Two trinuclear Ru(II) complexes of hetero-tritopic bridging ligands: synthesis,characterization, theoretical calculations,photophysical and electrochemical properties

Two hetero-tritopic bridging ligands L¹ and L² based on 2,2′-bipyridine and 1,10-phenanthroline moieties, and their corresponding Ru(II) complexes [{Ru(bpy)₂}₃(µ₃?L¹)](PF₆)₆ and [{Ru(bpy)₂}₃(µ₃?L²)](PF₆)₆ (bpy = 2,2′-bipyridine), were synthesized. The molecular structures of both complexes were deduced by ¹H NMR, ESI-MS, ESI-HRMS, elemental analyses, and IR spectroscopy. Quantum calculations on the free bridging ligands and their complexes are also presented. Both complexes display MLCT absorptions at around 454 nm, and emissions at around 613 nm in CH₃CN solution at room temperature and at around 590 nm in EtOH–MeOH glassy matrix at 77 K. Cyclic and differential pulse voltammetry studies of both complexes reveal one reversible Ru(II)-centered oxidation and three reversible ligand-centered reductions, in each case.     

Effects of a novel ultrasound contrast agent with long persistence on right ventricular pressure: Comparison with SonoVue

This work investigated the effect of infusion of a self-made ultrasound contrast agent with long persistence (named ZHIFUXIAN) on rat right ventricular pressure and made a preliminary evaluation on the relative safety of the novel microbubbles. Normal saline, SonoVue and ZHIFUXIAN were injected through caudal vein at the total volume of 0.5 ml for each injection. The right ventricular systolic pressure (RVSP) and end-diastolic pressure (RVEDP) were monitored and the changes of the pressure were compared with baseline readings. RVSP increased when saline, SonoVue or ZHIFUXIAN were injected, the greatest change being after SonoVue (about 2 mm Hg), but there was no statistical significance compared with baseline (P > 0.05). There was no significant difference in RVSP between saline, SonoVue and ZHIFUXIAN at any time point. Also, there was no significant difference in RVEDP between groups at each time point and between different time points in each group. The results indicate that the self-made microbubbles effect on right ventricular hemodynamics is equivalent to that of normal saline at the same volume needed for effective enhanced imaging, demonstrating that it does not produce changes in right ventricular blood pressure under the study conditions. Pathological examination also showed it had no obvious influence on lung, liver and kidney.     

耦合时空混沌的模糊混沌神经网络鲁棒自适应控制

将模糊逻辑系统和混沌神经网络结合起来,利用模糊逻辑系统的逼近能力和混沌神经网络的时空混沌行为,对模型未知的耦合时空混沌系统提出了一种模糊混沌神经网络自适应控制方案;同时考虑系统扰动、未建模动态特性和建模误差的影响,设计自适应补偿器,增强时空混沌系统控制的鲁棒性;并用Laypunov方法证明了该方案的稳定性;仿真验证了方案的有效性和鲁棒性。     

Photosynthetic Fixation of CO2 in Alkenes by Heterogeneous Photoredox Catalysis with Visible Light

Light-driven fixation of CO₂ in organics has emerged as an appealing alternative for the synthesis of value-added fine chemicals. Challenges remain in the transformation of CO₂ as well as product selectivity due to its thermodynamic stability and kinetic inertness. Here we develop a boron carbonitride (BCN) with the abundant terminal B/N defects around the mesoporous walls, which essentially enhances surface active sites as well as charge transfer kinetics, boosting the overall rate of CO₂ adsorption and activation. In this protocol, anti-Markovnikov hydrocarboxylation of alkenes with CO₂ to an extended carbon chain is achieved with good functional group tolerance and specific regioselectivity under visible-light irradiation. The mechanistic studies demonstrate the formation of CO₂ radical anion intermediate on defective boron carbonitride, leading to the anti-Markovnikov carboxylation. Gram-scale reaction, late-stage carboxylation of natural products and synthesis of anti-diabetic GPR40 agonists reveal the utility of this method. This study sheds new insight on the design and application of metal-free semiconductors for the conversion of CO₂ in an atom-economic and sustainable manner.     

Di- and trinuclear Ru(II) complexes of 1,10-phenanthroline and 2,2′-bipyridine derivatives; synthesis,photophysical and electrochemical properties

Three heterotopic ligands L¹, L², and L³ based on 1,10-phenanthroline and 2,2′-bipyridine moieties have been synthesized and characterized. The Ru(II) complexes [{Ru(bpy)₂}₃(µ₃-L¹)](PF₆)₆, [{Ru(bpy)₂}₃(µ₃-L²)](PF₆)₆, and [{Ru(bpy)₂}₂(µ₂-L³)](PF₆)₄ (bpy = 2,2′-bipyridine) have been prepared by refluxing Ru(bpy)₂Cl₂·2H₂O with each ligand in ethanol. All three complexes display MLCT absorptions at around 455 nm and emissions at around 618 nm. Electrochemical studies of the complexes reveal one Ru(II)-centered quasi-reversible oxidation at around 1.32 V and three ligand-centered reductions in each case.     

手性毛细管气相色谱法测定微生物产生的环氧化物的对映体组成

在选择的修饰β－环糊精中,２,６－Ｏ－二戊基－３－Ｏ－三氟乙酰基－β环糊精（２,６－Ｏ－ＤＰ－３－Ｏ－ＴＦＡ－β－ＣＤ）是毛细管气相色谱法分离１－氯（溴）－２,３－环氧丙烷对映体较好的手性固定相,环氧丙烷对映体即使在室温下也不能拆分。由五株甲烷利用菌和一株乙烯利用菌产生的３－氯（溴）－１,２－环氧丙烷的对映体组成的测定结果表明,甲烷利用菌形成外消旋环氧化物,乙烯利用菌主要形成（Ｓ）－１－氯－２,３－环氧丙烷     

形状记忆合金在结构主被动振动控制中的应用

开状记忆合金是一类应用前景广阔的智能材料系统,利用形状记忆合金材料控制结构振动是最能体现这种先进材料应用价值的重要研究方向之一．本文首先介绍形状记忆合金的主要力学行为,包括形状记忆效应和超弹性效应;其次概述描述其力学行为的本构关系模型;最后重点论述实现结构主被动控制的原理和方法及其国内外研究进展,指出存在的问题和改进方法．     

弹性钢丝绳理论研究进展

对弹性钢丝绳理论的研究现状进行了较为全面、系统的介绍和总结,重点概述了离散模型的发展情况,对其它模型如半离散模型,则作了简要介绍;将几种离散模型的计算结果与实验情况进行了对照研究,提出并讨论了目前钢丝绳理论的某些不足之处及今后的研究方向．     

Analysis of High Power Millimeter Wave Waveguide Mode Converters with Input Mode Mixture

Based on the coupled mode theory, this paper presents the study on the influence of input mode mixture in circular oversized waveguide mode converters. Three kinds of commonly used waveguide mode converters, including the waveguide mode converters with varying wall radius or small axis perturbations, and the waveguide mode converters with bent structures, are taken as the examples. The results show that the spurious input modes do not simply superimpose onto the output modes, and in some cases they may deteriorate the conversion efficiency for the main output mode. Methods for transforming such spurious input mode mixture simultaneously into the main output mode are also presented in this paper.     

Long-Life Lead-Carbon Batteries for Stationary Energy Storage Applications

Owing to the mature technology, natural abundance of raw materials, high recycling efficiency, cost-effectiveness, and high safety of lead-acid batteries (LABs) have received much more attention from large to medium energy storage systems for many years. Lead carbon batteries (LCBs) offer exceptional performance at the high-rate partial state of charge (HRPSoC) and higher charge acceptance than LAB, making them promising for hybrid electric vehicles and stationary energy storage applications. Despite that, adding carbon to the negative active electrode considerably enhances the electrochemical performance. However, carbon brings some adverse effects, such as the severe hydrogen evolution reaction (HER) in the NAM due to the low overpotential of carbon material, promoting severe water loss in LCBs. From a practical application point of view, the irreversible sulfation of the negative active material (NAM) and extreme shedding and softening of the positive active material (PAM) are the main obstacles for next-generation LCBs. Recently, a lead-carbon composite additive delayed the parasitic hydrogen evolution and eliminated the sulfation problem, ensuring a long life of LCBs for practical aspects. This comprehensive review outlines a brief developmental historical background of LAB, its shifting towards LCB, the failure mode of LAB, and possible potential solutions to tackle the failure problems. The detailed LCB′s development towards long life was discussed in light of the reported literature to guide the researcher to date progress. More emphasis was directed toward the new applications of LCBs for stationary energy storage applications. Finally, state-of-the-art progress and further research gaps were pointed out for future work in this exciting era.