Synthesis and micellization of amphiphilic poly(sebacic anhydride)–poly(ethylene glycol)–poly(sebacic anhydride) block copolymers

Amphiphilic biodegradable block copolymers [poly(sebacic anhydride)–poly(ethylene glycol)–poly(sebacic anhydride)] were synthesized by the melt polycondensation of poly(ethylene glycol) and sebacic anhydride prepolymers. The chemical structure, crystalline nature, and phase behavior of the resulting copolymers were characterized with ¹H NMR, Fourier transform infrared, gel permeation chromatography, and differential scanning calorimetry. Microphase separation of the copolymers occurred, and the crystallinity of the poly(sebacic anhydride) (PSA) blocks diminished when the sebacic anhydride unit content in the copolymer was only 21.6%. ¹H NMR spectra carried out in CDCl₃ and D₂O were used to demonstrate the existence of hydrophobic PSA domains as the core of the micelle. In aqueous media, the copolymers formed micelles after precipitation from water‐miscible solvents. The effects on the micelle sizes due to the micelle preparation conditions, such as the organic phase, dropping rate of the polymer organic solution into the aqueous phase, and copolymer concentrations in the organic phase, were studied. There was an increase in the micelle size as the molecular weight of the PSA block was increased. The diameters of the copolymer micelles were also found to increase as the concentration of the copolymer dissolved in the organic phase was increased, and the dependence of the micelle diameters on the concentration of the copolymer varied with the copolymer composition. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1271–1278, 2006     

Synthesis and properties of noncoplanar rigid‐rod aromatic polyhydrazides and poly(1,3,4‐oxadiazole)s containing phenyl or naphthyl substituents

Two new phenyl‐ and naphthyl‐substituted rigid‐rod aromatic dicarboxylic acid monomers, 2,2′‐diphenylbiphenyl‐4,4′‐dicarboxylic acid ( 4 ) and 2,2′‐di(1‐naphthyl)biphenyl‐4,4′‐dicarboxylic acid ( 5 ), were synthesized by the Suzuki coupling reaction of 2,2′‐diiodobiphenyl‐4,4′‐dicarboxylic acid dimethyl ester with benzeneboronic acid and naphthaleneboronic acid, respectively, followed by alkaline hydrolysis of the ester groups. Four new polyhydrazides were prepared from the dicarboxylic acids 4 and 5 with terephthalic dihydrazide (TPH) and isophthalic dihydrazide (IPH), respectively, via the Yamazaki phosphorylation reaction. These polyhydrazides were amorphous and readily soluble in many organic solvents. Differential scanning calorimetry (DSC) indicated that these hydrazide polymers had glass transition temperatures in the range of 187–234 °C and could be thermally cyclodehydrated into the corresponding oxadiazole polymers in the range of 300–400 °C. The resulting poly(1,3,4‐oxadiazole)s exhibited T_g's in the range of 252–283 °C, 10% weight‐loss temperature in excess of 470 °C, and char yield at 800 °C in nitrogen higher than 54%. These organo‐soluble polyhydrazides and poly(1,3,4‐oxadiazole)s exhibited UV–Vis absorption maximum at 262–296 and 264–342 nm in NMP solution, and their photoluminescence spectra showed maximum bands around 414–445 and 404–453 nm, respectively, with quantum yield up to 38%. The electron‐transporting properties were examined by electrochemical methods. Cyclic voltammograms of the poly(1,3,4‐oxadiazole) films cast onto an indium‐tin oxide (ITO)‐coated glass substrate exhibited reversible reduction redox with E_onset at ?1.37 to ?1.57 V versus Ag/AgCl in dry N,N‐dimethylformamide solution. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6466–6483, 2006     

Highly substituted poly(2,3‐diphenyl‐1,4‐phenylenevinylene) derivatives having bulky phenyl and fluorenyl pendant groups: Synthesis,characterization, and electro‐optical properties

Two series of poly(2,3‐diphenyl‐1,4‐phenylenevinylene) (DP‐PPV) derivatives containing multiple bulky substituents were synthesized. In the first series, two different groups were incorporated on C‐5,6 positions of the phenylene moiety to increase steric hindrance and to obtain blue‐shifted emissions. In the second series, bulky fluorenyl groups with two hexyl chains on the C‐9 position were introduced on two phenyl pendants to increase the solubility as well as steric hindrance to prevent close packing of the main chain. Polymers with high molecular weights and fine‐tuned electro‐optical properties were obtained by controlling the feed ratio of different monomers during polymerization. The maximum photoluminescent emissions of the thin films are located between 384 and 541 nm. Cyclic voltammetric analysis reveals that the band gaps of these light‐emitting materials are in the range from 2.4 to 3.3 eV. A double‐layer EL device with the configuration of ITO/PEDOT/P4/Ca/Al emitted pure green light with CIE′1931 at (0.24, 0.5). Using copolymer P6 as the emissive layer, the maximum luminescence and current efficiency were both improved when compared with the homopolymer P4. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6738–6749, 2006     

Novel photoswitching dithienylethenes with ferrocene units

Two novel dithienylethenes with ferrocene units were synthesized by Wittig reaction. The structure of 2a has been established by X‐ray diffraction studies. They could reversibly interconvert between two thermally stable forms, an open and a closed one, using light of different wavelengths as triggers. Copyright © 2006 John Wiley & Sons, Ltd.     

Synthesis of double silylene-bridged binuclear titanium complexes and their use as catalysts for ethylene polymerization

Five new double silylene-bridged binuclear titanium complexes were synthesized by the reaction of RCpTiCl₃ and Li₂[μ,μ-(SiMe₂)₂ (C₅H₃)₂] in toluene. They were all well characterized. These complexes activated with methylaluminoxane (MAO) are highly active catalysts (2.33 × 10⁵ g PE/mol Cat h) for the polymerization of ethylene even at low Al/Ti (Al/Ti = 300). The molecular weight distribution of the polymer indicates broad or bimodal (MWD = 26.76) distribution.     

关于Tchebycheff—Fourier级数的（H,λ）平均的逼近

我们定义了（Ｈ，λ）求和法，它含有（Ｎ，ｐｎ），（Ｒ＾ｒｎ）和（Ｖｍｎ）求和法。讨论了函数ｆ（ｘ）∈Ｃ＾ｒ［－１，１］（ｒ∈Ｎ０）以及ｆ（ｘ）∈Ｗ＾ｒＨ＾ａ（ｒ∈Ｎ０，０＜ａ＜１）的切比晓夫－富里埃级数的逼近阶。     

加权增量卡尔曼滤波法在ICP－AES中的应用

卡尔曼滤波法用于ＩＣＰ－ＡＥＳ分析时，在白色噪音情况下能给出准确的分析结果，当试样的某些组分未知时，测量噪音将不是白色的，分析结果将不准确。本文提出了一种加权增量卡尔曼滤波法来解决这个问题。     

激光二极管泵浦的高重复频率Nd：YAG激光器

报道两个１．５Ｗ连续激光二极管端面泵浦的声光调ＱＮｄ：ＹＡＧ激光器，输出激光脉冲的最高重复频率为３０ｋＨｚ重复频率１ｋＨｚ时，最窄脉宽为１２ｎｓ，最高峰值功率为１２．１ｋＷ。     

MnBiDy(Sm)永磁膜的结构和磁性

报道了采用真空蒸镀的方法制备的MnBiDy(Sm)永磁膜的结构和磁性.Mn:Bi:Dy(Sm)的投料比为2:1:0.10.薄膜经过退出处理(350—425℃,保温4h)后,具有NiAs型hcp结构,C轴垂直膜面,剩余磁感应强度B=3.4-6.5kG,内禀矫顽力_MH_c≈3-8kOe,最大磁能积(BH)_(max)=13.39MG·Oe.实验发现,薄膜厚度对MnBiDy(Sm)永磁膜的结构和磁性具有很大的影响. 关键词：     

Extraction mechanism of monovalent ion-pairs by polyurethane foams

The extractability sequence of K(+) approximately Rb(+) > Cs(+) > Na(+) > Li(+) for the extraction with polyether foam suggests that the cation chelation mechanism might be operative. However, the same order was obtained for the extraction with 100% polypropylene oxide polyether foam which does not normally adopt a helical structure to form oxygen-rich cavities as easily or as effectively as polyethylene oxide to accommodate alkali metal ions. This result indicates that a hole-size/cation-diameter relationship may not be required for the high extraction of K(+). The extraction of alkali metal DPAs and hydroxides from methanol demonstrates the importance of the solvent effect. It indicates that the water-structure enforced ion-pairing (WSEIP) is the driving force for extraction of the ion-pairs. The extraction mechanism for ionic species can be described as an ion-pair extraction process. The overall effect of ion-pair formation in water and interaction of the extracted ions with foam appears to determine the extractability of the ions of the extractable ion-pair.