壳聚糖/直链淀粉共混物相容性的分子动力学模拟
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摘要
由于壳聚糖和淀粉在机械、力学及热学特性上具有良好的互补作用,研究两者组分之间的共混性质具有重要的意义。为了预测壳聚糖与淀粉的共混相容性,本文在恒温恒压(NPT)系统和COMPASS力场下,利用分子动力学模拟方法,对直链淀粉/壳聚糖(完全脱乙酰化)在不同质量比下的Flory-Huggins参数χ、原子对之间的径向分布函数及聚合物链的扩散系数进行模拟。研究结果显示,在298 K下,相对直链淀粉/壳聚糖质量比为70/30和50/50而言,质量比为30/70时,其共混体系的χ值最小,分子链的分子间作用力最大,两者聚合物链段的扩散系数都为最大,表明此时的共混相容性要优于质量比为70/30和质量比为50/50的共混体系;直链淀粉能够降低壳聚糖体系中链段的弛豫速率和结晶速率,从而抑制其聚合物链的分子流动性。
Miscibility in chitosan/amylose blends is of great significance in research, as chitosan and starch show good complementary effects in terms of mechanical and thermal properties. In order to predict the miscibility of chitosan with starch, the Flory-Huggins parameter χ, radial distribution function of atom pair, and diffusion coefficient of the polymer chain were simulated by molecular dynamics simulation, and under the condensed-phase optimized molecular potential for atomistic simulation studies(COMPASS) force field and NPT ensemble. Results indicated that the value of parameter χ was the smallest, the bonding force of molecular chains and diffusion coefficient between amylose and chitosan chain segment were the largest when the mass ratio of amylose/chitosan was 30/70 at the same temperature when compared to the mass ratios of 70/30 and 50/50. This showed that the miscibility of the binary system(mass ratio of 30/70) was better than that of the other two systems. The addition of amylose into chitosan suppressed the mobility of chitosan chains due to a decrease in crystallization and relaxation rate of chitosan caused by amylose chain segments.
Miscibility in chitosan/amylose blends is of great significance in research, as chitosan and starch show good complementary effects in terms of mechanical and thermal properties. In order to predict the miscibility of chitosan with starch, the Flory-Huggins parameter χ, radial distribution function of atom pair, and diffusion coefficient of the polymer chain were simulated by molecular dynamics simulation, and under the condensed-phase optimized molecular potential for atomistic simulation studies(COMPASS) force field and NPT ensemble. Results indicated that the value of parameter χ was the smallest, the bonding force of molecular chains and diffusion coefficient between amylose and chitosan chain segment were the largest when the mass ratio of amylose/chitosan was 30/70 at the same temperature when compared to the mass ratios of 70/30 and 50/50. This showed that the miscibility of the binary system(mass ratio of 30/70) was better than that of the other two systems. The addition of amylose into chitosan suppressed the mobility of chitosan chains due to a decrease in crystallization and relaxation rate of chitosan caused by amylose chain segments.
引文
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[31]Castro R E N,Toledo E A,Rubira A F,et al.Crystallisation and miscibility of poly(ethylene oxide)/poly(vinyl chloride)blends[J].Journal of Materials Science,2003,38(4):699-703
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[33]Rao Z,Wang S,Peng F.Self diffusion of the nano-encapsulated phase change materials:a molecular dynamics study[J].Applied Energy,2012,100:303-308.
[34]Chang K S,Wang Y L,Kang C H,et al.Molecular dynamics simulations of polymeric structure and alcohol-membrane surface affinity of aromatic polyamide membranes[J].Journal of Membrane Science,2011,382(1):30-40
[35]Zhou Q H,Li M,Yang P,et al.Effect of hydrogen bonds on structures and glass transition temperatures of maleimide-isobutene alternating copolymers:molecular dynamics simulation study[J].Macromolecular Theory and Simulations,2013,22(2):107-114
[36]Martinez de Arenaza I,Meaurio E,Coto B,et al.Molecular dynamics modelling for the analysis and prediction of miscibility in polylactide/polyvinilphenol blends[J].Polymer,2010,51(19):4431-4438
[2]董静,刘群.甲壳素/壳聚糖及其衍生物的最新应用进展[J].医学综述,2011,17(6):921-922DONG Jing,LIU Qun.The latest research progress in use of chitin/chitosan and their derivates[J].Medical Recapitulate,2011,17(6):921-922
[3]Zhuang P Y,Li Y L,Fan L,et al.Modification of chitosan membrane with poly(vinyl alcohol)and biocompatibility evaluation[J].International Journal of Biological Macromolecules,2012,50(3):658-663
[4]Ojagh S M,Rezaei M,Razavi S H,et al.Development and evaluation of a novel biodegradable film made from chitosan and cinnamon essential oil with low affinity toward water[J].Food Chemistry,2010,122(1):161-166
[5]陈达佳,赵利,袁美兰,等.胶原蛋白与壳聚糖复合膜的机械性能[J].食品科学,2014,35(9):112-117CHEN Da-jia,ZHAO Li,YUAN Mei-lan,et al.Mechanical properties of collagen-chitosan composite film[J].Journal of Food Science,2014,35(9):112-117
[6]No H K,Meyers S P,Prinyawiwatkul W,et al.Applications of chitosan for improvement of quality and shelf life of foods:a review[J].Journal of Food Science,2007,72(5):87-100
[7]Li Z,Zhuang X P,Liu X F,et al.Study on antibacterial O-carboxymethylated chitosan/cellulose blend film from Li Cl/N,N-dimethylacetamide solution[J].Polymer,2002,43(4):1541-1547
[8]Mir S,Yasin T,Halley P J,et al.Thermal,rheological,mechanical and morphological behavior of HDPE/chitosan blend[J].Carbohydrate Polymers,2011,83(2):414-421
[9]Tripathi S,Mehrotra G K,Dutta P K.Preparation and physicochemical evaluation of chitosan/poly(vinyl alcohol)/pectin ternary film for food-packaging applications[J].Carbohydrate Polymers,2010,79(3):711-716
[10]Fakhreddin Hosseini S,Rezaei M,Zandi M,et al.Preparation and functional properties of fish gelatin-chitosan blend edible films[J].Food Chemistry,2013,136(3):1490-1495
[11]Prakash Maran J,Sivakumar V,Sridhar R,et al.Development of model for mechanical properties of tapioca starch based edible films[J].Industrial Crops and Products,2013,42:159-168
[12]Bruno I J,Cole J C,Edgington P R,et al.New software for searching the cambridge structural database and visualizing crystal structures[J].Acta Crystallographica Section B:Structural Science,2002,58(3):389-397
[13]Saleem A,Azam S S,Zarina S.Docking and molecular dynamics simulation studies on glycation-induced conformational changes of human paraoxonase 1[J].European Biophysics Journal,2012,41(2):241-248
[14]Gu C,Gu H,Lang M.Molecular simulation to predict miscibility and phase separation behavior of chitosan/poly(?-caprolactone)binary blends:a comparison with experiments[J].Macromolecular Theory and Simulations,2013,22(7):377-384
[15]Brandrup,Johannes,et al.eds.Polymer handbook.Vol.89.New York:Wiley,1999
[16]邱福生,任力,王家鸣,等.分子动力学模拟预测壳聚糖的玻璃化转变温度[J].化工学报,2012,63(7):2285-2289QIU Fu-Sheng,REN Li,WANG Jia-Ming,et al.Prediction of glass transition temperature of chitosan through molecular dynamic simulation[J].CIESC Journal,2012,63(7):2285-2289
[17]付一政,刘亚青,兰艳花.聚丙烯玻璃化转变温度的分子动力学模拟[J].高分子材料科学与工程,2009,25(10):53-56FU Yi-zheng,LIU Ya-qing,LAN Yan-hua.Molecular simulation on the glass transition of polypropylene[J].Polymer Materials Science and Engineering,2009,25(10):53-56
[18]Yang S,Qu J.Computing thermomechanical properties of crosslinked epoxy by molecular dynamic simulations[J].Polymer,2012,53(21):4806-4817
[19]Luo Z,Jiang J.Molecular dynamics and dissipative particle dynamics simulations for the miscibility of poly(ethylene oxide)/poly(vinyl chloride)blends[J].Polymer,2010,51(1):291-299
[20]曾鲁红.分子动力学模拟研究直链淀粉的增塑[D].镇江:江苏科技大学,2012ZENG Lu-hong.Research of amylose plasticized by molecular dynamics simulation[D].Zhenjiang:Jiangsu University of Science and Technology,2012
[21]Ionita M,Iovu H.Mechanical properties,urea diffusion,and cell cultural response of poly(vinyl alcohol)-Chitosan bioartificial membranes via molecular modelling and experimental investigation[J].Composites Part B:Engineering,2012,43(5):2464-2470
[22]薛兆君.聚合物共混体系相容性的分子模拟[D].上海:华东理工大学,2012XUE Zhao-jun.Molecular simulation of the miscibility for polymer blends[D].Shanghai:East China University of Science and Technology,2012
[23]齐晓飞,张晓宏,李吉祯,等.NC/NG共混体系的分子动力学模拟研究[J].兵工学报,2013,34(1):93-99QI Xiao-fei,ZHANG Xiao-hong,LI Ji-zhen,et al.Molecular dynamics simulation of NC/NG blends[J].Acta Arwamentarii,2013,34(1):93-99
[24]Fu Y,Liao L,Lan Y,et al.Molecular dynamics and mesoscopic dynamics simulations for prediction of miscibility in polypropylene/polyamide-11 blends[J].Journal of Molecular Structure,2012,1012:113-118
[25]Suknuntha K,Tantishaiyakul V,Espidel Y,et al.Molecular modeling simulation and experimental measurements to characterize chitosan and poly(vinyl pyrrolidone)blend interactions[J].Journal of Polymer Science Part B:Polymer Physics,2008,46(12):1258-1264
[26]Gupta J,Nunes C,Jonnalagadda S.A molecular dynamics approach for predicting the glass transition temperature and plasticization effect in amorphous pharmaceuticals[J].Molecular Pharmaceutics,2013,10(11):4136-4145
[27]Wu C,Xu W.Atomistic molecular simulations of structure and dynamics of crosslinked epoxy resin[J].Polymer,2007,48(19):5802-5812
[28]Gupta K M,Hu Z,Jiang J.Molecular insight into cellulose regeneration from a cellulose/ionic liquid mixture:effects of water concentration and temperature[J].RSC Advances,2013,3(13):4425-4433
[29]董仕晋.分子动力学与介观动力学模拟在聚合物多相体系中的应用[D].长春:吉林大学,2011DONG Shi-jin.Application of molecular dynamics and mesoscopic dynamics simulations in polymeric muti-phase systems[D].Changchun:Jilin University,2011
[30]丁丽颖,耿春宇,赵月红,等.甲烷水合物分解及自保护效应的分子动力学模拟[J].中国科学:B辑,2008,38(2):161-169DING Li-ying,GENG Chun-yu,ZHAO Yue-hong,et al.Molecular dynamics simulation of dissociation and the protective effect of methane hydrate[J].Science in China:Series B,2008,38(2):161-169
[31]Castro R E N,Toledo E A,Rubira A F,et al.Crystallisation and miscibility of poly(ethylene oxide)/poly(vinyl chloride)blends[J].Journal of Materials Science,2003,38(4):699-703
[32]Wu C.Simulated glass transition of poly(ethylene oxide)bulk and film:a comparative study[J].The Journal of Physical Chemistry B,2011,115(38):11044-11052.
[33]Rao Z,Wang S,Peng F.Self diffusion of the nano-encapsulated phase change materials:a molecular dynamics study[J].Applied Energy,2012,100:303-308.
[34]Chang K S,Wang Y L,Kang C H,et al.Molecular dynamics simulations of polymeric structure and alcohol-membrane surface affinity of aromatic polyamide membranes[J].Journal of Membrane Science,2011,382(1):30-40
[35]Zhou Q H,Li M,Yang P,et al.Effect of hydrogen bonds on structures and glass transition temperatures of maleimide-isobutene alternating copolymers:molecular dynamics simulation study[J].Macromolecular Theory and Simulations,2013,22(2):107-114
[36]Martinez de Arenaza I,Meaurio E,Coto B,et al.Molecular dynamics modelling for the analysis and prediction of miscibility in polylactide/polyvinilphenol blends[J].Polymer,2010,51(19):4431-4438