Visible-Light-Driven Halogen Bond Donor Based Molecular Switches: From Reversible Unwinding to Handedness Inversion in Self-Organized Soft Helical Superstructures

Visible-light-driven molecular switches endowing reversible modulation of the functionalities of self-organized soft materials are currently highly sought after for fundamental scientific studies and technological applications. Reported herein are the design and synthesis of two novel halogen bond donor based chiral molecular switches that exhibit reversible photoisomerization upon exposure to visible light of different wavelengths. These chiral molecular switches induce photoresponsive helical superstructures, that is, cholesteric liquid crystals, when doped into the commercially available room-temperature achiral liquid crystal host 5CB, which also acts as a halogen-bond acceptor. The induced helical superstructure containing the molecular switch with terminal iodo atoms exhibits visible-light-driven reversible unwinding, that is, a cholesteric–nematic phase transition. Interestingly, the molecular switch with terminal bromo atoms confers reversible handedness inversion to the helical superstructure upon irradiation with visible light of different wavelengths. This visible-light-driven, reversible handedness inversion, enabled by a halogen bond donor molecular switch, is unprecedented.     

Hierarchically Ordered Porous Carbon with Atomically Dispersed FeN4 for Ultraefficient Oxygen Reduction Reaction in Proton-Exchange Membrane Fuel Cells

The low catalytic activity and poor mass transport capacity of platinum group metal free (PGM-free) catalysts seriously restrict the application of proton-exchange membrane fuel cells (PEMFCs). Catalysts derived from Fe-doped ZIF-8 could in theory be as active as Pt/C thanks to the high intrinsic activity of FeN₄; however, the micropores fail to meet rapid mass transfer. Herein, an ordered hierarchical porous structure is introduced into Fe-doped ZIF-8 single crystals, which were subsequently carbonized to obtain an FeN₄-doped hierarchical ordered porous carbon (FeN₄/HOPC) skeleton. The optimal catalyst FeN₄/HOPC-c-1000 shows excellent performance with a half-wave potential of 0.80 V in 0.5 m H₂SO₄ solution, only 20 mV lower than that of commercial Pt/C (0.82 V). In a real PEMFC, FeN₄/HOPC-c-1000 exhibits significantly enhanced current density and power density relative to FeN₄/C, which does not have an optimized pore structure, implying an efficient utilization of the active sites and enhanced mass transfer to promote the oxygen reduction reaction (ORR).     

An Activatable Polymeric Reporter for Near-Infrared Fluorescent and Photoacoustic Imaging of Invasive Cancer

Discriminative detection of invasive and noninvasive breast cancers is crucial for their effective treatment and prognosis. However, activatable probes able to do so in vivo are rare. Herein, we report an activatable polymeric reporter (P-Dex) that specifically turns on near-infrared (NIR) fluorescent and photoacoustic (PA) signals in response to the urokinase-type plasminogen activator (uPA) overexpressed in invasive breast cancer. P-Dex has a renal-clearable dextran backbone that is linked with a NIR dye caged with an uPA-cleavable peptide substrate. Such a molecular design allows P-Dex to passively target tumors, activate NIR fluorescence and PA signals to effectively distinguish invasive MDA-MB-231 breast cancer from noninvasive MCF-7 breast cancer, and ultimately undergo renal clearance to minimize the toxicity potential. Thus, this polymeric reporter holds great promise for the early detection of malignant breast cancer.     

单层类水滑石纳米片的可控合成及规模生产展望

水滑石(LDHs)是一种阴离子黏土材料,由于其主体层板厚度的可调性,使其在光/电催化、电池、超级电容器、传感器以及生物医药等领域都具有广泛应用。降低层厚至单层可使材料的物理化学性质发生根本改变,从而优化催化性能。近期研究表明,利用自上而下,自下而上的方法,可以实现单层LDHs类材料的合成,但是受限于产量(g级)以及成本设备等问题,目前规模化制备高质量单层LDHs类材料还没有工业案例。成核晶化隔离法是目前唯一规模化合成纳米LDHs的工业化方法,具有成本低,产量可吨级放大等优点。本综述从合成方法、表征手段、应用三个角度讨论了单层及超薄LDHs的精准调控,详细论述了近期关于单层及超薄LDHs合成突破以及LDHs的规模化生产进展,并对其性能进行了总结,为后续设计高性能单层LDHs提供思路。     

二维纳米片层孔洞化策略及组装材料在超级电容器中的应用

功率密度高、倍率性能优异和循环性能好等特性使得超级电容器在储能领域显示了巨大的应用前景。尽管二维层状材料剥离形成的纳米片层不仅可为电化学反应提供独特的纳米级反应空间,而且由其组装的层状纳米电极材料具有化学和结构上的氧化还原可逆性及纳米片层水平方向上离子或电子快速传输通道。但是,纳米片层组装电极材料在纳米片层垂直方向上离子或电子传输存在障碍,对于超级电容器功率密度和能量密度的提高及实现快速能量储存非常不利。因此,如何通过改善离子或电子的快速传输,实现超级电容器大功率密度下的高能量密度是超级电容器电极材料发展的方向之一。本文主要综述了二维层状材料剥离成纳米片层,纳米片层孔洞化策略及组装孔洞化材料在超级电容器电极材料中的应用。纳米层孔洞化技术是改善层状电极材料在纳米片层垂直方向离子或电子传输的有效手段,为实现高比电容下的高倍率性能超级电容器电极材料制备提供了方法学。最后,对开发大功率密度下的高能量密度超级电容器电极材料提出了展望。     

全固态钠离子电池硫系化合物电解质

全固态钠离子电池具有资源丰富、安全性高等优势,作为未来大规模储能的重要选择而成为近年来先进二次电池前沿研究热点。钠离子硫系化合物电解质室温离子电导率高、弹性模量高、容易冷压成型,能增强电极/电解质界面接触、减小界面阻抗、缓冲电极材料在充放电过程中的应力/应变,是全固态钠离子电池的研究重点。本文对钠离子硫系化合物固态电解质的结构及性质进行了总结,讨论了硫系化合物电解质的本征特性、与电极的界面稳定性,并介绍了硫系化合物全固态钠离子电池的研究现状,最后分析了硫系化合物电解质面临的挑战及今后的发展方向。     

在线固相萃取-液相色谱-串联质谱法检测蘑菇中毒患者尿液中痕量α -鹅膏毒肽

建立了在线固相萃取-液相色谱-串联质谱（online SPE-LC-MS/MS）测定蘑菇中毒患者尿液中痕量α -鹅膏毒肽的分析方法。样品经甲酸酸化的乙腈-甲醇（5：1,v/v）沉淀蛋白质,反相液液微萃取去除样品提取液中的有机溶剂,毒素经ODS微柱（5 mm×2.1 mm,5 μm）在线SPE净化,XBridge^TM BEH C₁₈ 色谱柱（150 mm×3.0 mm,2.5 μm）分离,MS/MS测定。采用基于定量环的快速阀切换技术作为在线SPE和LC-MS/MS模块的接口,使得两个分离模块互相独立,无论是流动相还是压力,都不会互相干扰,保证了系统的稳定性;在线系统的精准净化,有效消除了后续质谱检测的基质效应,确保了尿液中痕量水平α -鹅膏毒肽的定性定量检测。尿液中α -鹅膏毒肽在0.1~50 μg/L范围内线性关系良好,相关系数（r ² ）为0.9983;检出限（LOD）为0.03 μg/L;α -鹅膏毒肽的加标（0.1、2.0和20 μg/L）平均回收率为84.3%~91.7%,相对标准偏差（RSD）为3.8%~7.2%。体内鹅膏毒肽代谢迅速,生物基质中痕量水平毒素的检测是其中毒实验室鉴定的主要难题,通过实际样品检测,证明该法操作简单,准确、灵敏;溶剂沉淀蛋白质和反相液液微萃取去除有机相和脂溶性基质的简单操作,可以作为水溶性毒素在线SPE-LC-MS/MS检测时快速且有效的配套前处理方法;基于在线SPE精准净化技术,可以实现尿液中α -鹅膏毒肽的高灵敏度测定（LOD为0.03 μg/L）,解决了中毒时患者体内痕量水平α -鹅膏毒肽定性确证的难题,部分患者α -鹅膏毒肽中毒实验室鉴定的时间可以扩展到90 h以上;同时,痕量水平的定量检测技术,可以为中毒后迅速代谢的α -鹅膏毒肽在体内的剂量反应关系研究提供可靠的技术支撑。     

手性环丙烯构建策略用于对映选择性合成偕二氟亚甲基三元环化合物

作为最小的不饱和环状分子,环丙烯独特的刚性结构和多变的反应活性吸引了化学家的研究兴趣.自1922年Demjanov[1]报道了环丙烯化合物的首例合成以来,现已发展了一系列环丙烯的合成方法.手性环丙烯的合成是通过炔烃和重氮化合物的[2+1]不对称环加成反应.根据底物的不同,这些不对称环加成反应可以分为四类:(a)末端炔烃和单取代重氮化合物的反应,(b)末端炔烃和双取代重氮化合物的反应,(c)非末端炔烃和双取代重氮化合物的反应,(d)非末端炔烃和单取代重氮化合物的反应.在这四类反应中,末端炔烃和单取代重氮化合物的不对称反应相对容易进行.1992年,Doyle和Müller等[2]报道了手性铑催化剂[Rh2(5R-MEPY)4]促进的末端炔烃和重氮醋酸酯之间的不对称环丙烯基化反应(Scheme 1a).随后各种手性催化剂包括[Rh2(OAc)-(DPTI)3][3]、Ir(salen)衍生物[4]和[Co(3,5-diMes-Chen-Phyrin)][5]等被先后报道用于末端炔烃和单取代重氮化合物的不对称[2+1]环加成反应.     

Expedient Synthesis of Ketones via N‐Heterocyclic Carbene/Nickel‐Catalyzed Redox‐Economical Coupling of Alcohols and Alkynes†

An N‐heterocyclic carbene/nickel‐catalyzed direct coupling of alcohols and internal alkynes to form α‐branched ketones has been developed. This methodology provides a new approach to afford branched ketones, which are difficult to access through the hydroacylation of simple internal alkenes with aldehydes. This redox‐neutral and redox‐economical coupling is free from any oxidative or reductive additives as well as stoichiometric byproducts. These reactions convert both benzylic and aliphatic alcohols and alkynes, two basic feedstock chemicals, into various α‐branched ketones in a single chemical step.     

Intriguing generative metabolism discovery of reactive metabolite nitroso of lapatinib and relevant structural modification

Lapatinib is required as a therapy for advanced or metastatic breast cancer. However, its reactive metabolite (RM) nitroso was implicated in idiosyncratic hepatotoxicity. Density functional theory was performed to explore the metabolism of nitroso formation. Primary hydroxylation amine is a critical intermediate to produce nitroso. Three pathways from secondary alkylamine lapatinib to primary hydroxylation amine were designed and discussed. Calculation results show that it is difficult to form primary hydroxylation amine through common proposed hydrolysis nitrone with a barrier of 36.67 kcal/mol (path A), but it is smoothly formed by paths B and C with moderate determined barriers of 15.09 kcal/mol and 16.56 kcal/mol, respectively. Subsequently, we demonstrate that the mechanism of nitroso formation from primary hydroxylation amine should be a double hydrogen atom transfer rather than the previously proposed hydrolysis primary dihydroxylation amine. The barrier of the former is obviously lower than the latter. Based on metabolism results and structure analysis, several lapatinib derivatives are designed. Molecular docking of designed compounds with epidermal growth factor receptor (EGFR) shows that they share a similar binding mode with lapatinib. In particular, 2a to 2d show similar binding energy to lapatinib. This work showed metabolism details of nitroso formation from lapatinib and its structure modification, which can enrich the metabolism of amine drugs and provide guidance for drug optimization and design.