两例LnⅢ3配合物的构筑、晶体结构及生物活性

利用多齿席夫碱配体H₂L(H₂L=(E)-6-(羟甲基)-N′-((6-甲氧基吡啶-2-基)亚甲基)吡啶酰肼)与Ln(dbm)₃·2H₂O反应,通过溶剂热法,设计与构筑了 2例新的三核稀土配合物[Ln₃(dbm)₅(L)₂(CH₃OH)₂]·CH₂Cl₂,其中 Ln=Pr (1)、Ho (2),Hdbm=二苯甲酰甲烷。单晶 X射线衍射分析表明：配合物 1与 2同构,其结构由 3个 Ln(Ⅲ)离子、5个二苯甲酰甲烷阴离子(dbm^-)、2个席夫碱配体 L^2-、2个配位的 CH₃OH及 1个结晶 CH₂Cl₂分子组成。3个中心 Ln(Ⅲ)离子通过 4个 μ₂-O原子相互连接,形成折线形的 Ln₃核。生物活性研究表明,配体H₂L、Ln(dbm)₃·2H₂O及配合物1和2均具有较好的抑菌活性。与配体H₂L及Ln(dbm)₃·2H₂O相比较,稀土配合物具有更强的抑菌活性。此外,采用紫外光谱法、循环伏安法和荧光光谱法研究了配合物1和2与小牛胸腺DNA(ctDNA)之间的相互作用,结果表明配合物主要以插入键合的方式与ctDNA结合。     

时基反馈控制的Tesla变压器初级电源

LC谐振充电是Tesla变压器常用的初级电容充电技术,但存在对控制时序要求高、易受电磁干扰和不具备故障保护能力等缺陷。针对这个问题,提出了一种时基反馈控制的LC谐振充电电源。该电源与传统LC谐振电源的主要区别在于,采用特殊设计的时基反馈电路取代多路时基控制器,将能量回收开关反向阻断瞬间的电压突变调制为谐振晶闸管触发信号,从而在能量回收结束时刻启动谐振充电,实现各工作回路准确按照预定时序运行。时基反馈电路由高压元件构成,不易受电磁干扰,且在原理上具备负载短路保护能力。该技术已经应用于CKP1000,CKP5000等多台Tesla型超宽谱脉冲源。实验结果表明,在强脉冲辐射环境下,该电源能够1000 Hz重频稳定运行,且能够在Tesla变压器初级短路故障时进行快速自动保护。     

Synthesis,Structural Investigations,and In Vitro/In Silico Bioactivities of Flavonoid Substituted Biguanide: A Novel Schiff Base and Its Diorganotin (IV) Complexes

Quercetin is one of the most powerful bioactive dietary flavonoids. The in vivo biological study of quercetin is extremely difficult due to its very low solubility. However, diorganotin complexes of quercetin are more useful when contrasted with quercetin due to increased solubility. In the present study, quercetin, substituted biguanide synthesized in the form of Schiff base and its di-alkyl/aryl tin (IV) complexes were obtained by condensing Schiff base with respective di-alkyl/aryl tin (IV) dichloride. Advanced analytical techniques were used for structural elucidation. The results of biological screening against Gram-positive/Gram-negative bacteria and fungi showed that these diorganotin (IV) derivatives act as potent antimicrobial agents. The in silico investigation with dihydropteroate (DHPS) disclosed a large ligand–receptor interaction and revealed a strong relationship between the natural exercises and computational molecular docking results.     

地下爆炸冲击波引起的基底滑移隔震建筑的动力响应

对埋置在土体中的圆形衬砌内发生意外爆炸引起的附近地表的滑移隔震建筑 (考虑了土 结构相互作用 )的动力响应进行了研究。在土 结构相互作用分析中 ,分别采用有限元、无穷元和集中质点体系建立了衬砌周围的有限土区、四周的无限土区以及基底滑移隔震建筑的计算模型 ;在基底滑移隔震分析中 ,提出了用连续摩擦力模型取代传统的库仑摩擦力模型 ,避免跟踪啮合滑移的过渡边界并可减小计算误差。通过数值模拟 6层基底滑移隔震建筑在遭受地下爆炸冲击波作用且考虑土 结构相互作用所产生的动力响应 ,分析了基底滑移隔震效果以及不同隔震参数对隔震效果的影响 ,为相关的理论研究和工程实践提供了依据。     

新型轻质阻尼基座设计与隔振性能研究

为了减少船体振动与辐射噪声,采用声子玻璃和弧形衔接结构设计了一种新型轻质阻尼基座。然后用加速度振级落差表征其隔振性能,开展了水泵电机激励下的基座隔振性能试验研究, 结果表明阻尼基座在20$\sim$10 000 Hz的频率范围具有显著的隔振效果,相较于同尺寸钢制基座,其振动落差总级可达12.93dB。研究结果充分验证了本文设计的轻质阻尼基座具备高强度、高阻尼、宽频隔振的特点,在舰船机械设备等减振降噪领域具有广泛的潜在应用价值。     

温度对高应变率扭-拉复合加载下形状记忆合金本构关系影响的研究

利用分离式扭-拉复合加载Hopkinson杆装置,在20℃和500℃下研究了温度对高应变率扭-拉复合加载下铁基形状记忆合金本构的影响.试验结果表明:该材料在高应变率扭-拉复合加载下的名义剪切屈服强度、剪切强度极限和名义拉伸屈服极限、拉伸强度极限均随温度的升高而降低.拉伸和扭转之间具有相互藕合作用.     

Cu (II) and Co (II/III) complexes of N,O‐chelated Schiff base ligands: DNA interaction,protein binding,cytotoxicity, cell death mechanism and reactive oxygen species generation studies

A series of copper (II) ( 1 and 3 ) and cobalt (II/III) ( 2 , 4 and 5 ) complexes comprising different imino‐phenolate ligands DCH , DTH and DBH ₂ (where DCH = 2,4‐dichloro‐6‐((mesitylimino)methyl)phenol, DTH = 2,4‐di‐tert‐butyl‐6‐((mesitylimino)methyl) phenol and DBH ₂ = 2,4‐dibromo‐6‐((mesitylimino)methyl)phenol) have been prepared with excellent yield and high purity. By utilizing different spectroscopic tools such as UV–visible, electrospray ionization (ESI)‐mass, Fourier‐transform infrared (FTIR) spectrometry and elemental analysis, the prepared complexes ( 1 – 5 ) were thoroughly characterized. The molecular structure of the synthesized complexes was ascertained by using single‐crystal X‐ray diffraction studies (SCXRDs). The experiment reveals that Complexes 1 – 5 bind to calf thymus DNA (CT‐DNA) through non‐intercalative way with good interacting abilities. However, 1 – 5 are excellent quenchers of the fluorescence intensity of bovine serum albumin (BSA) following the static pathway. Additionally, they had shown remarkable cytotoxic potential against MCF‐7 (mammary gland adenocarcinoma) and A549 (lung adenocarcinoma) cell lines. The IC₅₀ values associated with these complexes were much lower than the conventional drug cisplatin. Apoptosis‐induced cell death was confirmed from the DNA fragmentation studies and Hoechst 33342 staining. The 2′,7′‐dichlorofluorescein diacetate (DCFDA) assay indicates that the complex mediated reactive oxygen species (ROS) generation is accountable for governing the apoptosis mechanism via oxidative cell distress. Apart from these studies, by carrying out density functional theory (DFT) method, highest occupied molecular orbital–lowest unoccupied molecular orbital (HOMO–LUMO) energy gap calculations and optimized structures of the synthesized complexes were accomplished.     

Control of Protonated Schiff Base Excited State Decay within Visual Protein Mimics: A Unified Model for Retinal Chromophores

Artificial biomimetic chromophore-protein complexes inspired by natural visual pigments can feature color tunability across the full visible spectrum. However, control of excited state dynamics of the retinal chromophore, which is of paramount importance for technological applications, is lacking due to its complex and subtle photophysics/photochemistry. Here, ultrafast transient absorption spectroscopy and quantum mechanics/molecular mechanics simulations are combined for the study of highly tunable rhodopsin mimics, as compared to retinal chromophores in solution. Conical intersections and transient fluorescent intermediates are identified with atomistic resolution, providing unambiguous assignment of their ultrafast excited state absorption features. The results point out that the electrostatic environment of the chromophore, modified by protein point mutations, affects its excited state properties allowing control of its photophysics with same power of chemical modifications of the chromophore. The complex nature of such fine control is a fundamental knowledge for the design of bio-mimetic opto-electronic and photonic devices.     

高效液相色谱手性固定相法拆分BETTI碱及其衍生物对映体

在纤维素三（3,5-二甲基苯基氨基甲酸酯）（Chiralcel OD-H）和Pirkle型(R, R)-Whelk-O1手性柱上对手性氨基酚1-(α-氨基苄基)-2-萘酚（Betti 碱）及其衍生物1-(α-苄氨基苄基)-2-萘酚和1-(α-哌啶基苄基)-2-萘酚对映体分离进行了研究,分别考察了在正己烷流动相中,碱性添加剂、醇类添加剂的种类和浓度对手性拆分的影响。结果表明：溶质在Chiralcel OD-H柱上的分离效果好,而在(R, R)-Whelk-O1手性柱上只有1-(α-苄氨基苄基)-2-萘酚部分分离。研究了空间立体结构因素对手性分离的影响,初步探讨和比较了溶质在这2种手性柱上的手性识别机理。发现对(R, R)-Whelk-O1柱,溶质与固定相之间的吸引作用很小,而对于Chiralcel OD-H柱,溶质在手性空腔中的空间适应性很可能是手性识别的关键。