Metal-Free Phosphination and Continued Functionalization of Pyridine: A Theoretical Study

This study investigates the mechanism of metal-free pyridine phosphination with P(OEt)₃, PPh₃, and PAr₂CF₃ using density functional theory calculations. The results show that the reaction mechanism and rate-determining step vary depending on the phosphine and additive used. For example, phosphination of pyridine with P(OEt)₃ occurs in five stages, and ethyl abstraction is the rate-determining step. Meanwhile, 2-Ph-pyridine phosphination with PPh₃ is a four-step reaction with proton abstraction as the rate-limiting step. Energy decomposition analysis of the transition states reveals that steric hindrance in the phosphine molecule plays a key role in the site-selective formation of the phosphonium salt. The mechanism of 2-Ph-pyridine phosphination with PAr₂CF₃ is similar to that with PPh₃, and analyses of the effects of substituents show that electron-withdrawing groups decreased the nucleophilicity of the phosphine, whereas aryl electron-donating groups increased it. Finally, TfO⁻ plays an important role in the C–H fluoroalkylation of pyridine, as it brings weak interactions.     

Discovery of Quinacrine as a Potent Topo II and Hsp90 Dual-Target Inhibitor,Repurposing for Cancer Therapy

Topo II and Hsp90 are promising targets. In this study, we first verified the structural similarities between Topo IIα ATPase and Hsp90α N−ATPase. Subsequently, 720 compounds from the Food and Drug Administration (FDA) drug library and kinase library were screened using the malachite green phosphate combination with the Topo II-mediated DNA relaxation and MTT assays. Subsequently, the antimalarial drug quinacrine was found to be a potential dual−target inhibitor of Topo II and Hsp90. Mechanistic studies showed that quinacrine could specifically bind to the Topo IIα ATPase domain and inhibit the activity of Topo IIα ATPase without impacting DNA cleavage. Furthermore, our study revealed that quinacrine could bind Hsp90 N−ATPase and inhibit Hsp90 activity. Significantly, quinacrine has broad antiproliferation activity and remains sensitive to the multidrug−resistant cell line MCF−7/ADR and the atypical drug−resistant tumor cell line HL−60/MX2. Our study identified quinacrine as a potential dual−target inhibitor of Topo II and Hsp90, depending on the ATP−binding domain, positioning it as a hit compound for further structural modification.     

中国塑性力学的开拓者——李敏华院士

介绍了李敏华院士历经国难艰苦求学以及毕生奉献塑性力学的经历.她在抗战期间随清华大学南迁至昆明西南联大,再漂洋过海到美国麻省理工学院(Massachusetts Insti-tude of Technology, MIT)攻读,在抚育两个幼子的情况下获得了博士学位,成为MIT工科的第一位女博士.她在美国国家航空咨询委员会(National Advisory Committee for Aeronautics, NACA)的工作期间,以独特的构思解决了旋转盘强度问题,得到国际塑性力学界的关注.正当她与丈夫吴仲华在美国工作如日中天之时,他们冲破重重阻力于1954年回到了祖国.她积极投身到中国科学院力学研究所的筹建工作,为我国塑性力学的建立、发展和人才的培养倾注了毕生的心血.李敏华关心我国航空事业的发展,在航空发动机涡轮轴断裂故障处理的课题中,她认识到研究疲劳问题的重要性,尽管当时已经60高龄还毅然转行带领学生开始低周疲劳的科研工作.李敏华作为一位女科学家,她在处理科研工作与家庭事务的关系方面亦是我们学习的典范.     

带陡化间隙的触发真空开关触发源研制

针对主电极间距20 mm以上的沿面击穿型多棒极触发真空开关（TVS）,研制了开关触发源。触发源利用脉冲变压器产生脉冲高压输出,在脉冲变压器高压侧并联小容值电容并在电容后串联陡化间隙。陡化间隙的加入可以使触发源输出不受触发沿面金属蒸气沉积的影响。通过调节间隙击穿电压也可以提高电容充电电压及储存能量,从而增加TVS触发沿面被击穿时注入到其中的触发能量。使用该触发源对TVS进行导通实验,结果表明,加入陡化间隙后的触发源输出能量大幅提高且不受触发沿面金属蒸气沉积的影响,能够实现TVS的100%可靠导通。     

Solid Sampling Pyrolysis Adsorption-Desorption Thermal Conductivity Method for Rapid and Simultaneous Detection of N and S in Seafood

In this work, a rapid method for the simultaneous determination of N and S in seafood was established based on a solid sampling absorption-desorption system coupled with a thermal conductivity detector. This setup mainly includes a solid sampling system, a gas line unit for controlling high-purity oxygen and helium, a combustion and reduction furnace, a purification column system for moisture, halogen, SO₂, and CO₂, and a thermal conductivity detector. After two stages of purging with 20 s of He sweeping (250 mL/min), N₂ residue in the sample-containing chamber can be reduced to <0.01% to improve the device’s analytical sensitivity and precision. Herein, 100 s of heating at 900 °C was chosen as the optimized decomposition condition. After the generated SO₂, H₂O, and CO₂ were absorbed by the adsorption column in turn, the purification process executed the vaporization of the N-containing analyte, and then N₂ was detected by the thermal conductivity cell for the quantification of N. Subsequently, the adsorbed SO₂ was released after heating the SO₂ adsorption column and then transported to the thermal conductivity cell for the detection and quantification of S. After the instrumental optimization, the linear range was 2.0–100 mg and the correlation coefficient (R) was more than 0.999. The limit of detection (LOD) for N was 0.66 μg and the R was less than 4.0%, while the recovery rate ranged from 95.33 to 102.8%. At the same time, the LOD for S was 2.29 μg and the R was less than 6.0%, while the recovery rate ranged from 92.26 to 105.5%. The method was validated using certified reference materials (CRMs) and the measured N and S concentrations agreed with the certified values. The method indicated good accuracy and precision for the simultaneous detection of N and S in seafood samples. The total time of analysis was less than 6 min without the sample preparation process, fulfilling the fast detection of N and S in seafood. The establishment of this method filled the blank space in the area of the simultaneous and rapid determination of N and S in aquatic product solids. Thus, it provided technical support effectively to the requirements of risk assessment and detection in cases where supervision inspection was time-dependent.     

介质壁加速腔加速结构优化

为了在介质壁加速器中增大轴向加速电场, 提高加速梯度的同时抑制径向电场对束包络的扩张, 提出了在每个加速电极上添加金属栅网结构。采用基于粒子云网格方法的电磁粒子模拟软件对不加栅网与添加栅网的电极结构进行了数值仿真, 分析了不同结构下加速管道中的电场分布和束包络变化。通过实验对比了两种不同结构下经过相同的加速长度获得的粒子能量。结果表明：添加金属栅网结构相对于不加栅网的金属小孔式结构, 轴向加速电场强度提高20%, 同时径向电场得到有效抑制;栅网结构下, 被加速的粒子束在自由漂移空间中的径向发散基本得到抑制;在相同的加速长度下加速H3+粒子, 栅网结构得到的能量增益提高了一倍。     

介质壁直线加速器加速单元间的电路耦合及解耦

中国工程物理研究院流体物理研究所研发的介质壁直线加速器是基于固态脉冲形成线、GaAs光导开关和高梯度绝缘介质壁三项关键技术的新型直线脉冲加速器。在加速器调试阶段,测量出获得加速的质子束流能量远低于预期值,在排除功率源负载能力因素之后,发现脉冲功率源因连接回路引起的电路耦合效应是导致束流能量低的主要原因。基于介质壁直线加速器加速单元放电回路结构的分析,确认了加速单元之间的电路耦合的必然性。并通过测量回路电流,研究了几种不同工作模式下的电路耦合效应。结合电路耦合的特点,给出了两种基于磁芯隔离的解耦方法,并测量了这两种方法的解耦效率。     

基于Kr工质的离子推力器栅极PIC仿真

Kr是新型低成本离子推力器的优选工质之一。采用三维PIC粒子模拟方法对Kr等离子体在栅极系统中的输运过程进行仿真,并与Xe工质仿真结果进行对比,分析工质类型对束流分布、离子通过率、发散角损失和推力等参数特性和分布的影响。结果表明：相比于Xe工质,Kr工质条件下,屏栅上游鞘层区域更大,屏栅离子通过率略有上升;Kr+在加速栅孔轴向速度较大,径向位移小,撞击加速栅几率小,加速栅电流相对较小;Kr工质和Xe工质的发散角损失相当,但Kr工质工作电流区域更高;相比于Xe工质,相同功率条件下Kr工质的推力值约降低20%。     

Interfacial Charge Transfer Induced Electronic Property Tuning of MoS_2 by Molecular Functionalization

The modulation of electrical properties of MoS_2 has attracted extensive research interest because of its potential applications in electronic and optoelectronic devices.Herein,interfacial charge transfer induced electronic property tuning of MoS_2 are investigated by in situ ultraviolet photoelectron spectroscopy and x-ray photoelectron spectroscopy measurements.A downward band-bending of MoS_2-related electronic states along with the decreasing work function,which are induced by the electron transfer from Cs overlayers to MoS_2,is observed after the functionalization of MoS_2 with Cs,leading to n-type doping.Meanwhile,when MoS_2 is modified with 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane(F_4-TCNQ),an upward band-bending of MoS_2-related electronic states along with the increasing work function is observed at the interfaces.This is attributed to the electron depletion within MoS_2 due to the strong electron withdrawing property of F_4-TCNQ,indicating p-type doping of MoS_2.Our findings reveal that surface transfer doping is an effective approach for electronic property tuning of MoS_2 and paves the way to optimize its performance in electronic and optoelectronic devices.