Dendrimers with peripheral stilbene chromophores

Two types of dendritic nanoparticles were prepared, which contain (E)-stilbene chromophores in the terminal positions of the dendrons. The compounds showed a highly efficient photoreactivity in the course of which statistical CC bond formations led to a crosslinking of the particles. Finally, all stilbene chromophores reacted and the typical (E)-stilbene absorption and fluorescence disappeared completely.     

Porphyrins Like Boron After All

The central core and the macrocycle skeleton of porphyrins both offer room for boron, and a gap in the chemistry of nonmetal-containing porphyrins has now been filled. In one case a four-membered B₂O₂ ring coordinates to a porphyrin cavity that has been distorted to a rectangle ( A ), and in the other case four boron atoms are located in the meso positions of a tetrathiaporphyrinogen ( B ).     

含硅的树枝状大分子的研究进展

树枝状大分子是一类具有规则的、高度支化的三维结构的高分子 ,含硅的树枝状大分子是以硅原子作为两代之间的支化点的树枝状大分子。本文主要综述了硅氧烷型、碳硅烷型、硅烷型树枝状大分子的合成方法及含硅的树状金属络合物的研究进展。     

Novel Carbosiloxane Dendrimers with End-Grafted Highly Functionalized Building Blocks

This article concentrates on the divergent growth method for the preparation of SiOCH₂CH₂CH₂-based carbosiloxane dendrimers by applying repetitive hydrosilylation-alcoholysis cycles. The silicon atoms thereby act as the branching points producing a tetrahedral four directional core as well as 1→1 and 1→2 branching centres.     

Stilbenoid Dendrimers

A convergent synthesis in which all trans double bonds were constructed by Wittig–Horner reactions produces dendrimers of the general structure 1 . With long-chain alkoxy residues on the periphery of the benzene rings, the first two generations display liquid crystalline behavior.     

Towards Carotenoid Dendrimers: Carotenoid Diesters and Triesters with Aromatic Cores

For the evaluation of the synthesis of dendritic esters from carotenoids, various carotenols or their succinates were reacted with bi‐ and trifunctional aromatic acids and alcohols. Several methods were tested, from which the Steglich esterification was found to give the best yields. Apocarotenoids showed higher reactivity in most of the reactions and served as model compounds for C₄₀ carotenoids and their derivatives. The synthesized triesters can be regarded as first generation dendrimers.     

SMTP-1: The First Functionalized Metalloporphyrin Molecular Sieves with Large Channels

Robust hexagonal cavities (dimensions: 17×20×15 Å), encompassed by the pyridyl groups of cyclic metalloporphyrin hexamers (see picture), are the characteristic structural motifs of the nanoporous materials [{M(tpyp)}₆]⋅n G (M=Co, Mn; tpyp=tetrakis(4-pyridyl)porphyrinato; G=guest molecule), which were prepared from MCl₂ and H₂tpyp under hydrothermal conditions. The rhombohedral crystal lattice with infinite hexagonal channels is thermally stable up to 400°C, even after the removal of the guest molecules.     

树枝状大分子聚酰胺-胺的荧光特性

聚酰胺-胺( PAMAM) 树形大分子是近年来得到迅速发展的一类新型聚合物,其独特结构、功能化和应用价值引起了化学家们的极大研究兴趣.并在多个领域显示出良好的应用前景.近来又发现(PAMAM)在适当的pH值条件下发射较强的荧光,本文主要介绍了PAMAM对荧光物质的增强作用,PAMAM作为模板制备纳米粒子中的荧光效应,以及PAMAM自身荧光的发现及对其荧光机理的研究,并对PAMAM的荧光应用进行了展望.PAMAM 树型大分子由于具有良好的生物相容性、优异的能量转移机制等,有可能成为新型的生物荧光标记物.     

树枝状大分子在荧光生物成像中的研究进展

树枝状大分子是一种具有精确三维结构的纳米材料。目前,对于树枝状大分子的研究,逐渐从合成和表征各式各样的树枝状大分子转向到对其特殊功能和应用的研究。传统的荧光成像探针大多数为小分子化合物,其发展受到特异性低、稳定性差、停留时间短、可修饰基团少和毒性大等缺点的限制。树枝状大分子具备独特的分子结构如大量可设计性的末端官能团和广阔的分子内空腔以及选择多样化的优势,使其在荧光生物成像领域中有良好的应用前景。本文重点介绍了基于树枝状大分子的有机荧光探针和量子点探针在生物成像方面最新的研究进展。     

聚酰胺-胺树状大分子的应用

聚酰胺-胺(PAMAM)树状大分子是目前树状大分子化学中研究较为成熟的一类，是三种已经商品化的树状大分子之一，其功能化和应用是目前树状大分子领域的热点。PAMAM已在多个领域显示出良好的应用前景。本文主要对PAMAM在表面活性剂、催化剂、纳米复合材料、金属纳米材料、膜材料、导电材料等方面的应用进行评述。     

生物材料聚酰胺-胺树状大分子在医学领域研究进展

聚酰胺－胺（PAMAM）树状大分子是一类新型纳米生物材料，这类分子可通过有机合成的方法精确控制分子的结构和相对分子质量，其独特的分子结构使之在许多领域获得广泛应用，本文着重介绍了PAMAM树状大分子作为基因载体，药物载体，磁共振造影剂和硼中子俘获治疗试剂等在医学领域中的研究进展。     

Multioperational Oxidase Biosensors Based on Carbosilane Dendrimers with Interacting Ferrocenes

The bioelectrocatalytical properties and kinetic characteristics of new oxidase biosensors based on two different carbosilane dendrimers are described. The best glucose biosensor developed displayed, in an ascorbate interference free work potential interval, a strictly linear range from 0 to 4.0 mM, a detection limit of 40,6 μM and a response time less than 3 s. The lactate biosensor displayed a linear range from 0 to 0.8 mM, a detection limit of 0.73 µM and a response time less than 2 s. The apparent Michaelis–Menten constants were calculated to be 4.39 mM and 2.08 mM respectively, according to Lineweaver–Burk equation.     

Convergent Route to Organometallic Dendrimers Composed of Platinum–Acetylide Units

The third‐generation dendrimer with 45 platinum atoms (shown schematically) was synthesized efficiently by a convergent methodology in which two different trialkylsilyl groups (symbolized by the nodal points) are used to protect the bridging triethynylbenzene derivatives. PT=[Pt(PEt₃)₂].     

Multistate Structural Switching of [3]Catenanes with Cyclic Porphyrin Dimers by Complexation with Amine Ligands

Catenanes with multistate switchable properties are promising components for next-generation molecular machines and supramolecular materials. Herein, we report a ligand-controlled switching method, a novel method for the multistate switching of catenanes controlled by complexation with added amine ligands. To verify this method, a [3]catenane comprising cyclic porphyrin dimers with a rigid π-system has been synthesized. Owing to the rigidity, the relative positions among the cyclic components of the [3]catenane can be precisely controlled by complexation with various amine ligands. Moreover, ligand-controlled multistate switching affects the optical properties of the [3]catenanes: the emission intensity can be tuned by modulating the sizes and coordination numbers of integrated amine ligands. This work shows the utility of using organic ligands for the structural switching of catenanes, and will contribute to the further development of multistate switchable mechanically interlocked molecules.     

Multiplurifunctionalized Phosphorus Dendrimers: Selective Functionalization of P(X)CL2 Terminal Groups

Abstract

Dendrimers are hyperbranched macromolecules constituted of repetitive branched units. They are synthesized step-by-step, a method which ensures a perfectly defined structure. This mini-review reports examples of rare “multiplurifunctionalized” dendrimers that have several types of functional groups precisely located on each terminal branching point. They are obtained thanks to the specificity of the reactivity of each Cl of P(X)Cl₂ (X = generally S, but also O) terminal groups on the surface of poly(phosphorhydrazone) dendrimers.     

Dendrimers: From Design to Application—A Progress Report

A unique combination of a clearly defined particle structure and a very highly functionalized surface is offered by the topical dendrimers. Many groups work on this unusual molecular architecture to develop new applications. The most advanced progress in this respect is an MRI contrast agent based on dendrimers (see schematic representation) that facilitate the visualization of bloodstreams.     

表面修饰富勒烯的聚酰胺-胺树枝状分子与生物膜的相互作用研究

采用粗粒化的分子动力学模拟,研究了末端修饰富勒烯(C60)的聚酰胺-胺(PAMAM)树枝状分子在水溶液中的结构变化以及其与磷脂膜相互作用行为.发现修饰后的PAMAM分子大小随嫁接数目的增多而减小,而形状变化并不明显,分子仍是近球形结构;同时发现C60分子因疏水作用聚集在一起.与膜作用后,因C60分子插入到双层膜内,导致分子由球形稍微向椭球形改变,分子大小也稍微增大.同时发现PAMAM分子紧紧分布在磷脂膜表面,局域膜厚度变小.     

有机及金属有机苯乙炔树状分子体系的非线性光学性质的理论研究

应用密度泛函理论研究了一系列有机及金属有机苯乙炔树状分子的激发态性质和非线性光学性质。计算的电子吸收光谱显示这些树状分子均在低能区域有一个最强的吸收;此外,金属有机体系的吸收光谱和有机体系相比发生了明显的红移。响应性质的计算结果表明共轭体系的扩展和金属有机基团的引入都使得苯乙炔树状分子的非线性光学极化率显著增加,尤其是含Ru体系,其β和γ值呈数量级增长。对于有机体系和含Pd体系,发生在共轭体系内部的π→π*电荷跃迁是产生分子一阶和二阶超极化率的主要原因。而含Ru体系相当大的非线性响应则主要起源于Ru的轨道到共轭体系的π*的跃迁,同时与Ru相邻的C≡C到共轭体系的π→π*跃迁起着辅助贡献。     

新型树枝功能化萘酰亚胺类发光材料的合成及其光放大效应

在树枝(dendron)上引入特定的功能单元,将多个具有特定功能团(咔唑)连接起来．形成功能化树枝状周边分子团簇,然后将它们分别与核心色素萘酰亚胺相连接,合成新型周边树枝状功能化的有机发光材料(共三代)。稳态荧光研究发现周边功能团吸收的能量能以较高的效率传递给中心核色素萘酰亚胺。其传输效率与化合物的树枝代数密切相关,具有特殊的光采集、光放大效应。瞬态荧光研究表明树枝化合物中的咔唑单元都呈双指数衰减特征,其中较短荧光寿命成分是咔唑和萘酰亚胺单元之间的相互作用。