Hole Migration in Telomere-Based Oligonucleotide Anions and G-Quadruplexes

Vacuum ultraviolet photoionization of a gas-phase oligonucleotide anion leads to the formation of a valence hole. This hole migrates towards an energetically favorable site where it can weaken bonds and ultimately lead to bond cleavage. We have studied Vacuum UV photoionization of deprotonated oligonucleotides containing the human telomere sequence dTTAGGG and G-quadruplex structures consisting of four dTGGGGT single strands, stabilized by NH₄⁺ counter ions. The oligonucleotide and G-quadruplex anions were confined in a radiofrequency ion trap, interfaced with a synchrotron beamline and the photofragmentation was studied using time-of-flight mass spectrometry. Oligonucleotide 12-mers containing the 5'-TTAGGG sequence were found to predominantly break in the GGG region, whereas no selective bond cleavage region was observed for the reversed 5'-GGGATT sequence. For G-quadruplex structures, fragmentation was quenched and mostly non-dissociative single and double electron removal was observed.     

金属卤化物钙钛矿光催化的研究进展

太阳能驱动光催化反应降解污染物、制备化学燃料或其他高附加值产品是绿色化学和可再生能源研究的重要方向.近年来,在传统的金属氧化物半导体材料之外,金属卤化物钙钛矿类化合物凭借其优异的光电特性也被逐步应用于高效光催化反应中.这篇文章综述了以铅卤钙钛矿为主的金属卤化物钙钛矿材料近年来在光催化领域的研究进展,总结了金属卤化物钙钛矿材料在光（电）催化产氢、CO₂还原反应和有机物高附加值转化反应中的应用与反应机制及其关键挑战,最后展望了高效稳定的金属卤化物钙钛矿光催化剂的发展方向和前景.     

BiOCl/蒙脱土复合光催化剂的制备及其光催化活性

为优化BiOCl光催化剂的结构,改善其对有机污染物的吸附性能,进而提高光催化反应活性,采用超声辅助化学沉淀法制备了BiOCl/蒙脱土(MMT)复合光催化剂,并考察了MMT质量分数(w(MMT))对复合光催化剂结构及光催化反应活性的影响。 X射线粉末衍射(XRD)、扫描电子显微镜(SEM)、傅里叶红外光谱(FTIR)和紫外-可见漫反射光谱(DRS)等的表征结果表明,所得催化剂呈微球状结构,禁带宽度为3.24 eV。 随着w(MMT)的增加,催化剂的微球状结构逐渐被破坏,但带隙能未发生明显变化。 以8-羟基喹啉为目标物考察了复合催化剂的吸附及光催化反应活性。 结果表明,随着w(MMT)增加,催化剂对8-羟基喹啉的吸附和光催化氧化活性逐渐增加,这可归因于与MMT的复合增大了比表面积并降低了光生载流子复合效率。 当w(MMT)为15%时,催化剂的吸附及光催化性能达到最佳,光照50 min后,8-羟基喹啉的降解率达到85.6%,矿化率达到51.0%。 光生空穴和超氧自由基负离子为主要的氧化活性物种。 复合催化剂还可高效降解邻苯二酚和对氨基苯甲酸。 同时,复合光催化剂表现出较强的化学稳定性,表明其具有较强的实际应用价值,可用于处理含有机酚类污染物的工业废水。     

低相对分子质量有机酸对α-FeO(OH)吸附As(Ⅲ)的影响

制备并表征了α-FeO(OH),探究了4种低相对分子质量有机酸(LMW)对α-FeO(OH)吸附As(Ⅲ)的影响,并阐明了机理。 单一和混合LMW对α-FeO(OH)吸附As(Ⅲ)均有抑制作用,4种LMW的影响大小顺序为:草酸(OA)>柠檬酸(CA)>乳酸(LA)、水杨酸(SA)。 混合LMW的影响为:OA会加剧CA对α-FeO(OH)吸附As(Ⅲ)的影响,而SA几乎不起作用。 当ρ(As(Ⅲ))较低,LMW通过与α-FeO(OH)的静电引力、与α-FeO(OH)表面的铁离子形成配合物、生成沉淀从而影响α-FeO(OH)对As(Ⅲ)的吸附;当ρ(As(Ⅲ))较高,LMW还通过阻碍As(Ⅲ)在α-FeO(OH)上的扩散和沉淀作用产生影响。 实验结果为土壤中As(Ⅲ)的迁移转化、污染治理提供技术支撑。     

基于次血红素六肽的过氧化氢和葡萄糖灵敏比色方法

采用次血红素六肽(DhHP-6)催化H₂O₂氧化4-氨基安替吡啉-氯代苯酚显色体系,建立了测定H₂O₂和葡萄糖的方法。 研究了pH值、底物浓度和DhHP-6浓度对实验的影响,检测了比色方法的反应线性、稳定性、相关性和回收率。 在最佳反应条件下,DhHP-6在不同时间及温度条件下,活性要优于过氧化物酶(POD);DhHP-6催化H₂O₂ 的米氏常数(K_m)和最大反应速率(v_max)分别为0.171 mmo/L和4.22×10^-6 mol/s;H₂O₂响应的线性范围为0.39~25.0 mmol/L;高、中、低 3水平测定的变异系数(CV)和加标回收率分别在1.29%~2.16%和94.5%~101.1%之间;与葡萄糖商品试剂盒比较相关系数R²=0.9946;36例血液样品中的葡萄糖浓度在4.26~17.48 mmol/L之间。 与葡萄糖检测商品试剂盒之间的两组数据经统计差异不显著(P>0.05)。 该方法是一种简单、廉价、方便、灵敏的比色测定方法。     

生物化学中酶促"不可逆"反应及其相关问题辨析

在生物化学教学和研究中,一些酶促反应被归类为不可逆反应。然而,此处的"不可逆"与物理化学中的"不可逆"有所不同,这一表述本身常导致学生的困惑。不仅如此,"不可逆"的实际含义及其衍生的观念可能进一步使学生产生很多对基本生化反应过程的严重误解。本文以物理化学所定义的"不可逆"为准,重新讨论生物化学中所指"不可逆"的准确含义,并举例讨论了包括"速控步""限速酶""高能磷酸键"在内的若干因生物化学中"不可逆"的不准确定义造成的认知误区。     

多孔硅/TiO2纳米线光阳极的制备及其光电催化性能

使用金属辅助化学刻蚀(MACE)法与水热法,改变贵金属粒子的刻蚀时间,制备不同n型多孔硅/TiO_2纳米线光阳极。通过扫描电镜(SEM)和X射线衍射仪(XRD)对光阳极样品进行表征,结果显示多孔硅宏孔的尺寸会随着刻蚀时间延长而增大,由0.1μm变化到0.4μm,多孔硅表面长有TiO_2纳米线为金红石相及少量锐钛矿相。测试结果显示刻蚀35 min的多孔硅/TiO_2样品具有最高的减反射率,在模拟太阳光下具有较高的光电流(光电流密度)活性,且在1.5 V外加偏压下具有最高的光电催化活性。这是由于刻蚀35 min的多孔硅基底具有优异的减反射性能,同时多孔硅与Ti O_2纳米线复合形成光阳极之后具有异质结效应和窗口效应,使得多孔硅/TiO_2纳米线光阳极具有优异光电化学性能。     

A Computational Study on Iridium‐Catalyzed Production of Acetic Acid from Ethanol and Water Solution

The mechanism for the production of acetic acid from ethanol and water mixture catalyzed by iridium catalyst has been theoretically investigated. The cooperation of the iridium center and bpyO ligand is highlighted, which plays an important role in the catalytic activity. The hydrogen release from the iridium center is the rate‐determining step, with an energy barrier of 22.5 kcal/mol. The electronic structure analysis suggests electron‐donating substituents could decrease the energy barrier.     

Design,Synthesis and Antifungal Activity of Benzofuran and Its Analogues

Benzofuran has antifungal activity as the inhibitor of N‐myristoyltransferase. Twenty‐nine novel benzofuran‐semicarbazide hybrids were designed and synthesized by principle of drug combinationatory. On this basis, the benzofuran ring was simplified to a resorcinol structure, and sixteen novel 1,3‐dialkoxybenzene‐semicarbazide hybrids were designed and synthesized. All structures of the target compounds were characterized by HRMS and NMR. The in vitro antifungal activity of target compounds was evaluated using the microdilution broth method against eight strains of pathogenic fungi with fluconazole as positive control. According to the results of the target compounds, structure‐activity relationship (SAR) is summarized. The inhibitory activity against the tested strains of simplified compounds ( K01 — K16 ) has different levels improvement compared with compounds Z01 — Z29 . K01 — K16 showed significant antifungal activities against A. fumigatus, C. kruseii, and sensitive C. albicans 5314. Notably, compounds Z20 , Z22 , K10 , K11 and K16 also displayed different activities against two fluconazole‐resistance strains that were isolated from AIDS patients. The minimal inhibitory concentration (MIC) values against fluconazole‐resistant strains were in the range of 2—8 μg/mL and 4—32μg/mL, respectively. Furthermore, molecular docking was performed to investigate the binding affinities and interaction modes between the target compound and N‐myristoyltransferase.