Acyclic diene metathesis polymerization of tailor-made monomers towards sequence-regulated vinyl copolymers

 Acyclic diene metathesis polymerization (ADMET) enables convenient transfer of sequential information of the designed monomers to the corresponding sequence-regulated copolymers. In this study, two structurally symmetric monomers, M1 and M2, were synthesized via atom transfer radical addition (ATRA) of diethyl meso-2,5-dibromohexanedioate with 1,5-hexadiene and 1,7-octadiene, respectively. Thus, sequenced segment of VB-EA-EA-VB (VB and EA represent vinyl bromide and ethyl acrylate, respectively) was incorporated into the ADMET diene monomers. ADMET polymerization of these two monomers with Grubbs first generation catalyst (Grubbs-I) was performed in CH₂Cl₂ at 40℃ for 5 days under nitrogen purge. Effects of catalyst amount, monomer concentration and methanol precipitation on the M_p and PDI of polymers were investigated by GPC, and the structures of the formed polymers were characterized by NMR. Our results indicate that using 3.0 mol% of Grubbs-I to monomer can afford polymers with high M_p. Moreover, selective precipitation in methanol enables complete removal of low molecular weight components from the crude products. Meanwhile, M2 exhibits higher ADMET polymerization reactivity than M1 due to its capability of suppressing negative neighboring group effect.     

端基含甘露糖的聚赖氨酸的合成及其聚集行为

设计合成了2种含炔基的甘露糖衍生物(A-Man和A-DiMan)及2-[2-(2-叠氮乙氧基)-乙氧基]-乙胺(N3-TEG-NH2).以N3-TEG-NH2为引发剂引发Nε-苄氧羰基-L-赖氨酸酸酐(Lys(Z)-NCA)的开环聚合,得到2种分子量不同的端基含叠氮基团的聚赖氨酸,N3-P(Lys(Z))15和N3-P(Lys(Z))35,分别与A-Man和A-DiMan进行点击化学反应得到4种端基含甘露糖的聚合物.用透射电镜研究了4种聚合物在水溶液中的聚集行为,结果表明,基于P(Lys(Z))15的2种糖聚合物聚集形成囊泡,而基于P(Lys(Z))35的2种糖聚合物则聚集形成胶束.     

可聚合脂质体的研究 Ⅱ．含桐酸脂质体的稳定性和穿透能力的研究

he stability of mixed liposomes containing β-eleostearic acid (β-ESA>and dimyristoylphosphatidylcholine (DMPC) have been studied by measuring therelease of trapped 5(6)-carboxyfluorescein (5(6)-CF) from the inner phase of liposomes. The results showed that the stability of the mixed liposomes decreased withthe increase of the content of β-ESA in liposomes. Addtion of ethanol and TritonX-100 into the liposome suspensions could damage the liposome structure or induceliposome aggregation, followed by the release ofdye;but less release was observed for the polymerized liposomes when thesame amount of ethanol or Triton X-100 were added, which revealed the increase of stability by polymerization.     

受约束控制系统中变分原理的应用*

本文分别对LQ控制问题及非线性控制问题建立了约束变量的正则方程,进而讨论了等式约束和不等式约束时约束变量的极值原理,最后通过例题验证了本文所得到的结论。本文工作为受约束LQ控制系统及非线性控制系统的深入研究打下了基础。     

Hamilton体系下介电弹性体圆形薄膜的动力学建模与辛求解

采用辛算法研究了Hamilton体系下介电弹性体圆形薄膜的动力学响应。首先,将该问题引入Hamilton对偶变量体系,借助Legendre变换,给出系统的广义动量和Hamilton函数,通过对Hamilton函数作用量的变分,得到Hamilton体系下的正则方程。其次,对于得到的正则方程给出了辛Runge-Kutta的计算格式。最后,采用二级四阶辛Runge-Kutta算法对动力学系统进行了数值求解,和四级四阶经典Runge-Kutta算法进行对比,结果表明,二级四阶辛Runge-Kutta算法具有保能量以及长时间数值稳定的优势,同时说明四级四阶经典Runge-Kutta算法对于步长依赖的局限性。     

非线性动力系统的自适应显式Magnus数值方法

基于最近发展的矩阵李群上非线性微分方程的显式Magnus展式,给出了非线性动力系统的有效的数值算法,并且在数值求解过程中具有自适应的步长控制特点,可以显著地提高计算效率．最后,通过非线性动力系统典型问题Duffing方程和强刚性的Van derPol方程以及非线性振子的Hamilton方程的数值实验来说明方法的有效性．     

用投影方法求耗散广义Hamilton约束系统的李群积分

针对耗散广义Hamilton约束系统,通过引入拉格朗日乘子和采用投影技术,给出了一种保持动力系统内在结构和约束不变性的李群积分法．首先将带约束条件的耗散Hamilton系统化为无约束广义Hamilton系统, 进而讨论了无约束广义Hamilton系统的李群积分法,最后给出了广义Hamilton约束系统李群积分的投影方法．采用投影技术保证了约束的不变性,引入拉格朗日乘子后,在向约束流形投影时不会破坏原动力系统的李群结构．讨论的内容仅限于完整约束系统, 通过数值例题说明了方法的有效性．     

Mossbauer Investigation of Nanocrystalline LaFeO3 Materials

Introduction Owing to their potentially physical, mechanical and chemical properties nanocrystalline solid materials have recently received considerable attention. Mssbauer effect has been proved to be highly useful for studying nanocrystalline solid material and has been applied to the investigation of the magnetic properties and     

Poisson比对弯曲波在变截面梁中传播特性的影响

基于Timoshenko理论和梁几何不连续处位移连续和力平衡条件,得到弯曲波在变截面梁中反射和透射系数矩阵,进而研究材料Poisson比对弯曲波在梁变截面处传播特性的影响.结果显示,在负Poisson比阶段,透射传播波的振幅和能量有显著下降趋势,反射传播波振幅和能量上升明显.这说明负Poisson比有利于反射传播波在变截面处的生成,对透射传播波有抑制作用.此外通过对衰减波能量的分析,得到Euler-Bernoulli理论即使在低频范围内,有时会产生较大误差,因此在使用Euler-Bernoulli理论时应慎重.     

Influence of Surfactant-polymer Complexes on Crystallization and Aggregation of CaCO3

Hollow calcium carbonate(CaCO₃) microspheres with different morphologies were synthesized via the precipitation reaction of calcium chloride with sodium carbonate in the presence of different surfactant-polymer complexes. The selected anionic surfactants were sodium dodecyl sulfonate(SDS) and sodium dodecyl benzenesulfonate(SDBS), respectively. The selected water-soluble polymers were polyacrylic acid(PAA) and polyvinyl pyrrolidone(PVP). In this work, SDS-PVP “pearl-necklace model” micellar complex was formed via hydrophobic effectiveness between SDS and PVP and it served as the spherical template to generate spherical CaCO₃ aggregates with hollow microspheres composed of about 500 nm irregular shaped particles. SDS-PAA complexes and SDBS-PAA complexes formed “core-shell model” aggregates with calcium ions serving as the medium to link the anionic surfactant and the polymer. SDS-PAA “core-shell model” aggregates would act as templates for hollow CaCO₃ microspheres consisting of 30-50 nm irregular shaped crystallites. SDBS-PAA “core-shell model” aggregates served as the spherical aggregate templates to generate spherical CaCO₃ aggregates consisted of many small spherical particles which had grown together. All the obtained CaCO₃ hollow microspheres are calcite particles. This research may provide new insight into the control of morphologies of hollow CaCO₃ microspheres in the presence of surfactant- polymer complexes.