Preparation,characterization and photocatalytic performance of noble metals (Ag,Pd, Pt,Rh) deposited on sponge-like ZnO microcuboids

Novel sponge-like ZnO microcuboids with a hierarchical structure were fabricated via an alcoholic thermal process. Then a series of noble metals (Ag, Pd, Pt, Rh) was loaded onto the microcuboids. The samples obtained were characterized by nitrogen physical adsorption, powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), UV-vis diffuse reflectance spectroscopy (DRS), and X-ray photoelectron spectroscopy (XPS). The results show that the ZnO microcuboids have a high surface area and a sponge-like hierarchical structure. Activity tests for the degradation of acid orange II dye showed that the noble metals enhanced the activity of ZnO to different extents. For loading of 0.5 wt.%, the activity enhancement decreased in the order Pd>Ag>Pt>Rh. Co-loading of Pd and Ag had a detrimental effect on activity compared to single loading. The enhanced photocatalytic performance can be attributed to an increase in the rate of separation of photogenerated e^–/h⁺ pairs induced by the noble metals.     

Re/Ga2O3/WO3/ZrO2催化剂对正己烷异构化反应的催化性能

通过浸渍法制备了系列Re/Ga2O3/WO3/ZrO|2(ReGWZ)催化剂,采用X射线衍射、氢气程序升温还原和氨气程序升温脱附等方法对催化剂进行了表征,考察了该催化剂催化正己烷异构化反应性能.结果表明,Re的引入改变了催化剂的氧化还原性能和酸中心分布,且使催化剂由单一的酸中心催化变成由酸中心与金属中心共同催化,因而正己烷异构化率和2,2-二甲基丁烷选择性显著增加.在195℃,1.0MPa,LHSV=1.0h-1和n(H2)/n(C6)=2.0的反应条件下,1.0Re/1.0GWZ催化剂上正己烷转化率、异己烷选择性和2,2-二甲基丁烷选择性分别达到84.8%,97.7%和20%,裂解产物(C5-)选择性为2.1%.150h的稳定性实验表明该催化剂性能稳定.     

Sol-gel derived S,I-codoped mesoporous TiO2 photocatalyst with high visible-light photocatalytic activity

A mesoporous S,I-codoped TiO₂ photocatalyst with high visible light photocatalytic activity was synthesized through the hydrolysis and condensation of titanium isopropoxide with thiourea and iodic acid as the precursors. The as-prepared catalysts were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), UV-vis diffuse reflectance (DRS), X-ray photoelectron spectroscopy (XPS), Fourier translation infrared spectroscopy (FT-IR), and N₂ adsorption. The results showed that the cations of S⁶⁺ and I⁵⁺ could substitute for some of the lattice titanium (Ti⁴⁺). The S,I-codoping forms the new bands above the valence band and narrows the band-gap of the TiO₂, then shifts the absorption edge from UV light region to visible light range. The activity of the catalyst was examined by photodegradation of methylene blue in an aqueous solution under visible light irradiation. The activity of the S,I-codoped catalyst is far superior to that of single S or I-doped TiO₂ counterpart. The high visible light photocatalytic activity could be attributed to the strong absorption of light, well-crystalline anatase phase, and mesoporous microstructure.     

S‐Click Reaction for Isotropic Orientation of Oxidases on Electrodes to Promote Electron Transfer at Low Potentials

Electrochemical sensors are essential for point‐of‐care testing (POCT) and wearable sensing devices. Establishing an efficient electron transfer route between redox enzymes and electrodes is key for converting enzyme‐catalyzed reactions into electrochemical signals, and for the development of robust, sensitive, and selective biosensors. We demonstrate that the site‐specific incorporation of a novel synthetic amino acid (2‐amino‐3‐(4‐mercaptophenyl)propanoic acid) into redox enzymes, followed by an S‐click reaction to wire the enzyme to the electrode, facilitates electron transfer. The fabricated biosensor demonstrated real‐time and selective monitoring of tryptophan (Trp) in blood and sweat samples, with a linear range of 0.02–0.8 mm . Further developments along this route may result in dramatic expansion of portable electrochemical sensors for diverse health‐determination molecules.     

硅藻土基吸附与光催化材料在水处理中的应用

硅藻土是一种由硅藻遗骸所形成的多孔材料,具有比表面积大、抗腐蚀性好和绿色无毒等优点。作为一种原料易得且价格低廉的吸附与催化载体材料,硅藻土在水处理方面表现出广泛的应用前景。天然硅藻土中含有不同比例的金属氧化物杂质,会降低硅藻土的孔隙率和影响其吸附及催化活性。因此,表面修饰和复合改性增强硅藻土吸附及催化性能是目前硅藻土材料应用于水处理方向的研究重点。本文从吸附和光催化原理出发,分析了不同表面修饰及复合改性方法对硅藻土结构与性能的影响,总结了硅藻土基材料在有机废水,富营养污水和重金属离子废水等污水处理方面的应用进展,并对硅藻土基吸附与光催化材料的发展和研究方向进行分析和展望。     

铜锌超氧化物歧化酶的突变与神经退行性紊乱的生物无机化学

本文简单介绍了铜锌超氧化物歧化酶的结构、功能及其相互关系,较为详细地讨论了与神经退行性紊乱,尤其是与肌萎性脊髓侧索硬化症有关的铜锌超氧化物歧化酶突变体的生物无机化学的研究进展,提出由该酶突变而引起的蛋白质局部结构变化和金属离子缺失,以及由此导致的氧化损伤和聚集作用可能是导致神经退行性紊乱的主要原因之一.     

Peptide Stapling by Crosslinking Two Amines with α-Ketoaldehydes through Diverse Modified Glyoxal-Lysine Dimer Linkers

α-Ketoaldehydes play versatile roles in the ubiquitous natural processes of protein glycation. However, leveraging the reactivity of α-ketoaldehydes for biomedical applications has been challenging. Previously, the reactivity of α-ketoaldehydes with guanidine has been harnessed to design probes for labeling Arg residues on proteins in an aqueous medium. Herein, a highly effective, broadly applicable, and operationally simple protocol for stapling native peptides by crosslinking two amino groups through diverse imidazolium linkers with various α-ketoaldehyde reagents is described. The use of hexafluoroisopropanol as a solvent facilitates rapid and clean reactions under mild conditions and enables unique selectivity for Lys over Arg. The naturally occurring GOLD/MOLD linkers have been expanded to encompass a wide range of modified glyo xal-l ysine d imer (OLD) linkers. In a proof-of-concept trial, these modular stapling reactions enabled a convenient two-round strategy to streamline the structure–activity relationship (SAR) study of the wasp venom peptide anoplin, leading to enhanced biological activities.     

药物结晶中的经典与非经典结晶路径

晶体的结晶路径分为经典结晶路径和非经典结晶路径。经典结晶路径往往涉及一些简单的化学结构,晶体的成核、生长是通过单体的依次添加实现的,经过长期研究,目前研究人员已对其有了较为深刻的理解并形成了一套相对完善的理论体系;但对于非经典的结晶路径,由于涉及复杂中间态粒子的形成和多步结晶过程,尚未获得全面、统一的理论支持。在药物结晶领域,有机分子构象自由度的引入增加了体系的复杂性,分子间弱的相互作用使得固态药物分子存在多晶型现象。由于药物的理化性质及生物利用度与其晶型息息相关,同时,药物结晶过程中出现的一些复杂中间态粒子往往会改变最终得到的药物晶型,因此迫切需要加强对药物晶体成核和生长路径的研究,以期发展能实现对药物晶体成核和生长过程主动控制的方法。本文简要综述了目前药物在溶液或熔体中结晶的经典与非经典结晶路径,包括奥斯特瓦尔德阶段定律、独立成核、交叉成核。从溶液化学的角度看,分子在浓溶液中会通过自组装形成结构合成子,成核与溶液中的生长单元、结构合成子密切相关。从分子水平上探索溶液中有关分子运动的信息、分析各体系下晶核与结构合成子之间的关系是区分两种结晶路径的关键所在,非经典结晶在药物结晶领域是机遇也是挑战。     

大环铜(Ⅱ)配合物与DNA结合的ESR及自旋捕获测定

与DNA结合前后的大环铜(Ⅱ)配合物(CuL²⁺，如图1所示)ESR谱表明CuL²⁺与DNA碱基有配位作用。以DMPO为自旋捕获剂进行的自旋捕获实验则证实了活性氧中间产物·OH的存在，在CuL²⁺的引导下导至DNA氧化损伤。     

激光引发的氯自由基与1，2-二氯乙烷的反应研究

1,2-二氯乙烷裂解反应是一个自由基链反应。在热反应中,为了克服引发自由基反应所需要的能量,反应必须在较高温度下进行。但是在光化学反应中,特别是应用了激光引发自由基,使得这一裂解反应可以在较低的温度下进行。因此利用激光引发的自由基链反应,不仅在理论上有浓厚的兴趣,并且在工业上有广阔的应用前景。Wolfrum曾详细地研究过利用准分子激光(KrF激光)裂解1,2-二氯乙烷的反应。由于1,2-二氯乙烷对KrF激光有较强的吸收,容易产生氯自由基,使整个链反应速率决定步骤由链的引发变为链的传递,而降低反应温度。因为光化学反应温度低,抑止了很多副反应,从而提高反应的选择性。