银离子对结冷胶/聚丙烯酰胺双网络水凝胶的增强作用
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摘要
首先,以结冷胶(GG)为基体,丙烯酰胺(AAm)为单体,N,N′-亚甲基双丙烯酰胺(MBA)为交联剂,通过"一锅法"制备GG/PAAm双网络水凝胶(GG/PAAm DN);然后将GG/PAAm DN浸泡在硝酸银溶液中制得Ag~+增强的GG/PAAm DN(GG-Ag~+/PAAm DN)。通过扫描电子显微镜、流变仪、原子吸收光谱仪、力学性能测试等手段研究了AAm、MBA用量及Ag~+对水凝胶流变性能、微观形貌、力学性能的影响。结果表明:与GG/PAAm DN相比,GG-Ag~+/PAAm DN的储能模量升高,力学性能明显增强,压缩强度由4.88 MPa增大到11.8 MPa,,断裂伸长率由236%增大到320%,断裂强度由0.1MPa提高到0.26MPa。抗菌实验表明GG-Ag~+/PAAm DN具有良好的抗菌性能。
The GG/PAAm double network hydrogel was prepared by a simple"one pot method"of aqueous mixture of gellan gum(GG),acrylamide(AAm),containing N,N′-methylenebisacrylamide(MBA)as crosslinking agent,the Ag~+enhanced GG/PAAm double network hydrogel was obtained after soaking in silver nitrate solution.The effects of AAm,MBA content and Ag~+on the hydrogel rheological properties,microstructure and mechanical properties were studied.The results showed that a series of hydrogels could be prepared by changing the amount of crosslinking agent MBA in the system,SEM showed the double network hydrogel has an interconnected porous structure,the storage modulus of GG/PAAm hydrogels increased and tanδdecreased significantly with the increase of MBA content in the hydrogel,due to the fact that an increasingly perfect network structure is formed inside the GG/PAAm hydrogel,indicating that the elastic properties are dominant in the hydrogel.After immersed in silver nitrate solution,Ag~+can reorganizes the network structure,both the storage modulus and mechanical performance of GG/PAAm hydrogel is obviously enhanced,the storage modulus of hydrogel rapidly increases from 7.5 kPa to 38 kPa,which is more than 5 times higher than that of the GG/PAAm hydrogel,the compressive strength can reach 11.8 MPa,much higher than GG/PAAm hydrogel(compression strength is 4.88 MPa),and elongation at break increased from 236%to 320%,and fracture strength increased from 0.1 MPa to 0.26 MPa.Meanwhile,antibacterial experiments show that Ag~+enhanced GG/PAAm double network hydrogel has good antibacterial properties.Considering these excellent performance,this composite hydrogels have great potential application in antibacterial materials.
The GG/PAAm double network hydrogel was prepared by a simple"one pot method"of aqueous mixture of gellan gum(GG),acrylamide(AAm),containing N,N′-methylenebisacrylamide(MBA)as crosslinking agent,the Ag~+enhanced GG/PAAm double network hydrogel was obtained after soaking in silver nitrate solution.The effects of AAm,MBA content and Ag~+on the hydrogel rheological properties,microstructure and mechanical properties were studied.The results showed that a series of hydrogels could be prepared by changing the amount of crosslinking agent MBA in the system,SEM showed the double network hydrogel has an interconnected porous structure,the storage modulus of GG/PAAm hydrogels increased and tanδdecreased significantly with the increase of MBA content in the hydrogel,due to the fact that an increasingly perfect network structure is formed inside the GG/PAAm hydrogel,indicating that the elastic properties are dominant in the hydrogel.After immersed in silver nitrate solution,Ag~+can reorganizes the network structure,both the storage modulus and mechanical performance of GG/PAAm hydrogel is obviously enhanced,the storage modulus of hydrogel rapidly increases from 7.5 kPa to 38 kPa,which is more than 5 times higher than that of the GG/PAAm hydrogel,the compressive strength can reach 11.8 MPa,much higher than GG/PAAm hydrogel(compression strength is 4.88 MPa),and elongation at break increased from 236%to 320%,and fracture strength increased from 0.1 MPa to 0.26 MPa.Meanwhile,antibacterial experiments show that Ag~+enhanced GG/PAAm double network hydrogel has good antibacterial properties.Considering these excellent performance,this composite hydrogels have great potential application in antibacterial materials.
引文
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[16]黄迎,雷昆,黎朝,等.基于儿茶酚基功能化聚乙二醇水凝胶的制备及其力学性能[J].功能高分子学报,2018,31(4):315-321.
[17]王健强,肖艳.基于聚肽和海藻酸钠自交联水凝胶的制备与表征[J].功能高分子学报,2018,31(1):69-74.
[18] KIM J S,KUK E,YU K N,et al.Antimicrobial effects of silver nanoparticles[J].Nanomedicine Nanotechnology Biology&Medicine,2007,3(1):95-101.
[19] ZHANG S,TANG Y,VLAHOVIC B.A review on preparation and applications of silver-containing nanofibers[J].Nanoscale Research Letters,2016,11(1):1-8..
[20] CHENG F,GAO J,WANG L,et al.Composite chitosan/poly(ethylene oxide)electrospun nanofibrous mats as novel wound dressing matrixes for the controlled release of drugs[J].Journal of Applied Polymer Science,2015,132(24):1-8.
[21]汪争光,胡朵,吴东蔚,等.结冷胶与聚乙二醇丙烯酸酯双网络凝胶的制备及生物相容性评价[J].高等学校化学学报,2017,38(2):275-283.
[22] MIYOSHI E,TAKAYA T,NISHINARI K.Rheological and thermal studies of gel-sol transition in gellan gum aqueous solutions[J].Carbohydrate Polymers,1996,30(2):109-119.
[23] MORRIS E R,NISHINARI K,RINAUDO M.Gelation of gellan:A review[J].Food Hydrocolloids,2012,28(2):373-411.
[24]李璠,朱家壁.新型高分子材料结冷胶的性质和应用[J].中国药业,2007,16(9):1-3.
[2] OSMALEK T,FROELICH A,TASAREK S.Application of gellan gum in pharmacy and medicine[J].International Journal of Pharmaceutics,2014,466(1-2):328-340.
[3] CARVALHO C R,WROBEL S,MEYER C,et al.Gellan gum-based luminal fillers for peripheral nerve regeneration:An in vivo study in the rat sciatic nerve repair model[J].Biomaterials Science,2018,6(5):1059-1075.
[4] FUCHIGAMI M, TERAMOTO A. Texture and structure of high-pressure-frozen gellan gum gel[J].Food Hydrocolloids,2003,17(6):895-899.
[5] KANG K S,VEEDER G T,MIRRASOUL P J,et al.Agar-like polysaccharide produced by apseudomonas species:Production and basic properties[J].Appl Environ Microbiol,1982,43(5):1086-1091.
[6] FERRIS C J,GILMORE K J,WALLACE G G,et al.Modified gellan gum hydrogels for tissue engineering applications[J].Soft Matter,2013,9(14):3705-3711.
[7] SURI S,BANERJEE R.In vitro evaluation of in situ gels as short term vitreous substitutes[J].Journal of Biomedical Materials Research Part A,2006,79A(3):650-664.
[8] GIAVASIS I,HARVEY L M,MCNEIL B.Gellan gum[J].Critical Reviews in Biotechnology,2000,20(3):177-211.
[9] SMITH A M,SHELTON R M,PERRIE Y,et al.An initial evaluation of gellan gum as a material for tissue engineering applications[J].Journal of Biomaterials Applications,2007,22(3):241-254.
[10] SAHRARO M,BARIKANI M,DAEMI H.Mechanical reinforcement of gellan gum polyelectrolyte hydrogels by cationic polyurethane soft nanoparticles[J].Carbohydrate Polymers,2018,187:102-109.
[11] WANG F,WEN Y,BAI T.Thermal behavior of polyvinyl alcohol-gellan gum-Al3+composite hydrogels with improved network structure and mechanical property[J].Journal of Thermal Analysis&Calorimetry,2017,127(3):2447-2457.
[12] WANG F,WEN Y,BAI T.The composite hydrogels of polyvinyl alcohol-gellan gum-Ca2+with improved network structure and mechanical property[J].Mater Sci Eng C:Mater Biol Appl,2016,69:268-275.
[13] BAKARICH S E,PIDCOCK G C,BALDING P,et al.Recovery from applied strain in interpenetrating polymer network hydrogels with ionic and covalent cross-links[J].Soft Matter,2012,8(39):9985-9988.
[14] COUTINHO D F,SANT S H,OLIVEIRA J T,et al.Modified gellan gum hydrogels with tunable physical and mechanical properties[J].Biomaterials,2010,31(29):7494-7502.
[15] ZHOU Q,KANG H,BIELEC M,et al.Influence of different divalent ions cross-linking sodium alginate-polyacrylamide hydrogels on antibacterial properties and wound healing[J].Carbohydrate Polymers,2018,197:292-304.
[16]黄迎,雷昆,黎朝,等.基于儿茶酚基功能化聚乙二醇水凝胶的制备及其力学性能[J].功能高分子学报,2018,31(4):315-321.
[17]王健强,肖艳.基于聚肽和海藻酸钠自交联水凝胶的制备与表征[J].功能高分子学报,2018,31(1):69-74.
[18] KIM J S,KUK E,YU K N,et al.Antimicrobial effects of silver nanoparticles[J].Nanomedicine Nanotechnology Biology&Medicine,2007,3(1):95-101.
[19] ZHANG S,TANG Y,VLAHOVIC B.A review on preparation and applications of silver-containing nanofibers[J].Nanoscale Research Letters,2016,11(1):1-8..
[20] CHENG F,GAO J,WANG L,et al.Composite chitosan/poly(ethylene oxide)electrospun nanofibrous mats as novel wound dressing matrixes for the controlled release of drugs[J].Journal of Applied Polymer Science,2015,132(24):1-8.
[21]汪争光,胡朵,吴东蔚,等.结冷胶与聚乙二醇丙烯酸酯双网络凝胶的制备及生物相容性评价[J].高等学校化学学报,2017,38(2):275-283.
[22] MIYOSHI E,TAKAYA T,NISHINARI K.Rheological and thermal studies of gel-sol transition in gellan gum aqueous solutions[J].Carbohydrate Polymers,1996,30(2):109-119.
[23] MORRIS E R,NISHINARI K,RINAUDO M.Gelation of gellan:A review[J].Food Hydrocolloids,2012,28(2):373-411.
[24]李璠,朱家壁.新型高分子材料结冷胶的性质和应用[J].中国药业,2007,16(9):1-3.