卟啉超分子的组装合成及其应用新进展

卟啉超分子已被广泛地用于光学、催化、仿生等方面的研究,部分研究成果已获得实际应用．本文综述了卟啉超分子在组装合成及应用方面的新进展,包括基于不同结构卟啉砌块的新型二维与三维超分子的构筑以及卟啉超分子在光学、催化和分子识别等方面的应用．     

含酚羟基Schiff碱化合物的阴离子识别研究

近年来,超分子化学及其应用研究越来越受到科学家的重视[1].许多氢键供体已成功应用于阴离子识别研究中,如酰胺[2]、硫脲[3]及吡咯大环[4]化合物等.含有酚羟基的Schiff碱型化合物常被用于阳离子识别体系中[5,6],而以其为阴离子识别位点的研究相对较少.作为研究超分子化合物的合成、识别性能等工作的一部分[7],我们设计合成了三种具有多位点识别且含有酚羟基的Schiff 碱新型受体.考察了主-客体配合物中所形成的氢键数目对阴离子选择性识别的影响.     

分子内电荷转移双重荧光体识别阴离子研究

设计合成阴离子受体是近年来超分子化学中一个颇为活跃的研究领域[1～ 7] .其中荧光法以其高灵敏度和高选择性等特点使发光受体的设计合成备受关注 [6 ,7] .分子内电荷转移 (Intramolecular charge transfer,ICT)原理已被成功地用于构筑阳离子荧光传感体系[8] ,但将其应用于阴离子识别的研究尚鲜见报道[9～ 12 ] .本文设计合成了 ICT荧光体对二甲氨Scheme 1　 The structures of anion receptors基苯甲酰肼 (DMABH,结构见 Scheme 1 ) ,研究了 DMABH与阴离子如 HSO- 4,Ac O- ,H2 PO- 4,Cl O- 4,NO- 3,Cl- 和 Br- 等结合后的光…     

有机阳离子-无机多阴离子复合物:高分子体系中的组装及其自组装

有机阳离子包覆多金属氧簇无机多阴离子形成的具有确定化学组成、两亲性核壳结构超分子复合物,具有易于调控和集成有机和无机组分结构与功能的特性.以此类复合物为预组装体的自组装和高分子功能杂化材料展现了一类具有多方面构筑超分子组装体的新型构筑基元体系.如何实现预组装体复合物在结构稳定、具有良好加工性基材中的组装和功能化成为这一领域的重要研究内容.本文系统地总结了基于此类超分子复合物的高分子纳米复合材料和溶液中组装方面的研究进展与发展趋势.     

二联体卟啉的光致电荷转移行为

卟啉聚集体在光合作用和生物体新陈代谢过程中发挥着极为重要的作用[1,2 ] .但是在复杂的自然界体系中 ,研究卟啉聚集体中的电子转移行为非常困难 ,所以借助于简单的二联体卟啉和多聚体卟啉作为生物体新陈代谢过程中活性位点的模型来研究其间的电荷转移行为[3] .近年来 ,人们在二联体卟啉和多聚体卟啉合成及性质表征方面做了大量的工作 ,特别是利用各种光谱来研究它们的电子和光生电子行为以及它们与具有生物活性的分子和特殊气体分子之间的电荷转移过程 [4 ,5] .本文利用表面光电压谱 (SPS)技术对二联体卟啉的光伏响应进行了研究 ,发现二…     

水玻璃为原料在开放体系中快速合成介孔材料MCM-41

自从 M41 S系列硅基介孔分子筛被人工合成以来[1,2 ] ,有关分子筛的合成、性能、形成机理、结构和应用等方面的研究报道不断出现[3～ 5] .目前 ,由有机 -无机离子经分子水平的自组装结合而产生介孔材料的合成机理主要归结于在合成过程中表面活性剂的模板效应 ,如液晶模板机理[1,2 ] 、棒状自组装模型[6 ] 、电荷匹配机理[7] 、层状折皱模型[8] 和使用非离子表面活性剂合成介孔材料等效应[9] .本文以水玻璃作为硅源 ,以十六烷基三甲基溴化铵 (CTAB)阳离子表面活性剂为模板剂 ,在温和条件下 ,采用开放体系合成出具有 MCM-4 1结构特点的介…     

并入两个四氢键组装单体的卟啉衍生物的合成研究

报道了一个新的卟啉四氢键超分子聚合物组装单体29的合成研究。通过对 Gong等最近报道的四氢键二聚体组装板块进行修饰，合成了两个相应的新的苯甲酸 衍生物中间体11和21，以间－硝基苯甲醛为原料以较高产率合成了一个二硝基四苯 基卟啉26，氯化亚锡还原得到另－卟啉二胺中间体28。以DCC为缩合剂，该卟啉二 胺与其中一个酸11发生缩合反应得到相应卟啉组装单体目标分子29。化合物29在弱 极性溶剂中具有良好的溶解度。     

两个基于多金属氧酸盐和冠醚基超分子阳离子的有机无机杂化材料的合成及晶体结构（英文）

以二苯并18-冠-6,3-氟-4-甲基苯铵盐以及多金属氧酸盐[Mo6O19]2-为原料,使用溶剂挥发法合成了有机无机杂化材料[(3-F-4-Me Anis)(DB[18]crown-6)]2[Mo6O19]·2CH3CN(1)(3-F-4-Me Anis=3-氟-4-甲基苯铵盐;DB[18]crown-6=二苯并18-冠-6);以18-冠-6,2-氟-4-甲基苯铵盐以及多金属氧酸盐[SMo12O40]2-为原料,运用H管扩散法制备了晶体材料[(2-F-4-Me Anis)([18]crown-6)]2[SMo12O40]·2CH3CN(2)(2-F-4-Me Anis=2-氟-4-甲基苯铵盐;[18]crown-6=18-冠-6)。通过红外光谱、元素分析、热重分析和X射线单晶结构分析对化合物进行了表征。结构分析表明,晶体1和2通过非共价键自组装作用构建而成,冠醚基超分子阳离子是通过N-H…O氢键作用形成。在晶体1和2中,超分子阳离子和多酸阴离子交错堆积形成包合物结构,沿着a轴方向观察,发现每个多酸阴离子被6个超分子阳离子包围着形成六边形堆积结构。通过晶体结构研究和热重分析表明,二苯并18-冠-6中的苯环在维持晶体1的稳定性方面具有重要的作用。     

两个基于[SMo_(12)O_(40)]~(2-)和冠醚基超分子阳离子的无机-有机杂化晶体的合成及晶体结构（英文）

以18-冠-6和4-碘-苯铵盐,二苯并30-冠-10和3-氟-4-氯-苯铵盐为超分子阳离子构建单元,分别引入到Keggin型[SMo_(12)O_(40)]~(2-)中,使用H管扩散法和溶剂挥发法合成了无机-有机杂化材料[(4-I-Anis)([18]crown-6)]2[SMo12O40]·CH3CN (1)和[(3-F-4-Cl-Anis)2(DB[30]crown-10)][SMo12O40]·2CH3CN (2)(4-I-Anis=4-碘-苯铵盐;3-F-4-Cl-Anis=3-氟-4-甲基苯铵盐;DB[30]crown-10=二苯并30-冠-10)。通过红外光谱、元素分析、热重分析、固态漫反射光谱和X射线单晶结构分析对化合物进行了表征。结构分析表明,晶体1和2通过非共价键自组装作用构建而成,冠醚基超分子阳离子是通过N-H…O氢键作用形成。晶体1中,在bc平面,每个[SMo_(12)O_(40)]~(2-)多酸阴离子被6个超分子阳离子(4-I-Anis)([18]crown-6)围绕,形成六边形的结构;晶体2中,在bc平面,每个[SMo_(12)O_(40)]~(2-)多酸阴离子被4个大的超分子阳离子(3-F-4-Cl-Anis)2(DB[30]crown-10)围绕,形成四边形的结构。热重分析表明,氢键在维持晶体1和2的稳定性上起着主要的作用。固态漫反射光谱表明,[SMo_(12)O_(40)]~(2-)和冠醚基超分子阳离子之间存在电荷转移作用。     

杯[4]吡咯与含氧阴离子及其离子对弱相互作用的理论研究

在M06-2X/6-31+G(d,p)计算水平上,对杯[4]吡咯(CP)与3种不同构型的含氧阴离子OH-(C(v)、NO3-(D3h)、ClO4-(Td)形成的组装体系进行了理论研究。比较了各体系的构型、结合能、自然键轨道(NBO),利用多功能波函数软件Multiwfn对相互作用力等进行可视化分析。结果发现,无论主-客体的组装计量比是1∶1还是2∶1,阴离子的构型直接影响组装体系的构型。阴离子空间构型越大、整体电负性越强,越倾向于2∶1复合体系。考虑到杯[4]吡咯是典型的离子对受体,本文还研究了主体与NH4+-阴离子的离子对体系的相互作用。在离子对的组装过程中,由于阴、阳离子间的作用占据了主导,从而减弱了阴离子与主体间氢键作用,无论阴离子构型如何,主体与离子对的组装都倾向于1∶1的作用体系。本文结果对深入理解杯吡咯类受体的离子识别作用本质,拓展该类超分子主体的应用范围具有重要的理论意义。     

多重环境刺激响应性聚苄醚型树状分子凝胶制备及性能研究

环境刺激响应性超分子凝胶材料在传感器、光开关、人工触角、药物缓释等领域表现出潜在的应用前景。本文设计合成了一种新型的核心含偶氮苯官能团聚苄醚型树枝状分子凝胶因子CA-G2。成胶性能测试表明,该凝胶因子在23种有机溶剂和混合溶剂中均可以形成稳定的淡黄色凝胶,其中在苯中表现出最优的成凝胶性能,临界成胶浓度(CGC)可达2.0mg/mL(0.23(wt)%),相当于一个树枝状分子可以固定1.5×10⁴个溶剂分子,表明该凝胶因子具有非常优异的成凝胶性能。并且,该类凝胶材料能够同时对热、超声和触变等外界环境刺激产生响应,并伴随着宏观上凝胶-溶胶的相互转变。此外,该类凝胶对罗丹明B染料分子具有优异的吸附性能,吸附效率高达96.7%。     

Syntheses of dendritic branches based on L-lysine: is the stereochemistry preserved throughout the synthesis?

This paper reports the syntheses of individual dendritic branches based on L-lysine and functionalised with either Boc or Bz surface groups. Convergent and divergent synthetic approaches were employed and the preservation of stereochemistry during the syntheses was monitored using polarmetry, NMR and HPLC. In addition, racemic dendritic branches based on D,L-lysine were synthesised for comparative purposes. It was observed that the preservation of stereochemistry in the dendritic peptide was dependent on the method of synthesis, with divergent methodology being preferred. The results are discussed in terms of the known stereochemical outcomes of traditional peptide coupling processes, and are generalised to the synthesis of other dendritic peptides. Such observations about the chirality of dendritic peptides are of relevance to chemists developing dendritic systems for applications where single enantiomer dendrimers would clearly be preferred, such as enantioselective catalysis or pharmaceutical chemistry.     

Synthesis of novel dendritic 2,2'-bipyridine ligands and their application to Lewis acid-catalyzed diels-alder and three-component condensation reactions

A series of dendritic ligands with a 2,2'-bipyridine core was synthesized through the coupling of 4,4'-dihydroxy-2,2'-bipyridine with poly(aryl ether) dendrons. The corresponding dendritic Cu(OTf)2 catalysts were used for Diels-Alder and three-component condensation reactions. The dendritic Cu(OTf)2-catalyzed Diels-Alder reaction proceeded smoothly, and these dendritic catalysts could be recycled without deactivation by reprecipitation. Three-component condensation reactions such as Mannich-type reactions also proceeded not only in dichloromethane but also in water. Furthermore, a positive dendritic effect on chemical yields was observed in both Diels-Alder reactions and aqueous-media three-component condensation reactions.     

Polyaryl ether dendrimer with a 4-phenylacetyl-5-pyrazolone-based terbium(III) complex as core: synthesis and photophysical properties

A series of novel dendritic beta-diketone ligands, 1-phenyl-3-[G-n]-4-phenylacetyl-5-pyrazolone (n = 0-3, G stands for polyaryl ether), were synthesized by introducing Fréchet-type dendritic branches. The corresponding Tb3+-cored dendritic complexes were characterized by X-ray crystallography, elemental analysis, ESI mass spectra, and FT-IR spectra. These dendritic complexes, prepared from aqueous solution, exhibit high stability. Interestingly, the study of photophysical properties shows that the luminescence quantum yields of the dendritic Tb-complexes increase from 0.1 to 2.26% with an increase of the dendritic generation from 0 to 3. Importantly, an "energy-reservoir effect" was observed in the dendritic system using the method based on the resonance energy transfer from these complexes to rhodamine 6G. With the increase of the dendritic generation, the metal-centered luminescence quantum yield was almost the same, and the energy transfer (phi(transfer)) from the ligand to Tb(3+) increased. Further measurements of the triplet state and oxygen quenching of these dendritic complexes verify that this enhancement of the energy transfer (phi(transfer)) is attributed to both an "antenna effect" and a "shell effect".     

Synthesis of dendritic catalysts and application in asymmetric transfer hydrogenation

Frechet-type core-functionalized chiral diamine-based dendritic ligands and hybrid dendritic ligands condensed from polyether wedge and Newkome-type poly(ether-amide) supported multiple ligands were designed and synthesized. The solubility of hybrid dendrimers was found to be finely controlled by the polyether dendron. The catalytic efficiency and recovery use of dendritic ruthenium complexes were compared in the transfer hydrogenation of acetophenone. The core-functionalized dendritic catalysts demonstrated much better recyclability, which verified the stabilizing effects of the bulky polyether wedge on the catalytically active complex. Moreover, the dendritic catalysts were applied in the asymmetric transfer hydrogenation of ketones, enones, imine, and activated olefin, and moderate to excellent enantioselectivitiy was achieved comparable to that of monomeric catalysts.     

新型树枝状PNP铬催化剂的合成及催化性能

以1.0代聚酰胺-胺(PAMAM)为配体骨架,氯代二苯基膦为原料,通过取代反应合成了1种含有较大空间位阻的新型树枝状PNP配体,再以Cr Cl3(THF)3为络合试剂,通过络合反应合成树枝状PNP铬催化剂.采用傅里叶变换红外光谱(FTIR)、紫外-可见分光光度计(UV-Vis)、核磁共振波谱(NMR)、电喷雾电离质谱(ESI-MS)和元素分析等手段证实合成的新型树枝状PNP配体及其铬催化剂的结构与理论设计的结构一致.以甲基铝氧烷(MAO)为助催化剂,对乙烯齐聚反应进行了研究,考察了溶剂种类、反应温度、反应压力及Al/Cr摩尔比对该催化剂活性和选择性的影响.结果表明,以甲苯为溶剂,MAO为助催化剂,当反应温度为25℃,反应压力为0.9 MPa,Al/Cr摩尔比为500时,该催化剂的活性高达2.15×105g/(mol Cr·h),催化剂对乙烯三聚、四聚反应的选择性共达到36.76%.     

Dendrimer-based hydrogen-bonded liquid crystalline complexes: Synthesis and characterization

Three generations of dendritic polyester macromolecules based on 5-hydroxyisophthalic acid were synthesized by the divergent growth approach. The characterization of dendritic fragments was performed using a combination of ¹H NMR, ¹³C NMR spectroscopy and elemental analysis. The dendritic hydrogen-bonded supramolecular liquid crystalline complexes were prepared from different generation of dendritic acids and stilbazole derivative containing pyridyl units. The polarizing optical microscopy (POM) and differential scanning calorimetry (DSC) were used for investigation of the liquid crystalline properties of the hydrogen-bonded dendritic supramolecular complexes.     

Self-assembly of two-component peptidic dendrimers: dendritic effects on gel-phase materials

The self-assembly of diaminododecane solubilised by different dendritic peptides, possessing increasing levels of dendritic branching, was investigated. The dendritic peptides were based on l-lysine building blocks and were of first, second and third generation, containing one, three and seven amino acid repeat units respectively. By applying these structures as potential gelator units, the dendritic effect on gelation was investigated. The degree of structuring was modulated, with the dendritic peptide controlling the aggregate morphology and the ability of the self-assembled state to manifest itself macroscopically as gelation. First generation gelator units (G1) did not induce macroscopic gelation with diaminododecane under any conditions, whilst those self-assemblies based on second (G2) and third (G3) generation branches did form gel-phase materials. Furthermore, gel-phase materials based on G2 exhibited optimum gelation behaviour compared to those based on G3(in terms of the thermal strength of the materials). Circular dichroism showed that the dendritic effect, programmed in at the molecular level, is directly related to the degree of chiral organisation within the self-assembled state. The dendritic generation of the peptide controls the pattern of amide-amide hydrogen bonding in terms of binding strength and alignment as determined using NMR methods. The mode of self-assembly can be qualitatively rationalised in terms of an attractive enthalpic interaction (i.e., amide-amide hydrogen bonding), a repulsive interaction (i.e., steric interactions between dendritic peptides) and an entropic term related to the hierarchical organisation of the gelator building blocks. It is argued that the balance between these factors determines the nature of the dendritic effect.     

树形聚酰胺胺与 Cu2＋的络合作用

合成了4.0代聚酰胺胺 (PAMAM)树形分子 ,并合成出端基为羟基的PAMAM树形分子衍生物。用分光光度法研究了4.0代PAMAM树形分子及其衍生物与Cu2 的络合作用。结果表明当存在树形聚酰胺胺分子时 ,Cu2 水溶液的最大吸收波长显著紫移 ,随n(Cu2 )/n(PAMAM)增加 ,最大吸收波长红移 ;PAMAM树形分子与Cu2 的络合作用有多种形式 ,对端胺基树形分子主要存在Cu -N4 和Cu -N2 两种配位方式 ;对端羟基树形分子主要存在Cu -N2 的配位方式 ;随Cu2 的加入 ,络合形式和各种络合形式的相对比例发生变化 ;pH对络合形式有较大影响;随代数的增加 ,树形分子所能络合Cu2 的最大数目不断增加 ,但理论值与实验值有一定的误差     

Synthesis of a PEG-PNIPAm thermosensitive dendritic copolymer and investigation of its self-association

A Novel thermosensitive dendritic copolymer based on polyethylene glycol(PEG) and poly(Nisopropylacrylamide)(PNIPAm) with a cloud point(CP) around 36 ?C was successfully synthesized by preparation of a dendritic polyol and followed by atom transfer radical polymerization(ATRP) of N-isopropylacrylamide. The dendritic copolymer was characterized using gel-permeation chromatography(GPC), FTIR and 1H-NMR spectroscopy. The selfassociation behavior of the copolymer in aqueous medium was investigated by dynamic light scattering(DLS) and transmission electron microscopy(TEM). These investigations confirmed that the dendritic copolymer showed different association behaviors at various temperatures.