杯芳烃-卟啉化合物的合成及性质

杯芳烃和卟啉通过共价键连结或者分子间作用力聚集形成的杯芳烃-卟啉化合物在分子识别、分子催化、分子自组装等方面有潜在的用途. 本工作综述了杯芳烃-卟啉化合物的合成及性质.     

杯芳烃-卟啉化合物及其金属配合物的Langmuir-Blodgett膜研究

通过对杯芳烃-卟啉化合物及其锌、钯配合物LB膜的表面压-表面积等温线、紫外可见光谱和傅里叶变换红外光谱的检测,研究了它们在气/液界面和Langmuir-Blodgett膜中的性质,并用量子力学方法优化了杯芳烃-卟啉化合物的构型.结果表明,成膜时3种化合物分子中卟啉环都倾斜地排列在亚相表面,且卟啉环间存在π-π相互作用.连接杯芳烃和卟啉之间的碳氢链在膜性质中起着重要的作用,杯芳烃-卟啉化合物分子中这种碳氢链的有序性小于其锌、钯配合物分子中的这种碳氢链有序性.     

杯芳烃-卟啉化合物及其锌、钯配合物的制备与成膜性能研究

将广泛用作分子构架和分子载体的杯芳烃和卟啉结合,合成了具有更多功能和用途的杯芳烃-卟啉化合物及其锌、钯配合物,并成功地在气/液界面得到它们的单分子膜,并对其成膜性能作了初步的探讨.结果表明,无论是杯芳烃-卟啉化合物还是它的锌、钯配合物均能形成稳定的单分子膜.     

杯芳烃-金属卟啉仿酸酶模型化合物的合成及其电子光谱研究

本文首次报导杯芳烃-金属卟啉键联化合物作为仿细胞色素P-450酶模型的合成。对紫外-可见光谱进行了较详细的研究,将模型化合物与相应未键联杯芳烃的卟啉化合物光谱比较,发现兰移现象,从而说明杯芳烃卟啉键联物中, 杯环与卟啉环之间存在相互影响。金属离子插入后其相互作用加强。     

杯芳烃-金属卟啉仿酶模型化合物的合成及其电子光谱研究(英文)

本文首次报道杯芳烃-金属卟啉键联化合物作为仿细胞色素P-450酶模型的合成。对紫外-可见光谱进行了较详细的研究,将模型化合物与相应未键联杯芳烃的卟啉化合物的光谱比较,发现兰移现象,从而说明杯芳烃卟啉键联物中,杯环与卟啉环之间存在相互影响。金属离子插入后其相互作用加强。     

杯[6]芳烃-双金属卟啉仿P450酶模型的研究 Ⅰ.对环己烯环氧化反应的催化活性

研究了杯［６］芳烃－双金属卟啉仿Ｐ４５０酶模型化合物对环己烯环氧化反应的催化性能．考察了温度、氧源浓度、催化剂浓度、底物浓度、卟啉环中位苯基上取代基、溶剂等因素对反应的影响．结果表明,杯［６］芳烃－双金属卟啉的催化性能优于相应的简单金属卟啉单体,且反应遵从Ｍｉｃｈａｅｌｉｓ－Ｍｅｎｔｅｎ规律．这是由于作为疏水结合部位的杯［６］芳烃大环的引入,导致多部位识别协同催化,从而极大地提高了金属卟啉的催化性能．     

杯[6]芳烃-双金属卟啉仿P-450酶模型的研究Ⅳ.对异丙苯氧化的催化行为

研究了杯[6]芳烃-双金属卟啉在氧化异丙苯中的催化行为，结果表明杯[6]芳烃-双金属卟啉比之相应的金属卟啉具有更高的催化活性，并表现同样的选择性，生成苯乙酮和醇组份。此一结果同通常酞菁或其它如西弗碱大分子金属络合物催化下生成丙酮和酚不同。还考察了温度、轴向配体、催化剂用量及金属离子种类等对反应的影响，仔细地通过测定反应速度比较了反应的活性。     

双杯芳烃研究进展

双杯芳烃是杯芳烃家族中的重要一员。它由两个杯芳烃单元通过化学键联结而形成，一般常有上缘-下缘、下缘-下缘、下缘-上缘3种桥联方式，其结构更复杂，性质也更为丰富多彩。双杯芳烃具有两个相同或不相同的结合部位，可同时络合两个相同或不相同的底物，还可表现出特殊的协同作用、更强的络合能力、变构象以及粒子雾荡等新的性质。本文根据杯芳烃亚单元的种类，综述了双杯芳烃的研究进展，重点描述了不同桥联方式的双杯[4]芳烃的合成方法，而且对一些具有特殊性能的双杯芳烃进行了较为详细的介绍。最后对双杯芳烃的发展前景作了展望。     

杯芳烃化金属卟啉及其苯乙烯环氧化的催化性能

将单功能化四苯基卟啉与对叔丁基杯［４］芳烃通过单链相连，随后插入金属离子，合成了杯芳烃化金属卟啉１－３．在两相条件下对苯乙烯环氧化催化反应研究表明，化合物２的锰络合物中杯芳烃的存在对氧化反应有明显影响．可以根据连接于卟啉分子中憎水杯芳烃造成催化活性中心微环境差异来解释观察到的现象．各杯芳烃化锰卟啉的催化性能按以下次序降低：１ｂ＞２ｂ＞３ｂ－７．     

杯芳烃衍生物在主-客体识别荧光分析中的应用及进展

综述了近年来杯芳烃衍生物在主一客体识别荧光分析中的研究与应用进展，主要从杯芳烃母体官能化作主体分子和杯芳烃与冠醚、环糊精及卟啉构成偶联物作主体分子两方面进行了评述，并对今后工作进行了展望。引用文献62篇。     

Thermal condensation of phthalimide with malonic acid

When phthalimide is reacted with malonic acid in the presence of zinc acetate, 1-hydroxy-1-methyl-1H-3-(1-oxoisoindolin-3-ylidenemethyl)isoindole, the zinc complex of 1-hydroxy-8,1322,27-diimino-1,615,20-dinitrilotetrabenzo[b,d,l,q]eicosin, and zinc tetrabenzoporphin are formed depending on the temperature. The compounds have been characterized by their electronic absorption spectra, IR and mass spectra, and also by their x-ray photoelectron spectra. A possible scheme for the synthesis of zinc tetrabenzoporphin has been proposed.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 480–484, April, 1988.     

Synthesis and characterization of mononuclear zinc aryloxide complexes supported by nitrogen/sulfur ligands possessing an internal hydrogen bond donor

Treatment of a dinuclear zinc hydroxide complex ([(bmnpaZn)(2)(mu-OH)(2)](ClO(4))(2) (1) or [(benpaZn)(2)(mu-OH)(2)](ClO(4))(2) (2)) with excess equivalents of an aryl alcohol derivative (p-HOC(6)H(4)X; X = NO(2), CHO, CN, COCH(3), Br, H, OCH(3)) yielded the nitrogen/sulfur-ligated zinc aryloxide complexes [(bmnpa)Zn(p-OC(6)H(4)NO(2))](ClO(4)) (3), [(benpa)Zn(p-OC(6)H(4)NO(2))](ClO(4)) (4), [(benpa)Zn(p-OC(6)H(4)CHO)](ClO(4)) (5), [(benpa)Zn(p-OC(6)H(4)CN)](ClO(4)) (6), [(benpa)Zn(p-OC(6)H(4)COCH(3))](ClO(4)) x 0.5H(2)O (7), [(benpa)Zn(p-OC(6)H(4)Br)](ClO(4)) (8), [(benpa)Zn(p-OC(6)H(5))](ClO(4)) (9), and [(benpa)Zn(p-OC(6)H(5)OCH(3))](ClO(4)) (10). The solid state structures of 2, 3, 5, and 6 have been determined by X-ray crystallography. While 3 and 6 exhibit a mononuclear zinc ion possessing a distorted five-coordinate trigonal bipyramidal geometry, in 5 each zinc center exhibits a distorted six-coordinate octahedral geometry resulting from coordination of the aldehyde carbonyl oxygen of another zinc-bound aryloxide ligand, yielding a chain-type structure. Zinc coordination of the aldehyde carbonyl of 5 is indicated by a large shift (>40 cm(-)(1)) to lower energy of the carbonyl stretching vibration (nu(C[double bond]O) in solid state FTIR spectra of the complex. In the solid state structures of 3, 5, and 6, a hydrogen-bonding interaction is found between N(3)-H of the supporting bmnpa/benpa ligand and the zinc-bound oxygen atom of the aryloxide ligand (N(3)...O(1) approximately 2.78 A). Solution (1)H and (13)C NMR spectra of 3-10 in CD(3)CN and FTIR spectra in CH(3)CN are consistent with all of the aryloxide complexes having a similar solution structure, with retention of the hydrogen-bonding interaction involving N(3)-H and the oxygen atom of the zinc-coordinated aryloxide ligand. For this family of zinc aryloxide complexes, a correlation was discovered between the chemical shift position of the N(3)-H proton resonance and the pK(a) of the parent aryl alcohol. This correlation indicates that the strength of the hydrogen-bonding interaction involving the zinc-bound aryloxide oxygen is increasing as the aryloxide moiety increases in basicity.     

N-萘甲基多乙撑多胺类荧光化学敏感器

荧光化学敏感器（ＦｌｕｏｒｅｓｃｅｎｃｅＣｈｅｍｉｃａｌＳｅｎｓｏｒ,ＦＣＳ）是近年来得到迅速发展用以检测外来物种的一种新方法．一般说来,它由下列三个部分所组成：（１）外来物种的接受体部分,（２）荧光发射部分,（３）连接体部分．作为接受体部分的设计是决定ＦＣＳ在检测物种时的选择性或专一性的关键所在．因此其设计往往要和拟检测物种的结构特征相联系．荧光发射部分的选定则和ＦＣＳ的灵敏度相关,适当的选择会使ＦＣＳ的接受体在接受外来物种后,能灵敏地引起荧光发射强度或特征发射波长的变化,使人们可敏锐地发觉所…     

A Dye-sensitized Nanocrystalline Solid State Photovoltaic Cell

Dye-sensitized photovoltaic cells based on nanocrystalline TiO, film are of considerabletechnological interest because of their high conversion efficiency and potential low cost.However the liquid junction photovoltaic cells have a series of technological problems inpractical applications. Recently, the replacement of liquid electrolyte by solid stateconductors such as ionic conducting polymers' and organic hole tfansport materialsZ hasbeen tested. In this papef, we report the fabrication of …     

环形金属双卟啉与5，15-双吡啶卟啉组装体系的笼子效应

利用模板辅助合成的方法合成了一个环形双锌卟啉1,该分子具有灵活的空腔且能扩张到足够的大小以容纳5,15-双吡啶卟啉客体3,包合物13通过Zn—N弱作用力连接,因为笼子效应的存在而构筑成非常稳定的实体（Kassoc=1．45×10^6L／mol）．对于主一客体之间作用力较小的包合物,笼子效应对它们的稳定性起着决定性的作用．这样的主．客体包合物体系具有类似于分子陀螺仪的特点,即主客体两构件之间能灵活地实现相对运动．研究中用1H NMR,UV-vis和荧光光谱滴定的手段对包合物的形成和组装特点进行了详细的研究,同时通过比较它们包合常数（Kassoc）的差异来定量地评价笼子效应在包合物形成中的贡献．     

溶液中N—乙酸基取代氮氧杂大环的构象及其配合物的NMR研究

用~1HNMR方法研究了溶液中大环化合物1,12-二氮杂-3,4:9,10-二本并-5,8-二氧杂环十五烷-N,N’-二乙酸盐的构象.NMR变温实验表明,在溶液中大环与Zn(Ⅱ)、Ni(Ⅱ)、Co(Ⅱ)的配合物环上醚氧不参与配位,其中Ni(Ⅱ)配合物为低自旋反磁性的平面四方形配位.     

Studies on asterosaponins—V : A novel steroid conjugate, 5α-pregn-9(11)-ene-3β,6α-diol-20-one-3-sulfate,from a starfish saponin,asterosaponin A

A new crystalline steroid conjugate was obtained by partial acid hydrolysis of asterosaponin A, a steroidal saponin from the starfish, Asterias amurensis. The structure of the conjugate was established as 5α-pregn-9(11)-ene-3β,6α-diol-20-one-3-sulfate (2) on the basis of elemental analysis, IR and PMR spectra measurement and chemical reaction. Solvolysis of compound 2 yielded 5α-pregn-9(11)-ene-3β,6α-diol-20-one. Oxidation with chromium trioxide-pyridine complex followed by solvolysis afforded a new steroid, 5α-pregn-9(11)-ene-3β-ol-6,20-dione, whose structure was deduced by the measurement of ORD curve and PMR spectra. Thus, the location of carbohydrate moiety in asterosaponin A has been assigned to 6α-hydroxy group of the steroid conjugate.     

The binding of manganese(II) and zinc(II) to the synthetic oligonucleotide d(C-G-C-G-A-A-T-T-C-G-C-G)2. A 1H NMR study

The interaction of the synthetic oligonucleotide d(C-G-C-G-A-A-T-T-C-G-C-G)2 with two different transition-metal ions has been investigated in aqueous solution by means of 1H NMR spectroscopy. The effects on the DNA due to the presence of manganese(II) or zinc(II) have been monitored by observing the paramagnetic broadening and diamagnetic shifts of the non-exchangeable proton resonance lines, respectively. The 1H NMR spectra acquired during the course of the manganese(II) titration show very distinct broadening effects on certain DNA resonance lines. Primarily, the H8 resonance of G4 is affected, but also the H5 and H6 resonances of C3 are clearly affected by the metal. The results imply that the binding of manganese(II) to DNA is sequence specific. The 1H spectra obtained during the zinc(II) titration reveal diamagnetic shift effects which largely conform with the paramagnetic broadening effects due to the presence of manganese(II), although this picture is somewhat more complex. The H8 resonance of G4 displays a clearly visible high-field shift, while for the other guanosine H8 protons this effect is absent. The H1' and H2' protons of C3 show an effect of similar strength, although in the opposite direction, while H5 and H6 of C3 are only slightly affected. Local differences in the structure of the DNA and the basicities of potential binding sites on different base steps in the sequence might account for the observed sequence selectivity.     

Cyclic flow-injection analysis for the repetitive determination of zinc with 2-(5-bromo-2-pyridylazo)-5-[N-n-propyl-N-(3-sulfopropyl)amino]phenol and EDTA.

A circulatory flow-injection method (cyclic FIA) for the repetitive determination of zinc has been proposed. The procedure involves the use of 2-(5-bromo-2-pyridylazo)-5-[N-n-propyl-N-(3-sulfopropyl)amino]phenol (5-Br-PAPS) together with EDTA as a reagent carrier solution, which is recycled in a single-line flow system via a reservoir. The formed 5-Br-PAPS-Zn(II) complex was measured spectrophotometrically at 552 nm, and the signal intensity corresponded to the zinc concentration. After passing through a flow-through cell, the carrier stream then returned to the reservoir, and the main reagent, 5-Br-PAPS, was successfully regenerated by a ligand-exchange reaction with EDTA, allowing the repetitive determination of zinc. The calibration curve for zinc was linear in the concentration range from 0.4 to 10.0 mg dm(-3) with a correlation coefficient of 0.9995 (n = 6). The detection limit of this method was 0.02 mg dm(-3) (S/N= 3). This method allowed as many as 300 repetitive determinations of 2.0 mg dm(-3) zinc solution with only 100 cm3 of the circulating carrier solution, providing a reduction in the consumption of reagents and an elimination of waste, an important approach towards clean chemistry.     

乙二胺三乙酸与锌(Ⅱ)、钴(Ⅱ)相互作用的固体和溶液化学特性

在水热和弱酸性反应条件下,螯合型表面活性剂前驱体乙二胺三乙酸分别与氯化锌、氯化钴反应,形成水合乙二胺三乙酸金属配合物[M(H₂O)₆][M(ED3A)(H₂O)]₂·2H₂O[M=Zn(1),Co(2);H₃ED3A=乙二胺三乙酸,C₈H₁₄N₂O₆]。 产物经元素分析、红外、热重、液体核磁共振和X射线单晶衍射结构表征。 乙二胺三乙酸和锌(Ⅱ)、钴(Ⅱ)五配位,并与水一起形成典型的[MN₂O₄]或[MO₆]八面体结构。 ¹³C核磁共振实验结果表明,溶液中乙二胺三乙酸与锌形成配合物在弱酸性条件下(pH值3~7)稳定存在,在酸性溶液中完全解离,乙二胺三乙酸进一步经分子内成环反应生成3-酮哌嗪二乙酸(H₂kpda=C₈H₁₂N₂O₅)。