冷压与热压处理对YBa2Cu3O7-δ的结构相变和超导电性的影响

 本文研究了冷压（2.2~5.2 GPa）与热压（2.2 GPa,2.50~950 ℃）对YBa₂Cu₃O_7-δ的正交→四方相转变区和超导电性的影响。冷压保持其正交结构,但破坏了超导性,在98 K（失超点）到室温呈半导体特性,再在空气中烧结,可恢复液氮温区的零电阻状态。以Cu锅密封样品,热压处理至950 ℃,不发生Cu的析出。热压处理后,98 K（失超点）到室温呈半导体特性,再经通氧烧结,于86 K出现零电阻。热压处理过程,从450~950 ℃为正交→四方转变区。950 ℃为转变结束温度,大大高于氧气、空气、氮气、真空状态的温度。400 ℃附近为起始转变温度,低于氮气、氧气气氛的温度。因此相变区加宽。T_0-t结束温度升高,与Cu锅的抑制还原作用有密切关系。如降低高压淬火速率（<<10² ℃/s）,或随后辅以氧气氛中的后处理,将有利于获得既有高密度又有高T_c的YBa₂Cu₃O_7-δ超导体。     

Anomalies in magnetic susceptibility of nonstoichiometric Nd2NiO4+δ (δ=0.049, 0.065, 0.077, 0.234)

We have investigated the influence of oxygen excess on structural and physical properties of the Nd₂NiO_4+δ compounds. Using the citrate method and subsequent annealing in air and in a reducing atmosphere a various oxygen-doped compounds were prepared. X-ray diffraction at room temperature shows that structure is strongly oxygen excess dependent. Thus, by increasing δ by up to 0.077, the compounds adopt a tetragonal structure gradually with a biphasic domain between orthorhombic and tetragonal structures. And at higher δ values, the structure becomes orthorhombic. Moreover, Rietveld analysis shows that for δ<0.077 the presence of two crystalline phases with different oxygen excess: it should be the signature of interstitial oxygen, which is distributed in heterogeneous way. The biphasic products are composed of a stoichiometric Nd₂NiO₄ phase (orthorhombic structure) and a tetragonal Nd₂NiO_4.077 phase. Magnetic susceptibility shows a deviation from Curie-Weiss law for lower oxygen excess (δ?0.077). Moreover, some anomalies in dc magnetic susceptibility curves was observed at 45, 95 and 130 K for δ<0.077. These transitions are connected to the tetragonal phase, and were attributed, respectively, to an antiferromagnetic transition, possible charge ordering and structural transition.     

Fluorescent microscopic determination of cadmium in water samples with the self-ordered ring of α,β,γ,δ-tetra(5-sulfophenyl)porphine formed on the solid support of glass slides

A self-ordered ring (SOR) technique is first proposed for the determination of trace metal ions based on the capillary effect of solvent on a solid support. At pH 9.1, α,β,γ,δ-tetra(5-sulfophenyl)porphine could form an SOR on the surfaces of hydrophobic glass slides with the aid of poly(vinyl alcohol), and the fluorescence intensity of the SOR was found to be quantitatively quenched by Cd(II). An SOR method for the determination of Cd(II) was established in the range 1.0×10⁻¹⁴ to 2.0×10⁻¹³ mol, and the limit of detection was 5 fmol (3σ). Water samples were analyzed with an R.S.D. of 3.2-3.8%. The quantification basis of the SOR method, the relationships between the radius of the SOR and volume of the droplet are theoretically discussed.     

Copper mediated scalemic organolithium reagents in alkaloid syntheses

Scalemic 2-pyrrolidinylcuprates generated via asymmetric deprotonation of N-Boc-pyrrolidine followed by treatment with THF soluble CuCN·2LiCl react with ω-functionalized vinyl halides to afford 2-alkenyl-N-Boc-pyrrolidines. N-Boc deprotection and cyclization via intramolecular N-alkylation generates the pyrrolizidine or indolizidine skeletons. Subsequent functional group manipulation affords enantioenriched (+)-heliotridane, (+)-isoretronecanol, a formal synthesis of (+)-laburnine, (+)-(R)-2,3,5,7a-tetrahydro-1H-pyrrolizine, (R)-1,2,3,5,6,8a-hexahydroindolizine, (+)-ent-δ-coniceine, (+)-tashiromine and (+)-5-epitashiromine.     

FLAPW方法研究δ-钚单层表面几何和电子结构

采用全势线性缀加平面波（FLAPW）方法, 在广义梯度近似（GGA）下研究了单层δ-钚（100）和（111）面的几何和电子结构. 结果表明,自旋-轨道耦合对平衡几何结构的影响强于自旋极化,与体相相比,表面晶格常数显著收缩,实验上可选择晶格常数相对较小的物质作为δ-钚薄膜的沉积基体. 表面原子由于近邻原子数目的减少,5f电子波函数重叠几率的降低,更多地表现出局域化特征,（100）面5f电子的局域化程度强于（111）面.     

Studies on Synthesis and Electrochemical Performance of Li1+δNi1-xCoxO2-yFy Cathode Materials for Lithium-ion Rechargeable Batteries

It is a technological problem of LiNiO2 cathode material for lithium-ion secondary batteries because of the difficult preparation and hard purification, instable performance, remarkable capacity fading at initial discharge, worse thermal stability and safety of Ni-series cathode materials,and it is also the key factor of hindering LiNiO2 cathode material from practical applications.Recently, by doping some metal cations such as Co, Mn, Mg, Al, Cr and so on[1-5] into LiNiO2, the preparation difficulty and the purification hardness can be obviously improved, and the initial irreversible discharge capacity can be reduced, and the ratio of the initial discharge to charge capacity can be enhanced. But the cyclic stability, thermal stability and safety of LiNiO2 are not enough to satisfy the demand of commercial use.At present, the synthesis of LiNiO2 cathode material must be sintered under oxygen atmosphere in most cases, and the improved effect of fluoride doping on the electrochemical properties of LiNiO2 has seldom been reported in the literatures.In this paper, the cobalt cation and fluorine anion co-doping cathode materials Li1+δNi1-xCoxO2-yFy( 0≤δ≤0.2, 0≤x≤0.5, 0≤y≤0.1 ) were synthesized by solid state reaction method at 650℃ ～750℃ under air atmosphere, and characterized by XRD、 SEM、 TEM、 BET、 laser particle-size distribution measurement and electrochemical performance testing, the effect of different nickel sources on the properties of as-synthesized cathode materials was investigated. The results demonstrated that the cobalt and fluorine ions co-doping cathode materials Li1+δNi1-xCoxO2-yFy have complete layered structure, uniform surface morphology and better particle-size distribution as well as excellent electrochemical performances. At 20～25℃, 0.15～0.25mA charge and discharge current,4.25～2.70V cut-off voltage, 0.2～0.5C charge and discharge rate and 0.2～0.5 mA/cm2 current density,LiNi0.8Co0.2O1.95F0.05 cathode material has higher initial charge and discharge capacity and better cyclic properties which can be mainly attributed to the doping of the higher electronegativity fluorine which improves the structural stability and the synergistic reaction of cobalt and fluorine ions co-doping on the cathode materials. Under the above conditions, the initial charge and discharge capacity of LiNi0.8Co0.2O1.95F0.05 is 165.70mAh/g and 146.10mAh/g, respectively. After 50 cycles, it has more than 140mAh/g of discharge capacity and displays preliminary application possibility in the future.     

Spectrophotometric Determination of δ4 -3-Ketosteroids Using Oxalyldihydrazide

Abstract

A novel spectrophotometric method for the assay of δ⁴ -3-Ketosteroids in formulations is presented. Oxalyldihydrazide in methanol reacts selectively with δ⁴-3-Ketosteroids at pH 2 forming stable hydrazones which exhibit intense absorption specta at 300 nm. and high molar absorpitivities ranging from 14480–18750 for most steroids studied. Methyltestosterone showed exception ally high sensitivity where its molar absorpitivity was 21630. As little as 5–30 μg steroid were determined with 99.28 ± 0.65–100.16 ± 0.94% accuracy. The method was applied successfully to the micro-determination of cortisone, hydrocortisone, hydrocortisone acetate, norethisterone, norethisterone acetate, norgestrel and methyltestosterone in substance as well as in different pharmaceutical dosage forms. The precision of assay was compareble with existing spectrometric methods for ketosteroid drugs. The method is simple, accurate mean - while selective and more sensitive than the INH-method.     

Facile transformation of glutamic acid into proline residue inside a tripeptide backbone

In this Letter we present a simple reaction pathway which allows the conversion of the glutamic acid residue of a tripeptide into a proline residue. The reaction was performed by using Boc-Val-Glu-Phe-NH₂ as a starting material and is based on a NaH-induced intraresidue alkylation under reaction conditions analogous to that adopted during the Freidinger lactams formation.     

水溶性聚苯胺/SmBaCu0.7Mn0.3O5+δ材料的制备与氨敏性能研究

采用化学氧化法制备了水溶性聚苯胺（PANI）,用溶胶-凝胶法制备了 SmBaCu1-yMnyO5+δ（y=0, 0.1, 0.2, 0.3,0.4, 0.5, 0.6）（SBCM）粉体,用微粒填充法制备了 PANI / SBCM 复合材料。利用 FT-IR、XRD、TEM 多种手段对产物进行表征,并制成气敏元件,在室温操作温度下测试其对氨气的灵敏度。结果表明,在相同条件下,在 PANI元件、SBCM 元件及 PANI / SBCM 元件气敏测试中,PANI/SmBaCu0.7Mn0.3O5+δ（PANI/SBC70M30） 元件对氨气的气敏性能最优,对体积分数为 100×10–6的 NH3灵敏度在室温条件下达到最大值为 4.66,同时还具有较好的选择性、响应-恢复特性与稳定性,响应时间和恢复时间分别为 16 和 121 s。