Synthesis and MALDI-TOF-MS of PS-PMA and PMA-PS block copolymers

The synthesis of well-defined block copolymers from styrene and methyl acrylate via ATRP is discussed in this contribution. Kinetic studies on these block copolymerizations as well as characterization studies were performed to investigate the monomer composition in the respective PS and PMA blocks. MALDI-TOF-MS was performed to clarify the exact number of repeating units of each block and the total number of units in the block copolymer. Block copolymers up to 22 kDa could be analyzed by MALDI-TOF-MS, whereby polymers with PMA as first block showed a large second distribution corresponding to PMA homopolymers. However, SEC demonstrated that only a small amount of homopolymer was present indicating that care needs to be taken with interpreting MALDI-TOF-MS data, which is a qualitative rather than a quantitative technique.     

Effect of sequence distribution on the isothermal crystallization kinetics and successive self-nucleation and annealing (SSA) behavior of poly(ε-caprolactone-co-ε-caprolactam) copolymers

Two types of miscible poly(ε-caprolactone-co-ε-caprolactam) copolymers were studied. In both cases catalyzed hydrolytic ring-opening polymerization was employed. For the first type, the comonomers were added simultaneously to obtain random copolymers. For the second type, the comonomers were added sequentially to obtain block copolymers. Successive self-nucleation and annealing (SSA) and isothermal crystallization studies were performed to both types of copolymers. The SSA results reflect the differences in molecular microstructure: block versus random copolymers. In a wide composition range only the polycaprolactam sequences were capable of crystallization in the random copolymers. Avrami indexes of approximately 3-4 were obtained corresponding to the spherulitic crystallization of these units within the copolymers. The block copolymer samples experienced a relatively small reduction of crystallization kinetics with composition, and this was attributed to the dilution effect caused by the miscible non-crystalline polycaprolactone units. On the other hand, for the random copolymers, the rate of crystallization strongly increased with polycaprolactam content while the energy barrier for secondary nucleation decreased exponentially. The comparison between miscible block and random copolymers provides a unique opportunity to distinguish the dilution effect of the polycaprolactone units (a moderate effect) on the isothermal crystallization and melting of the polyamide phase from the molecular microstructural effect in the random copolymers case (a dramatically strong effect), where the polycaprolactam sequences are interrupted statistically by polycaprolactone sequences.     

Effects of ozone in surface modification and thermal stability of SEBS block copolymers

SEBS block copolymers were treated under mild conditions in an ozone atmosphere, producing very slightly chemically-modified surfaces. The thermal stability was analysed by chemiluminescence and related to morphological changes observed by AFM. The intrinsic thermal stability was diminished by ozone exposure, but the oxidation induction times were delayed which indicates an enhancement of thermal stability under oxidative conditions. Also, chemiluminescence analysis showed the presence of a typical order-disorder transition at temperatures around 120 °C. Two different sets of samples which showed different morphological patterns were imaged by AFM. The effects of micro-domain separation and inter-domain structure on thermal properties are discussed and explained by a coarsening of the internal interface induced by ozone. A detailed 2D Fourier transformed analysis of AFM images allowed us to identify a regular wrinkled nano-pattern induced by uniaxial strain combined with ozone treatment, offering new opportunities in applications ranging from organic electronics to bio-patterning.     

Adsorption interaction parameter of polyethers in ternary mobile phases: The critical adsorption line

It is shown that in LC of polymers, the interaction parameter in ternary mobile phases can be described by a plane, which is determined by the dependencies in binary mobile phases. Instead of a critical adsorption point, critical conditions are observed along a straight line of composition between the two critical points in binary mobile phases. Consequently, a separation of block copolymers under critical conditions for one block by an adsorption mechanism for the other block can be achieved in ternary mobile phases of different compositions, which allows an adjustment of the retention of the adsorbing block.     

西加拿大盆地M区块层序地层与油砂资源评价

<正>确认识油层平面分布是油砂资源评价的基础,无井区油层厚度的预测需要以地质认识为指导。以钻井资料为基础,对M区块的层序地层与沉积特征进行了研究,分析层序格架和储层展布;并在此基础上开展油层分布预测与油砂资源评价,取得了以下新认识:(1)首次对区块进行了层序地层划分。区块可划分为2个长期旋回和6个中期旋回和10个短期旋回。(2)首次系统厘定了区块的沉积相类型及发育特征。区块发育河流、三角洲、滨岸、河口湾和浅海5类沉积相,11类沉积亚相和15类沉积微相。(3)评价结果改变了前人认识,大幅度增加了区块的资源潜力。评价认为区块油砂资源量为2.2×10~8t,比前人评价结果增加22.5%;钻探结果证实了评价结果的正确性,发现区块东部为资源最富集区,改变了前人认为区块西部为主力区的认识。     

Non-neural BOLD variability in block and event-related paradigms

Block and event-related stimulus designs are typically used in fMRI studies depending on the importance of detection power or estimation efficiency. The extent of vascular contribution to variability in block and event-related fMRI-BOLD response is not known. With scaling, the extent of vascular variability in the fMRI-BOLD response during block and event-related design tasks was investigated. Blood oxygen level-dependent (BOLD) contrast data from healthy volunteers performing a block design motor task and an event-related memory task requiring performance of a motor response were analyzed from the regions of interest (ROIs) surrounding the primary and supplementary motor cortices. Average BOLD signal change was significantly larger during the block design compared to the event-related design. In each subject, BOLD signal change across voxels in the ROIs had higher variation during the block design task compared to the event-related design task. Scaling using the resting state fluctuation of amplitude (RSFA) and breath-hold (BH), which minimizes BOLD variation due to vascular origins, reduced the within-subject BOLD variability in every subject during both tasks but significantly reduced BOLD variability across subjects only during the block design task. The strong non-neural source of intra- and intersubject variability of BOLD response during the block design compared to event-related task indicates that study designs optimizing for statistical power through enhancement of the BOLD contrast (for, e.g., block design) can be affected by enhancement of non-neural sources of BOLD variability.     

系统框图化简的一种易忽略的思路

为方便分析控制系统,对可化简的单输入-单输出线性系统框图,介绍一种常易忽略的等效化简思路,以将复杂系统框图一步一步顺利化简,并给出了复杂框图化简实例。该思路适用于由线性系统框图求取传递函数,进而方便进行相应的系统性能分析。     

Reduction of micellar size of PEO−PPO−PEO triblock copolymer in presence of ionic liquid in aqueous solutions: A SANS study

The interaction of ionic liquids (ILs) with non-ionic triblock copolymer, Pluronic® P123, in aqueous solutions has been investigated using Small Angle Neutron Scattering (SANS) measurements. The micellar structural parameters are obtained by fitting the SANS scattering data with model composed of core-shell form factor and a hard sphere structure factor of interaction, as a function of cationic head group of ILs. With the addition of ILs, a decrease in the micellar core, aggregation number, and hard sphere radius of P123 micelles was noticed. The results are discussed and explained as a function of cationic head groups of N-octylpyridinium/imidazolium chloride.     

矩阵DA的特征值及在系统稳定性分析中的应用

本文分析了矩阵ＤＡ的特征值，并提出了一种新的矩阵稳定性问题：Ｄ－－稳定性和块Ｄ－－稳定性．这里Ｄ是一个正对角阵，Ａ是给定的矩阵．应用劳斯判据及李雅普诺夫方法等，详细地分析了此类稳定性问题，提出了一些易于验证的结果，可用于分析多变量奇异摄动系统稳定问题．