Porphyrin/Quinoidal-Bithiophene-Based Macrocycles and Their Dications: Template-Free Synthesis and Global Aromaticity

We report the template-free synthesis and characterization of a new type of porphyrin/quinoidal-bithiophene-based conjugated macrocycle. X-ray crystallographic analysis of the dimer ( 2MC ) revealed a cyclophane-like geometry with large dihedral angles between the porphyrin and the neighboring thiophene rings, and NMR measurements and theoretical calculations confirmed a localized aromatic character of the porphyrin/thiophene rings and quinoidal character of the bithiophene linkers. Restricted rotation of the thiophene rings linked to the porphyrin unit was observed by variable-temperature NMR measurements. The dication ( 2MC²⁺ ) adopts a chair-shaped conformation to facilitate π-electron delocalization around the whole macrocycle. As a result, the molecule is globally aromatic, with a dominant 54 π conjugation pathway. The trimer ( 3MC ) also shows localized aromatic character of porphyrin rings and conformational flexibility, but its dication ( 3MC²⁺ ) is rigid and globally aromatic with a dominant 82 π conjugation pathway.     

Self-Assembly of Highly Stable Zirconium(IV) Coordination Cages with Aggregation Induced Emission Molecular Rotors for Live-Cell Imaging

The self-assembly of highly stable zirconium(IV)-based coordination cages with aggregation induced emission (AIE) molecular rotors for in vitro bio-imaging is reported. The two coordination cages, NUS-100 and NUS-101, are assembled from the highly stable trinuclear zirconium vertices and two flexible carboxyl-decorated tetraphenylethylene (TPE) spacers. Extensive experimental and theoretical results show that the emissive intensity of the coordination cages can be controlled by restricting the dynamics of AIE-active molecular rotors though multiple external stimuli. Because the two coordination cages have excellent chemical stability in aqueous solutions (pH stability: 2–10) and impressive AIE characteristics contributed by the molecular rotors, they can be employed as novel biological fluorescent probes for in vitro live-cell imaging.     

“Self-Lockable” Liquid Crystalline Diels–Alder Dynamic Network Actuators with Room Temperature Programmability and Solution Reprocessability

Novel main-chain liquid crystalline Diels—Alder dynamic networks (LCDANs) were prepared that exhibit unprecedented ease for actuator programming and reprocessing compared to existing liquid crystalline network (LCN) systems. Following cooling from 125 °C, LCDANs are deformed with aligned mesogens self-locked at room temperature by slowly formed Diels–Alder (DA) bonds, which allows for the formation of solid 3D actuators capable of reversible shape change, and strip walker and wheel-capable light-driven locomotion upon either thermally or optically induced order–disorder phase transition. Any actuator can readily be erased at 125 °C and reprogrammed into a new one under ambient conditions. Moreover, LCDANs can be processed directly from melt (for example, fiber drawing) and from solution (for example, casting tubular actuators), which cannot be achieved with LCNs using exchangeable covalent bonds. The combined attributes of LCDANs offer significant progress toward developing easily programmable/processable LCN actuators.     

石墨相氮化碳可见光下活化过一硫酸盐氧化降解光惰性邻苯二甲酸二甲酯的机理研究（英文）

近几年过一硫酸盐(PMS)活化技术备受关注,其中利用太阳能活化PMS具有可持续和环保的优势,但PMS本身不吸收可见光.因此,本文提出利用具有可见光响应的石墨相氮化碳(g-C3N4)激发产生光电子进而活化PMS.首先利用三聚氰胺前驱体通过热缩聚法制备g-C3N4,通过X射线衍射(XRD)、傅里叶变换红外光谱(FT-IR)、紫外-可见光漫反射(UV-Vis)、荧光光谱(PL)、透射电镜(TEM)、N2吸附脱附测试(BET)、电化学等一系列方法对g-C3N4进行表征,研究其表面性质及光学性能.结果显示, g-C3N4具有典型的片层结构和可见光活性,禁带宽度为2.7 e V.本文选取光惰性的内分泌干扰物邻苯二甲酸二甲酯(DMP)为目标污染物,系统地研究了其降解动力学和降解机理.研究发现,在短波紫外光(254和300nm)照射下,直接光解和·OH参与的反应机理能实现DMP的光降解,而在可见光照射下g-C3N4介导的光催化过程不能使DMP分解;但当添加PMS时,体系主导自由基由·O2–转化为SO4·–和·OH,从而实现DMP的有效降解和矿化.研究还发现,高浓度的PMS和高剂量的g-C3N4均可以提高PMS的活化量和相应的DMP降解效率,但提高催化剂剂量的方式能更充分的利用PMS.尽管高浓度的DMP阻碍了PMS和光催化剂g-C3N4的有效接触,但可以提高PMS的利用率.当p H低于零电荷点(5.4)时, DMP的降解效率较高.此外,使用两种淬灭剂(乙醇和叔丁醇)与DMP进行竞争性实验,结合电子自旋共振检测,表明SO4·–和·OH都是体系主要的自由基.此外,还对g-C3N4的可持续性能进行考察,四次循环实验结果显示,该催化剂具有良好的可重复利用性.对DMP降解进行总有机碳测定,发现降低了19%.最后,利用液相色谱质谱联用对DMP降解产物进行定性定量分析,发现DMP主要通过SO4·–和·OH对苯环的攻击以及脂肪族链的氧化断键这两种途径进行降解.综上可见,利用可见光激发g-C3N4产生的光电子能有效活化PMS降解顽固型有机污染物,可为实现太阳能活化PMS技术提供有力的技术参考.     

多功能Fe3O4@SiO2 Janus颗粒

采用溶剂热法和溶胶-凝胶法制备了顺磁性Fe₃O₄@SiO₂颗粒,以Pickering乳液界面保护法实现颗粒表面分区获得Fe₃O₄@SiO₂ Janus颗粒,进一步选区复合生长Pt或Ag纳米颗粒制备Fe₃O₄@SiO₂-Pt和Fe₃O₄@SiO₂-Ag Janus颗粒.Fe₃O₄@SiO₂-Pt Janus颗粒的Pt一侧进行催化过氧化氢的反应,具有自驱动功能.因其顺磁性和两亲性,Fe₃O₄@SiO₂-Ag Janus颗粒能够作为磁响应颗粒乳化剂稳定油水乳液,并将Ag的催化功能引入界面.     

Methanol synthesis from CO2: a DFT investigation on Zn-promoted Cu catalyst

Research on Chemical Intermediates - The reaction steps during methanol synthesis from CO2/H2 are influenced by the type of catalysts such as pure Cu and Zn-decorated Cu. In this study, density...     

Remote regioselective organocatalytic asymmetric [3+2] cycloaddition of N-2,2,2-trifluoroethyl isatin ketimines with cyclic 2,4-dienones

An organocatalytic asymmetric [3+2] cycloaddition of trifluoromethyl-containing azomethine ylides with cyclic 2,4-dienones was developed.The process enables efficient incorporation of CF3 groups into functionalized spiro [pyrro lid in-3,2'-oxindoles] in high yields with good to excellent enantio-and diastereoselectivities.     

有机电极材料固定化策略

有机电极材料因其理论比容量高、低成本、环境友好以及分子结构可设计性强等特点,有望成为下一代可持续和多功能能量储存设备的有效电极材料。然而,根据“相似相溶”原理,该类材料极易溶解在有机电解液中,导致电池容量衰减快、循环稳定性和倍率性能也较差。目前已有许多研究致力于通过“固定化”过程解决有机电极材料的溶解问题。本综述针对有机电极材料的固定化策略展开评述,介绍了有机电极材料的固定化机理,以及各种固定化策略在不同种类有机电极材料中所起的作用,指出了有机电极材料面临的挑战,并对未来的研究和改进方向进行展望。     

Recent Advance of Tellurium for Biomedical Applications

Tellurium(Te) nanomaterials have aroused a wide interest in semiconductor, thermoelectric, piezoelectric, as well as biomedical applications. The last decades of reports indicated a major nanostructure of one-dimensional (1D) Te on account of its inherent structural anisotropy. Two-dimenional(2D) Te has been newly developed and drawn a lot of interests recently. This review presents the intrinsic biological potential of Te-based nanomaterials and summarizes their up-to-date advance in phototherapy and reactive oxygen species(ROS)-related applications in the biomedical field.