“推—拉”型偶氮苯分子的光谱性质和二阶非线性光学性质

研究了具有“推－拉”电子结构的４‘－（Ｎ，Ｎ－二羟乙基）氨基４－硝基偶氮苯（Ｒ－ＨＡＮＢ）衍生物的光谱性质和二阶非线性光学性质，Ｒ－ＨＡＮＢ是一类假芪型偶氮苯分子其激发态具有相似的能级结构，且在不同状态下均具有较高的二阶非线性光学活性，其粉末二次谐波信号多数强于分散红１，一阶超极化率与基太偶极矩动量 合量用溶为色法测得为〉３．４×１０＾８２Ｃ＾２ｍ＾４／Ｖ＾２，其５％掺杂聚甲基丙烯酸甲酯薄膜以电晕     

"推-拉"型偶氮苯化合物的质谱分析

“推－ 拉”型偶氮苯化合物分子的共振结构决定了其关键碎裂方式, 有内氢键作用时偶氮则附着于给电子端, 而后续的碎裂过程则遵循各自主要官能团的裂解规律。     

巯基偶氮苯单分子电子传输的取代基效应

用密度泛函理论B3LYP/6-31G**计算巯基偶氮苯分子及分子离子的空间构型和电子结构, 研究取代基对巯基偶氮苯单分子电子传输的影响. 结果表明, 拉电子基(—COOH、—NO2)的引入, 可以提高巯基偶氮苯单分子电子传输体系的稳定性, 使体系LUMO的离域性增高、S原子反应活性增强、HOMO-LUMO能隙显著减小, 进而降低电子传输能垒, 有利于分子电子传输. 相同取代基的分子离子比分子具有更小的HOMO-LUMO能隙, S—Au键更易形成, 金属-分子-金属结构的电子传输性更强.     

用核磁共振表征对硝基偶氮苯衍生物

用一维＾１ＨＮＭＲ，＾１３ＣＮＭＲ方法研究了对硝基偶氮苯衍生物的结构，并通过二维＾１Ｈ－＾１Ｈ同核相关、＾１３Ｃ－＾１Ｈ异核相关及＾１３－＾１Ｈ异核远程相关谱进一步地确定了该衍生物的＾１Ｈ谱和＾１３Ｃ谱中各谱峰的归属。     

新显色剂 2,6-二溴-4-羧基苯偶氮重氮氨基苯偶氮苯与汞的显色反应研究和应用

研究了新合成显色剂 2,6-二溴-4-羧基苯偶氮重氮氨基苯偶氮苯(BCADAB)的理化性质及其与汞(Ⅱ)的灵敏显色反应.在有 Triton X -100 存在的 pH 11.2 的氨水-氯化铵缓冲液中,汞(Ⅱ)与显色剂生成 1∶2 的稳定橙红色配合物,其最大吸收波长为 520 nm ,表观摩尔吸光系数为 1.17×105 L.mol-1.cm-1.Hg(Ⅱ)在 0～35 μg/25 mL 范围内符合比耳定律.本法已用于环境水样中微量汞的测定.     

含咔唑和偶氮苯的乙炔衍生物的合成

采用Sonagashira偶联反应和N-烷基化反应合成了含有咔唑和偶氮苯的乙炔衍生物:3-乙炔基-9-(4-[4-(硝基)苯基偶氮苯]氧)亚丁基咔唑3.其结构通过IR,1H NMR,13C NMR,元素分析和X-射线单晶衍射法测定.标题化合物属单斜晶系,P21/c空间群;a=9.238(3),b=28.240(8),c...     

对甲氧在偶氮苯衍生物的核磁共振表征

用一维＾Ｈ ＮＭＲ、＾１３Ｃ ＮＭＲ方法研究了对甲氧基偶氮苯衍生物的结构,并通过二维＾１Ｈ－＾１Ｈ同核相关谱（ＣＯＳＹ）、＾１３Ｃ－＾１Ｈ异核相关谱（ＨＥＴＣＯＲ）及＾１３Ｃ－＾１Ｈ异核远程相关谱进一步地确定了该类衍生物的＾１Ｈ和＾１３Ｃ谱中各谱峰的归属,为研究侧链液晶聚合物结构提供了有价值的数据。     

2-巯基苯并噻唑衍生物的合成进展

2-巯基苯并噻唑具有很好的经济价值.为了增强和完善2-巯基苯并噻唑的应用性能,通过将其作为一种中间体,与油溶性基团的活性元素结合在同一分子内,开发和研究了其一系列新型的具有良好性能的衍生物,可用作配体、染料、硫化促进剂、蛋白质酶抑制剂以及杀菌、除草和抗病毒药物.对通过包括苯环、巯基上的S、杂环上的N等3个位置上的取代或加成来合成这些衍生物的简单可行方法进行了综述.     

对甲氧基偶氮苯衍生物的核磁共振表征

用一维１ Ｈ ＮＭＲ、１３Ｃ ＮＭＲ 方法研究了对甲氧基偶氮苯衍生物的结构, 并通过二维１ Ｈ－ １ Ｈ 同核相关谱（ＣＯＳＹ） 、１３ Ｃ－ １ Ｈ 异核相关谱（ ＨＥＴＣＯＲ） 及１３Ｃ－ １ Ｈ 异核远程相关谱进一步地确定了该类衍生物的１ Ｈ 谱和１３ Ｃ 谱中各谱峰的归属, 为研究侧链液晶聚合物结构提供了有价值的数据。     

新显色剂4,4′-二偶氮苯重氮氨基偶氮苯测定水中微量锌的研究

本文报告在四硼酸钠体系中和Triton X-100存在下,锌与新显色剂4,4′-二偶氮苯重氮氨基偶氮苯有灵敏的显色反应。红色络合物在525nm处摩尔吸光系数为1.63×10~5L·mol~(-1)·cm~(-1),并研究了测定锌的各种条件和40余种共存离子对测定的影响。     

6-三氟甲基苯并噻吩衍生物的合成

本文研究了苯环上含强吸电子基的2,6-二硝基-4-三氟甲基苯腈等在Na~2S-DMF-H~2O体系下与一些卤代化合物作用, 经桥接, 关环, 合成了一些2位取代的3-胺基-6-三氟甲基苯并噻吩及未环化的硫醚异构体, 并对其生成机理和^1H NMR进行了探讨.     

Synthesis and characterization of side-chain liquid crystal polyurethanes

A series of liquid crystal α-[bis(2-hydroxyethyl)amino]-ω-(4-nitroazobenzene-4′-oxy)alkanes (Cn-diol) with different alkyl chain length has been synthesized. All Cn-diols exhibit a smectic phase that has been identified by means of polarizing microscopy and differential scanning calorimetry. These compounds are suitable monomers for the synthesis of side-chain liquid crystalline polyurethanes and polyesters. They were polymerized with hexamethylene diisocyanate to corresponding SCLC polyurethanes in which the spacer length was varied from 2 to 12 methylene units. Polyurethanes (CnP) with spacer lengths n ≥ 4 exhibited liquid crystalline behavior. Fourier transform infrared temperature studies of the CnP were done focusing on H-bonds between the N H and CO groups of the urethane backbone. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 2871–2888, 1997     

Synthesis and characterization of thermally crosslinked polyimide with second-order nonlinear optical chromophore

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新型偶氮苯金属液晶化合物的合成与性能研究

合成了新型偶氮苯金属配合物。 分别采用光谱分析、热分析及X射线衍射测试技术对样品进行了表征。结果表明,连接偶氮苯和金属配合物之间碳链的长度对该化合物的相转变和荧光特性具有特殊的影响。 该系列化合物在紫外光和热作用下具有99%以上的偶氮苯顺-反异构化反应效率;具有290和560 nm这2个波段荧光发射光谱。由其中一个金属液晶化合物分散在聚甲基丙烯酸甲酯网络而形成的介质可作为全息信息存储材料而实现全息图像的写入和读出。     

Synthesis and characterization of an azobenzene‐ and acrylamide‐based photoresponsive copolymer and gel

This article reports the synthesis and characterization of a new type of copolymer consisting of acrylamide and trans‐4‐methacroyloxyazobenzene and their gel. Free‐radical polymerization initiated with 2,2′‐azobisisobutyronitrile was used to conduct the synthesis although N,N′‐methylene bisacrylamide was used as a crosslinking agent for the gel synthesis. Despite the insolubility of the different monomers in a single solvent, a certain ratio of water/tetrahydrofuran (THF) enabled the propagating species to stay in the solution and thus to facilitate chain growth. The solubility, Fourier transform infrared spectra, and solid‐state ¹³C NMR investigations revealed that two monomers in the copolymer were chemically bonded. The compositions of the incorporated acrylamide and azobenzene in the copolymer and the gel were determined by NMR spectroscopy. Because the potential actuating behavior of such materials was due to the volume change involved in reversible solvent uptake, the sorption and evaporation of the gel were also investigated and showed that the gel could absorb about 460% water, which corresponded to a polymer content of the weight gel of 18% and was compatible with thermogravimetric analysis of a saturated gel that revealed about 83 wt % of a swollen gel was lost within 12 h. Finally, photoinduced trans–cis isomerization kinetics of the copolymer was investigated in a 30:70 mixture of water and THF against irradiation time. A photostationary state was reached within 5.5 min with a corresponding conversion of 70% of the trans isomer to the cis form. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2886–2896, 2004     

Synthesis and characterization of novel push-pull oligomer based on naphthodithiophene-benzothiodiazole for OFETs application

A novel push-pull oligomeric semiconductor, ENBT based on naphthodithiophene-benzothiodiazole was successfully designed and synthesized. ENBT was fully characterized by ¹H NMR, MS, thermogravimetric analysis (TGA), UV–vis spectra, and cyclic voltammetry (CV). Furthermore, ENBT-based OFETs were fabricated by solution-processed dip-coating technique and its charge transporting property was investigated. The film of ENBT exhibited a hole mobility as high as 1.4?×?10^?2?cm²/(Vs) with a current on/off ratio of 10⁶–10⁷ after annealed at 160?°C. In order to give an insight to the transporting property of ENBT films, thin film morphologies after annealing at different temperatures were also studied by atomic force microscopy (AFM).     

2-取代苯并噁唑衍生物的合成及生物活性

疏基苯并噁唑;2-取代苯并噁唑衍生物的合成及生物活性     

Synthesis,characterization and fungicidal activity of zinc diethyldithiocarbamate and phosphate

Monolayers of amphiphilic di-block copolymer, PEO₄₀-b-PMA(Az)₁₉ on water surface and solid surfaces, such as silicon wafer and quartz glass, were analyzed by surface pressure — molecular area (π-A) isotherm, UV-Vis spectroscopy, atomic force microscopy (AFM) and total X-ray reflectivity (TXR). The monolayer prepared at 22 mN m-1 consisted of H aggregated azobezene (Az) moieties, which orientated perpendicular to the solid surface. The monolayer structure, including H aggregated Az and orientation of Az, was stable after annealing at 98°C, at which temperature the hydrophilic PEO domain was the liquid phase and the hydrophobic PMA(Az) was in the smectic A phase.     

Synthesis and photochromic behavior of some azo-polysiloxanes modified with nucleobases or donor-acceptor groups

This paper presents the syntheses, characterization and photochromic behavior of some new azo-polysiloxanes modified with uracil, cytosine or nitro-phenolic groups. Taking into consideration the possibility of generating H-bonds or donor/acceptor interactions, this class of materials present a potential applicability in the immobilization of biomolecules and their nano-manipulations. Also, such compounds are capable of producing a fluid phase, with directional flowing capacity. For all these polymers, the molecular modeling simulations have shown disordered structures, which would generate amorphous phases, a very important aspect for molecules’ nano-manipulation. The photochromic behavior in the presence of UV irradiation was also evaluated.      

The effect of 2,2-dicyanovinyl groups as electron acceptors in push-pull substituted oligo(1,4-phenylenevinylene)s

The newly synthesized oligo(1,4-phenylenevinylene) series 2a-d with bis(2-hexyloctyl)amino groups as electron donors and 2,2-dicyanovinyl groups as electron acceptors represents conjugated oligomers with strong push-pull effects. Due to the decrease of the intramolecular charge transfer with increasing numbers of repeat units (n=1-4), the long-wavelength transition shows a particularly great hypsochromic shift for the extension of the chromophore.