含硒杂环化合物的合成和对超氧阴离子作用的ESR研究

引言硒作为人体必需的微量元素,其主要生化作用与谷胱甘肽过氧化物酶密切相关.在体内,该酶可以催化许多过氧化物的分解,并且与谷胱甘肽一起组成一个强有力的细胞防御体系,发挥其抗氧化作用.近几年来,人们发现了一种小分子有机硒化物2-苯基-1,2-苯并异硒唑酮-3(简称Ebselen)具有类似谷胱甘肽过氧化物酶的活性.它能有效地抑制活性氧自由基的产生而引起的细胞损伤,具有良好的抗炎活性,且毒性极低(大鼠LD_(50)>6180mg/os).因而,普遍认为Ebselen及其类似物是一类具有广谱抗炎活性的潜在药物,在医药领域具有广阔的应用前景.     

四（2,4—二叔戊基苯氧基）酞菁铜（Ⅱ）的合成及其LB膜

合成了标题酞菁铜衍生物,并通过元素分析,高压液相色谱,紫外光谱,红外光谱,核磁共振谱,电镜,顺磁共振谱及质谱加以确认。该化合物在稀氯仿溶液和LB膜中各以单,双分子缔合的形式存在。Z型沉积形成的单层LB膜对氨气有很高的灵敏度和选择性。     

可逆反应的热静力学研究法

化学反应的焓变△H和平衡常数K的测定是热静力学研究的重要任务。通常用量热法可以此较准确地测定△H,但要从量热数据直接得到K则是在六十年代初才开始有所探索。在达方面,Drago和Christensen的工作是值得借鉴的。本文建立了一种中性配位体与一价金属离子络合反应体系的热静力学研究法,并用这种方法研究了二苯并18-冠-6与Na~+的络合反应,同时得到了反应的△H和平衡常数K。实验值与文献值符合。     

Local Electronic Structure Modulation Enables Fast-Charging Capability for Li-Rich Mn-Based Oxides Cathodes With Reversible Anionic Redox Activity

Anionic and cationic redox chemistries boost ultrahigh specific capacities of Li-rich Mn-based oxides cathodes (LRMO). However, irreversible oxygen evolution and sluggish kinetics result in continuous capacity decay and poor rate performance, restricting the commercial fast-charging cathodes application for lithium ion batteries. Herein, the local electronic structure of LRMO is appropriately modulated to alleviate oxygen release, enhance anionic redox reversibility, and facilitate Li⁺ diffusion via facile surface defect engineering. Concretely, oxygen vacancies integrated on the surface of LRMO reduce the density of states of O 2p band and trigger much delocalized electrons to distribute around the transition metal, resulting in less oxygen release, enhancing reversible anionic redox and the MnO₆ octahedral distortion. Besides, partially reduced Mn and lattice vacancies synchronously stimulate the electrochemical activity and boost the electronic conductivity, Li⁺ diffusion rate, and fast charge transfer. Therefore, the modified LRMO exhibits enhanced cyclic stability and fast-charging capability: a high discharging capacity of 212.6 mAh·g⁻¹ with 86.98% capacity retention after 100 cycles at 1 C is obtained and to charge to its 80%, SOC is shortened to 9.4 min at 5 C charging rate. This work will draw attention to boosting the fast-charging capability of LRMO via the local electronic structure modulation.     

Simultaneous CO2 and H2O Activation via Integrated Cu Single Atom and N Vacancy Dual-Site for Enhanced CO Photo-Production

Photocatalytic conversion of CO₂ into fuels using pure water as the proton source is of immense potential in simultaneously addressing the climate-change crisis and realizing a carbon-neutral economy. Single-atom photocatalysts with tunable local atomic configurations and unique electronic properties have exhibited outstanding catalytic performance in the past decade. However, given their single-site features they are usually only amenable to activations involving single molecules. For CO₂ photoreduction entailing complex activation and dissociation process, designing multiple active sites on a photocatalyst for both CO₂ reduction and H₂O dissociation simultaneously is still a daunting challenge. Herein, it is precisely construct Cu single-atom centers and two-coordinated N vacancies as dual active sites on CN (Cu₁/N_2CV-CN). Experimental and theoretical results show that Cu single-atom centers promote CO₂ chemisorption and activation via accumulating photogenerated electrons, and the N_2CV sites enhance the dissociation of H₂O, thereby facilitating the conversion from COO* to COOH*. Benefiting from the dual-functional sites, the Cu₁/N_2CV-CN exhibits a high selectivity (98.50%) and decent CO production rate of 11.12 µmol g⁻¹ h⁻¹. An ingenious atomic-level design provides a platform for precisely integrating the modified catalyst with the deterministic identification of the electronic property during CO₂ photoreduction process.     

一种面向RDSM系统的基于遗传算法优化色散矩阵的方法

矩形差分空间调制（rectangular differential spatial modulation,RDSM）是一种多天线非相干调制技术,该技术频谱效率高,低功耗且无信道估计开销,特别适用于信道快速变化的车联网、物联网、6G蜂窝网络等未来通信系统。然而发射端的稀疏酉矩形空时色散矩阵（dispersion matrix,DM）的构造问题一直是个难点,而当前使用的随机搜索优化方法具有极高的计算复杂度,对此,提出了一种低复杂度遗传算法（genetic algorithm, GA）。根据秩与行列式标准最大化准则（rank and determinant criterion,RDC）的方法计算适应度值,可避免差分系统中所需的分类讨论。根据星座旋转对称性的特点,降低 GA 单次迭代的计算复杂度。仿真结果表明,优化得到的DMs（DM set）显著改善了RDSM系统误比特率（bit error rate,BER）性能,对比随机搜索,低复杂度遗传算法有效提高了RDSMS的DMs优化效率,优化DMs所需的计算复杂度约为随机搜索的0.1%。     

D2D通信中一种基于非数据辅助误差适量幅度的同信道干扰控制方法及其性能分析

针对D2D通信系统中广泛存在的同信道干扰问题,该文提出一种基于非数据辅助误差矢量幅度(NDA-EVM)进行同信道干扰分析的方法.以NDA-EVM作为信道质量评估参量,推导信号在M-QAM调制下的NDA-EVM统一计算模型,利用信道增益建立NDA-EVM同信道干扰分布模型,并进一步求解该模型的性能上限,从而量化同信道干扰.理论分析和仿真实验表明,相对于传统算法,该文所提上限的计算时间复杂度由O(M 2)降为O(M),提高了信道评估时效性;推导性能上限与理论值吻合度高,特别是在低SNR时为紧上界,两者最小均方根误差RMSE低至0.2615.     

Thermal reaction of HNCO with NO2 at moderate temperatures

The thermal reaction of HNCO with NO₂ has been studied in the temperature range of 623 to 773 K by FTIR spectrometry. Major products measured are CO₂ and NO with a small amount of N₂O. Kinetic modeling of the time resolved concentration profiles of the reactants and products, aided by the thermochemical data of various likely reactive intermediates computed by means of the BAC-MP4 method, allows us to conclude that the reaction is initiated exclusively by a new bimolecular process: with a rate constant, k₁ = 2.5 × 10¹²e^?13,100/T cm³/mols. The well-known bimolecular reaction is the only strong competitive process in this important reactive system throughout the temperature range studied. Kinetic modeling of NO formation and NO₂ decay rates gave rise to values of k₁₀ which were in close agreement with literature data. © 1993 John Wiley & Sons, Inc.     

Direct observation of eta 2-imine formation through beta-H abstraction between amide ligands. Neutron and X-ray diffraction structure of a dihydride imine ditantalum complex

Reactions of Ta(NMe2)5 with D2SiR'Ph (R' = Me, Ph) were found to give a dideuteride eta 2-imine complex (Me2N)3Ta(mu-D)2(mu-N-eta 2-N,C-CH2NMe)Ta(NMe2)3(1-d2) through C-H activation of an amide ligand via beta-H abstraction, and the structure of 1 was confirmed by single crystal neutron and X-ray diffraction.