Complexation of Caffeic and Ferulic Acids by Transition-Metal Ions

Potentiometric titration and IR and UV spectroscopies are used to study complexation of caffeic and ferulic acids by metal ions. Caffeic and ferulic acids, which occur in lignin, are shown to react with metal ions mainly through an ionic mechanism. However, coordination bonding is also possible depending on the nature of the ligand and metal ion and the ratio of starting components. The strongest complex forms between caffeic acid and CuCl ₂ (2:1 ratio)     

Synthesis,Structure, Spectroscopic Studies,and Complexation of Novel Crown Ether Butadienyl Dyes

Butadienyl dyes of the benzothiazole series with various fragments of benzocrown ethers 1a – c were synthesized for the first time. The structures and spectral properties of crown‐containing butadienyl dyes and their complexes with alkali and alkaline‐earth metal cations were studied by X‐ray diffraction analysis and ¹H‐NMR, UV/VIS, and resonance Raman spectroscopy. To interpret the experimental results, quantum‐chemical calculations were performed. In the case of Sr²⁺ and Ba²⁺ ions, the formation of strong sandwich complexes [M( 1b )₂]²⁺ of an unusual structure involving stacking interactions was established; the dye molecules are arranged one above another in the complex according to the ‘head‐to‐head' pattern.     

Synthesis and Photochromism of Crowned Spirobenzothiapyran: Facilitated Photoisomerization by Cooperative Complexation of Crown Ether and Thiophenolate Moieties with Metal Ions

Spirobenzothiapyrans bearing monoaza-12-crown-4, -15-crown-5, -18-crown-6, and oligooxyethylene moieties were synthesized, and their photochromism was examined in the presence of cations in acetonitrile. The cation complexation by their crown ether moieties cannot induce thermal isomerization to their corresponding colored merocyanine form, unlike the corresponding spirobenzopyran derivatives. The UV-light-induced isomerization was, however, facilitated by the cation complexation of the crown ether moieties and the affinity of the merocyanine thiophenolate anion to metal ions, especially in the presence of Li(+) and Ag(+). The presence of Ag(+) brought about the most remarkable effect in the facilitation of photoisomerization of the spirobenzothiapyrans and the thermal stability of the colored merocyanine form mainly due to the powerful interaction of the thiophenolate anion with the soft metal ion.     

取代芳香族冠醚配合物的合成、晶体结构及其与DNA相互作用的研究

合成了冠醚3,3′-二甲基二苯并-18-冠-6(MDB18-C-6),并以该化合物为配体分别与镍(Ⅱ)、钯(Ⅱ)和K2(i-mnt)作用,进一步合成了配合物[K(MDB18-C-6)(CH3COCH3)]2[Ni(i-mnt)2](1)及配合物[K(MDB18-C-6)(CH3SOCH3)]2[Pd(i-mnt)2](2)。通过元素分析、红外光谱、紫外光谱、核磁共振氢谱、质谱等测试手段对其结构进行表征,用X-射线单晶衍射测定了配合物1和配合物2的晶体结构。利用紫外吸收光谱、荧光光谱和圆二色光谱等光谱分析法研究了配合物与小牛胸腺DNA(CT-DNA)的作用,结果表明两种配合物与DNA都具有相互作用,配合物主要是通过影响DNA的螺旋结构,从而引起DNA的构象变化,并且配合物2的作用性能大于配合物1。     

取代芳香族冠醚配合物的合成、晶体结构及其与DNA相互作用的研究

合成了冠醚3,3’-二甲基二苯并-18-冠-6（MDB₁₈-C-6）,并以该化合物为配体分别与镍（Ⅱ）、钯（Ⅱ）和K₂（i-mnt）作用,进一步合成了配合物[K（MDB18-C-6）（CH₃COCH₃）]₂[Ni（i-mnt）₂]（1）及配合物[K（MDB18-C-6）（CH₃SOCH₃）]₂[Pd（i-mnt）₂]（2）。通过元素分析、红外光谱、紫外光谱、核磁共振氢谱、质谱等测试手段对其结构进行表征,用X-射线单晶衍射测定了配合物1和配合物2的晶体结构。利用紫外吸收光谱、荧光光谱和圆二色光谱等光谱分析法研究了配合物与小牛胸腺DNA（CT-DNA）的作用,结果表明两种配合物与DNA都具有相互作用,配合物主要是通过影响DNA的螺旋结构,从而引起DNA的构象变化,并且配合物2的作用性能大于配合物1。     

Synthesis and Characterization of New Phthalocyanines Peripherally Fused to Four 21-Membered Dithiacrown Ether Macrocycles

Summary. A novel metal-free phthalocyanine and its nickel(II) and copper(II) phthalocyaninato complexes were prepared. The new compounds were characterized by elemental analyses, ¹H- and ¹³C-NMR, IR, UV-Vis, and mass spectral data. The NMR and/or UV-Vis spectra of these compounds showed extremely broad bands and/or peaks. This phenomenon seems to be related to the presence of the sulfur substituents, which is consistent with the data observed for similar compounds. The absorption spectra of these compounds were greatly affected by aggregation processes. Corresponding author. E-mail: dismail@ktu.edu.tr Received July 24, 2002; accepted August 2, 2002 Published online April 7, 2003     

Synthesis and Complexation Properties of Pyrimidine-Derived Crown Ether Ligands

Five new proton-ionizable macrocyclic ligands containing a pyrimidone-subcyclic unit, 6–10 , were prepared from the previously prepared pyrimidinocrown ethers 1–5 (see Figure 1 and Scheme 1). One of the new proton-ionizable crown ethers is chiral. The proton-ionizable pyrimidonocrown ethers were prepared in high yields by treating the appropriate methoxy-substituted pyrimidinocrown with 5 M sodium hydroxide in a 50% alcohol-water mixture. Complexation properties of four of the pyrimidine-derived macrocycles were studied by various nmr techniques. Pyrimidono-18-crown-6 (9) forms a strong complex with benzylammonium perchlorate and also forms a complex with benzylamine. (S, S)-Dimethyl-substituted pyrimidino- and pyrimidono-18-crown-6 ligands 4 and 9 form stronger complexes with the (R)-form of α-(1-naphthyl)ethylammonium perchlorate than with the (S)-form. (S, S)-Dimethyl-substituted pyrimidono-18-crown-6 ( 9 ) also forms a stronger complex with (R)-α-(1-naphthyl)ethylamine than with the (S)-form. The crystal structure for compound 7 is reported.     

四甲氧基取代的二苯并并四苯(DBN)的合成, 晶体结构及聚集效应

本文从商品化的间溴苯甲醚和对甲氧基苯甲醛出发，通过傅-克酰基化反应、串联的羟醛缩合及1,4-迈克尔加成反应，得到三芳基取代的1,5-二酮，然后用查尔酮（Chalcone）作氧化剂，二酮与BF₃.Et₂O 反应形成吡喃鎓盐，再与苯基乙酸钠盐缩合得到芳香二溴代衍生物，产物的DMA溶液在DBU和钯催化剂的作用下，160°C 加热12 h进行脱卤化氢环化反应, 生成四甲氧基取代的二苯并并四苯（DBN）类衍生物。并报道了产物的晶体结构和在溶液中的聚集效应。     

Pyrimidino- and Proton-ionizable Pyrimidono-crown Ether Ligands: Synthesis and Preliminary Complexation Studies

Pyrimidino-crown ethers were prepared in 30-50% yields by reactingthe ditosylate derivative of the appropriate oligoethylene glycol with4-methoxy-5-methyl-2,6-pyrimidinedimethanol under basic conditions. A newmacrocyclic ligand containing a proton-ionizable pyrimidone subcyclic unitwas prepared in 88% yield by treating the appropriatepyrimidino-crown ether with 5 M NaOH in 50% (v/v) aqueous methanol.Preliminary complexation properties of some of these new compounds werestudied using various NMR spectral techniques. Good enantiomeric recognitionwas exhibited by a chiral pyrimidino-crown ether for the enantiomers of1-(-naphthyl)ethylammonium perchlorate.     

铌取代型杂多钨酸盐的合成、表征、生物活性及晶体结构

合成了铌、过氧化铌取代的钨硅、钨锗杂多配合物M     

Substituted 2-Phenacylbenzoxazole Difluoroboranes: Synthesis,Structure and Properties

Novel fluorescent dyes such as benzoxazole-boron complexes, bearing β-ketoiminate ligands, have been synthesized and characterized with a focus on the influence of a substituent on the basic photophysical properties. ¹H, ¹¹B, ¹³C, ¹⁵N, and ¹⁹F nuclear magnetic resonance (NMR) spectra of substituted 2-phenacylbenzoxazole difluoroboranes have been recorded and discussed. It is worth mentioning that a high correlation coefficient was found between ¹⁵N-NMR parameters and substituent constants. The photophysical properties of these new dyes have been investigated by fluorescence and ultraviolet-visible (UV-Vis) absorption spectroscopy. The geometry optimization, vibrational spectra, and the HOMO and LUMO energies were calculated based on density functional theory with the use of the B3LYP functional and 6-311++G(d,p) basis set.     

新型丁二炔-二酰胺大环化合物的合成及与TTF和DNP在溶液中的络合行为

由三甘醇和四甘醇出发,经炔丙基烷基化、Mitsunobu反应和Eglinton偶联反应3步合成了2个含均苯四甲酸二酰亚胺结构单元以及丁二炔结构单元的大环化合物,关环产率分别为81%和85%.大环化合物及中间体的化学结构经核磁共振氢谱、碳谱、低分辨质谱、高分辨质谱或元素分析等确认.通过氘代丙酮中1HNMR实验以及氯仿中紫外滴定实验研究了这类大环化合物与客体分子四硫富瓦烯(TTF)和1,5-二甲氧基萘(DNP)在溶液中的相互作用,结果发现,大环化合物的核磁化学位移及紫外光谱均发生变化.通过得到的主-客体间的络合常数可知,此类新型大环化合物与TTF和DNP之间有一定的络合作用.     

二芳醚基哌嗪类衍生物的合成及细胞毒活性研究

根据拼合原理, 设计并合成了21个未见报道的新的二芳醚基哌嗪类衍生物, 其结构用1H NMR, ESI-MS, HRMS进行了确证, 初步生物活性测定实验证明部分目标化合物具有良好的细胞毒活性. 化合物4i分别对人食管癌(Eca109)细胞株和人鼻咽癌(CNE)细胞株的IC50为7.13和4.54 μmol•L－1, 与对照品顺铂(DDP)相近. 化合物5d对人鼻咽癌细胞株也表现较好的活性, 其IC50为8.49 μmol•L－1.     

N-取代氮杂冠醚的合成和络合萃取性能研究进展

综述了N-取代氮杂冠醚的合成和对金属离子的选择性络合和萃取研究的新进展.     

取代萘并吡喃的合成和晶体结构研究

以芳醛、丙二腈（或氰乙酸酯）、β－萘酚为原料在六氢吡啶存在下以乙醇为 溶剂一锅合成了取代萘并吡喃，产物的结构通过单晶X射线衍射分析确定。