Clean,One‐Pot Synthesis of Naphthopyran Derivatives in Aqueous Media

A general and practical one‐pot synthesis of naphthopyran derivatives using hexadecyltrimethylammonium bromide (HTMAB) as catalyst (10 mol%) is described. This method provides several advantages such as neutral conditions, high yields and simple workup procedure. The catalyst is low cost, facile, active, environmentally friendly, and reusable. In addition, water is chosen as a green solvent.     

Asymmetric total synthesis of (+)-monocerin

A concise asymmetric total synthesis of (+)-monocerin has been accomplished. The cis-fused furobenzopyranone of monocerin was efficiently constructed via a Lewis acid-mediated stereoselective cyclization of 1,2,4-triols intermediate.     

Synthesis and characterization of side chain cholesteric liquid crystalline elastomers derived from chiral bisolefinic crosslinking units

In this work we prepared a nematic monomer (4′‐allyloxybiphenyl 4′‐ethoxybenzoate, M₁ ), a chiral crosslinking agent (isosorbide 4‐allyloxybenzoyl bisate, M₂ ) and a series of new side chain cholesteric liquid crystalline elastomers derived from M₁ and M₂ . The chemical structures of the monomers and polymers were confirmed by FTIR and ¹H NMR spectroscopy. The mesomorphic properties were investigated by differential scanning calorimetry, thermogravimetric analysis, polarizing optical microscopy and X‐ray diffraction. The effect of the content of the crosslinking unit on phase behaviour of the elastomers is discussed. Polymer P₁ showed a nematic phase, P₂ –P₇ showed a cholesteric phase; P₆ formed a blue Grandjean texture over a broad temperature range 145–209.6°C, with no changed on the cooling. Polymers P₄ –P₇ , with more than 6?mol?% of chiral crosslinking agent, gave rise to selective reflection. Elastomers containing less than 15?mol?% of the crosslinking units displayed elasticity, reversible phase transition with wide mesophase temperature ranges, and high thermal stability. Experimental results demonstrated that, with increasing content of crosslinking agent, the glass transition temperatures first fell and then increased; the isotropization temperatures and mesophase temperature ranges decreased.     

径向电场对纳米管中水分子通量的影响

水分子在纳米通道中的运动对于生命活动、纳米器件的设计等都有着重要的意义. 现在已经证实, 在(6,6)的碳纳米管中, 水分子会以单分子水链的形式协同通过碳纳米管. 但是如何控制水分子的流量仍然是一个困难的课题. 本文研究了在径向电场作用下, 碳纳米管中水分子通量的变化趋势和碳纳米管的开关行为.发现在碳纳米管两端存在200 MPa的压力差时, 电场强度从1 V·nm^-1增加到3 V·nm^-1, 水分子通量线性减小. 当径向电场强度增加到3 V·nm^-1时, 碳纳米管处于关闭状态, 水分子无法通过碳纳米管. 进一步, 我们发现水偶极与碳纳米管管轴夹角的平均值的概率分布和翻转频率都与水分子在纳米管中的个数有很大关系.     

Aliphatic Organoimido Derivatives of Polyoxometalates Containing a Bioactive Ligand

A series of aliphatic organoimido derivatives of hexamolybdate based on amantadine, namely (nBu₄N)₂[Mo₆O₁₈(?NC₁₀H₁₅)] ( 1 ), (nBu₄N)₂ {cis‐[Mo₆O₁₇(?NC₁₀H₁₅)₂]} ( 2 ), (nBu₄N)₂{trans‐[Mo₆O₁₇(?NC₁₀H₁₅)₂]} ( 3 ), and (nBu₄N)₂[Mo₆O₁₆(?NC₁₀H₁₅)₃] ( 4 ), was synthesized in reasonable yield by dehydration with N,N′‐dicyclohexylcarbodiimide (DCC). They were characterized by IR and UV/Vis spectroscopy, elemental analysis, ESI mass spectrometry, and single‐crystal X‐ray structure analysis. The spectral and structural similarities and differences between monosubstituted, cis‐disubstituted, and trans‐disubstituted organoimido derivatives were elucidated and may provide guidance for related work on organoimido‐functionalized Lindqvist‐type polyoxometalates. In addition, trans‐disubstituted and polysubstituted derivatives containing aliphatic organoimido ligands have not yet been reported, and the crystal structure of the trans isomer may lead us to a deeper understanding of disubstituted derivatives. Furthermore, proliferation and morphology of MCF‐7 cells were studied with compound 1 . The present results show that the DCC‐dehydrating protocol could be an efficient approach to covalently graft bioactive ligands such as amantadine onto POMs and enhance their application in clinical cancer treatment.     

Gold‐Catalyzed 1,2‐Acyloxy Migration/Intramolecular [3+2] 1,3‐Dipolar Cycloaddtion Cascade Reaction: An Efficient Strategy for Syntheses of Medium‐Sized‐Ring Ethers and Amines

A highly efficient strategy for the formation of medium‐sized‐ring ethers and amines based on a gold‐catalyzed cascade reaction, involving enynyl ester isomerization and intramolecular [3+2] cyclization, has been developed. Various multisubstituted medium‐sized‐ring unsaturated ethers and amines were obtained through this transformation. This method represents one of the relatively few transition metal catalyzed intramolecular cycloaddition reactions for medium‐sized ring synthesis.     

铅镉重金属离子在铋膜电极上的相互影响

采用原位镀铋电极的方式,以玻碳电极为工作电极,通过改变Cd2+和Pb2+的比例,考察不同Pb2+和Cd2+浓度条件下,两者同时存在时的相互影响。实验发现,Cd2+和Pb2+同时存在时,存在相互的影响,特别是对于Cd2+的检测,由于Pb2+较正的析出电位,对于Cd2+的析出有一定的辅助作用。考察了Cd2+和Pb2+单独存在时的分析性能,Pb2+沉积时间为60 s时,在1~80μg/L范围内呈线性关系,检出限为0.5μg/L;Cd2+的沉积时间为120 s,在1~25μg/L和30~200μg/L范围内有良好的线性关系,检出限为1.0μg/L。考察了铋膜电极在不同实际水样中对Pb2+和Cd2+的分析,获得了较好的一致性。     

四卤化锰(Ⅱ)配合物的结构调控及力致发光性能

力致发光是一种力刺激诱导的发光现象。由于其独特的发光方式,使得力致发光材料在结构损伤检测、压力传感、显示和安全标记等方面展现出了巨大的应用价值。目前已报道的力致发光材料大多基于无机材料体系,而有机力致发光材料体系相对较少,并且人们对其发光机理的认识仍不清晰。在本文中,我们发现锰(Ⅱ)配合物[BPP]2[Mn Br4]具有力致发光特性,并在此基础上设计合成了一系列具有力致发光性质的四卤化锰(Ⅱ)配合物。改变有机阳离子配体或者卤素阴离子可对其光物理性质进行有效调控。固态下,这些锰(Ⅱ)配合物均显示出了较强的光致发光现象,同时表现出了明显的力致发光特性。晶体结构分析表明,分子内/分子间强的C―H…X (X=Br或Cl)相互作用对锰(Ⅱ)配合物的力致发光起到了至关重要的作用,它可在较大程度上降低由分子振动和旋转造成的能量损失。本工作将为力刺激响应型材料体系的拓展提供一定的参考价值。     

Total Synthesis of (−)‐Pepluanol B: Conformational Control of the Eight‐Membered‐Ring System

The first total synthesis of the Euphorbia diterpenoid pepluanol B in both racemic and enantioenriched form involves 20 steps from a known bicyclic diol. This synthesis features an unprecedented bromo‐epoxidation to control the eight‐membered‐ring conformation. In addition, salient reactions for the construction of the tetracyclic backbone include a sterically challenging aldol reaction to establish the quaternary center, a ring closing metathesis (RCM) to forge the eight‐membered ring, and a diastereoselective cyclopropanation to assemble the embedded cyclopropane motif.