Understanding the Origins of Nucleophilic Hydride Reactivity of a Sodium Hydride–Iodide Composite

Sodium hydride (NaH) has been commonly used as a Brønsted base in chemical syntheses, while it has rarely been employed to add hydride (H^?) to unsaturated electrophiles. We previously developed a procedure to activate NaH through the addition of a soluble iodide source and found that the new NaH–NaI composite can effect even stereoselective nucleophilic hydride reductions of nitriles, imines, and carbonyl compounds. In this work, we report that mixing NaH with NaI or LiI in tetrahydrofuran (THF) as a solvent provides a new inorganic composite, which consists of NaI interspersed with activated NaH, as revealed by powder X‐ray diffraction, and both solid‐state NMR and X‐ray photoelectron spectroscopies. DFT calculations imply that this remarkably simple inorganic composite, which is comprised of NaH and NaI, gains nucleophilic hydridic character similar to covalent hydrides, resulting in unprecedented and unique hydride donor chemical reactivity.     

Dynamics-based nonsingular interval model and luffing angular response field analysis of the DACS with narrowly bounded uncertainty

Nonlinear Dynamics - This paper develops a dynamics-based nonsingular interval model and proposes a first-order composite function interval perturbation method (FCFIPM) for luffing angular response...     

Synthesis of Gd(III)-MOF: Dy3+ phosphor and kinetics study of its thermal decomposition

Journal of Thermal Analysis and Calorimetry - Due to their ability to form white light by mixture of blue emission and yellow emission from Dy3+ ions, Dy3+-doped phosphors have attracted much...     

Reactivity and Operational Stability of N‐Tailed TAMLs through Kinetic Studies of the Catalyzed Oxidation of Orange II by H2O2: Synthesis and X‐ray Structure of an N‐Phenyl TAML

The catalytic activity of the N‐tailed (“biuret”) TAML (tetraamido macrocyclic ligand) activators [Fe{4‐XC₆H₃‐1,2‐( N COCMe₂ N CO)₂NR}Cl]^2? ( 3 ; N atoms in boldface are coordinated to the central iron atom; the same nomenclature is used in for compounds 1 and 2 below), [X, R=H, Me ( a ); NO₂, Me ( b ); H, Ph ( c )] in the oxidative bleaching of Orange II dye by H₂O₂ in aqueous solution is mechanistically compared with the previously investigated activator [Fe{4‐XC₆H₃‐1,2‐( N COCMe₂ N CO)₂CMe₂}OH₂]^? ( 1 ) and the more aggressive analogue [Fe(Me₂C{CON(1,2‐C₆H₃‐4‐X) N CO}₂)OH₂]^? ( 2 ). Catalysis by 3 of the reaction between H₂O₂ and Orange II (S) occurs according to the rate law found generally for TAML activators (v=k_Ik_II[Fe^III][S][H₂O₂]/(k_I[H₂O₂]+k_II[S]) and the rate constants k_I and k_II at pH 7 both decrease within the series 3 b > 3 a > 3 c . The pH dependency of k_I and k_II was investigated for 3 a . As with all TAML activators studied to‐date, bell‐shaped profiles were found for both rate constants. For k_I, the maximal activity was found at pH 10.7 marking it as having similar reactivity to 1 a . For k_II, the broad bell pH profile exhibits a maximum at pH about 10.5. The condition k_I?k_II holds across the entire pH range studied. Activator 3 b exhibits pronounced activity in neutral to slightly basic aqueous solutions making it worthy of consideration on a technical performance basis for water treatment. The rate constants k_i for suicidal inactivation of the active forms of complexes 3 a – c were calculated using the general formula ln([S₀]/[S_∞])=(k_II/k_i)[Fe^III]; here [Fe^III], [S₀], and [S_∞] are the total catalyst concentration and substrate concentration at time zero and infinity, respectively. The synthesis and X‐ray characterization of 3 c are also described.     

Defining statistical relative complexity measure: Application to diversity in atoms

A statistical relative complexity measure, based on the Kullback-Leibler distance measure defining the relative information and the Carbó quantum similarity index defining the relative disequilibrium is proposed. It is shown that with the specific choice of prior density corresponding to the atom at the beginning of the subshell, this measure reveals the diversity of atoms as the subshells are filled across the periodic table. Numerical tests are reported using the non-relativistic Hartree-Fock as well as the relativistic Dirac-Fock density for all atoms in the periodic table.     

基于STC89C52单片机测量管道长度

采用STC89C52单片机,利用声音在管道内形成驻波,通过测量驻波发生时的共振频率,进而求得管道长度.文中对单片机实现的系统硬件结构、软件设计作了具体的说明,并给出了几个测量实例.     

偏心电子注激励周期加载波导角向非对称模衍射辐射

周期加载波导中匀速带电粒子的衍射辐射是产生较高频段可调谐太赫兹电磁辐射（频率高于1 THz）的有效方法.对圆柱形周期加载波导中偏心电子注产生的衍射辐射现象,进行了严格的理论分析和粒子模拟验证.研究表明,偏心电子注在波导中除了激励起角向对称模（TM₀波）以外,还将激励起角向模式为1（HE₁波）和2（HE₂波）的角向非对称模.并且电子注偏离轴线距离越大,激励的角向非对称模场强越强.每个模式的功率随电子注的激励位置呈变态贝塞尔函数平方关系变化,与电子注电流平方成正比.理论分析与计算机模拟的结果符合较好.研究结果将为发展该类可调谐太赫兹辐射源提供理论依据.     

Distribution regimes of intense laser beam in a self-consistent plasma channel

In the present work, we investigate the distributed regimes of an intense laser beam in a self-consistent plasma channel. As the intensity of the laser beam increases, the relativistic mass effect as well as the ponderomotive expulsion of electrons modifies the dielectric function of the medium due to which the medium exhibits nonlinearity. Based on Wentzel–Kramers–Brillouin and paraxial ray theory, the steady-state solution of an intense, Gaussian electromagnetic beam is studied. A differential equation of the beamwidth parameter with the distance of propagation is derived, including the effects of relativistic self-focusing (SF) and ponderomotive self-channeling. The nature of propagation and radial dynamics of the beam in plasma depend on the power, width of the beam, and Ω _p, the ratio of plasma to wave frequency. For a given value of Ω _p (<1), the distribution regimes have been obtained in beampower–beamwidth plane, characterizing the regimes of propagation as steady divergence, oscillatory divergence, and SF. The related focusing parameters are optimized introducing plasma density ramp function, and spot size of the laser beam is analyzed for inhomogeneous plasma. This results in overcoming the diffraction and guiding the laser beam over long distance. Numerical computations are performed for typical parameters of relativistic laser–plasma interaction studies.     

Spin-coating deposition of PbS and CdS thin films for solar cell application

In this work, we describe a simple spin-coating deposition technique for lead sulphide (PbS) and cadmium sulphide (CdS) films from a methanolic metal–thiourea complex. The characterization of the films by X-ray diffraction and X-ray photoelectron spectroscopy techniques revealed that pure cubic phase PbS and CdS layers were formed via this method. As shown by atomic force microscopy and scanning electron microscopy results, both films were homogeneous and presented a smooth surface. Optical properties showed that the energy band gap of PbS and CdS films were around 1.65 and 2.5 eV, respectively. The PbS film is p-type in nature with an electrical conductivity of around 0.8 S/cm. The hole concentration and mobility were 2.35 × 10¹⁸ cm^?3 and 2.16 × 10^?3 cm²/V/s, respectively, as determined from Hall measurement. Both films were used to develop a thin film solar cell device of graphite/PbS/CdS/ITO/glass. Device characterization showed the power conversion efficiency of around 0.24 %. The corresponding open circuit voltage, short circuit current and fill factor were 0.570 V, 1.32 mA/cm² and 0.32, respectively.     

用三角波电流励磁改进交流磁滞回线实验简

改进行了交流磁滞回线实验的励磁方法。研制了三角波电流交流恒流源驱动励磁线剖励磁．使软磁环形样品被交流磁化双向交替达到饱和,磁化场H的波形仍为三角波。维持三角波电流的周期和幅值不变．可使H变化的波形和变化的速率不变。可在H匀速变化的条件下观测样舳的交流磁滞回线;能在磁化场相同的条件下观测不同样品的交流磁滞回线;还可直接观测样品的微分磁导率曲线。