显色剂1-羟基-2-(5-NO2-2-吡啶偶氮)-8-氨基-3,6-萘二磺酸与镍显色反应的研究

探讨了显色剂 1 羟基 2 (5 NO2 2 吡啶偶氮 ) 8 氨基 3,6 萘二磺酸 (简称 5 NO2 PAH )与镍离子显色的适宜条件及其共存离子的影响 ,建立了 5 NO2 PAH测定镍的新显色体系。结果表明 ,在 pH 8.5～ 10 .0范围内 ,镍与试剂形成稳定的 1∶2配合物 ,其最大吸收峰位于 6 5 3nm ,表观摩尔吸光系数εNi=1.0 7× 10 5L·mol- 1·cm- 1,镍的浓度在 0～ 5 μg/ 10ml范围内遵守比耳定律。方法用于合金中镍的测定 ,结果满意。     

Optical Rotatory Feature of （R or S）—1,1’—Binaphthalene—2,2’—diol（BINOL）in various Solvents

The changes of the specific rotation and sign of optically active BINOL have been studied in polar/non-polar solvents and at the different pH values of solvent.It is considered that these changes are determined by the equilibriurn studies between cisoid and transoid conformations of BINOL with the same configuration(R or S) which related to the change of the dihedral angle between two naphthalene ring planes of BINOL.     

外消旋萘普生酯类在(S,S)-Whelk-O1与CDMPC手性柱上的对映体分离及手性识别机理的比较

在Pirkle型的(S,S)-Whelk-O 1与纤维素衍生物型的CDMPC两种手性柱上对六种 外消旋萘普生酯进行了对映体分离，通过研究烷氧基结构上的差异以及流动相中不 同的醇类添加剂对手性识别的影响，探讨和比较了外消旋萘普生酯在两种手性固定 相上手性识别的机理。对于 (S,S)-Whelk-O 1， 溶质与固定相之间的吸引作用于 手性识别的主要因素，而对于CDMPC，溶质在手性空腔中的空间适应性很可能是手 性识别的关键。     

新型多取代2，7—萘二酸二乙酯的合成

以4，6－二甲基－2－甲氧基－1，3－苯二甲酸二乙酯为原料，经Micheal加成、环化、溴化、消除等5步反应，合成新型的多取代2，7－萘二甲酸二乙酯。该合成路线步骤少，收率高，反应条件温和、产物中的4个新化合物的结构均经元素分析、核磁共振、红外光谱和质谱确证。     

新型LB成膜材料—两亲性侧链取代酞菁锌的合成

本文合成了一种新型的两亲性硬脂酸侧链取代的酞菁化合物。利用LB膜技术制备了致菁化合物与正十六烷混合的单层和多层LB膜,LB膜内酞菁分子大环与基片大体平行,表明该分子具有良好的成膜性能。     

CH/π, CH/O弱氢键在2,6-二(α-苯基苄基)-1,5-萘二酚主体分子包结物构筑中的作用

设计、合成了一种新的主体分子2,6-二(α-苯基苄基)-1,5-萘二酚 (1). 它可与许多有机小分子形成配位包合物. 用IR和¹H NMR表征了配位包结物, 并测定了主客体分子的摩尔比: 1•DMF (1∶1), 1•DMSO (1∶2), 1•吡啶 (1∶1), 1•喹啉(1∶2), 1•N-甲基吡咯烷酮(1∶1). 用单晶X衍射分析了包结物 (1)•DMF的晶体结构, 属三斜晶系, 晶胞参数为P-1, a＝0.9085(9) nm, b＝0.9501(6) nm, c＝2.0995(6) nm, α＝99.59(3)°, β＝90.13(4)°, γ＝96.20(7)°, V＝1.776(2) nm³, D_c＝1.898 g•cm^－3. 结果表明, 主体分子间的CH/π弱氢键在决定主体分子的层状框架结构和客体分子在层间的填充方式中发挥了重要作用; 两种不等效的客体分子与主体分子的作用方式是不同的, 一种客体分子是通过CH/π, CH/O弱氢键与同层的不同主体分子相互作用, 另一种是通过CH/π, CH/O弱氢键与相邻层的不同主体分子相互作用.     

SYNTHESIS OF CHIRAL CONJUGATED POLYBINAPHTHYLS BY SONOGASHIRA REACTION

Chiral polymers P-1 and P-2 were synthesized by the polymerization of （R）-3,3＇-diiodo-2,2＇-bisbutoxy-1,1＇- binaphthyl （M- 1 ） with 2,5-di（4-ethynylphenyl）- 1,3,4-oxadiazole （M-3） and （R）-3,3＇-diethylnyl-2,2＇-bisbutoxy- 1,1 ＇-binaphthyl （M-2） with 1,2-di（4-bromophenyl）acetylene （M-4） under Sonogashira reaction, respectively. Both monomers and polymers were analyzed by NMR, MS, FT-IR, UV-Vis spectroscopy, DSC-TGA, fluorescence spectroscopy, GPC and CD spectroscopy. CD spectra of P-1 and P-2 are similar due to the same chiral center units and main chain structure. The long wavelengths CD effect of P-1 and P-2 can be regarded as the more extended conjugated structure and a highly rigid backbone in the polymer chain. Polymers have strong blue fluorescence due to the efficient energy migration from the extended n-electronic structure of the polymers to the chiral binaphthyl core and are expected to provide understanding of the relationship between molecular structure and fluorescent property of the chiral polymers.     

含杂萘联苯结构聚合物膜的直接甲醇燃料电池性能

质子交换膜是直接甲醇燃料电池(DMFC)的关键组成部分. 通过磺化制备了磺化杂萘联苯聚醚酮(SPPEK)、磺化杂萘联苯聚醚砜(SPPES)和磺化杂萘联苯聚醚砜酮(SPPESK)三种含杂萘联苯结构的新质子交换膜, 测试了其热稳定性、质子导电性和甲醇透过性能. SPPESK的热分解温度比相近离子交换容量(IEC)的SPPEK和SPPES约低100 ℃, 三种膜均具有良好的导电和阻醇性能; 分别以三种膜为电解质组装DMFC考察了其性能, DMFC的开路电压随膜的阻醇性的提高而增大, 三种膜的开路电压均高于Nafion115膜, 但在较高电流密度的区域三种新膜的性能均比Nafion115膜差.     

1-萘甲酰苯胺和2-萘甲酰苯胺的分子内电荷转移研究

A series of 1-naphthanilides (1) and 2-naphthanilides (2) with varied substituents at the para- or meta-position of anilino phenyl ring were prepared and their absorption and fluorescence spectra in a nonpolar solvent cyclohexane were investigated. An abnormal long wavelength emission assigned to the charge transfer (CT) state was found for all of the prepared naphthanilides in cyclohexane. A linear free energy correlation between the CT emission energies and the Hammett constants of the substituent was found within series 1 and 2. The value of the linear slope with 1 (0.42 eV) was higher than that with 2 (0.32 eV) being close to that of the substituted benzanilides 3 (0.31 eV) The higher slope value suggested higher charge separation extent in the CT state of 1 than that of 2. It was found that the corresponding linear slope of anilino-substituted benzanilides remained unchanged when para-, meta-, ortho-, or ortho, ortho-methyls were introduced into the anilino moiety, which ruled out the possible contribution of the difference in the steric effect and the electron accepting ability of the naphthoyl acceptor in 1 and 2. Compared with the early reported N-substituted-benzoyl-aminonaphthalene derivatives 4 and 5, it was considered that 1-naphthoyl enhanced the charge transfer in 1 and the proximity of its ^1La and ^1Lb states was suggested to be responsible. It was shown that 1- and/or 2-substituted naphthalene cores acting as either electron acceptor (naphthoyl) or electron donor (aminonaphthalene) were different in not only electron accepting (donating) ability but also shaping the charge transfer pathway.     

Synthesis and Characterization of Donor-Acceptor-Donor Triads Containing Tetrathiafulvalene and Naphthalene Diimide Units： Towards Regulation of the Intermolecular Charge-Transfer Interaction by Varying the Attached Side Groups

Introduction Extensive studies have been performed on electron donor-acceptor supramolecular systems, which have been used as models to investigate charge-transfer interactions,1 photoinduced electron and energy transfer reactions (for understanding the natural photosynthesis mechanisms).2 In recent years, molecular devices such as molecular shuttles and molecular switches based on electron donor-acceptor supramolecules have been proposed and studied.3 Since the synthesis of tetrathiafulvalene…