HA-CaCO_3纳米复合凝胶的制备及性能表征
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摘要
由于透明质酸(hyaluronic acid,HA)水凝胶的机械强度较弱,使其应用受到一定限制。以HA为原料、1,4-丁二醇二缩水甘油醚(1,4-butanediol diglycidyl ether,BDDE)为交联剂对HA进行交联制备HA凝胶,并在交联的同时用浸泡法在凝胶内复合碳酸钙(CaCO_3),以期形成力学性能优异的HA-CaCO_3复合凝胶。利用扫描电镜、红外光谱仪、热重分析仪和X射线衍射仪等对HA凝胶和HA-CaCO_3复合凝胶进行表征和分析,考察CaCO_3对HA凝胶的影响。结果表明,该方法制备的HA-CaCO_3复合凝胶的断裂伸长率达到401%,是单纯HA凝胶的2. 73倍。HA-CaCO_3复合凝胶中CaCO_3的质量分数为27. 3%,晶型为方解石,尺寸在30～80 nm,达到了纳米级别。HA-CaCO_3复合凝胶以其优异的力学性能进一步拓展了HA类凝胶的应用。
Hyaluronic acid( HA) hydrogel is an ideal biomedical material due to its biocompatibility,biodegradability,biological activity and no immunogenicity.However,the application of HA hydrogel has been limited due to its weak mechanical strength.Herein,1,4-butanediol diglycidyl ether( BDDE) is employed as a crosslinking agent for HA to prepare HA hydrogel.While it is cross linking,CaCO_3 is composited into HA hydrogel through soaking method for the purpose of fabricating HA-CaCO_3 composite hydrogel with excellent mechanical properties. The properties of HA hydrogel and HA-CaCO_3 nanocomposite hydrogel are characterized by scanning electron microscope,infrared spectrometer,thermo gravimetric analyzer and X ray diffractometer to investigate the influence of CaCO_3 on HA hydrogel.The results indicate that the elongation at break of composite hydrogel reaches 401%,2. 73 times that of HA hydrogel.The mass fraction of CaCO_3 in composite hydrogel is 27. 3%,CaCO_3 exhibits calcite crystal form with sizes between 30-80 nm.Hence,by means its excellent mechanical properties,HA-CaCO_3 composite hydrogel is expected to further extend the application scope of HA hydrogel.
Hyaluronic acid( HA) hydrogel is an ideal biomedical material due to its biocompatibility,biodegradability,biological activity and no immunogenicity.However,the application of HA hydrogel has been limited due to its weak mechanical strength.Herein,1,4-butanediol diglycidyl ether( BDDE) is employed as a crosslinking agent for HA to prepare HA hydrogel.While it is cross linking,CaCO_3 is composited into HA hydrogel through soaking method for the purpose of fabricating HA-CaCO_3 composite hydrogel with excellent mechanical properties. The properties of HA hydrogel and HA-CaCO_3 nanocomposite hydrogel are characterized by scanning electron microscope,infrared spectrometer,thermo gravimetric analyzer and X ray diffractometer to investigate the influence of CaCO_3 on HA hydrogel.The results indicate that the elongation at break of composite hydrogel reaches 401%,2. 73 times that of HA hydrogel.The mass fraction of CaCO_3 in composite hydrogel is 27. 3%,CaCO_3 exhibits calcite crystal form with sizes between 30-80 nm.Hence,by means its excellent mechanical properties,HA-CaCO_3 composite hydrogel is expected to further extend the application scope of HA hydrogel.
引文
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[2]Valles-lluch A,Poveda-Reyes S,Amoros P,et al.Hyaluronic acidsilica nanohybrid gels[J]. Biomacromolecules,2013,14(12):4217-4225.
[3]Bhattacharyya S,Guillot S,Dabboue H,et al.Carbon nanotubes as structural nanofibers for hyaluronic acid hydrogel scaffolds[J].Biomacromolecules,2008,9(2):505-509.
[4]Domingues R M A,Silva M,Gershovich P,et al.Development of injectable hyaluronic acid/cellulose nanocrystals bionanocomposite hydrogels for tissue engineering applications[J]. Bioconjugate Chemistry,2015,26(8):1571-1581.
[5]Haraguchi K,Takehisa T. Nanocomposite hydrogels:A unique organic-inorganic network structure with extraordinary mechanical,optical,and swelling/de-swelling properties[J]. Advanced Materials,2002,14(16):1120.
[6]王杰,王梦雪,沈睦贤,等.聚甲基丙烯酸/Laponite纳米复合水凝胶的制备及其黏接性能[J].华东理工大学学报(自然科学版),2016,42(3):297-300.
[7]Sharma N,Tiwari A.Nano-ZnO-loaded poly(acrylamide-co-itaconic acid)hydrogel as adsorbent for effective removal of iron from contaminated water[J]. Desalination and Water Treatment,2016,57(14):6463-6476.
[8]Sudheesh Kumar P T,Lakshmanan V K,Anilkumar T V,et al.Flexible and microporous chitosan hydrogel/nano zno composite bandages for wound dressing:In vitro and in vivo evaluation[J].ACS Applied Materials&Interfaces,2012,4(5):2618-2629.
[9]Kumar P T S,Lakshmanan V K,Biswas R,et al.Synthesis and biological evaluation of chitin hydrogel/nano zno composite bandage as antibacterial wound dressing[J].Journal of Biomedical Nanotechnology,2012,8(6):891-900.
[10]Jiang Y Y,Zhu Y J,LI H,et al.Preparation and enhanced mechanical properties of hybrid hydrogels comprising ultralong hydroxyapatite nanowires and sodium alginate[J].Journal of Colloid and Interface Science,2017,497:266-275.
[11]Jiang X,Wu H,Zheng L,et al. Effect of synthesized nanohydroxyapatite/collagen composite hydrogel on osteoblasts growth[J].Journal of Biomaterials and Tissue Engineering,2015,5(7):523-531.
[12]Huang Y,Zhang X,Wu A,et al.An injectable nano-hydroxyapatite(n-HA)/glycol chitosan(G-CS)/hyaluronic acid(Hy A)composite hydrogel for bone tissue engineering[J]. RSC Adv,2016,6(40):33529-33536.
[13]Sa Y,Wang M,Deng H,et al.Beneficial effects of biomimetic nanosized hydroxyapatite/antibiotic gentamicin enriched chitosan-glycerophosphate hydrogel on the performance of injectable polymethylmethacrylate[J].RSC Adv,2015,5(110):91082-91092.
[14]Wu W,Zhang X,Chen J,et al.Synthesis of nano-CaCO3composite particles and their application[J]. Journal of University of Science and Technology Beijing,Mineral,Metallurgy,Material,2008,15(1):67-73.
[15]Zhang H,Chen J F,Zhou H K,et al.Preparation of nano-sized precipitated calcium carbonate for PVC plastisol rheology modification[J]. Journal of Materials Science Letters,2012,21(16):1305-1306.
[16]Guo T,Wang L,Zhang A,et al.Effects of nano calcium carbonate modified by a lanthanum compound on the properties of polypropylene[J].Journal of Applied Polymer Science,2005,97(3):1154-1160.
[17]Jin F L,Pang Q Q,Zhang T Y,et al.Synergistic reinforcing of poly(lactic acid)-based systems by polybutylene succinate and nanocalcium carbonate[J].Journal of Industrial and Engineering Chemistry,2015,32:77-84.
[18]Yuan S,Xu H,Gu H. Fractal analysis of polypropylene composite filled with nano-calcium carbonate[J]. Journal of Applied Polymer Science,2008,110(4):1955-1960.
[19]Wu D Y,Svazas A.Micro-and nano-sized calcium carbonate toughened polystyrene[J]. Journal of Nanoscience and Nanotechnology,2006,6(12):3919-3922.
[20]Maurya S D,Purushothaman M,Krishnan P S G,et al. Effect of nano-calcium carbonate content on the properties of poly(urethane methacrylate)nanocomposites[J]. Journal of Thermoplastic Composite Materials,2014,27(12):1711-1727.
[21]Jiang J,Liu J,Liu C,et al.Roles of oleic acid during micropore dispersing preparation of nano-calcium carbonate particles[J].Applied Surface Science,2011,257(16):7047-7053.
[22]Fang Q,Song B,Tee T T,et al.Investigation of dynamic characteristics of nano-size calcium carbonate added in natural rubber vulcanizate[J].Composites Part B:Engineering,2014,60:561-567.
[23]Sun S,Mao L B,Lei Z,et al. Hydrogels from amorphous calcium carbonate and polyacrylic acid:Bio-inspired materials for“mineral plastics”[J]. Angewandte Chemie International Edition,2016,55(39):11765-11769.
[24]Li A,Jia Y,Sun S,et al. Mineral-enhanced polyacrylic acid hydrogel as an oyster-inspired organic-inorganic hybrid adhesive[J].ACS Applied Materials&Interfaces,2018,10(12):10471-10479.
[25]Gebauer D,Gunawidjaja P N,Ko J Y P,et al.Proto-calcite and proto-vaterite in amorphous calcium carbonates[J]. Angewandte Chemie International Edition,2010,49(47):8889-8891.
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[27]Xiao J,Yang S. Bio-inspired synthesis:Understanding and exploitation of the crystallization process from amorphous precursors[J].Nanoscale,2012,4(1):54-65.
[28]Pouget E M,Bomans P H H,Goos J A C M,et al.The initial stages of template-controlled CaCO3formation revealed by cryo-TEM[J].Science,2009,323(5920):1455-1458.
[29]Abu Elella M H,Mohamed R R,Sabaa M W. Synthesis of novel grafted hyaluronic acid with antitumor activity[J]. Carbohydrate Polymers,2018,189:107-114.