Tuning PtII-Based Donor–Acceptor Systems through Ligand Design: Effects on Frontier Orbitals,Redox Potentials,UV/Vis/NIR Absorptions,Electrochromism, and Photocatalysis

Asymmetric platinum donor–acceptor complexes [(pimp)Pt(Q²⁻)] are presented in this work, in which pimp=[(2,4,6-trimethylphenylimino)methyl]pyridine and Q²⁻=catecholate-type donor ligands. The properties of the complexes are evaluated as a function of the donor ligands, and correlations are drawn among electrochemical, optical, and theoretical data. Special focus has been put on the spectroelectrochemical investigation of the complexes featuring sulfonyl-substituted phenylendiamide ligands, which show redox-induced linkage isomerism upon oxidation. Time-dependent density functional theory (TD-DFT) as well as electron flux density analysis have been employed to rationalize the optical spectra of the complexes and their reactivity. Compound 1 ([(pimp)Pt(Q²⁻)] with Q²⁻=3,5-di-tert-butylcatecholate) was shown to be an efficient photosensitizer for molecular oxygen and was subsequently employed in photochemical cross-dehydrogenative coupling (CDC) reactions. The results thus display new avenues for donor–acceptor systems, including their role as photocatalysts for organic transformations, and the possibility to introduce redox-induced linkage isomerism in these compounds through the use of sulfonamide substituents on the donor ligands.     

A new anti-proliferative acylated flavonol glycoside from Fuzhuan brick-tea

Fuzhuan brick-tea (FBT) is unique for a fungal fermentation stage in its manufacture process and is classified in dark tea. A new acylated flavonol glycoside, kaempferol 3-O-[E-p-coumaroyl-(→2)][α-l-arabinopyranosyl-(1→3)][α-l-rhamnopyranosyl(1→6)]-β-d-glucopyranoside, which was trivially named as camellikaempferoside A (1), was isolated from FBT along with camelliquercetiside C (2). Their structures were unambiguously elucidated by combination of spectroscopic and chemical methods. Compound 1 showed anti-proliferative activity against MCF-7 and MDA–MB-231 cells with IC₅₀ values of 7.83 and 19.16 μM, respectively.     

Ligand-protein docking using a quantum stochastic tunneling optimization method

A novel hybrid optimization method called quantum stochastic tunneling has been recently introduced. Here, we report its implementation within a new docking program called EasyDock and a validation with the CCDC/Astex data set of ligand-protein complexes using the PLP score to represent the ligand-protein potential energy surface and ScreenScore to score the ligand-protein binding energies. When taking the top energy-ranked ligand binding mode pose, we were able to predict the correct crystallographic ligand binding mode in up to 75% of the cases. By using this novel optimization method run times for typical docking simulations are significantly shortened.     

Application of wake oscillators to two-dimensional vortex-induced vibrations of circular cylinders in oscillatory flows

A nonlinear time-domain simulation model for predicting two-dimensional vortex-induced vibration (VIV) of a flexibly mounted circular cylinder in planar and oscillatory flow is presented. This model is based on the utilization of van der Pol wake oscillators, being unconventional since wake oscillators have typically been applied to steady flow VIV predictions. The time-varying relative flow–cylinder velocities and accelerations are accounted for in deriving the coupled hydrodynamic lift, drag and inertia forces leading to the cylinder cross-flow and in-line oscillations. The system fluid–structure interaction equations explicitly contain the time-dependent and hybrid trigonometric terms. Depending on the Keulegan–Carpenter number (KC) incorporating the flow maximum velocity and excitation frequency, the model calibration is performed, entailing a set of empirical coefficients and expressions as a function of KC and mass ratio. Parametric investigations in cases of varying KC, reduced flow velocity, cylinder-to-flow frequency ratio and mass ratio are carried out, capturing some qualitative features of oscillatory flow VIV and exploring the effects of system parameters on response prediction characteristics. The model dependence of hydrodynamic coefficients on the Reynolds number is studied. Discrepancies and limitations versus advantages of the present model with different feasible solution scenarios are illuminated to inform the implementation of wake oscillators as a computationally efficient prediction model for VIV in oscillatory flows.     

Kustaanheimo–Stiefel变量与二体问题的正规化

本文叙述Kustaanheimo–Stiefel变量及其从四元数发展形成的过程,以及Kustaanheimo–Stiefel变换在二体问题正规化中的应用。

     

Global well-posedness and blow-up for the 2-D Patlak–Keller–Segel equation

In this paper, we prove that for every nonnegative initial data in $L^1({\mathbb{R}}^2)$, the Patlak–Keller–Segel equation is globally well-posed if and only if the total mass $M\le 8\pi$. Our proof is based on some monotonicity formulas of nonnegative mild solutions.     

Unit-linked life insurance policies: Optimal hedging in partially observable market models

In this paper we investigate the hedging problem of a unit-linked life insurance contract via the local risk-minimization approach, when the insurer has a restricted information on the market. In particular, we consider an endowment insurance contract, that is a combination of a term insurance policy and a pure endowment, whose final value depends on the trend of a stock market where the premia the policyholder pays are invested. To allow for mutual dependence between the financial and the insurance markets, we use the progressive enlargement of filtration approach. We assume that the stock price process dynamics depends on an exogenous unobservable stochastic factor that also influences the mortality rate of the policyholder. We characterize the optimal hedging strategy in terms of the integrand in the Galtchouk–Kunita–Watanabe decomposition of the insurance claim with respect to the minimal martingale measure and the available information flow. We provide an explicit formula by means of predictable projection of the corresponding hedging strategy under full information with respect to the natural filtration of the risky asset price and the minimal martingale measure. Finally, we discuss applications in a Markovian setting via filtering.     

(Vapour + liquid) equilibrium data for the {1,1-difluoroethane (R152a) + 1,1,1,3,3-pentafluoropropane (R245fa)} system at temperatures from (323.150 to 353.150) K

In this paper, (vapour + liquid) equilibrium (VLE) for the {1,1-difluoroethane (R152a) + 1,1,1,3,3-pentafluoropropane (R245fa)} system was determined by a static-analytical method at T = (323.150 to 353.150) K. Values of the VLE were correlated by the Peng–Robison equation of state (PR EoS) using two different models, the van der Waals (vdWs) mixing rule and the Huron–Vidal (HV) mixing rule involving the non-random two-liquid (NRTL) activity coefficient model. The correlated results show good agreement with the experimental values. For the two models, the maximum average absolute deviations of the vapour phase mole fraction are 0.0034 and 0.0035, respectively.     

Stress-assisted nucleation and growth of γ″ and γ′ precipitates in a Cu–1.2 wt%Be–0.1 wt%Co alloy aged at 320°C

An investigation by high-resolution transmission electron microscopy of the precipitation process during ageing a Cu–1.2?wt%Be–0.1?wt%Co alloy at 320°C has revealed that the transition phases follow a γ″→ γ″?+?γ′?→?γ sequence. The γ′ phase heterogeneously precipitates on the γ″ phase. The effects of an external stress on the nucleation and growth of disc-shaped γ″ and plate-shaped γ′ precipitates have been examined for the alloy aged at 320°C. A compressive stress applied in the [001] direction during ageing preferentially accelerates the nucleation and growth of the γ″ variant normal to the [001] axis among three crystallographically equivalent variants and the specific four γ′ variants formed on the γ″ variant normal to the [001] axis. A tensile stress does not significantly affect those of γ″ and γ′ precipitates. The critical diameter of the disc-shaped γ″ nucleus is estimated as about 1?nm from evaluation of the interaction energy between the applied stress and the misfit strains of γ″ precipitates. It is proposed that applied external stress does not affect the diffusion rate but the interphase boundary velocity.