Synthesis of μ2-Oxo-Bridged Iron(III) Tetraphenylporphyrin–Spacer–Nitroxide Dimers and their Structural and Dynamics Characterization by using EPR and MD Simulations

Iron(III) porphyrins have the propensity to form μ₂-oxo-dimers, the structures of which resemble two wheels on an axle. Whereas their crystal structure is known, their solution structure and internal dynamics is not. In the present work, the structure and dynamics of such dimers were studied by means of electron paramagnetic resonance (EPR) spectroscopy and quantum chemistry based molecular dynamics (MD) simulations by using the semiempirical tight-binding method (GFN-xTB). To enable EPR investigation of the dimers, a nitroxide was attached to each of the tetraphenylporphyrin cores through a linear and a bent linker. The inter-nitroxide distance distributions within the dimers were determined by continuous-wave (cw)-EPR and pulsed electron–electron double resonance (PELDOR or DEER) experiments and, with the help of MD, interpreted in terms of the rotation of the porphyrin planes with respect to each other around the Fe–O–Fe axis. It was found that such rotation is restricted to the four registers defined by the phenyl substituents. Within the registers, the rotation angle swings between 30° and 60° in the proximal and between 125° and 145° in the distal register. With EPR, all four angles were found to be equally populated, whereas the 30° and 145° angles are strongly favored to the expense of the 60° and 125° angles in the MD simulation. In either case, the internal dynamics of these dimers thus resemble the motion of a step motor.     

Enhanced output voltage of nano energy harvester with diverse textiles

Abstract

We demonstrate the electrical properties of nano energy harvesters (NEHs) with various textiles for smart textiles that can be applied to the next generation wearable electronics. Output voltages and currents of NEHs with various fabrics, such as a cotton, rayon and wool that have different triboelectricity were measured. Cotton, rayon and wool shows the maximum output voltages of 1.250, 3.313 and 4.063 V, respectively. In addition, output currents of those textiles were 0.75, 4.4, 1.063 μA, respectively. Wool, in particular, which has the highest triboelectricity of 350 V exhibits the highest output voltage.     

Wave packet dynamics of nonlinear Gazeau–Klauder coherent states of a position-dependent mass system in a Coulomb-like potential

AD = 1 position-dependent mass approach to constructing nonlinear quantum states for a modified Coulomb potential is used to generate Gazeau–Klauder coherent states. It appears that their energy eigenvalues are scaled down by the quantum number and the nonlinearity coefficient. We study the basic properties of these states, which are found to be undefined on the whole complex plane, and some details of their revival structure are discussed.     

从废水到新能源:光催化燃料电池的优化与应用

随着经济的飞速发展,社会对能源的需求日益扩大,对工业废水的无害化处理也提出了更高的要求。光催化燃料电池 (photocatalytic fuel cell, PFC) 在燃料电池中引入半导体光催化材料作为电极,实现了有机污染物高效降解和同步对外产电的双重功能,在废水无害化与资源化利用方面具有潜在的应用价值。半导体光催化电极是PFC系统高效运行的核心组件,增强其可见光响应和光生载流子分离是提高PFC性能的关键策略。反应器结构设计和运行参数优化也有利于改善PFC性能。本文从PFC基本原理和应用入手,综述了PFC在环境污染物资源化处理中的研究进展,并详细阐述了提高PFC的污染控制性能和产电效率的优化手段,为进一步设计高效稳定的PFC系统并实现其在水污染控制和清洁能源生产中的应用提供理论指导。     

Portable single-sided NMR measurements at variable temperatures: Implementation of a thermo-controlled device and application to the heating of bread dough

A temperature control unit was implemented to vary the temperature of samples studied on a commercial Mobile Universal Surface Explorer nuclear magnetic resonance (MOUSE-NMR) apparatus. The device was miniaturized to fit the maximum MOUSE sampling depth (25 mm). It was constituted by a sample holder sandwiched between two heat exchangers placed below and above the sample. Air was chosen as the fluid to control the temperature at the bottom of the sample, at the interface between the NMR probe and the sample holder, in order to gain space. The upper surface of the sample was regulated by the circulation of water inside a second heat exchanger placed above the sample holder. The feasibility of using such a device was demonstrated first on pure water and then on several samples of bread dough with different water contents. For this, T1 relaxation times were measured at various temperatures and depths and were then compared with those acquired with a conventional compact closed-magnet spectrometer. Discussion of results was based on biochemical transformations in bread dough (starch gelatinization and gluten heat denaturation). It was demonstrated that, within a certain water level range, and because of the low magnetic field strength of the MOUSE, a linear relationship could be established between T1 relaxation times and the local temperature in the dough sample.     

Experimental determination of interfacial energy for solid Al in the Al-Sn-Mg eutectic system with Bridgman-type apparatus

The equilibrated grain boundary groove shape of solid Al in equilibrium with Al-Sn-Mg eutectic liquid was observed by using a Bridgman type directional solidification apparatus. The ratio of the thermal conductivity of the equilibrated liquid to the thermal conductivity of solid Al has been obtained as 0.91. In addition, the average Gibbs-Thomson coefficient, $\bar{\mathrm{\Gamma }}=(4.20\pm 0.35)\times {10}^{-8}\mathrm{Km}$, the solid-liquid interfacial energy, ${\sigma }_{SL}=180.68\pm 23.48\text{mJ}/{\text{m}}^2$ and the grain boundary energy, ${\sigma }_{GB}=309.30\pm 29.47\text{mJ}/{\text{m}}^2$, in the Al/Al-Sn-Mg system have been calculated from the measured grain boundary shapes.     

Force-field parametrization based on radial and energy distribution functions

We propose a novel force-field-parametrization procedure that fits the parameters of potential functions in a manner that the pair distribution function (DF) of molecules derived from candidate parameters can reproduce the given target DF. Conventionally, approaches to minimize the difference between the candidate and target DFs employ radial DFs (RDF). RDF itself has been reported to be insufficient for uniquely identifying the parameters of a molecule. To overcome the weakness, we introduce energy DF (EDF) as a target DF, which describes the distribution of the pairwise energy of molecules. We found that the EDF responds more sensitively to a small perturbation in the pairwise potential parameters and provides better fitting accuracy compared to that of RDF. These findings provide valuable insights into a wide range of coarse graining methods, which determine parameters using information obtained from a higher-level calculation than that of the developed force field. © 2019 The Authors. Journal of Computational Chemistry published by Wiley Periodicals, Inc.     

Discrete element modelling of large soil deformations under heavy vehicles

This paper addresses the challenges of creating realistic models of soil for simulations of heavy vehicles on weak terrain. We modelled dense soils using the discrete element method with variable parameters for surface friction, normal cohesion, and rolling resistance. To find out what type of soils can be represented, we measured the internal friction and bulk cohesion of over 100 different virtual samples. To test the model, we simulated rut formation from a heavy vehicle with different loads and soil strengths. We conclude that the relevant space of dense frictional and frictional-cohesive soils can be represented and that the model is applicable for simulation of large deformations induced by heavy vehicles on weak terrain.     

Statistical structure of the velocity field in cavitating flow around a 2D hydrofoil

Transformation of flow turbulence structure with cavitation occurrence, determination of the flow conditions favorable for nucleation of cavitation bubbles, influence of the statistical structure of turbulence on this process and the inverse effect of cavitation on the flow dynamics are challenging problems in modern fluid mechanics. The paper reports on the results of statistical processing of the velocity fields measured by a PIV technique in cavitating flow over a 2D symmetric hydrofoil for four flow conditions, starting from a cavitation-free regime and finishing by unsteady cloud cavitation. We analyze basic information on the statistical structure of velocity fluctuations in the form of histograms and Q-Q diagrams along with profiles of the mean velocity and turbulent kinetic energy. The research reveals that the flow turbulence pattern and distributions of turbulent fluctuations change significantly with the cavitation development. Under unsteady cloud cavitation conditions, the probability density function of the fluctuating velocity has a two-mode distribution, which indicates switching of two alternating flow conditions in a region above the hydrofoil aft part due to periodic passing of cavitation clouds. Behaviors of the mean and most probable velocities unexpectedly appear to be different with a monotonous increase of the incoming flow velocity. This finding must be caused by modification of the skewness coefficient of the fluctuating velocity.     

Nucleon effective mass splitting and density-dependent symmetry energy effects on elliptic flow in heavy ion collisions at E_(lab)= 0.09 ～ 1.5 GeV/nucleon

By incorporating an iso spin-dependent form of the momentum-dependent potential in the ultra-relativistic quantum molecular dynamics(UrQMD) model,we systematically investigate effects of the neutron-proton effective mass splitting m*_(n-p)=m*_n-m*_p/m and the density-dependent nuclear symmetry energy E_(sym)(ρ) on the elliptic flow v_2 in~(197)Au+~(197) Au collisions at beam energies from 0.09 to 1.5 GeV/nucleon.It is found that at higher beam energies(≥0.25 GeV/nucleon) with the approximately 75 MeV difference in slopes of the two different E_(sym)(ρ),and the variation of m*_(n-p) ranging from-0.03 to 0.03 at saturation density with isospin asymmetry δ=(ρ_n-ρ_p)/ρ-0.2,the E_(sym)(ρ) has a stronger influence on the difference in v_2 between neutrons and protons,i.e.,v_2~n-v_2~p,than m*_(n-p) has.Meanwhile,at lower beam energies(≤0.25 GeV/nucleon),v_2~n-v_2~p is sensitive to both the E_(sym)(ρ) and the m*_(n-p).Moreover,the influence of m*_(n-p) on v_2~n-v_2~p is more evident with the parameters of this study when using the soft,rather than stiff,symmetry energy.