Supramolecular assembly of a new squaraine and β-cyclodextrin for detection of thiol-containing amino acids in water

A new unsymmetrical aniline-based squaraine (SQ2) bearing binding unit of Hg²⁺ ion was designed and synthesised. SQ2 can form 1:2 inclusion complex with β-cyclodextrin, and the resulting complex, which undergoes absorption and fluorescence bleaching upon binding Hg²⁺, can serve as a turn-on colorimetric or fluorescent chemosensor in organic solvent-free aqueous solution for thiol-containing amino acids with high selectivity and tunable measuring range.     

Influence of branched chains on the mesomorphic properties of symmetrical and unsymmetrical triphenylene discotic liquid crystals

A series of novel symmetrical and unsymmetrical triphenylene‐based discotic liquid crystalline materials with one or six branched peripheral alkoxy chains have been prepared. These materials have been compared with analogous known symmetrical and unsymmetrical compounds to reveal a balance between steric and space‐filling effects of the peripheral branched chains, which significantly affects intermolecular forces of attraction and packing, and hence affects melting and isotropisation temperatures of the liquid crystalline materials. The desired result of reduction of melting points and enhancement of isotropisation temperatures has been accomplished by use of branched alkoxy chains in both symmetrical and unsymmetrical materials.     

不对称α-烃基-α-羟基丙二酰胺衍生物的合成新方法

N,N-二甲基氨甲酰基三甲基硅烷与一系列N-甲基-N-甲氧甲基α-羰基酰胺在无水无氧、105℃的条件下反应,合成了不对称α-烃基-α-羟基丙二酰胺类化合物或不对称α-烃基-α-三甲基硅氧基丙二酰胺衍生物,收率71%～86%,其结构用元素分析、1H NMR、13C NMR和IR等方法进行了表征.通过研究反应的影响因素发现,反应底物α-羰基酰胺中与α-羰基直接相连的烃基的空间位阻是该加成反应的重要影响因素,而α-羰基直接相连的芳环上取代基的电子效应则主要影响反应完成的时间.并提出了可能的反应机理.     

Synthesis,spatial structure and spectral properties of pyrylo‐4 (thio) squaraines variously substituted in cyclobutene moiety

Synthetic routes have been developed to a number of (thio) squaraine dyes containing the residues of CH‐acids at the central cyclobutene ring. The electronic and spatial structure as well as the chemical conversions and optical behaviour of the compounds obtained have been studied both theoretically and by X‐ray diffraction analysis, ¹H NMR and electronic spectroscopy. As shown, the electronic nature and sterical characteristics of the central ring substituents give rise to some general conformational features and crystal packing regularities and also govern the spectral position of the first π–π^* absorption band. The structure–property relationships established in the study provide guidance for the purposeful design of deeply coloured (thio) squaraines. Copyright © 2015 John Wiley & Sons, Ltd.     

偏二甲肼纯度分析方法的改进

采用毛细管气相色谱内标法代替标准工作曲线法测定偏二甲肼纯度(UDMH),内标法的使用避免了微量进样不准确的缺陷.结果显示,该方法线性范围宽,偏二甲肼的标准曲线相关系数为0.9959,样品加标回收率98.39%,样品的测定标准偏差为0.0015,方法的准确度高、重现性好.     

方酸菁荧光探针的应用研究进展

功能性方酸菁染料具有独特的D-A-D共轭结构,其在可见光和近红外区域有强烈的吸收和荧光发射。方酸菁染料作为近红外荧光探针母体被应用于蛋白质、氨基酸、一些生物小分子、环境污染物及金属离子等的检测。本文结合课题组近几年工作综述了方酸菁染料在蛋白质、氨基酸、生物小分子、阳离子和其它物质检测方面的应用。     

An Aggregating Amphiphilic Squaraine: A Light-up Probe That Discriminates Parallel G-Quadruplexes

G-quadruplexes (G4s) are peculiar DNA or RNA tertiary structures that are involved in the regulation of many biological events within mammalian cells, bacteria, and viruses. Although their role as versatile therapeutic targets has been emphasized for 35 years, G4 selectivity over ubiquitous double-stranded DNA/RNA, as well as G4 differentiation by small molecules, still remains challenging. Here, a new amphiphilic dicyanovinyl-substituted squaraine, SQgl , is reported to act as an NIR fluorescent light-up probe discriminating an extensive panel of parallel G4s while it is non-fluorescent in the aggregated state. The squaraine can form an unconventional sandwich π-complex binding two quadruplexes, which leads to a strongly fluorescent (Φ_F=0.61) supramolecular architecture. SQgl is highly selective against non-quadruplex and non-parallel G4 sequences without altering their topology, as desired for applications in selective in vivo high-resolution imaging and theranostics.     

Crown Inclusion Compounds with 3,4-Diamino-1,2,5-Oxadiazole. X-Ray Structures of Its 1:1 Inclusion Complexes with 15-Crown-5 and Benzo-15-crown-5

The X-ray crystal structures of two closely related molecular complexes of 15-crown-5 and benzo-15-crown-5 with 3,4-diamino-1,2,5-oxadiazole are reported (I and II). Both complexes are of 1:1 stoichiometry with the host–guest alternation in the infinitechains formed due to the unsymmetrical H-bonding patterns between the components. Crystals of I are monoclinic, P2_1/c, a = 7.856(3), b = 12.994(1), c = 16.033(1) , = 94.79(2)°, Z = 4, final R-factor is 0.0488. Crystals of II are orthorhombic, P2₁2₁2₁, a = 8.260(4), b = 15.692(5),c = 13.955(7) , Z = 4, final R-factor is 0.0522.     

Mechanism of the interaction of color reagent 1, 3-N, N'-bis-4-(4'-nitro benzenediazo) phenyl squaraine with oxoacid anions

By AM1 method, the interactions between 1, 3-N, N′-Bis-4-(4′-nitro benzenediazo) phenyl squaraine (BNBPS) and several oxoacid anions have been studied on the basis of the proposed model. The mechanism of the color reactions is suggested and the answers to the question of whether or not BNBPS colorates with HCO_3~-, CO_3~(2-), NO_2~(-), NO_3~-, etc. are given. It is theoretically predicted that BNBPS might be used as the color reagent for SO_4~(2-).     

Synthesis and characterization of new meso -substituted unsymmetrical metalloporphyrins

The synthesis and characterization of new meso-substituted unsymmetrical metalloporphyrins has been described. A new modified Adler method was used for the synthesis of two unsymmetrical porphyrins. Reactions of these unsymmetrical porphyrins with metal acetates afforded the corresponding metalloporphyrins in high yields with excellent purity. These porphyrins and their metal derivatives were characterized by spectroscopic methods. However, the copper complexes were further studied by ESR spectra and zinc complex by fluorescence spectrum.