Polyelectrolyte complexes. VI. Polycation structure,polyanion molar mass,and polyion concentration effects on complex nanoparticles based on poly(sodium 2‐acrylamido‐2‐methylpropanesulfonate)

The formation and characterization of some interpolyelectrolyte complex (IPEC) nanoparticles based on poly(sodium 2‐acrylamido‐2‐methylpropanesulfonate) (NaPAMPS), as a function of the polycation structure, polyanion molar mass, and polyion concentration, were followed in this work. Poly(diallyldimethylammonium chloride) and two polycations (PCs) containing (N,N‐dimethyl‐2‐hydroxypropyleneammonium chloride) units in the backbone (PCA₅ and PCA₅D₁) were used as starting polyions. The complex stoichiometry, (n^?/n⁺)_iso, was pointed out by optical density at 500 nm (OD₅₀₀), polyelectrolyte titration, and dynamic light scattering. IPEC nanoparticle sizes were influenced by the polycation structure and polyanion molar mass only before the complex stoichiometry, which was higher for the more hydrophilic polycations (PCA₅ and PCA₅D₁) and for a higher NaPAMPS molar mass, and were almost independent of these factors after that, at a flow rate of the added polyion of about 0.28 mL × (mL PC)^?1 × h^?1. The IPEC nanoparticle sizes remained almost constant for more than 2 weeks, both before and after the complex stoichiometry, at low concentrations of polyions. NIPECs as stable colloidal dispersions with positive charges in excess were prepared at a ratio between charges (n^?/n⁺) of 0.7, and their storage colloidal stability, as a function of the polycation structure and polyion concentration (from 0.8 to ca. 7.8 mmol/L), was demonstrated. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2495–2505, 2004     

New liquid‐crystalline poly(ester amide)s: The role of nitro groups in the phase behavior

New hydrogen‐bonded liquid‐crystalline poly(ester amide)s (PEA)s were obtained from 1,4‐terephthaloyl[bis‐(3‐nitro‐N‐anthranilic acid)] (5) or 1,4‐terephthaloyl[bis‐(N‐anthranilic acid)] (6), with or without nitro groups, respectively, through the separate condensation of each with hydroquinone or dihydroxynaphthalene. The dicarboxylic monomers were synthesized from 2‐aminobenzoic acid. The phase behavior of the monomers and polymers were studied with differential scanning calorimetry, polarized light microscopy, and wide‐angle X‐ray diffraction methods. Monomer 5, containing nitro groups, exhibited a smectic liquid‐crystalline phase, whereas the texture of monomer 6 without nitro groups appeared to be nematic. The PEAs containing nitro groups exhibited polymorphism (smectic and nematic), whereas those without nitro groups exhibited only one phase transition (a nematic threaded texture). The changes occurring in the phase behavior of the polymers were explained by the introduction of nitro groups. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1289–1298, 2004     

Segmental and secondary dynamics in hydrogen‐bonded poly(4‐vinylphenol)/poly(methyl methacrylate) blends

Broadband dielectric spectroscopy was used to study the segmental (α) and secondary (β) relaxations in hydrogen‐bonded poly(4‐vinylphenol)/poly(methyl methacrylate) (PVPh/PMMA) blends with PVPh concentrations of 20–80% and at temperatures from ?30 to approximately glass‐transition temperature (T_g) + 80 °C. Miscible blends were obtained by solution casting from methyl ethyl ketone solution, as confirmed by single differential scanning calorimetry T_g and single segmental relaxation process for each blend. The β relaxation of PMMA maintains similar characteristics in blends with PVPh, compared with neat PMMA. Its relaxation time and activation energy are nearly the same in all blends. Furthermore, the dielectric relaxation strength of PMMA β process in the blends is proportional to the concentration of PMMA, suggesting that blending and intermolecular hydrogen bonding do not modify the local intramolecular motion. The α process, however, represents the segmental motions of both components and becomes slower with increasing PVPh concentration because of the higher T_g. This leads to well‐defined α and β relaxations in the blends above the corresponding T_g, which cannot be reliably resolved in neat PMMA without ambiguous curve deconvolution. The PMMA β process still follows an Arrhenius temperature dependence above T_g, but with an activation energy larger than that observed below T_g because of increased relaxation amplitude. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3405–3415, 2004     

厚度对非极性聚合物薄膜驻极体电荷储存及电荷动态特性的影响

以Du Pont公司的商用Teflon FEP A型薄膜为例，通过热脉冲技术、等温表面电位衰减测量和开路热刺激放电电流谱分析等实验结果，讨论了经常温和高温电晕充电后样品厚度对薄膜驻极体的沉积电荷密度、薄膜驻极体的内电场、体电导率以及电荷储存稳定性的影响.通过热脉冲技术组合电导率温度曲线的测量，研究了在不同温度条件下样品厚度对沉积电荷层的平均电荷重心移动的影响.结果表明：在充电参数一定的条件下，随着膜厚的降低，储存电荷密度上升，但电荷稳定性有所下降.因此，合理地调控薄膜厚度，可以有效地优化驻极体的电荷储存能 关键词： 厚度 驻极体 电荷储存能力 电荷稳定性     

掺氢与激励电路对钡蒸气激光输出特性的影响

对用Blumlein电路放电激励的钡蒸气激光在掺氢和不掺氢时的输出特性进行了实验研究.结果表明，用掺氢1.5%的氖气作缓冲气体能使激光功率增加近2倍.在此基础上，进一步比较了相互作用电路与Blumlein电路时钡蒸气激光的输出特性，发现相互作用电路能显著提高钡蒸气激光的输出功率和效率，获得了3W最大功率和0.4%效率的1.5μm波长激光输出.测量并分析了各工作参量与激光功率之间的关系，定性解释了掺氢与相互作用电路的作用机理 . 关键词： Blumlein电路 相互作用电路 掺氢 钡蒸气激光     

Non-protein amino acids in peptide design

An overview of the use of non-protein amino acids in the design of conformationally well-defined peptides, based on work from the author’s laboratory, is discussed. The crystal structures of several designed oligopeptides illustrate the useα-aminoisobutyric acid (Aib) in the construction of helices, D-amino acids in the design of helix termination segments and^DPro-Xxx segments for nucleating ofβ-hairpin structures.β- andγ-amino acid residues have been used to expand the range of designed polypeptide structures. Dedicated to Professor C N R Rao on his 70th birthday     

Optical Diffractive Memories: Angular Selectivity and Diffraction Efficiency in Dichromated Gelatin

Two thousand images of resolution 512×512 pixels as a regular matrix pattern of 10×10 elements are stored, where each element is angularly multiplexed 20 times in a 25 μm thickness of dichromated gelatin emulsion without cross-talk effect. The surface area of the matrix is 1 cm². We show good concordance of the angular selectivity between the experimental result and theory. The diffraction efficiency of each 20 multiplexed images is measured and has nearly the same value. Examples of reconstructed images for multiple applications are given, for example, storage of 160,000 images on a 3′1/2 floppy disc format, which is about 100 min of black and white film. Application can be made to automobile cartography and storage of X-ray images as well as weather forecast images. Colored diffractive images are also possible and are illustrated.     

Nano-electrochemical detection of hydrogen or protons using palladium nanoparticles: distinguishing surface and bulk hydrogen.

The benefits of using nanoparticle-modified electrodes are exemplified through the electrochemical detection of protons and/or hydrogen. It is shown that a palladium-nanoparticle-modified boron-doped diamond allows voltammetric information relating to the relative roles played by the surface and the bulk metal to be obtained for the proton-hydrogen system at palladium surfaces which is not accessible using palladium macroelectrodes or microelectrodes.     

Measurement of storage time, estimation of ion number and study of absorption line profile in a Paul trap

Europium (Eu⁺) ions were confined in a Paul trap and detected by non-destructive method. Storage time of Eu⁺ ions achieved in vacuum was improved by orders of magnitude employing buffer gas cooling. The experimentally detected signal was fitted to the ion response signal and the total number of ions trapped was estimated. It is found that the peak signal amplitude as well as the product of FWHM and the peak signal amplitude is proportional to the total number of trapped ions. The trapped ion secular frequency was swept at different rates and its effect on the absorption line profile was studied both experimentally and theoretically.     

A new insight into the understanding of the collapsed form of poly(N-isopropylacrylamide) molecules

Possible collapsed forms of poly(N-isopropylacrylamide) molecules are reviewed on the basis of first principle calculations. Various configurations and associated conformations are detailed. The calculated optimized structures exhibit different possibilities of creating networks of intra-molecular bonds of the hydrogen type. We show that the most remarkable one is able to form a local, self-saturated and well ordered helix. We also indicate in which direction the synthesis of the molecule should be oriented to improve its global behavior in term of hydrophobic/hydrophilic behavior.