Activation of Au–Ag Plasmonic Bimetallic Nanocatalysts with Cold Plasma: The Role of Loading Sequence of Plasmonic Metals and Discharge Atmosphere

The activation of Au–Ag plasmonic bimetallic nanocatalyst can make the nanocatalyst exhibit superior visible-light (VL) photocatalytic activity. An efficient activation of Au–Ag nanocatalyst by cold plasma requires the restructuring of Au and Ag species over catalyst surface to form Au–Ag alloy nanoparticles while suppressing agglomeration of the nanoparticles. We here report that the loading sequence of Au and Ag components on titanium dioxide (TiO₂) support during catalyst preparation and discharge atmosphere play important roles in the plasma activation. Preparation of AuAg/TiO₂ nanocatalyst by depositing Ag and Au in sequence could avoid the undesired loss of Ag component, and ensure an effective restructuring of Au and Ag species in O₂ plasma activation. Compared with the reductive (H₂) and inert (Ar and N₂) plasmas, discharge in oxidative O₂ establishes Coulomb field with the negatively charged species over catalyst surface and enable the restructuring and intimate interaction of Au and Ag species. The catalyst characterization and density functional theory calculations suggest that O₂ plasma endows AuAg/TiO₂ nanocatalyst with large numbers of Au–Ag alloy nanoparticles, small size of plasmonic nanoparticles, high density of coordinatively unsaturated sites, and high content of surface oxygen species in the activation, which facilitates the adsorption and activation of O₂, and thus CO oxidation reaction under VL irradiation.

     

香豆素343敏化TiO2纳米粒子光致电子转移的荧光和拉曼光谱

通过对香豆素343(C343)染料敏化TiO₂纳米粒子光致电子转移的荧光和拉曼光谱特性的研究表明,C343染料敏化TiO₂纳米粒子稳态吸收光谱和稳态荧光光谱的红移归因于从被吸附的C343染料分子激发态和C343/TiO₂复合物到TiO₂纳米粒子导带的光致电子转移. 由时间分辨荧光光谱确定了C343染料敏化TiO₂纳米粒子的逆向电子转移速率常数为τ₁=31 ps. C343 染料敏化TiO₂纳米粒子体系拉曼光谱的研究表明, 被吸附在界面处的染料分子主链碳键的伸缩振动和碳环的呼吸运动的振动模式对超快界面光致电子转移有着重要的促进作用.     

磺化杯芳烃修饰的金纳米粒的合成及其对多环芳烃的比色检测

通过偶联修饰的方法合成了水溶性磺化杯芳烃修饰的金纳米粒, 并研了其对多环芳烃的比色检测. 结果表明, 磺化杯芳烃修饰的金纳米粒对蒽具有良好的识别选择性. 该比色探针对蒽的检测限可达到2×10-6 mol/L. 这种比色传感器能够实现现场原位检测.     

基于结构的新型CDK7抑制剂的设计、合成及其抗肿瘤活性

根据细胞周期依赖性激酶7(CDK7)的蛋白结构, 利用Discovery Studio 2.1程序包中的LigandFit模块建立了CDK7抑制剂的分子对接模型, 采用受试者工作特征曲线(ROC)方法选择LigScore2为最佳打分函数(ROC曲线下的面积为0.95), 并验证了该模型的准确性. 利用该模型对设计的化合物与CDK7蛋白进行对接分析, 得到了2个打分最高的化合物16、17, 进而通过13步的合成路线, 以中等至高的收率得到目标化合物, 并测定其体外抗肿瘤活性. 结果表明, 所合成的化合物对急性前髓细胞性白血病细胞(HL60)、鼻咽癌细胞(KB)、肝肿瘤细胞(SMMC-7721)、结肠腺癌细胞(HCT-116)、肺癌细胞(A549)细胞株均有抑制作用(IC50值为0.84-19.70 μmol·L-1), 其中化合物16对HL60细胞株的IC50值最低, 为0.84 μmol·L-1.     

The effect of interfacial energy anisotropy on planar interface instability in a succinonitrile alloy under a small temperature gradient

The morphological stability of a planar interface with different crystallographic orientations is studied under a small positive temperature gradient using a transparent model alloy of succinonitrile.Novel experimental apparatus is constructed to provide a temperature gradient of about 0.37 K/mm.Under this small temperature gradient,the planar interface instability depends largely on the crystallographic orientation.It is shown experimentally that the effect of interfacial energy anisotropy on planar interface stability cannot be neglected even in a small temperature gradient system.Higher interfacial energy anisotropy leads the planar interface to become more unstable,which is different from the stabilizing effect of the interfacial energy on the planar interface.The experimental results are in agreement with previous theoretical calculations and phase field simulations.     

[Lu(POA)_3(phen)]_n的合成及晶体结构

稀土与羧酸多元配合物具有多种形式的分子构型及配体多面体 ,结构形式多种多样 [1]。它们在光、电、磁、萃取、分离、杀菌剂等很多方面有广泛的应用前景,一直为国内外学者所关 注 [2,3]。稀土和芳香族羧酸能形成聚合网络及链状结构 [4],本文报道了新的链状化合物 [Lu(POA)3(phen)]n的合成与结构,对于丰富稀土配合物不失为一项有意义的工作。 1实验部分 1.1配合物合成 称取氧化镥（ Lu2O3)0.1mmol,加入稍过量的 6mol· L－ 1 HCl使之溶解,在 80～ 90℃下蒸发至干,加入 5mL水, 5mL乙醇;苯氧乙酸 0.3mmol用 5mL 95％乙醇溶解,以 2…     

Metal-free C3-alkoxycarbonylation of quinoxalin-2(1H)-ones with carbazates as ecofriendly ester sources

Quinoxaline-3-carboxylates and analogues are prevalent key structural motifs in bioactive natural products and synthetic drugs.However, the practical protocol for preparation of these motifs from simple raw materials under mild conditions remains rare. In this article, we report a facile protocol for the efficient preparation of various quinoxaline-3-carbonyl compounds(30 examples,63%–92%) through oxidation coupling of quinoxalin-2(1H)-ones with readily available carbazates(or acyl hydrazines) in the presence of K_2S_2O_8 as an oxidant in metal-and base-free conditions. When tert-butyl carbazate was used as the coupling reagent,the decarboxylation product 3-(tert-butyl)-1-methylquinoxalin-2(1H)-one was obtained. The application of this process into a gram-scale synthesis can be easily accomplished. Mechanistic investigations reveal that the functionalization of quinoxalin-2(1H)-ones via a free-radical pathway.     

Evaluation of chemical labeling strategies for monitoring HCV RNA using vibrational microscopy

Raman and coherent anti-Stokes Raman scattering (CARS) microscopies have the potential to aid in detailed longitudinal studies of RNA localization. Here, we evaluate the use of carbon-deuterium and benzonitrile functional group labels as contrast agents for vibrational imaging of hepatitis C virus (HCV) replicon RNA. Dynamic light scattering and atomic force microscopy were used to evaluate the structural consequences of altering HCV subgenomic replicon RNA. Modification with benzonitrile labels caused the replicon RNA tertiary structure to partially unfold. Conversely, deuterium-modified replicon RNA was structurally similar to unmodified replicon RNA. Furthermore, the deuterated replicon RNA provided promising vibrational contrast in Raman imaging experiments. The functional effect of modifying subgenomic HCV replicon RNA was evaluated using the luciferase gene as a genetic reporter of translation. Benzonitrile labeling of the replicon RNA prevented translation in cell-based luciferase assays, while the deuterated replicon RNA retained both translation and replication competency. Thus, while the scattering cross-section for benzonitrile labels was higher, only carbon-deuterium labels proved to be non-perturbative to the function of HCV replicon RNA.