A velocity map ion-imaging study on C2H5SH and C3H7SH photodissociation at 243 nm

Photodissociation dynamics Of C2H5SH, i-C-3-H7SH and n-C3H7SH at 243.1 nm were investigated using velocity map ion-imaging method. H-atom photolysis products were detected by a (2 + 1) resonance enhanced ionization scheme. Both the angular distribution and translational energy distribution of the H-atom elimination processes were determined from the ion images of the H-atom products. The experimental results indicate that the H-atom eliminations from these molecules are mainly direct and fast dissociation processes from a repulsive potential energy state. And a more statistical dissociation process that likely occurs oil the ground state via internal conversion has also been observed. Dissociation energies of the S-H bonds are also derived from the H-atom product translational energy distributions. (C) 2002 Elsevier Science B.V. All rights reserved.

Helical single-lamellar crystals thermotropically formed in a synthetic nonracemic chiral main-chain polyester

Phase structures and transformation mechanisms of nonracemic chiral biological and synthetic polymers are fundamentally important topics in understanding their macroscopic responses in different environments. It has been known for many years that helical structures and morphologies can exist in low-ordered chiral liquid crystalline (LC) phases. However, when the chiral liquid crystals form highly ordered smectic liquid crystal phases, the helical morphology is suppressed due to the crystallization process. A double-twisted morphology has been observed in many liquid crystalline biopolymers such as dinoflaggellate chromosomes (in Prorocentrum micans) in an in vivo arrangement. Helical crystals grown from solution have been reported in the case of Bombyx mori silk fibroin crystals having the beta modification. This study describes a synthetic nonracemic chiral main-chain LC polyester that is able to thermotropically form helical single lamellar crystals. Flat single lamellar crystals can also be observed under the same crystallization condition. Moreover, flat and helical lamellae can coexist in one single lamellar crystal, within which one form can smoothly transform to the other. Both of these crystals possess the same structure, although translational symmetry is broken in the helical crystals. The polymer chain folding direction in both flat and helical lamellar crystals is determined to be identical, and it is always along the long axis of the lamellae. This finding provides an opportunity to study the chirality effect on phase structure, morphology, and transformation in condensed states of chiral materials. [S0163-1829(99)01042-5].

Laser light scattering of the molecular weight distribution of unfractionated phenolphthalein poly(aryl ether sulfone)

Two unfractionated samples of phenolphthalein poly( aryl ether sulfone) (PES-C) were characterized in CHCl3 at 25 degrees C by applying a recently developed laser light-scattering (LLS) procedure. The Laplace inversion of precisely measured intensity-intensity time correlation function lead us first to an estimate of the characteristic line-width distribution G(Gamma) and then to the translational diffusion coefficient distribution G(D). A combination of static and dynamic LLS results enabled us to determine D = (2.69 x 10(-4))M(-0.553), which agrees with the calibration of D = (2.45 x 10(-4))M(-0.55) previously established by a set of narrowly distributed PES-C samples. Using this newly obtained scaling between D and M, we were able to convert G(D) into a differential weight distribution f(w)(M) for the two PES-C samples. The weight-average molecular weights calculated from f(w)(M) are comparable to that obtained directly from static LLS. Our results showed that using two broadly distributed samples instead of a set of narrowly distributed samples have provided not only similar final results, but also a more practical method for the PES-C characterization. (C) 1997 John Wiley & Sons, Inc.

Laser light scattering studies of soluble high-performance polyimides: Solution properties and molar mass distributions

Two soluble high-performance polyimides, poly(BCPOBDA/DMMDA) and poly(ODPA/DMMDA), in CHCl3 at 25 degrees C have been studied using laser light scattering. We found that the z-average radius of gyration ([R(g)]) can be scaled to the weight-average molecular weight (M(w)) as [R(g)] (nm) = 4.95 x 10(-2)M(w)(0.52) and [R(g)] (nm) = 1.25 x 10(-2)M(w)(0.66) respectively for poly(BCPOBDA/DMMDA) and poly(ODPA/DMMDA), indicating that poly(ODPA/DMMDA) in CHCl3 at 25 degrees C has a more extended chain conformation than poly(BCPOBDA/DMMDA). Using the wormlike chain model approach, we found that the Flory characteristic ratios (C*) of poly(BCPOBDA/DMMDA) and poly(ODPA/DMMDA) are similar to 20 and similar to 31, respectively, indicating that both of them have a slightly extended chain conformation in comparison with typical flexible polymer chains, such as polystyrene, whose C-infinity is similar to 10. A combination of the weight-average molar mass (M(w)) with the translational diffusion coefficient distributions (G(D)) has led to D (cm(2)/s) = 3.53 x 10(-4)M(-0.579) and D (cm(2)/s) = 4.30 x 10(-4)M(-0.613) respectively for two soluble high-performance polyimides, poly(BCPOBDA/DMMDA) and poly(ODPA/DMMTA), in CHCl3 at 25 degrees C. Using these two calibrations, we have successfully characterized the molar mass distributions of the two polyimides from their corresponding G(D)s. The exponents of these two calibrations further confirm that both of the polyimides have a slightly extended coil chain conformation in CHCl3. The chain flexibility difference between these two polyimides has also been discussed.

Dynamic light-scattering characterization of the molecular weight distribution of a broadly distributed phenolphthalein poly(aryl ether ketone)

Using a recently developed laser light-scattering (LLS) procedure, we accomplished the characterization of a broadly distributed unfractionated phenolphthalein poly(aryl ether ketone) (PEK-C) in CHCl3 at 25 degrees C. The laplace inversion of precisely measured intensity-intensity time correlation function from dynamic LLS leads us first to an estimate of the characteristic line-width distribution G(Gamma) and then to the translational diffusion coefficient distribution G(D). By using a previously established calibration of D (cm(2)/s) = 2.37 X 10(-4)M(-0.57), were able to convert G(D) into a differential weight distribution f(w)(M). The weight-average molecular weight M(w) calculated from f(w)(M) agrees well with that directly measured in static LLS. Our results indicate that both the calibration and LLS procedure used in this study are ready to be applied as a routine method for the characterization of the molecular weight distribution of PEK-C. (C) 1996 John Wiley & Sons, Inc.

Laser light-scattering study of novel thermoplastics .2. Phenolphthalein poly(ether sulfone) (PES-C)

Five narrowly distributed fractions of phenolphthalein poly(ether sulfone) (PES-C) were studied in CHCl3 by both static and dynamic laser light scattering (LLS) at 25 degrees C. The dynamic LLS showed that the PES-C samples contain some large polymer clusters as in previously studied phenolphthalein poly(ether ketone)(PEK-C). These large clusters can be removed by a 0.1-mu m filter. Our results showed that [R(g)(2)](1/2)(z) = (3.35 +/- 0.13) x 10(-2) M(w)((0.52 +/- 0.03)) and [D] = (2.26 +/- 0.02) x 10(-4)M(w)-((0.54) +/- 0.03)) with [R(g)(2)](1/2)(z), M(w) and [D] being the z-average radius of gyration, the weight-average molecular weight, and the z-average translational diffusion coefficient, respectively. A combination of static and dynamic LLS results enabled us to determine D = (2.45 +/- 0.04) x 10(-4)M-((0.55 +/- 0.05)), where D and M correspond to monodisperse species. Using this scaling relationship, we have successfully converted the translational diffusion coefficient distribution into the molecular weight distribution for each of the five PES-C fractional The weight-average molecular weights obtained from dynamic light scattering have a good agreement with that obtained from static laser light-scattering measurements.

Laser light-scattering study of novel thermoplastics .1. Phenolphthalein poly(aryl ether ketone)

Five different molecular weight phenolphthalein poly(aryl ether ketone) (PEK-C) fractions in CHCl3 were studied by static and dynamic laser light scattering(LLS). The dynamic LLS revealed that the PEK-C samples contain some large polymer clusters. These large clusters can be removed by filtering the solution with a 0.1-mu m filter. We found that the persistence length of PEK-C in CHCl3 at 25 degrees C is similar to 2 nm and the Flory characteristic ratio, C-infinity is similar to 25. Our results showed that [R(g)(2)](1/2)(z) = (3.50+/-0.20) x 10(-2)M(w)(0.54+/-0.01) and [D] = (2.37+/-0.05) x 10(-4)M(w)(-0.55+/-0.01), with [R(g)(2)](1/2)(z), M(w), and [D] being the z-average radius of gyration, the weight-average molecular weight, and the z-average translational diffusion coefficient, respectively. A combination of static and dynamic LLS results enabled us to determine D = (2.20+/-0.10) x 10(-4)M(-0.555+/-0.015), where D and M correspond to monodisperse species. Using this calibration between D and M,we have determined molecular weight distributions of five PEK-C fractions from their corresponding translational diffusion coefficient distribution.

A DYNAMIC LASER LIGHT-SCATTERING STUDY OF CHITOSAN IN AQUEOUS-SOLUTION

The solution behavior of four chitosans (91% deacetylated chitin) with different molecular weights in 0.2M CH3COOH/0.1M CH3COONa aqueous solution was investigated at 25 degrees C by dynamic laser light scattering (LLS). The Laplace inversion of the precisely measured intensity-intensity time correlation function leads us to an estimate of the line-width distribution G(Gamma), which could be further reduced to a translational diffusion coefficient distribution G(D). By using a combination of static and dynamic LLS results, i.e. Mw and G(D), we were able to establish a calibration of D = k(D)M(-alpha D) with k(D) = (3.14 +/- 0.20) X 10(-4) and alpha(D) = 0.655 +/- 0.015. By using this calibration, we successfully converted G(D) into a molecular weight distribution f(w)(M). The larger alpha(D) value confirms that the chitosan chain is slightly extended in aqueous solution even in the presence of salts. This is mainly due to its backbone and polyelectrolytes nature. As a very sensitive technique, our dynamic LLS results also revealed that even in dilute solution chitosan still forms a small amount of larger sized aggregates that have ben overlooked in previous studies. The calibration obtained in this study will provide another way to characterize the molecular weight distribution of chitosan in aqueous solution at room temperature. (C) 1995 John Wiley & Sons, Inc.

STUDY ON C2H62+ DOUBLY CHARGED IONS - EVIDENCE FOR THE EXISTENCE OF C2H62+ IN GAS-PHASE

Collision-Induced Dissociation (CID) or Collision Activation (CA) of ion involves high kinetic energy colliding with neutral gas molecules. In part of the ions, the translational energy is converted into excitation energy, Which may lead to subsequent ion decomposition. CID has developed into an important technique for elucidating the

In vitro selected peptides bind with thymidylate synthase mRNA and inhibit its translation

Thymidylate synthase (TS), an essential enzyme for catalyzing the biosynthesis of thymidylate, is a critical therapeutic target in cancer therapy. Recent studies have shown that TS functions as an RNA-binding protein by interacting with two different sequences on its own mRNA, thus, repressing translational efficiency. In this study, peptides binding TS RNA with high affinity were isolated using mRNA display from a large peptide library (>10(13) different sequences). The randomized library was subjected up to twelve rounds of in vitro selection and amplification. Comparing the amino acid composition of the selected peptides (12th round, R12) with those from the initial random library (round zero, R0), the basic and aromatic residues in the selected peptides were enriched significantly, suggesting that these peptide regions might be important in the peptide-TS mRNA interaction. Categorizing the amino acids at each random position based on their physicochemical properties and comparing the distributions with those of the initial random pool, an obvious basic charge characteristic was found at positions 1, 12, 17 and 18, suggesting that basic side chains participate in RNA binding. Secondary structure prediction showed that the selected peptides of R12 pool represented a helical propensity compared with R0 pool, and the regions were rich in basic residues. The electrophoretic gel mobility shift and in vitro translation assays showed that the peptides selected using mRNA display could bind TS RNA specifically and inhibit the translation of TS mRNA. Our results suggested that the identified peptides could be used as new TS inhibitors and developed to a novel class of anticancer agents.

Zebrafish thymidylate synthase binds to its own mRNA in vitro and in vivo

Thymidylate synthase (TS), an essential enzyme for DNA de novo synthesis, is a critical therapeutic target in cancer therapy. Previous study has shown that TS was able to bind to its own mRNA in human and E.coli, resulting in translational repression. Zebrafish is the best animal model for vertebrate study. In order to study the regulatory mechanism of zebrafish TS, the enzyme were expressed in E. coli BL21 (DE3) and it was purified to homogeneity. Electrophoretic mobility shift assay (EMSA) was used to detect the interaction of zebrafish TS protein and its own TS transcript in vitro and the results showed that zebrafish TS could bound with its own mRNA specifically. Further study revealed that zebrafish TS was able to interact with its own mRNA in vivo using immunoprecipitation : RT-PCR technique. The results provide evidence that zebrafish may be developed as an useful model for studying the anti-metabolism agents.

Identification of a silicatein(-related) protease in the giant spicules of the deep-sea hexactinellid Monorhaphis chuni

Silicateins, members of the cathepsin L family, are enzymes that have been shown to be involved in the biosynthesis/condensation of biosilica in spicules from Demospongiae (phylum Porifera), e. g. Tethya aurantium and Suberites domuncula. The class Hexactinellida also forms spicules from this inorganic material. This class of sponges includes species that form the largest biogenic silica structures on earth. The giant basal spicules from the hexactinellids Monorhaphis chuni and Monorhaphis intermedia can reach lengths of up to 3 m and diameters of 10 mm. The giant spicules as well as the tauactines consist of a biosilica shell that surrounds the axial canal, which harbours the axial filament, in regular concentric, lamellar layers, suggesting an appositional growth of the spicules. The lamellae contain 27 kDa proteins, which undergo post-translational modification (phosphorylation), while total spicule extracts contain additional 70 kDa proteins. The 27 kDa proteins cross-reacted with anti-silicatein antibodies. The extracts of spicules from the hexactinellid Monorhaphis displayed proteolytic activity like the silicateins from the demosponge S. domuncula. Since the proteolytic activity in spicule extracts from both classes of sponge could be sensitively inhibited by E-64 (a specific cysteine proteinase inhibitor), we used a labelled E-64 sample as a probe to identify the protein that bound to this inhibitor on a blot. The experiments revealed that the labelled E-64 selectively recognized the 27 kDa protein. Our data strongly suggest that silicatein(-related) molecules are also present in Hexactinellida. These new results are considered to also be of impact for applied biotechnological studies.

五轴磨抛机器人补偿算法研究与实现

通过分析基于模型的补偿方法和非模型补偿方法的优缺点,结合一个五轴磨抛机器人的结构特点,提出了两种补偿方法相结合的混合补偿算法.针对平移关节误差的主要来源难于建模的特点,采用非模型的方法进行补偿;针对转动关节误差主要来源为几何参数误差,能够建模,但有些参数随机器人末端位置不同而变化的特点,采用二者相结合的混合方法进行补偿.通过对该机器人系统的实验,验证了方法的有效性和可行性.

一种适用于多指灵巧手的机电一体化驱动器概念

本文提出了一种机电一体化驱动器的概念,这种驱动器能够将电机的旋转运动转换为直线运动,并在不外加力和力矩传感器的基础上利用运动转换副上产生的微应变来估算电机的输出力矩和驱动器末端的牵引力信息。利用高精度、高灵敏度并带有温度和噪声补偿电路的应变片来测量微应变,以取得稳定而可靠的测量结果。应变片直接贴在驱动器的主体结构表面可以最小化尺寸,而且可以实现机电一体化而不是机械-电子集成系统。仿真实验表明,这种方法和传统的电流估算法相比,可以减少由于噪音和波动带来的电流信号误差,得到更加精确的信息,并且(与加入力或者力矩传感器相比)能够有效缩小外型尺寸,同时去除不必要的机械与电子接口,因此增加了系统的鲁棒性。

Photodissociation of 1-bromo-2-chloroethane at 266 nm

The photodissociation of CH2BrCH2Cl at 266 nm has been investigated on the universal crossed molecular beam machine. The primary dissociation step leads exclusively to the formation of CH2CH2Cl radicals and Br atoms in the electronic ground state as well as in the spin-orbit excited state, with a branching ratio 2 +/- 1:8 +/- 1. Photofragment total c.m. translational energy distribution P(E-t) has been obtained and about 64% of the available energy is partitioned into translational energy for Br channel and about 28.5% of the available energy is partitioned into translational energy for Br* channel. The anisotropy parameters are determined to be beta(Br*) = 0.8 +/- 0.2 and beta(Br) = -0.6 +/- 0.2, respectively. Some CH2CH2Cl radicals with large internal excitation (corresponding to formation of ground state Br channel) may undergo secondary dissociation to form CH2CH2 +/- Cl. The experimental results are discussed in terms of a model that involves the initial excitation of two repulsive electronic states: one from an parallel transition to the (3)Q(0) state, and the other from a perpendicular transition to the (3)Q(1), (1)Q states. (C) 1999 Elsevier Science B.V. All rights reserved.