tert‐Butyl (6S)‐4‐hydroxy‐6‐isobutyl‐2‐oxo‐1,2,5,6‐tetra­hydropyridine‐1‐carboxyl­ate and tert‐butyl (4R,6S)‐4‐hydroxy‐6‐iso­butyl‐2‐oxopiperidine‐1‐carboxyl­ate

X‐ray studies reveal that tert‐butyl (6S)‐6‐iso­butyl‐2,4‐dioxo­piperidine‐1‐carboxyl­ate occurs in the 4‐enol form, viz. tert‐butyl (6S)‐4‐hydroxy‐6‐iso­butyl‐2‐oxo‐1,2,5,6‐tetra­hydropyri­dine‐1‐carboxyl­ate, C₁₄H₂₃NO₄, when crystals are grown from a mixture of di­chloro­methane and pentane, and has an axial orientation of the iso­butyl side chain at the 6‐position of the piperidine ring. Reduction of the keto functionality leads predominantly to the corresponding β‐hydroxy­lated δ‐lactam, tert‐butyl (4R,6S)‐4‐hydroxy‐6‐iso­butyl‐2‐oxo­piperidine‐1‐car­boxyl­ate, C₁₄H₂₅NO₄, with a cis configuration of the 4‐hydroxy and 6‐iso­butyl groups. The two compounds show similar molecular packing driven by strong O—H⋯O=C hydrogen bonds, leading to infinite chains in the crystal structure.     

Synthesis and characterization of wholly aromatic poly(azomethine)s containing donor–acceptor triphenylamine moieties

N‐(4‐nitrophenyl)‐4′,4″‐bisformyl‐diphenylamine was synthesized from N‐(4‐nitrophenyl)‐diphenylamine by the Vilsmeier‐Haack reaction. Soluble aromatic poly(azomethine)s (PAMs) were prepared by the solution polycondensation of N‐(4‐nitrophenyl)‐4′,4″‐bisformyl‐diphenylamine and aromatic diamine in N‐methyl‐2‐pyrrolidone (NMP) at room temperature under reduced pressure. All the PAMs are highly soluble in various organic solvents, such as N,N‐dimethylacetamide (DMAc), chloroform (CHCl₃), and tetrahydrofuran (THF). Differential scanning calorimetry (DSC) indicated that these PAMs had glass‐transition temperatures (T_gs) in the range of 170–230 °C, and a 10% weight‐loss temperatures in excess of 490 °C with char yield at 800 °C in nitrogen higher than 60%. These PAMs in NMP solution showed UV‐Vis charge‐transfer (CT) absorption at 405–421 nm and photoluminescence peaks around 462–466 nm with fluorescence quantum efficiency (Φ_F) 0.10–0.99%. The highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels of these PAMs can be determined from cyclic voltammograms as 4.86–5.43 and 3.31–3.34 eV, respectively. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4921–4932, 2007     

Interactions of Eu3+ and Am3+ with humic acid extracted from soil of Yongkwang in the Okchon Basin of the Korean Peninsula

Summary The stability constants of Eu³⁺ and Am³⁺ with the site specific humic acid (YKHA) have been determined. The humic acid has been extracted from the soil of Yongkwang area belonging geologically to the Okchon Basin of the Korean Peninsula, where the nuclear power plant is located. The total carboxylate capacity, the acidity constant (pKa), and the binding constants with Eu³⁺ and Am³⁺ have been determined for humic acid.     

KxCoO2·yH2O(x《0.2,y≤0.8)的晶体结构、输运及磁学性质

利用熔融KOH和Co3O4在较低温度(480℃)下反应制备出K0.36CoO2,然后用高锰酸钾溶液和饱和的过硫酸钾溶液进行氧化处理.氧化的同时伴随有水分子嵌入.K0.36CoO2用高锰酸钾和过硫酸钾溶液处理后分别得到K0.12CoO2·0.8H2O和K0.16CO2·0.6H2O.这两种化合物都属于六角晶系,表现出金属行为,脱水后主相变为正交结构并且呈现出半导体特性.K0.16CoO2·0.6H2O在56K附近可能存在自旋玻璃转变行为或其他涨落.随着钾含量的减少和水含量的增多,样品的自旋玻璃行为受到抑制或发生磁性相分离.样品K0.12CoO2·0.8H2O在零场冷却和有场冷却曲线上的分叉现象基本上消失.还讨论了产生KxCoO2与NaxCoO2体系结构和物性差别的原因.     

稀土及杂质元素对ZA27合金晶间腐蚀的影响

为了从本质上了解杂质与稀土元素对锌铝合金晶间腐蚀的影响 ,探索抑制合金晶间腐蚀的有效途径 ,依据晶界的大角度重位点阵理论编制出相应计算机软件 ,建立含稀土、杂质及 η相颗粒的α相大角度晶界原子集团模型 ,采用递归法计算了α相晶界间的电荷转移 ,由此讨论了杂质 (Pb、Sn、Cd)及稀土元素 (La、Y)对Zn、Al电极电位的影响 .结果表明 ,杂质Pb、Sn、Cd增大原子间的电荷转移量 ,提高Zn、Al电极电位差 ,加速合金的腐蚀 ,稀土元素减小原子间的电荷转移量 ,降低Zn、Al电极电位差 ,具有抑制晶间腐蚀的作用 .     

A Mossbauer study of the magnetic coupling in iron phosphorous trisulfides

The polycrystalline sample of layered compound FePS_3 has been investigated by using M?ssbauer spectroscopy (12K to 300K), magnetic susceptibility measurements, x-ray diffraction and FTIR spectroscopy. The antiferromagnetic order exists below T_N=120.5±1K. The M?ssbauer spectra below T_N indicate that the magnetization axis is perpendicular to the layer of FePS_3, and the divalent iron cations are in their high spin configurations. By fitting the hyperfine field parameters near the Néel temperature, we obtain information on the nature of magnetic interactions in the material. The results show that the magnetic coupling can be treated by the two-dimensional Ising model, and it can be interpreted on the basis of a crystal-field effect.     

Metallo‐supramolecular micelles: Studies by analytical ultracentrifugation and electron microscopy

In aqueous solutions, amphiphilic block copolymers in which a polystyrene (PS) segment is connected to a poly(ethylene oxide) (PEO) block via a bis(2,2′:6′,2″‐ terpyridine ruthenium) complex can form micelles. Such micelles of the protomer type PS₂₀‐[Ru]‐PEO₇₀, according to the preparation procedure representing frozen micelles, were studied by sedimentation velocity and sedimentation equilibrium analysis in an analytical ultracentrifuge and by transmission electron microscopy, with different techniques applied for the sample preparation. The particles obtained were surprisingly multifarious in size. In ultracentrifugation experiments performed at relatively low salt concentrations, the distributions of the sedimentation coefficient s_20,w showed a pronounced peak at 9.6 S and a broad, only partly separated second peak around 14 S. The molar mass of the particles at the peak was around 430,000 g/mol, corresponding to an aggregation number of approximately 85. The average hydrodynamic diameter of the particles in the peak fraction was approximately 13 nm. In electron micrographs of negatively stained samples, spheres of diameters between 10 and 25 nm were the most abundant particles, but larger ones with a wide size range were also visible. The latter particles apparently were composed of smaller ones. The data from both sedimentation analysis and electron microscopy showed that (1) the studied compound formed primary micelles of diameters around 20 nm and (2) the primary micelles had a tendency toward aggregation. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3159–3168, 2003