基团立体屏蔽效应对取代咪唑离子液体酸性的影响

影响取代咪唑阳离子C2-H酸性(pKa)的重要因素有二:H原子所带的部分正电荷和取代基的立体屏蔽效应,前者可用C2-H的1H NMR化学位移δC2-H度量,后者用基团拓扑立体效应指数TSEI衡量.咪唑阳离子C2-H的pKa可由以下方程估算:pKa=58.10-4.208δC2-H+1.659TSEI该式的标准偏差只有0.28 pKa单位,估算结果与文献报导的pKa值相吻合.表明如要精确估算pKa,必须考虑取代基立体屏蔽效应;当希望用碱性较低的亲核试剂脱除取代咪唑阳离子的C2-H形成卡宾时,应采用芳香基取代的咪唑离子;若使用取代咪唑离子液体作溶剂,并且在碱性较强的条件下进行有机反应,则最好选择立体屏蔽效应大的非芳香基取代的咪唑离子.     

基于DSP平台的激光二极管控制系统

介绍了以DSP芯片TMS320F2812为核心设计的控制平台、利用半导体制冷器和光功率传感器调节激光二极管工作温度和发射功率的控制系统;设计了具有良好性能的模拟通道,提出了针对特定调节对象的PID算法.结合优化设计的执行单元实现了很好的控制效果,有效地提高了激光二极管系统的稳定性和可靠性;设计的控制系统在环境温度-10℃～50℃时能够达到±0.03℃的控制精度.     

Phosphofructokinase from mantle tissue of Mytilus galloprovincialis. Purification and effects of phosphorylation on the enzymatic activity

Phosphofructokinase purified from mantle tissue of the sea mussel Mytilus galloprovincialis, was phosphorylated "in vitro" by the catalytic subunit of cyclic AMP-dependent protein kinase. The incorporation of phosphate gave rise to an activation of the enzyme by increasing its affinity for fructose-6-phosphate, by decreasing its sensitivity to the inhibition by ATP and by enhancing the effect of allosteric activators (5'-AMP and fructose-2,6-bisphosphate). In addition, the effects of phosphorylation on the catalytic activity are pH-dependent.     

Single-Atom Metal Sites Anchored Hydrogen-Bonded Organic Frameworks for Superior “Two-In-One” Photocatalytic Reaction

Photoredox catalysis is a green solution for organics transformation and CO₂ conversion into valuable fuels, meeting the challenges of sustainable energy and environmental concerns. However, the regulation of single-atomic active sites in organic framework not only influences the photoredox performance, but also limits the understanding of the relationship for photocatalytic selective organic conversion with CO₂ valorization into one reaction system. As a prototype, different single-atomic metal (M) sites (M²⁺ = Fe²⁺, Co²⁺, Ni²⁺, Cu²⁺, and Zn²⁺) in hydrogen-bonded organic frameworks (M-HOF) backbone with bridging structure of metal-nitrogen are constructed by a typical “two-in-one” strategy for superior photocatalytic C N coupling reactions integrated with CO₂ valorization. Remarkably, Zn-HOF achieves 100% conversion of benzylamine oxidative coupling reactions, 91% selectivity of N-benzylidenebenzylamine and CO₂ conversion in one photoredox cycle. From X-ray absorption fine structure analysis and density functional theory calculations, the superior photocatalytic performance is attributed to synergic effect of atomically dispersed metal sites and HOF host, decreasing the reaction energy barriers, enhancing CO₂ adsorption and forming benzylcarbamic acid intermediate to promote the redox recycle. This work not only affords the rational design strategy of single-atom active sites in functional HOF, but also facilitates the fundamental insights upon the mechanism of versatile photoredox coupling reaction systems.     

A 2.20 eV Bandgap Polymer Donor for Efficient Colorful Semitransparent Organic Solar Cells

Semitransparent organic solar cells (ST-OSCs) have attracted increasing attention due to their promising prospect in building-integrated photovoltaics. Generally, efficient ST-OSCs with good average visible transmittance (AVT) can be realized by developing active layer materials with light absorption far from the visible light range. Herein, the development of ultrawide bandgap polymer donors with near-ultraviolet absorption, paired with near-infrared acceptors, is proposed to achieve high-performance ST-OSCs. The key points for the design of ultrawide bandgap polymers include constructing donor–donor type conjugated skeleton, suppressing the quinoidal resonance effect, and minimizing the twist of conjugated skeleton via noncovalent conformational locks. As a proof of concept, a polymer named PBOF with an optical bandgap of 2.20 eV is synthesized, which exhibited largely reduced overlap with the human eye photopic response spectrum and afforded a power conversion efficiency (PCE) of 16.40% in opaque device. As a result, ST-OSCs with a PCE over 10% and an AVT over 30% are achieved without optical modulation. Moreover, colorful ST-OSCs with visual aesthetics can be achieved by tuning the donor/acceptor weight ratio in active layer benefiting from the ultrawide bandgap nature of PBOF. This study demonstrates the great potential of ultrawide bandgap polymers for efficient colorful ST-OSCs.     

Finite-time optimal tracking control for a class of nonlinear systems with prescribed performance

In this paper, a finite-time optimal tracking control scheme based on integral reinforcement learning is developed for partially unknown nonlinear systems. In order to realize the prescribed performance, the original system is transformed into an equivalent unconstrained system so as to a composite system is constructed. Subsequently, a modified nonlinear quadratic performance function containing the auxiliary tracking error is designed. Furthermore, the technique of experience replay is used to update the critic neural network, which eliminates the persistent of excitation condition in traditional optimal methods. By combining the prescribed performance control with the finite-time optimization control technique, the tracking error is driven to a desired performance in finite time. Consequently, it has been shown that all signals in the partially unknown nonlinear system are semiglobally practical finite-time stable by stability analysis. Finally, the provided comparative simulation results verify the effectiveness of the developed control scheme.     

An optimized image watermarking algorithm based on SVD and IWT

The Journal of Supercomputing - With the wide spread of image information, it is an urgent problem to protect image property rights and crack down on piracy. Watermarking algorithm is an effective...     

Effect of Sintering Temperature on Magnetic and Electrical Properties of GdBaCo<Subscript>2</Subscript><Emphasis Type="Italic">O</Emphasis><Subscript>5 + <Emphasis Type="Italic">δ</Emphasis></Subscript>

In this study, we report the results of an investigation into the sintering temperature dependence of magnetic and transport properties for GdBaCo₂ O _{5 + δ} synthesized through a sol-gel method. The lowering of sintering temperature leads to the increase of oxygen content and the reduction of grain size. The increase of oxygen content results in the enhancement of magnetic interactions and the weakening of Coulomb repulsion effect, while the reduction of grain size improves the magnetoresistance effect. Metal-insulator transition accompanied with spin-state transition is observed in all samples.