High pressure 17O NMR study of solvent exchange on square planar complexes: Water exchange on [Pd(dien)H2O]2+

Abstract

The water exchange reaction of [Pd(dien)H₂O]²⁺ (dien = diethylenetriamine) was studied as function of temperature (268-308 K) and pressure 0.1-197 MPa) using ₁₇O NMR techniques. The rate and activation parameters are: k_cx = 5100 s^?1 at 298 K; ΔH^# =38 kJ mol^?1; ΔS^# = -47 JK^?1 mol^?1; ΔV^# = -2.8 cm³ mol^?1 at 296 K. The results are discussed in reference to solvent exchange data for other Pt(II) and Pd(II) complexes, and are interpreted in terms of an associatively activated substitution process.     

Ionic conductivity in three crystalline phases of LiBH4 under pressure

The AC electrical conductivity of LiBH₄ was investigated below 2 GPa between 1 Hz and 1.6 MHz. The high-temperature phase has an ionic conductivity of up to 0.01 S cm^?1, while the low-temperature phases have conductivities two orders of magnitude lower. All phases show an Arrhenius behaviour with activation energies E _a between 0.5 and 0.7 eV, in good agreement with earlier data except for phase III, which is found to have the highest activation energy of the phases studied. The high-temperature phase has a minimum in E _a near 1 GPa, close to the triple point, correlated with a sudden change in activation volume. These features may indicate an isostructural phase transition. The conductivities of the ambient temperature phases increase temporarily by an order of magnitude after transitions between these phases, probably due to new diffusion channels via structural defects. The phase diagram agrees well with earlier results.     

Nano hillock and complex crater formation by low-energy proton implantation with incident angle into lithium niobate single crystal

The formation of nano-size hillocks and simple and complex craters was observed as a result of ion–surface collisions with a lithium niobate single crystal on proton implantation. The low-energy ion implantation process is considered as a controllable and versatile tool for surface and near-surface modifications down to an atomic scale as an alternative to the swift heavy ion irradiation effect. Lithium niobate samples implanted by proton ions with a low energy of 120 keV at various fluences (10¹⁵ and 10¹⁶ protons/cm²) were studied using atomic force microscopy (AFM). The images of surface modification appear as simple and complex crater formation in the case of incident ions at normal to the surface. Varying the angle of incidence to θ=30° with respect to the normal to the surface, hillocks and multi-hillocks were observed. The complex craters with central uplifted, cone-shaped hillocks with a height of up to 4.3 nm are surrounded by low-height (1 nm) rims. The hillock height varies from a few nanometers to 16 nm with the basal diameter from 200 to 340 nm depending on the ion implantation conditions. The complex crater and hillock formation on the lithium niobate sample surface at the collision spot with the impact of incident angle is discussed.     

Image denoising using trivariate prior model in nonsubsampled dual-tree complex contourlet transform domain and non-local means filter in spatial domain

Image denoising is always the basic problem of image processing, and the main challenge is how to effectively remove the noise and preserve the detailed information. This paper presents a new image denoising algorithm based on the combination of trivariate prior model in nonsubsampled dual-tree complex contourlet transformlet transform (NSDTCT) domain and non-local means filter (NLMF) in spatial domain. Firstly, NSDTCT is constructed by combining the dual-tree complex wavelet transform (DTCWT) and nonsubsampled directional filter banks (NSDFB). The noisy image is decomposed by using NSDTCT. Secondly, based on the correlation between the interscale and intrascale dependencies of NSDTCT coefficients, the distribution of the high frequency coefficients is modeled with the trivariate non-Gaussian distribution model. A nonlinear trivariate shrinkage function is derived in the framework of Bayesian theory, and then the denoised coefficients are obtained and inverse NSDTCT is performed to get the initial denoised image. Finally, NLMF is used to smooth the initial denoised image. Simulation experiment shows that our algorithm can obtain better performances than those outstanding denoising algorithms in terms of peak signal-to-noise ratio (PSNR), mean structural similarity (MSSIM) as well as visual quality.     

A generalized Schrödinger equation via a complex Lagrangian of electrodynamics

In this paper we give a generalized form of the Schrödinger equation in the relativistic case, which contains a generalization of the Klein-Gordon equation. By complex Legendre transformation, the complex Lagrangian of electrodynamics produces a complex relativistic Hamiltonian H of electrodynamics, on the holomorphic cotangent bundle T′* M. By a special quantization process, a relativistic time dependent Schrödinger equation, in the adapted frames of (T′* M, H) is obtained. This generalized Schrödinger equation can be expressed with respect to the Laplace operator of the complex Hamilton space (T′*M, H). Finally, under some additional conditions on the proper time s of the complex space-time M and the time parameter t along the quantum state, by the method of separation of variables, we obtain two classes of solutions for the Schrödinger equation, one for the weakly gravitational complex curved space M, and the second in the complex space-time with Schwarzschild metric.     

Electric field assisted annealing effects on microstructure and ionic conductivity in ceria/YSZ oxide heterostructures

The effect of electric field assisted annealing on the microstructure, composition and ionic conductivity properties in CeO₂/YSZ oxide heterostructures have been investigated using molecular dynamics simulations. Amorphization–recrystallization steps were performed with and without external electric field of strength 10?MV/cm along three different orientations: in-plane (YZ), normal (X) and 45° resultant (XY) with respect to the oxide heterointerfaces. The microstructural and compositional differences at the interfaces and in the interior of the oxide heterolayers were evaluated and were found to show a clear correlation with the orientations of the applied field. In particular, the XY configuration displayed a compressive lattice strain of ～9% along with a reduced oxygen vacancy concentration when compared to the others. Ionic density profiles suggest pronounced segregation (～60% higher compared to the average value in the interior) of yttrium ions closer to the YSZ/CeO₂ interface for the XY configuration. Other configurations exhibit minimal to no such variations. These microstructural differences are found to affect the number of mobile charge carriers and the activation barriers associated with ionic migration through the oxide lattice and consequently, influence the ionic conductivity.     

Effect of Temperature on Cononsolvency of Polyvinylpyrrolidone in Water/Methanol Mixture

The behavior of polyvinylpyrrolidone in mixed water/methanol solvents was studied by rheoviscosimetry over a temperature range of 20°C–40°C. For the lower temperatures of this range, the intrinsic viscosity variation of the polymer vs. methanol molar fraction shows structural transitions (coil–globule–coil). This transition, which is usually attributed to the cononsolvency phenomenon, agrees with our previously published results obtained by dynamic light scattering. For higher temperatures, near 40°C, the intrinsic viscosity increase shows an expansion of the polymer over the alcohol molar fraction range 0.2 < X _A < 0.5. This last result can be attributed to the water/alcohol complex destruction under temperature increase. The “excess viscosity” of the polymer-mixed solvents vanishes with increasing temperature and becomes positive at 40°C. So, the polymer chain tends to transit from a globular to an ideal chain in the middle composition range of the mixed solvents.     

ON THE MIXED PROBLEMS IN AN EIASTIC PIANE WITH PERIODIC CRACKS

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电化学方法研究(phen)2Cu2+配合物与DNA的相互作用

用电化学循环伏安法和微分脉冲伏安法研究了1,10-邻菲咯啉铜配合物[（phen）2Cu^2＋]与小牛胸腺DNA（CTDNA）的相互作用。结果发现,在pH=7．4的三羟甲基胺基甲烷-盐酸缓冲溶液（Tris—HCl）中,（phen）2Cu^2＋配合物的铜离子在循环伏安图上呈现明显的准可逆氧化-还原波。当加入一定量的小牛胸腺DNA时,配合物（phen）,Cu^2＋的氧化和还原峰电流均有所下降。通过比较（phen）2Cu^2＋配合物中加入单链DNA和双链DNA后的氧化和还原峰电流下降的程度,前者比后者F降的程度小,可以得出（phen）2Cu^2＋配合物与小牛胸腺双链DNA的作用方式存在着插入式的沟槽结合模式。这个结论在本实验中由盐效应进一步得到证实。由此可知,（phen）2Cu^2＋配合物与小牛胸腺DNA形成了一种插入式的电惰性结合物,从而导致氧化还原峰电流下降。     

多层网络级联失效的预防和恢复策略概述

现实生活中,与国计民生密切相关的基础设施网络大多不是独立存在的,而是彼此之间相互联系或依赖的,于是用于研究这些系统的多层网络模型随之产生.多层网络中的节点在失效或者遭受攻击后会因"层内"和"层间"的相互作用而产生级联效应,从而使得失效能够在网络层内和层间反复传播并使得失效规模逐步放大.因此,多层网络比单个网络更加脆弱.多层网络级联失效产生的影响和损失往往是非常巨大的,所以对多层网络级联失效的预防和恢复的研究具有重大意义.就多层网络级联失效的预防而言,主要包含故障检测,保护重要节点,改变网络耦合机制和节点备份等策略.就多层网络发生级联失效后的恢复策略而言,主要包含共同边界节点恢复、空闲连边恢复、加边恢复、重要节点优先恢复、更改拓扑结构、局域攻击修复、自适应边修复等策略.