Pt/CrCeAlO催化剂对二氯甲烷的催化氧化性能

催化氧化是消除挥发性有机废气的有效手段,而二氯甲烷是含氯有机废气的代表性化合物。采用沉淀法制备了不同CrO_x含量的CrCeAlO催化剂,并用浸渍法制备了Pt/CrCeAlO催化剂,将其用于二氯甲烷催化氧化。结果表明,催化剂均表现出较好的活性,Cr_0.03Ce_0.05Al_0.95O₂催化剂在390 ℃时即可完全氧化二氯甲烷。而负载Pt后的催化剂活性明显提高,2.0Pt/Cr_0.03Ce_0.05Al₀.₉₅O₂催化剂表现出最好的活性,在340 ℃条件下,转化率即达100%。采用XRD、SEM、TEM、H₂-TPR和NH3-TPD对催化剂进行表征,表明催化剂的活性主要受其表面酸性和氧化还原性的影响,表面酸性位提供二氯甲烷化学吸附位,而催化剂表面氧化还原性则有利于反应中氧物种的活化。催化剂中添加Pt后,由于Pt、CeO₂ 和 CrO_x物种间的相互作用而增强了催化剂的氧化还原性,从而进一步促进了反应活性的提高。     

Anticancer Ruthenium(III) Complex KP1019 Interferes with ATP‐Dependent Ca2+ Translocation by Sarco‐Endoplasmic Reticulum Ca2+‐ATPase (SERCA)

Sarco‐endoplasmic reticulum Ca²⁺‐ATPase (SERCA), a P‐type ATPase that sustains Ca²⁺ transport and plays a major role in intracellular Ca²⁺ homeostasis, represents a therapeutic target for cancer therapy. Here, we investigated whether ruthenium‐based anticancer drugs, namely KP1019 (indazolium [trans‐tetrachlorobis(1H‐indazole)ruthenate(III)]), NAMI‐A (imidazolium [trans‐tetrachloro(1H‐imidazole)(S‐dimethylsulfoxide)ruthenate(III)]) and RAPTA‐C ([Ru(η⁶‐p‐cymene)dichloro(1,3,5‐triaza‐7‐phosphaadamantane)]), and cisplatin (cis‐diammineplatinum(II) dichloride) might act as inhibitors of SERCA. Charge displacement by SERCA adsorbed on a solid‐supported membrane was measured after ATP or Ca²⁺ concentration jumps. Our results show that KP1019, in contrast to the other metal compounds, is able to interfere with ATP‐dependent translocation of Ca²⁺ ions. An IC₅₀ value of 1 μM was determined for inhibition of calcium translocation by KP1019. Conversely, it appears that KP1019 does not significantly affect Ca²⁺ binding to the ATPase from the cytoplasmic side. Inhibition of SERCA at pharmacologically relevant concentrations may represent a crucial aspect in the overall pharmacological and toxicological profile of KP1019.     

某预应力混凝土空心板桥汽车静载试验分析

通过对某预应力混凝土空心板简支梁桥成桥后进行汽车静载试验,对试验结果进行了整理,并与理论计算结果进行比较,从而判断该桥梁成桥后的整体结构受力性能和使用条件,为交工验收提供技术依据。     

基于能量法的简支钢梁损伤识别试验及有限元分析

针对目前梁式结构损伤识别中识别精度和实际应用方面存在的不足,以能量耗散理论为基础,对简支工字形钢梁的损伤识别进行了数值分析及试验研究。通过结构损伤时每一单元的模态应变能耗散率与损伤前、后模态应变能变化之间的关系,推导出单元损伤变量的表达形式。研究结果表明:单元损伤变量只需要利用结构损伤前、后的模态振型即可算得,在实际应用中可通过模态扩阶技术解决实测自由度与理论自由度不匹配问题;该方法可准确识别出简支钢梁损伤单元的位置,并在一定程度上表征损伤程度。     

简支梁桥铅芯橡胶支座减震特性研究

以一座4×40m简支T形梁桥为例,对常规非隔震设计的板式橡胶支座和减隔震设计的铅芯橡胶支座(LRB)进行对比分析,比较了2种支座设计下桥梁结构的动力特性以及采用隔震设计后桥梁结构内力、位移响应与非隔震设计的差别。在其他条件一致前提下,研究了铅芯橡胶支座的力学参数对减隔震效果的影响。研究结果表明:铅芯橡胶支座较板式橡胶支座设计的桥梁可以延长结构的周期;设计的铅芯橡胶支座具有明显的减震效果,铅芯橡胶支座可以大幅度减小各墩墩底剪力及墩底弯矩,各墩所受地震力重新合理分配且受力趋于平衡;同时在减隔震设计中,只考虑增大铅芯橡胶支座的型号反而会给桥梁下部结构带来不利的影响。     

框支密肋复合墙结构模型振动台试验研究

对1/6缩尺框支密肋复合墙结构模型进行振动台试验,研究结构模型经历弹性阶段、开裂直至破坏的不同阶段动力特性及反应。以El Centro波、Taft波、人工波为输入地震波,分别对设防烈度7度及8度多遇、基本、罕遇、超罕遇地震作用进行试验,研究模型结构在各阶段地震作用下加速度、位移、应变反应及破坏形式、破坏机理。试验结果表明,框支密肋复合墙结构转换层破坏模式为剪切型破坏,塑性变形主要集中在转换层;框支密肋复合墙结构各层绝对加速度响应主要取决于前两阶振型,高阶振型影响较小,其中第一阶振型起绝对控制作用。     

An Enantioselective Recyclable Polystyrene‐Supported Threonine‐Derived Organocatalyst for Aldol Reactions

A series of primary amino acids covalently supported onto polystyrene through alkyne–azide cycloaddition reactions has been synthesized and evaluated as catalysts in asymmetric aldol reactions. A polymer‐supported threonine behaves as an easily recyclable, highly reactive and stereoselective (up to 99% ee) catalyst in the aldol reaction of both cyclic and acyclic ketone donors with aromatic aldehydes in aqueous environments. While cyclic ketones react with anti diastereoselectivity, syn adducts are predominantly obtained with acyclic substrates. The heterogenized threonine catalyst has been used for the sequential synthesis of a small library of enantiopure aldol products.

     

Atomically precise cluster catalysis towards quantum controlled catalysts

Catalysis of atomically precise clusters supported on a substrate is reviewed in relation to the type of reactions. The catalytic activity of supported clusters has generally been discussed in terms of electronic structure. Several lines of evidence have indicated that the electronic structure of clusters and the geometry of clusters on a support, including the accompanying cluster-support interaction, are strongly correlated with catalytic activity. The electronic states of small clusters would be easily affected by cluster–support interactions. Several studies have suggested that it is possible to tune the electronic structure through atomic control of the cluster size. It is promising to tune not only the number of cluster atoms, but also the hybridization between the electronic states of the adsorbed reactant molecules and clusters in order to realize a quantum-controlled catalyst.     

Modification of the structural and electrical properties of graphene layers by Pt adsorbates

The properties of graphene are strongly affected by metal adsorbates and clusters on graphene. Here, we study the effect of a thin layer of platinum (Pt) metal on exfoliated single, bi- and trilayer graphene and on chemical vapor deposition-grown single-layer graphene by using Raman spectroscopy and transport measurements. The Raman spectra and transport measurements show that Pt affects the structure as well as the electronic properties of graphene. The shift of peak frequencies, intensities and widths of the Raman bands were analyzed after the deposition of Pt with different thicknesses (1, 3, 5 nm) on the graphene. The shifts in the G and 2D peak positions of the Raman spectra indicate the n-type doping effect by the Pt metal. The doping effect was also confirmed by gate-voltage dependent resistivity measurements. The doping effect by the Pt metal is stable under ambient conditions, and the doping intensity increases with the increasing Pt deposition without inducing a severe degradation of the charge carrier mobility.     

Polymer‐Based Stimuli‐Responsive Recyclable Catalytic Systems for Organic Synthesis

The introduction of stimuli‐responsive polymers into the study of organic catalysis leads to the generation of a new kind of polymer‐based stimuli‐responsive recyclable catalytic system. Owing to their reversible switching properties in response to external stimuli, these systems are capable of improving the mass transports of reactants/products in aqueous solution, modulating the chemical reaction rates, and switching the catalytic process on and off. Furthermore, their stimuli‐responsive properties facilitate the separation and recovery of the active catalysts from the reaction mixtures. As a fascinating approach of the controllable catalysis, these stimuli‐responsive catalytic systems including thermoresponsive, pH‐responsive, chemo‐mechano‐chemical, ionic strength‐responsive, and dual‐responsive, are reviewed in terms of their nanoreactors and mechanisms.