Density functional study of aurophilic interaction in Cl(AuPH3) and in its dimerization

With the help of quantum mechanical calculations, the geometric structures and electronic structures of the closed‐shell systems Cl(AuPH₃) and [Cl(AuPH₃)]₂ have been determined by DFT and MP2 methods. Experimental structure parameters of the title compounds were reproduced at Xα level. The Mulliken population and HOMO–LUMO gaps were examined. The intermolecular aurophilic interactions in [Cl(AuPH₃)]₂ were analyzed and decomposed. A positive BE value (no bonding) was calculated. When 2PC was added, each pair Au… Au interaction energy was about 83 kJ/mol. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2009     

Structures and Magnetic Properties of Two Copper(II) Complexes with 2,5‐Dichloro‐3,6‐Dihydroxy‐1,4‐Benzoquinone Dianionic and Tetrachloroquinone Ligand

The polynuclear copper(II) complex [Cu₂(Hdpa)₂(μ‐ClDHBQ)(ClO₄)₂]_n, 1 is bridged by ClDHBQ^?2 (2,5‐dichloro‐3,6‐dihydroxy‐1,4‐benzoquinone dianionic) and 2,2′‐dipyridylamine (Hdpa). In the axial position, Cu is connected with the oxygen atom of ClO. The perchlorate anion may be envisaged as a monodentate O‐bound ligand. Through the bond bridge of O–Cu … O–Cl, the binuclear compound [Cu₂(Hdpa)₂(μ‐ClDHBQ)(ClO₄)₂] is strung together into a long chain compound. Tetrachlorocatechol underwent partial oxidation/hydrolysis/dechlorination processes to produce ClDHBQ^?2. The other mononuclear complex [Cu(Hdpa)(TeCQ)](DMF), 2 , in which tetrachloroquinone (TeCQ) was produced by oxidation of tetrachlorocatechol (TeCC), therefore complex 2 is in the quinone form. The magnetic susceptibility measurements show antiferromagnetic coupling with J = ?11.9 cm^?1, θ = 2.6 K, and g = 2.05 for complex 1. Complex 2 exhibits the typical paramagnetic behavior of s = 1/2.     

Non‐Isothermal Decomposition Kinetics,Specific Heat Capacity and Adiabatic Time‐to‐explosion of a Novel High Energy Material: 1‐Amino‐1‐Methylamino‐2,2‐Dinitroethylene (AMFOX‐7)

A novel high energy material, 1‐amino‐1‐methylamino‐2,2‐dinitroethlyene (AMFOX‐7), was synthesized by the reaction of 1,1‐diamino‐2,2‐dinitroethylene (FOX‐7) and methylamine aqueous solution in N‐methyl pyrrolidone at 80°C. The thermal behavior and non‐isothermal decomposition kinetics of AMFOX‐7 were studied with DSC and TG/DTG methods. The kinetic equation of thermal decomposition reaction can be expressed as: $ {\rm d\alpha /d}T = \frac{{10^{21.03}}}{{\rm \beta}}\frac{3}{2}\left({1 - {\rm \alpha}} \right)\left[{- 1{\rm n}\left({{\rm 1} - {\rm \alpha}} \right)} \right]^{\frac{1}{3}} \exp \left({- 2.292 \times 10^5 {\rm /}RT} \right) A novel high energy material, 1‐amino‐1‐methylamino‐2,2‐dinitroethlyene (AMFOX‐7), was synthesized by the reaction of 1,1‐diamino‐2,2‐dinitroethylene (FOX‐7) and methylamine aqueous solution in N‐methyl pyrrolidone at 80°C. The thermal behavior and non‐isothermal decomposition kinetics of AMFOX‐7 were studied with DSC and TG/DTG methods. The kinetic equation of thermal decomposition reaction can be expressed as: $ {\rm d\alpha /d}T = \frac{{10^{21.03}}}{{\rm \beta}}\frac{3}{2}\left({1 - {\rm \alpha}} \right)\left[{- 1{\rm n}\left({{\rm 1} - {\rm \alpha}} \right)} \right]^{\frac{1}{3}} \exp \left({- 2.292 \times 10^5 {\rm /}RT} \right) $. The critical temperature of thermal explosion of AMFOX‐7 is 244.89°C. The specific heat capacity of AMFOX‐7 was determined with micro‐DSC method and theoretical calculation method, and the standard molar specific heat capacity is 199.39 J·mol^?1·K^?1 at 298.15 K. Adiabatic time‐to‐explosion of AMFOX‐7 was also calculated to be 215.41 s. AMFOX‐7 has higher thermal stability than FOX‐7.     

The minimum heat consumption for heat-driven binary separation processes with linear phenomenological heat transfer law

The optimal performance of heat-driven binary separation processes with linear phenomenological heat transfer law(q∝△(T-1)) is analyzed by taking the processes as heat engines which work between high-and low-temperature reservoirs and produce enthalpy and energy flows out of the system,and the temperatures of the heat reservoirs are assumed to be time-and space-variables.A numerical method is employed to solve convex optimization problem and Lagrangian function is employed to solve the average optimal contr...     

An Amperometric Immunosensor Based on Layer‐by‐Layer Assembly of L‐Cysteine and Nanosized Prussian Blue on Gold Electrode for Determination of Human Chorionic Gonadotrophin

A novel amperometric immunosensor based on L ‐cysteine/nanosized Prussian blue bilayer films ({NPB/L ‐cys}₂) and gold nanoparticles (nano‐Au) was fabricated for determination of human chorionic gonadotrophin (HCG). First, L ‐cys and NPB was self‐assembled by layer‐by‐layer (LBL) technology to form {NPB/L ‐cys}₂ bilayer films on the gold electrode. Subsequently, nano‐Au layer was immobilized on the {NPB/L ‐cys}₂ bilayer films by electrodepositing gold chloride tetrahydrate and then anti‐HCG was assembly on the nano‐Au layer. Finally hemoglobin (Hb) was employed to block sites against nonspecific binding. With the electrocatalytic ability of Hb and NPB for the reduction of H₂O₂, the current signal of the antigen‐antibody reaction was amplified and the enhanced sensitivity was achieved. In this study, the assembly process and performance of the immunosensor were characterized by cyclic voltammetry (CV) and the morphology was researched by scanning electron microscopy (SEM). The immunosensor performed a high sensitivity and a wide linear response to HCG in two ranges from 0.5 to 10 mIU/mL and from 10 to 200 mIU/mL with a relatively low detection limit of 0.2 mIU/mL at 3 times the background noise, as well as good stability and long‐term life.     

Thermal runaway evaluation of α-methylstyrene and trans-β-methylstyrene with benzaldehyde

Styrene is an important chemical in the petrochemical industry. In recent years, there have been sporadic releases, runaway reactions, fires, and thermal explosion accidents incurred by styrene and its derivatives worldwide. The purpose of this study was to estimate the impact of styrene and its derivatives of α-methylstyrene (AMS) and trans-β-methylstyrene (TBMS) contacting with benzaldehyde. Experiments were carried out to evaluate the thermokinetic parameters estimated by differential scanning calorimetry (DSC) and thermal activity monitor III (TAM III). TAM III was used to determine the fundamental thermokinetics under various isothermal temperatures, 80, 90 and 100°C. This autocatalytic reaction was demonstrated in thermal curves. After styrene was contacted with benzaldehyde, the exothermic onset temperature (T ₀) and the total heat of reaction (Q _total) were altered by DSC tests. When benzaldehyde is mixed with AMS and TBMS, the reaction time will be shorter but the enthalpy reduced, as revealed by TAM III tests. As AMS and TBMS, respectively, were contacted with benzaldehyde, both exothermic phenomena were changed during the reaction excursion. According to the results of this research, an operator should dictate the oxygen concentration in order to avoid any potential hazards during handling and transportation.     

Thermal hazard evaluation of carbon nanotubes with sulfuric acid by DSC

Many concerns over unsafe or unknown properties of multi-walled carbon nanotubes (MWNTs) have been raised. The thermal characteristics regarding stability would represent potential hazards during the production or utilization stage and could be determined by calorimetric tests for various thermokinetic parameters. Differential scanning calorimetry (DSC) was employed to evaluate the thermokinetic parameters for MWNTs at various compositions. Thermoanalytical curves showed that the average heat of decomposition (ΔH _d) of the MWNTs samples in a manufacturing process was about 31,723 J g⁻¹, by identifying them as an inherently hazardous material. In this study, significant thermal analysis appeared in the presence of sulfuric acid (H₂SO₄). From the DSC experiments, the purification process of MWNTs could induce an unexpected reaction in the condition of batch addition with reactants of H₂SO₄. The results can be applied for designing emergency relief system and emergency rescue strategies during a perturbed situation or accident.     

A novel threefold‐interpenetrating primitive cubic network based on a dinuclear Zn2 node

In the mixed‐ligand metal–organic polymeric compound poly[[μ₂‐1,4‐bis(imidazol‐1‐yl)benzene](μ₂‐terephthalato)dizinc(II)], [Zn₂(C₈H₄O₄)₂(C₁₂H₁₀N₄)]_n or [Zn₂(bdc)₂(bib)]_n [H₂bdc is terephthalic acid and bib is 1,4‐bis(imidazol‐1‐yl)benzene], the asymmetric unit contains one Zn^II ion, with two half bdc anions and one half bib molecule lying around inversion centers. The Zn^II ion is in a slightly distorted tetrahedral environment, coordinated by three carboxylate O atoms from three different bdc anions and by one bib N atom. The crystal structure is constructed from the secondary building unit (SBU) [Zn₂(CO₂)₂N₂O₂], in which the two metal centers are held together by two bdc linkers with bis(syn,syn‐bridging bidentate) bonding modes. The SBU is connected by bdc bridges to form a two‐dimensional grid‐like (4,4)‐layer, which is further pillared by the bib ligand. Topologically, the dinuclear SBU can be considered to be a six‐connected node, and the extended structure exhibits an elongated primitive approximately cubic framework. The three‐dimensional framework possesses a large cavity with dimensions of approximately 10 × 13 × 17 Å in cross‐section. The potential porosity is filled with mutual interpenetration of two identical equivalent frameworks, generating a novel threefold interpenetrating network with an α‐polonium topology [Abrahams, Hoskins, Robson & Slizys (2002). CrystEngComm, 4 , 478–482].     

OPTIMAL ERROR ESTIMATES FOR NEDELEC EDGE ELEMENTS FOR TIME-HARMONIC MAXWELL'S EQUATIONS

In this paper, we obtain optimal error estimates in both L^2-norm and H（curl）-norm for the Nedelec edge finite element approximation of the time-harmonic Maxwell＇s equations on a general Lipschitz domain discretized on quasi-uniform meshes. One key to our proof is to transform the L^2 error estimates into the L^2 estimate of a discrete divergence-free function which belongs to the edge finite element spaces, and then use the approximation of the discrete divergence-free function by the continuous divergence-free function and a duality argument for the continuous divergence-free function. For Nedelec＇s second type elements, we present an optimal convergence estimate which improves the best results available in the literature.     

Nonarchimedean Green functions and dynamics on projective space

Let \({\varphi: \mathbb{P}^N_K\to\mathbb{P}^N_K}\) be a morphism of degree d ≥ 2 defined over a field K that is algebraically closed field and complete with respect to a nonarchimedean absolute value. We prove that a modified Green function \({\hat{g}_\varphi}\) associated to \({\varphi}\) is Hölder continuous on \({\mathbb{P}^N(K)}\) and that the Fatou set \({\mathcal{F}(\varphi)}\) of \({\varphi}\) is equal to the set of points at which \({\hat{g}_\Phi}\) is locally constant. Further, \({\hat{g}_\varphi}\) vanishes precisely on the set of points P such that \({\varphi}\) has good reduction at every point in the forward orbit \({\mathcal{O}_\varphi(P)}\) of P. We also prove that the iterates of \({\varphi}\) are locally uniformly Lipschitz on \({\mathcal{F}(\varphi)}\) .