The clinical efficacy of chemotherapeutic drugs is hindered by their poor aqueous solubility, low bioavailability and severe side effects. In recent years, polymeric nanocarriers have been used for drug delivery to im...The clinical efficacy of chemotherapeutic drugs is hindered by their poor aqueous solubility, low bioavailability and severe side effects. In recent years, polymeric nanocarriers have been used for drug delivery to improve the efficacy of many chemotherapeutics. In this study, a series of biodegradable phenylalaninebased poly(ester amide)(Phe-PEA) with tunable molecular weights(MWs) were synthesized to systematically investigate the relationship between the polymer MW and the efficacy of the corresponding polymeric nanoparticles(NPs). The results indicated that a range of polymers with different MWs can be obtained by varying the monomer ratio or reaction time. Doxorubicin(DOX), a classic clinical lymphoma treatment strategy, was selected as a model drug. The loading capacity and stability of the higher MW polymeric NPs were superior to those of the lower MW ones. Moreover, in vitro and in vivo data revealed that high MW polymeric NPs had better anticancer efficacy against lymphoma and higher biosafety than low MW polymeric nanoparticles and DOX. Therefore, this study suggests the importance of polymer MW for drug delivery systems and provides valuable guidance for the design of enhanced polymeric drug carriers for lymphoma treatment.展开更多
Samples of polyphenylsilsisquioxane (PPSQ)using CaF_2 or MgF_2 as the main catalysts hadbeen prepared under different polymerization conditions. The results were treated on anorthogonal design L_9 (3~4). All weight-av...Samples of polyphenylsilsisquioxane (PPSQ)using CaF_2 or MgF_2 as the main catalysts hadbeen prepared under different polymerization conditions. The results were treated on anorthogonal design L_9 (3~4). All weight-average molecular weights (M_W ) of PPSQ had beenmeasured by gel permeation chromatography (GPC). Effects of polymerization conditionsincluding reaction temperature, composition of the dual catalysts (CaF_2 or MgF_2 and DCC),mixture of solvents and reaction time on M_W of PPSQ have been discussed. The quantity of thecatalysts is the most important factor that affects M_W of PPSQ. Reaction temperature is thesecond important factor. Appropriate polymerization condition has been established to get PPSQwith high M_W.展开更多
Neodymium chloride isopropanol complex (NdCl3.3'prOH) activated by modified methylaluminoxane (MMAO) was examined in isoprene polymerization in hexane, with regards to Nd compounds, aluminum (Al) compounds, [Al...Neodymium chloride isopropanol complex (NdCl3.3'prOH) activated by modified methylaluminoxane (MMAO) was examined in isoprene polymerization in hexane, with regards to Nd compounds, aluminum (Al) compounds, [Al]/[Nd] ratio, polymerization temperature and time. NdCl3'3iprOH exhibited high activity producing polymers feasting high cis-l,4 stereospecificity (〉 96%), very high molecular weight (Mn 〉 1.0 × 10^6) and fairly narrow molecular weight distribution (MWD, Mw/Mn 〈 2.0) simultaneously. In comparison, neodymium isopropoxide also showed high activity providing polymers with narrow MWD (Mw/Mn = 2.07), but somewhat low cis-1,4 content (ca. 92%), while neodymium chloride had no activity under present polymerization conditions. The Al compounds affected the polymer yield in the order of Al(i-Bu)3 〉 MMAO 〉 Al(i-Bu)2H. MMAO as cocatalyst afforded polyisoprene with high Mn over 1.0 × 10^6, whereas as stronger chain transfer agent than MMAO, AI(i-Bu)3 and AI(i-Bu)EH yielded polymers with low Mn (1.0 × 10^5-8.0 × 10^5). NdCl3·3'PrOH/MMAO catalyst showed a fairly good catalytic activity even at relatively low [Al]/[Nd] ratio of 30, and the produced polymer remained high cis-1,4 content of 95.8% along with high Mn over 1.0× 10^6 even at elevated temperatures up to 70℃. The polymerization rate is of the first order with respect to the concentration of isoprene. The mechanism of active species formation was discussed preliminarily.展开更多
Antibacterial polymers of dimethylaminoethyl methacrylate benzyl ammonium chloride(DMAEMA-BC) with various molecular weights(Mws) were prepared under controlling radical polymerization conditions. The Mws of these...Antibacterial polymers of dimethylaminoethyl methacrylate benzyl ammonium chloride(DMAEMA-BC) with various molecular weights(Mws) were prepared under controlling radical polymerization conditions. The Mws of these polymers were determined by means of static multiangle laser light scattering and viscosity method. A Mark-Houwink equation was established to be [η]=0.154M0.764 for the Mw evaluation of poly(DMAEMA-BC)s. The effects of the Mws of these poly(DMAEMA-BC)s on their antibacterial activities against E. coli and S. aureus were investigated by various methods including viable cell counting, electrical conductivity titration, intracellular constituent leakage tests and electron microscopy. Our results indicate that the antibacterial efficiency of DMAEMA-BC was significantly enhanced after the monomers were polymerized into a polymer and increased obviously with the Mws,as a result of the increase of charge density. Further investigation of the molecular basis underlying the anti-bacterial role of these polymers revealed that poly(DMAEMA-BC) promoted the release of potassium ion from the membrane of bacterial cells and the release increased significantly with the Mws of the polymers used.展开更多
A L463^5 Box-Behnken design was used for developing a model to predict and optimize the molecular weight (Mw ) of polypropylene (PP) ; a second-order polynomial regression equation was derived to predict responses...A L463^5 Box-Behnken design was used for developing a model to predict and optimize the molecular weight (Mw ) of polypropylene (PP) ; a second-order polynomial regression equation was derived to predict responses. The significance of variables and their interactions were tested by means of the ANOVA with 95% confidence limits; the standardized effects were investigated by Pareto chart, the optimum values of the selected variables were obtained by analyzing the response surface contour plots. The optimized Mw value of 1. 217 × 10^5 g/mol was very close to the industrial value ( ( 1.22 ±0. 004) ×10^6 g/tool) at the optimum values.展开更多
本文合成了五种新型配合茂金属催化剂,并对其进行核磁等表征,然后利用其对乙烯均聚反应进行研究,考察催化剂的活性,并对生成的聚合物进行分子量及分布、动摩擦系数、冲击强度、粒径及其分布的表征。得到的共聚物的分子量较文献报道的有...本文合成了五种新型配合茂金属催化剂,并对其进行核磁等表征,然后利用其对乙烯均聚反应进行研究,考察催化剂的活性,并对生成的聚合物进行分子量及分布、动摩擦系数、冲击强度、粒径及其分布的表征。得到的共聚物的分子量较文献报道的有明显提高。聚合活性最高可达7.8 kg PE/g催化剂·2小时,聚合物的重均分子量最高可达38.5×10^(5)。展开更多
The ring-opening polymerization of D, L-lactide in the melt was systematically investigated by using stannous octoate as the initiator. The molecular weight of poly (D, L-lactide) was characterized with M,. Mn and Mw ...The ring-opening polymerization of D, L-lactide in the melt was systematically investigated by using stannous octoate as the initiator. The molecular weight of poly (D, L-lactide) was characterized with M,. Mn and Mw respectively. The results indicated that five variables, namely purity of monomer, initiator to monomer ratio, vacuum level, polymerization temperature and polymerization time had different influences on the molecular weight and molecular weight distribution of poly(D. L-lactide).展开更多
The copolymerization of styrene (St) and acrylonitrile (AN) complexed with CuCl_2 monomer by a free radicalmechanism was performed using benzoyl peroxide as an initiator at 65℃ under N_2 atmosphere for 150 min. The r...The copolymerization of styrene (St) and acrylonitrile (AN) complexed with CuCl_2 monomer by a free radicalmechanism was performed using benzoyl peroxide as an initiator at 65℃ under N_2 atmosphere for 150 min. The rate ofpolymerization (R_p) was found to increase linearly with the concentration (in mol/L) of CuCl_2, AN and St through scalingrelations. The activation energy of the copolymerization process in the presence and absence of CuCl_2 was found to be46.5 kJ/mol and 102 kJ/mol, respectively. The viscosity average molecular weigh of the copolymer and the k_p^2/k_t ratio weredctermired to further assess the accelerating effect of CuCl_2 on the copolymerization process. The copolymerization processin the presence of CuCl_2 has a radical complex mechanism.展开更多
基金supported by the National Natural Science Foundation of China (Nos. 51973243 and 52173150)International Cooperation and Exchange of the National Natural Science Foundation of China (No. 51820105004)+3 种基金China Postdoctoral Science Foundation(No. 2020M683058)Shenzhen Science and Technology Program(No. RCBS20210706092411033)the Science and Technology Planning Project of Shenzhen (No. JCYJ20190807155801657)Guangdong Innovative and Entrepreneurial Research Team Program (No.2016ZT06S029)。
文摘The clinical efficacy of chemotherapeutic drugs is hindered by their poor aqueous solubility, low bioavailability and severe side effects. In recent years, polymeric nanocarriers have been used for drug delivery to improve the efficacy of many chemotherapeutics. In this study, a series of biodegradable phenylalaninebased poly(ester amide)(Phe-PEA) with tunable molecular weights(MWs) were synthesized to systematically investigate the relationship between the polymer MW and the efficacy of the corresponding polymeric nanoparticles(NPs). The results indicated that a range of polymers with different MWs can be obtained by varying the monomer ratio or reaction time. Doxorubicin(DOX), a classic clinical lymphoma treatment strategy, was selected as a model drug. The loading capacity and stability of the higher MW polymeric NPs were superior to those of the lower MW ones. Moreover, in vitro and in vivo data revealed that high MW polymeric NPs had better anticancer efficacy against lymphoma and higher biosafety than low MW polymeric nanoparticles and DOX. Therefore, this study suggests the importance of polymer MW for drug delivery systems and provides valuable guidance for the design of enhanced polymeric drug carriers for lymphoma treatment.
基金This work was supported by the grants from the National Natural Science Foundation of China and the Polymer Physics Laboratory,Academia Sinica.
文摘Samples of polyphenylsilsisquioxane (PPSQ)using CaF_2 or MgF_2 as the main catalysts hadbeen prepared under different polymerization conditions. The results were treated on anorthogonal design L_9 (3~4). All weight-average molecular weights (M_W ) of PPSQ had beenmeasured by gel permeation chromatography (GPC). Effects of polymerization conditionsincluding reaction temperature, composition of the dual catalysts (CaF_2 or MgF_2 and DCC),mixture of solvents and reaction time on M_W of PPSQ have been discussed. The quantity of thecatalysts is the most important factor that affects M_W of PPSQ. Reaction temperature is thesecond important factor. Appropriate polymerization condition has been established to get PPSQwith high M_W.
基金supported by the Administration of Science and Technology of Jilin Province,China (No.200505254)
文摘Neodymium chloride isopropanol complex (NdCl3.3'prOH) activated by modified methylaluminoxane (MMAO) was examined in isoprene polymerization in hexane, with regards to Nd compounds, aluminum (Al) compounds, [Al]/[Nd] ratio, polymerization temperature and time. NdCl3'3iprOH exhibited high activity producing polymers feasting high cis-l,4 stereospecificity (〉 96%), very high molecular weight (Mn 〉 1.0 × 10^6) and fairly narrow molecular weight distribution (MWD, Mw/Mn 〈 2.0) simultaneously. In comparison, neodymium isopropoxide also showed high activity providing polymers with narrow MWD (Mw/Mn = 2.07), but somewhat low cis-1,4 content (ca. 92%), while neodymium chloride had no activity under present polymerization conditions. The Al compounds affected the polymer yield in the order of Al(i-Bu)3 〉 MMAO 〉 Al(i-Bu)2H. MMAO as cocatalyst afforded polyisoprene with high Mn over 1.0 × 10^6, whereas as stronger chain transfer agent than MMAO, AI(i-Bu)3 and AI(i-Bu)EH yielded polymers with low Mn (1.0 × 10^5-8.0 × 10^5). NdCl3·3'PrOH/MMAO catalyst showed a fairly good catalytic activity even at relatively low [Al]/[Nd] ratio of 30, and the produced polymer remained high cis-1,4 content of 95.8% along with high Mn over 1.0× 10^6 even at elevated temperatures up to 70℃. The polymerization rate is of the first order with respect to the concentration of isoprene. The mechanism of active species formation was discussed preliminarily.
基金Supported by the National Natural Science Foundation of China(No.50673101)the Project of Department of Education of Guangdong Province,China(No.cgzhzd0901)
文摘Antibacterial polymers of dimethylaminoethyl methacrylate benzyl ammonium chloride(DMAEMA-BC) with various molecular weights(Mws) were prepared under controlling radical polymerization conditions. The Mws of these polymers were determined by means of static multiangle laser light scattering and viscosity method. A Mark-Houwink equation was established to be [η]=0.154M0.764 for the Mw evaluation of poly(DMAEMA-BC)s. The effects of the Mws of these poly(DMAEMA-BC)s on their antibacterial activities against E. coli and S. aureus were investigated by various methods including viable cell counting, electrical conductivity titration, intracellular constituent leakage tests and electron microscopy. Our results indicate that the antibacterial efficiency of DMAEMA-BC was significantly enhanced after the monomers were polymerized into a polymer and increased obviously with the Mws,as a result of the increase of charge density. Further investigation of the molecular basis underlying the anti-bacterial role of these polymers revealed that poly(DMAEMA-BC) promoted the release of potassium ion from the membrane of bacterial cells and the release increased significantly with the Mws of the polymers used.
基金Supported by the R&D Program of Catalyst Company,SINOPEC(G8101-11-ZS-0016*)
文摘A L463^5 Box-Behnken design was used for developing a model to predict and optimize the molecular weight (Mw ) of polypropylene (PP) ; a second-order polynomial regression equation was derived to predict responses. The significance of variables and their interactions were tested by means of the ANOVA with 95% confidence limits; the standardized effects were investigated by Pareto chart, the optimum values of the selected variables were obtained by analyzing the response surface contour plots. The optimized Mw value of 1. 217 × 10^5 g/mol was very close to the industrial value ( ( 1.22 ±0. 004) ×10^6 g/tool) at the optimum values.
文摘本文合成了五种新型配合茂金属催化剂,并对其进行核磁等表征,然后利用其对乙烯均聚反应进行研究,考察催化剂的活性,并对生成的聚合物进行分子量及分布、动摩擦系数、冲击强度、粒径及其分布的表征。得到的共聚物的分子量较文献报道的有明显提高。聚合活性最高可达7.8 kg PE/g催化剂·2小时,聚合物的重均分子量最高可达38.5×10^(5)。
基金Funded by the Key Project of the Ministry of Science and Technology (No. 96 - 920 - 20 - 21)
文摘The ring-opening polymerization of D, L-lactide in the melt was systematically investigated by using stannous octoate as the initiator. The molecular weight of poly (D, L-lactide) was characterized with M,. Mn and Mw respectively. The results indicated that five variables, namely purity of monomer, initiator to monomer ratio, vacuum level, polymerization temperature and polymerization time had different influences on the molecular weight and molecular weight distribution of poly(D. L-lactide).
文摘The copolymerization of styrene (St) and acrylonitrile (AN) complexed with CuCl_2 monomer by a free radicalmechanism was performed using benzoyl peroxide as an initiator at 65℃ under N_2 atmosphere for 150 min. The rate ofpolymerization (R_p) was found to increase linearly with the concentration (in mol/L) of CuCl_2, AN and St through scalingrelations. The activation energy of the copolymerization process in the presence and absence of CuCl_2 was found to be46.5 kJ/mol and 102 kJ/mol, respectively. The viscosity average molecular weigh of the copolymer and the k_p^2/k_t ratio weredctermired to further assess the accelerating effect of CuCl_2 on the copolymerization process. The copolymerization processin the presence of CuCl_2 has a radical complex mechanism.