, Decker U. The effect of temperature on the kinetics of diacrylate photo polymerization studied by Realtime FTIR spectroscopy[J]. Polymer,2000,41(21): 7681-7690
[35]Andrzejewska E. Photopolymerization kinetics of multifunctional monomers[J]. Progress in Polymer Science,2001,26(4):605-665
[36]何芳,王玉林,万怡灶,等.光固化树脂及复合材料研究进展[J].工程塑应用,2003,31(11)：67-70
[37]李之轶,许乾慰.可见光固化齿料充填复合树脂挠曲强度研究[J].上海塑料,2005,3(1)：10-13
[38]Nie J, Bowman C N. Synthesis and photopolymerization of N,N'-dimethyl-N,N'-di(methacryloxy ethyl)-1,6-hexanediamine as a polymerizable amine coinitiator fur dental restorations[J]. Biomatedals,2002,23(4):1221-1226
[39]Morbert M, Ulrich S. New developments of polymeric dental composites[J]. Progress Polymer Science,2001,26(4):535-576
[40]Sideridou I, Achilidas D S, Spyroudi C, et al. Water sorption characteristics of light-cured dental resins andcomposites based on Bis-EMA/PCDMA[J]. Biomaterials, 2004,25(2):367-376
[41]Moszner N, Volkel T, Fischer UK, et al. Angew Makromol Chem,1999,265(1):31-35
[42]谭燕妮,刘咏,向其军.牙科光固化复合树脂材料的性能与展望[J].粉末冶金材料科学与工程,2007,12(3)：139-145
[43]Asmussen E, Peutzfeldt A. Influence of UEDMA,Bis-GMA and TEGDMA on selected mechanical properties of experimental resin composites[J]. Dent Mater,1998,14(1): 51-56
[44]Lu H, Stansbury J W, Nie J, et al. Development of highly reactive mono-(meth)acrylates as reactive diluents for dimethacrylate-based dental resin systems[J]. Biomaterials,2005, 26(12):1329-1336
[45]江峰,张丽华.齿科可见光固化复合树脂[J].中国胶黏剂,2006,15(11)：42-45
[46]Orlowskl, et al. Tetraacrylic and tetramethacrylic esters and dental materials containing same[P]. US 4420306,1983
[47]Chan D CN, et al. Dental Mater,1999,15:219
[48]Raul W A, Anabel L M, Manuel T A, et al. Mechanical properties of visible light-cured resins reinforced with hydroxyapatite for dental restoration[J]. Dental Materials, 2002,(18):49-57
[49]Ruddelld E, Maloneym M, Thompson J Y. Effect of novel filler particles on the mechanical and wear properties of dental composites[J]. Dental Materials,2002,18(1): 72-80
[50]吴刚强,肖浦,史素清,等.樟脑醌／乙二醇-3-吗啡啉基丙酸酯甲基丙烯酸酯引发牙科复合树脂的光聚合动力学研究[J].感光科学与光化学,2007,25(2)：130-135
[51]Park Y J, Chae K H, Rawls H R. Development of a new photoinitiation system for dental light-cure composite resins[J]. Dental Materiala,1999,15(2):120-127
[52]Sun G J, Chae K H. Properties of 2,3-butanedione and 1-phenyl-1,2-propanedione as new photo sensitizers for visible light cured dental resin composites[J]. Polymer,2000, 41(16):6205-6212
[53]Kucybala Z, Pietrzak M, Paczkowshi J, et al. Kinetic studies of a new photoinitiator hybrid system based on camphorquinone-N-phenylglicyne derivatives for laser polymerization of dental restorative and stereolithographic(3D) formulations[J]. Polymer, 1996,37(20):4585-4591
[54]刘建国.高强度光固化树脂充填后牙邻面龋[J].大理学院学报,2003,2(5)：79-83
[55]黄道庆,姜向东,王笃权,等.可见光固化树脂在义齿修理中的应用[J].中国现代临床医学,2004,3(2)：56-57
[56]张志忠,杨爱玲,任江涛,等.光固化树脂固位钉修复切角切缘缺损疗效观察[J].口腔材料器械杂志,2003,12(4)：220-222
[57]杨慧芳.光固化树脂在前牙修复及美容中的应用[J].卫生职业教育,2003,21(8)：139-140
[58]Jakubiak J, Allonas X, Fouassier J P,et al. Camphorquinone-amines photoinitating systems for the initiation of free radical polymerization polymer[J]. Polymer,2003, 44(18):5219-5226
[59]Rabek J F, Fouassier J P, Nie J, et al. Camphorquinone/amine photoinitiating system for photoeuring[J]. Trends in Photochemistry & Photobiology,1999,5:51-56
[60]Pallanza R, Scotti R, Beretta G, Cacalleri B, Arioli V. Antimicrob Agents Chemother, 1984,26:462-465
[61]Imazato S, Ebi N, Tarumi H, et al. Bacterial activity and cytotoxicity of antibacterial monomer MDPB. Biomateriala,1999,20:899-903
[62]Ratanasathien S, Wataha J C, Hanks C T, et al. Cytotoxic interactive effects of dentin bonding components onmouse fibroblasts[J]. J Dent Res,1995,74 (9):1602-1606
[63]Santos C, Clarke R L, Braden M, et al. Water absorption charactenstics of dental composites incorporating hydroxyapatite filler[J]. Biomaterials,2002,23(8):1897-1904
[64]Kalachandra S, Kusy R P. Comparison of water sorption by methacrylate and dimethacrylate monomers and their corresponding polymers. Polymer,1991,32: 2428-2434
[65]Diamant Y, Marom G, Broutman L J. The effect of network structure on moisture absorption of epoxy resins. Journal of Applied Polymer Science,1981,26:3015-3025
[66]Sumitomo T, Nagamune H, Maeda T, et al. Correlation between the bacterioclastic action of a bis-quaternary ammonium compound and outer membrane proteins. Biocontrol Science,2006,11:115-124
[2]陈治清.口腔生物材料学[M].北京：化学工业出版社.2004,1-2
[3]Jedrychowski J R, Caputo A A, Kerper S. Antibacterial and mechanical properties of restorative materials combined with chlorhexidines[J]. J Oral Rehabil,1983,10(4): 373-381
[4]Takemura K, Sakamoto Y, Staninec M, et al. Antibacterial activity of a bis-GMA based composite resin and antibacterial effect of chlorhexidine incorporation[J]. Jpn J Conserv Dent,1983,26(7):540-547
[5]Imazato S. Antibacterial properties of resin composites and dentin bonding systems[J]. Dent Mater,2003,19(6):449-457
[6]张林祺,高勃,杨聚才等.三种无机抗菌剂对常见牙体牙周致病菌的抗菌效果[J].现代口腔医学杂志,2007,21(1)：13-15
[7]张听,高保娇,朱勇等.季铵化聚乙烯亚胺的抗菌性能研究[J].高分子学报,2007,7：627-631
[8]Imazato S, Torii M, Tsuchitani Y, et al.Immobilization of an antibacterial component in composite resin. Dentistry in Japan,1993,30:63-68
[9]Imazato S, Torii M, Tsuchitani Y, et al. Incorporation of bacterial inhibitor into resin composite[J]. Journal of Dental Research,1994,73(8):1437-1443
[10]Imazato S, McCabe J F. Influence of incorporation of antibacterial monomer on curing behavior of a dental resin composite[J]. Journal of Dental Research,1994,73(15): 1641-1645
[11]Imazato S, Russell R R B, McCabe J F. Antibacterial activity of MDPB polymer incorporated in dental resin[J]. Journal of Dental Research,1995,23(3):177-181
[12]Imazato S, Tarumi H, Kato S, et al. Water sorption and colour stability of composites containing the antibacterial monomer MDPB[J]. Journal of Dental Research,1999, 27(4):279-283
[13]Imazato S, Kinomoto Y, Tarumi H, et al. Antibacterial activity and bonding characteristics of adhesive resin containing antibacterial monomer MDPB[J]. Dental Materials,2003,19(4):313-319
[14]Imazato S. Antibacterial properties of resin composites and dentin bonding systems[J]. Dental Materials,2003,19(6):449-457
[15]张朝武.应用广泛的季铵盐类消毒剂[J].现代预防医学,2006,33(5)：855-857
[16]佟会,邱树毅.季铵盐类抗菌剂及其应用研究进展[J].贵州化工,2006,31(5)：1-7
[17]孙洪,夏英,陈莉,等.国内外抗菌剂的研究现状及发展趋势[J].塑料工业,2006,34(9)：1-4
[18]Franklin T J, Snow G A. Biochemistry of antimicrobial action[M]. London:Chapman and hall,1981,32-33
[19]王蕊欣,高保娇.聚(4-乙烯基吡啶季铵盐-丙烯酰胺)的抗菌性能与机理研究[J].高等学校化学学报,2005,26(9)：1774-1776
[20]Koji T, Kan M,Yoshiharu L. Synthesis of α, α'-diaminocarboxylic acids [J]. Bulletin of the Chemical Society of Japan,1960,33:1529-1532
[21]郑静,周飞,张威.两种含羟基双季铵盐杀菌剂的合成与固定化[J].日用化学工业,2007,37(2)：92-96
[22]孙记夫,李秋小,李运玲.双癸基甲基羟乙基氯化铵的合成与杀菌性能[J].精细化工,2008,25(6)：565-275
[23]周娟,马云,屈撑囤,等.甲硝唑双季铵盐的合成与杀菌性能研究.西安石油大学学报(自然科学版),2009(5)：10-13
[24]Joerg C, Alexander M. Polymer surface derivatized with poly(vinyl-N-hexylpyridinium) kill airborne and waterborne bacteria[J]. Biotechnol Bioeng,2002,79(4):465-468
[25]Lin J, Qiu S Y, Klibanov A M. Bactercidal properties of flat surfaces and nanoparticles derivatized with alkylated polyethylenimines[J]. Biotechnol Prog,2002,18(5):1082
[26]Lin J, Qiu S Y, Klibanov A M. Mecheanism of bactericidal and fungicidal activities of textiles covalently modified weth alkylated polyethylenimine[M]. Wiley Periodicals, Inc, 2003
[27]Nudel R, Janauer G E, Schrier E E, et al. Water insoluble disinfectant composition:US, 4349646[P],1980
[28]Lewis K, Alexander M, Klibanov. Surpassing nature:rational design of sterile-surface materials. Trends in Biotechnology,2005,23 (7):343-348
[29]Sauvel G, Dupond S, Znierski, et al. Biocidal Polymers Activeby Contact Ⅴ:Synthesis of Polysiloxanes with Biocidal Activity[J]. J Apply Polym Sci,2000, (75):1005-1012
[30]张葵花,谭绍早,刘应亮.季铵盐改性蒙脱土的抗菌活性及抗菌机理[J].硅酸盐学报,2006,34(1)：87-92
[31]周轩榕,卢滇楠,邢晓东等.表面接枝季铵盐型高分子材料抗菌过程的特性研究[J].高等学校化学学报,2003,24(6)：1131-1135
[32]张昌辉,谢瑜,徐旋.抗菌剂的研究进展.化工进展,2007,26(9)：1237-1241
[33]Ayfer B, Dizman B, ElasriMO, et al. Synthesis and antibacterial activities of new quaternary ammonium monomers [J]. DesMonomers Polym,2005,8(5):437-451
[34]Scherzer T, Decker U. The effect of temperature on the kinetics of diacrylate photo polymerization studied by Realtime FTIR spectroscopy[J]. Polymer,2000,41(21): 7681-7690
[35]Andrzejewska E. Photopolymerization kinetics of multifunctional monomers[J]. Progress in Polymer Science,2001,26(4):605-665
[36]何芳,王玉林,万怡灶,等.光固化树脂及复合材料研究进展[J].工程塑应用,2003,31(11)：67-70
[37]李之轶,许乾慰.可见光固化齿料充填复合树脂挠曲强度研究[J].上海塑料,2005,3(1)：10-13
[38]Nie J, Bowman C N. Synthesis and photopolymerization of N,N'-dimethyl-N,N'-di(methacryloxy ethyl)-1,6-hexanediamine as a polymerizable amine coinitiator fur dental restorations[J]. Biomatedals,2002,23(4):1221-1226
[39]Morbert M, Ulrich S. New developments of polymeric dental composites[J]. Progress Polymer Science,2001,26(4):535-576
[40]Sideridou I, Achilidas D S, Spyroudi C, et al. Water sorption characteristics of light-cured dental resins andcomposites based on Bis-EMA/PCDMA[J]. Biomaterials, 2004,25(2):367-376
[41]Moszner N, Volkel T, Fischer UK, et al. Angew Makromol Chem,1999,265(1):31-35
[42]谭燕妮,刘咏,向其军.牙科光固化复合树脂材料的性能与展望[J].粉末冶金材料科学与工程,2007,12(3)：139-145
[43]Asmussen E, Peutzfeldt A. Influence of UEDMA,Bis-GMA and TEGDMA on selected mechanical properties of experimental resin composites[J]. Dent Mater,1998,14(1): 51-56
[44]Lu H, Stansbury J W, Nie J, et al. Development of highly reactive mono-(meth)acrylates as reactive diluents for dimethacrylate-based dental resin systems[J]. Biomaterials,2005, 26(12):1329-1336
[45]江峰,张丽华.齿科可见光固化复合树脂[J].中国胶黏剂,2006,15(11)：42-45
[46]Orlowskl, et al. Tetraacrylic and tetramethacrylic esters and dental materials containing same[P]. US 4420306,1983
[47]Chan D CN, et al. Dental Mater,1999,15:219
[48]Raul W A, Anabel L M, Manuel T A, et al. Mechanical properties of visible light-cured resins reinforced with hydroxyapatite for dental restoration[J]. Dental Materials, 2002,(18):49-57
[49]Ruddelld E, Maloneym M, Thompson J Y. Effect of novel filler particles on the mechanical and wear properties of dental composites[J]. Dental Materials,2002,18(1): 72-80
[50]吴刚强,肖浦,史素清,等.樟脑醌／乙二醇-3-吗啡啉基丙酸酯甲基丙烯酸酯引发牙科复合树脂的光聚合动力学研究[J].感光科学与光化学,2007,25(2)：130-135
[51]Park Y J, Chae K H, Rawls H R. Development of a new photoinitiation system for dental light-cure composite resins[J]. Dental Materiala,1999,15(2):120-127
[52]Sun G J, Chae K H. Properties of 2,3-butanedione and 1-phenyl-1,2-propanedione as new photo sensitizers for visible light cured dental resin composites[J]. Polymer,2000, 41(16):6205-6212
[53]Kucybala Z, Pietrzak M, Paczkowshi J, et al. Kinetic studies of a new photoinitiator hybrid system based on camphorquinone-N-phenylglicyne derivatives for laser polymerization of dental restorative and stereolithographic(3D) formulations[J]. Polymer, 1996,37(20):4585-4591
[54]刘建国.高强度光固化树脂充填后牙邻面龋[J].大理学院学报,2003,2(5)：79-83
[55]黄道庆,姜向东,王笃权,等.可见光固化树脂在义齿修理中的应用[J].中国现代临床医学,2004,3(2)：56-57
[56]张志忠,杨爱玲,任江涛,等.光固化树脂固位钉修复切角切缘缺损疗效观察[J].口腔材料器械杂志,2003,12(4)：220-222
[57]杨慧芳.光固化树脂在前牙修复及美容中的应用[J].卫生职业教育,2003,21(8)：139-140
[58]Jakubiak J, Allonas X, Fouassier J P,et al. Camphorquinone-amines photoinitating systems for the initiation of free radical polymerization polymer[J]. Polymer,2003, 44(18):5219-5226
[59]Rabek J F, Fouassier J P, Nie J, et al. Camphorquinone/amine photoinitiating system for photoeuring[J]. Trends in Photochemistry & Photobiology,1999,5:51-56
[60]Pallanza R, Scotti R, Beretta G, Cacalleri B, Arioli V. Antimicrob Agents Chemother, 1984,26:462-465
[61]Imazato S, Ebi N, Tarumi H, et al. Bacterial activity and cytotoxicity of antibacterial monomer MDPB. Biomateriala,1999,20:899-903
[62]Ratanasathien S, Wataha J C, Hanks C T, et al. Cytotoxic interactive effects of dentin bonding components onmouse fibroblasts[J]. J Dent Res,1995,74 (9):1602-1606
[63]Santos C, Clarke R L, Braden M, et al. Water absorption charactenstics of dental composites incorporating hydroxyapatite filler[J]. Biomaterials,2002,23(8):1897-1904
[64]Kalachandra S, Kusy R P. Comparison of water sorption by methacrylate and dimethacrylate monomers and their corresponding polymers. Polymer,1991,32: 2428-2434
[65]Diamant Y, Marom G, Broutman L J. The effect of network structure on moisture absorption of epoxy resins. Journal of Applied Polymer Science,1981,26:3015-3025
[66]Sumitomo T, Nagamune H, Maeda T, et al. Correlation between the bacterioclastic action of a bis-quaternary ammonium compound and outer membrane proteins. Biocontrol Science,2006,11:115-124