Single-step ethylene polymerization over a binary catalyst,including zirconocene precatalysts of various designs,has been studied to obtain polymer compositions based on ultrahigh-molecular-weight polyethylene(UHMWPE)...Single-step ethylene polymerization over a binary catalyst,including zirconocene precatalysts of various designs,has been studied to obtain polymer compositions based on ultrahigh-molecular-weight polyethylene(UHMWPE)and low-molecular-weight HDPE(LMWPE)directly in synthesis.Zirconocenes rac-(CH_(3))_(2)Silnd_(2)ZrCl_(2)(Zr-1)and rac-(C_(6)H_(10))CplndZrCl_(2)(Zr-2)activated with methylaluminoxane(MAO)were used as the components of the binary catalyst.It has been shown that the use of Zr-1/MAO and Zr-2/MAO in ethylene polymerization at 30℃leads to the production of UHMWPE with Mw=1000 kg-mol^(-1)and LMWPE with Mw=18 kg·mol^(-1),respectively.Reactor polymer compositions(RPC)with LMWPE fraction contents ranging from 9 wt%to 42 wt%were obtained when a molar fraction of Zr-2 in the binary catalyst(Zr-1+Zr-2)/MAO va ried in the range from 0.3 to 0.85.A study of the molecular weight characteristics of RPC showed that it has a wide bimodal molecular weight distribution(MWD)and includes UHMWPE(Mw=1000 kg·mol^(-1))and LMWPE(Mw=18 kg·mol^(-1))fractions.The degree of crystallinity of the polymer products was determined using the DSC method.The tensile properties and melt indices of the materials were studied depending on the LMWPE fraction content in the polymer composition.UHMWPE/LMWPE compositions with high tensile properties and fluidity at a load of 5 kg were obtained.展开更多
The lifespan of biological heart valve prostheses available in the market is limited due to structural alterations caused by calcium phosphate deposits formed from blood plasma in contact with the tissues.The objectiv...The lifespan of biological heart valve prostheses available in the market is limited due to structural alterations caused by calcium phosphate deposits formed from blood plasma in contact with the tissues.The objective of this work is to present a comparative methodology for the investigation of the formation of calcium phosphate deposits on bioprosthetic and tissue-engineered scaffolds in vitro and the influence of mechanical forces on tissue mineralization.Based on earlier investigations on biological mineralization at constant supersaturation,a circulatory loop simulating dynamic blood flow and physiological pressure conditions was developed.The system was appropriately adapted to evaluate the calcification potential of decellularized(DCV)and glutaraldehyde-fixed(GAV)porcine aortic valves.Results indicated that DCV calcified at higher,statistically nonsignificant,rates in comparison with GAV.This difference was attributed to the tissue surface modifications and cell debris leftovers from the decellularization process.Morphological analysis of the solids deposited after 20 h by scanning electron microscopy in combination with chemical microanalysis electron-dispersive spectroscopy identified the solid formed as octacalcium phosphate(Ca8(PO4)6H2·5H2O,OCP).OCP crystallites were preferentially deposited in high mechanical stress areas of the test tissues.Moreover,GAV tissues developed a significant transvalvular pressure gradient increase past 36 h with a calcium deposition distribution similar to the one found in explanted prostheses.In conclusion,the presented in vitro circulatory model serves as a valuable prescreening methodology for the investigation of the calcification process of bioprosthetic and tissue-engineered valves under physiological mechanical load.展开更多
基金financially supported by the Fundamental Research Program of the Russian Academy of Sciences for the Semenov Research Center of Chemical Physics,Russian Academy of Sciences。
文摘Single-step ethylene polymerization over a binary catalyst,including zirconocene precatalysts of various designs,has been studied to obtain polymer compositions based on ultrahigh-molecular-weight polyethylene(UHMWPE)and low-molecular-weight HDPE(LMWPE)directly in synthesis.Zirconocenes rac-(CH_(3))_(2)Silnd_(2)ZrCl_(2)(Zr-1)and rac-(C_(6)H_(10))CplndZrCl_(2)(Zr-2)activated with methylaluminoxane(MAO)were used as the components of the binary catalyst.It has been shown that the use of Zr-1/MAO and Zr-2/MAO in ethylene polymerization at 30℃leads to the production of UHMWPE with Mw=1000 kg-mol^(-1)and LMWPE with Mw=18 kg·mol^(-1),respectively.Reactor polymer compositions(RPC)with LMWPE fraction contents ranging from 9 wt%to 42 wt%were obtained when a molar fraction of Zr-2 in the binary catalyst(Zr-1+Zr-2)/MAO va ried in the range from 0.3 to 0.85.A study of the molecular weight characteristics of RPC showed that it has a wide bimodal molecular weight distribution(MWD)and includes UHMWPE(Mw=1000 kg·mol^(-1))and LMWPE(Mw=18 kg·mol^(-1))fractions.The degree of crystallinity of the polymer products was determined using the DSC method.The tensile properties and melt indices of the materials were studied depending on the LMWPE fraction content in the polymer composition.UHMWPE/LMWPE compositions with high tensile properties and fluidity at a load of 5 kg were obtained.
基金This research was funded by the People Program(Marie Curie Actions)of the European Union’s Seventh Framework FP7/2007–2013/under REA grant agreement n°317512.
文摘The lifespan of biological heart valve prostheses available in the market is limited due to structural alterations caused by calcium phosphate deposits formed from blood plasma in contact with the tissues.The objective of this work is to present a comparative methodology for the investigation of the formation of calcium phosphate deposits on bioprosthetic and tissue-engineered scaffolds in vitro and the influence of mechanical forces on tissue mineralization.Based on earlier investigations on biological mineralization at constant supersaturation,a circulatory loop simulating dynamic blood flow and physiological pressure conditions was developed.The system was appropriately adapted to evaluate the calcification potential of decellularized(DCV)and glutaraldehyde-fixed(GAV)porcine aortic valves.Results indicated that DCV calcified at higher,statistically nonsignificant,rates in comparison with GAV.This difference was attributed to the tissue surface modifications and cell debris leftovers from the decellularization process.Morphological analysis of the solids deposited after 20 h by scanning electron microscopy in combination with chemical microanalysis electron-dispersive spectroscopy identified the solid formed as octacalcium phosphate(Ca8(PO4)6H2·5H2O,OCP).OCP crystallites were preferentially deposited in high mechanical stress areas of the test tissues.Moreover,GAV tissues developed a significant transvalvular pressure gradient increase past 36 h with a calcium deposition distribution similar to the one found in explanted prostheses.In conclusion,the presented in vitro circulatory model serves as a valuable prescreening methodology for the investigation of the calcification process of bioprosthetic and tissue-engineered valves under physiological mechanical load.
