聚酰胺-胺型树枝状高分子PAMAM溶液的特性粘度

测定了树枝状高分子PAMAM(聚酰胺-胺型,乙二胺为内核)及其季铵盐在水溶液中的特性粘度[η].结果表明,PAMAM的[η]在代数G=2～3处有最大值,而其季铵盐则在此处有最小值.同时发现高分子的流体力学等效圆球半径R_η随G增大近似线性增长.通过对PAMAM及其季铵盐特性粘度的研究,揭示了不同代数高分子结构形态的变化规律.     

Dendrimer pattern formation in evaporating drops

The redistribution of organic solutes during drop evaporation is a nanoscale self-assembly process with relevance to technologies ranging from inkjet printing of organic displays to synthesis of biosmart interfaces for sensing and screening. We have used solutions of dendrimer molecules with incrementally varying terminal site chemistry to explore whether the condensed dendrimer patterns resulting from microdroplet evaporation sensitively depend on, and are characteristic of, the surface chemistry of the solute molecules. This hypothesis has been experimentally confirmed by comparing the behavior of microdroplets of G4, G4-25%C12, and G4-50%C12 dendrimers dissolved in pentanol and deposited on mica substrates. For the dilute concentration studied here, the presence of periodically 'scalloped' dendrimer rings is ubiquitous. The instability wavelength of the scalloped rings is found to be proportional to the width of the ring, similar to observations of the rim instability in dewetting holes. The effect of dendrimer surface chemistry is obvious in the detailed structure of the self-assembled rings. G4 rings are diffuse and disordered with no evidence for layered growth. G4-25%C12 exhibits highly ordered ring structures and the onset of monomolecular terracing. G4-50%C12 exhibits highly periodic scallops and very distinct monomolecular height terraced growth of the rings with flat terraces and sharply defined steps. On the basis of these results, it is likely that the morphology of condensed molecule-based ring patterns formed by evaporation of microdroplets on surfaces can be used as a 'fingerprint' to identify, for example, solute molecule surface chemistry and concentration and function as a sensor for a variety of biochemical events.     

Dendrimer with rotaxane-like mechanical branching

[reaction: see text] A dendrimer wherein the branching points are mechanical in nature has been synthesized. It contains two identical covalently linked bis-dendrons and a core unit fused to two rings that encircle the two bis-dendrons. A "threading-followed-by-stoppering" approach is used in the template-directed synthesis of a precursor bis[2]rotaxane, which undergoes stopper exchange four times to yield the dendrimer in which the two bis-dendrons act as stoppers within the two [2]rotaxane subunits.     

Electrostatically-driven Ordering in Model Dendrimer Polyelectrolytes: Effects of Concentration

In this study we extend our previous work in the self-organization of dendrimer polyelectrolytes (Macromolecules, 2008 , 41, 225) by examining the effects of dendrimer concentration and/or total volume fraction in the ordering process and the resulting structure, in the arrangement of counterions and dendrimer beads and in the diffusive motion of dendrimers at different strengths of Coulombic interactions. It is found that as long as the total volume fraction remains low (i.e. no jamming phenomena intervene) the symmetry of the resulted cubic phases is unaltered. At a higher volume fraction and at the strong electrostatic regime a kinetic arrest of the dendrimer molecules much in analogy to a colloidal glass-like transition is observed, inhibiting thus the ordering process. Changes in the strength of electrostatic interactions and dendrimer concentration induces a systematic variation of the counterion - counterion and the counterion - charged-dendrimer-bead spatial arrangement. These findings are in qualitative agreement with previous studies in systems with very different structural details of the considered solutes, indicating a more general behaviour in charged macroion/counterion solutions.     

Rapid Bacterial Recognition over a Wide pH Range by Boronic Acid-Based Ditopic Dendrimer Probes for Gram-Positive Bacteria

We have developed a convenient and selective method for the detection of Gram-positive bacteria using a ditopic poly(amidoamine) (PAMAM) dendrimer probe. The dendrimer that was modified with dipicolylamine (dpa) and phenylboronic acid groups showed selectivity toward Staphylococcus aureus. The ditopic dendrimer system had higher sensitivity and better pH tolerance than the monotopic PAMAM dendrimer probe. We also investigated the mechanisms of various ditopic PAMAM dendrimer probes and found that the selectivity toward Gram-positive bacteria was dependent on a variety of interactions. Supramolecular interactions, such as electrostatic interaction and hydrophobic interaction, per se, did not contribute to the bacterial recognition ability, nor did they improve the selectivity of the ditopic dendrimer system. In contrast, the ditopic PAMAM dendrimer probe that had a phosphate-sensing dpa group and formed a chelate with metal ions showed improved selectivity toward S. aureus. The results suggested that the targeted ditopic PAMAM dendrimer probe showed selectivity toward Gram-positive bacteria. This study is expected to contribute to the elucidation of the interaction between synthetic molecules and bacterial surface. Moreover, our novel method showed potential for the rapid and species-specific recognition of various bacteria.     

Impact of a Water-Soluble Gallic Acid-Based Dendrimer on the Color-Stabilizing Mechanisms of Anthocyanins

The interaction of two anthocyanins with a water-soluble polyanionic dendrimer was studied through UV/Vis, stopped-flow, and NMR spectroscopy. Cyanidin-3-glucoside (cy3glc) revealed a stronger interaction than malvidin-3-glucoside (mv3glc) at pH 1 according to their apparent association constants. A higher color increased was also obtained for cy3glc at pH 3.5 as a result of this stronger interaction. A high-frequency chemical shift of the cy3glc aromatic protons suggest the formation of ionic pairs. The interaction parameters (K≈700 m ⁻¹, n≈295) indicated the binding of approximately two anthocyanin molecules by each sulfate group. The equilibrium and rate constants of cy3glc in the presence of dendrimer showed an increased stability of the flavylium cation and a higher protection of this species from hydration (pK′_a and pK_h increased almost one pH unit). The tuning and color stabilization of anthocyanins by using this dendrimer allow novel applications as colorimetric sensors for food packaging.     

聚酰胺-胺型树枝状高分子水溶液的表面活性

树枝状化合物是一类三维的、高度有序的新型高分子.与传统高分子相比,这类化合物在合成时,可以在分子水平上严格控制,设计分子大小、形状、结构和功能基团,产物一般高度对称,单分散性好.因而具有广泛的潜在用途^[1,2].近年来,已引起广大化学工作者的重视.     

Dendrimer influenced supramolecular structure formation of block copolymers: II. Dendrimer concentration dependence

The dendrimer concentration dependence of the supramolecular structure formation of polystyrene-block-poly(acrylic acid) in dioxane/THF was investigated as a function of water content. The distribution as well as the localization of the dendrimer units inside the formed aggregates were determined by comparative studies of turbidity measurements and transmission electron microscopy. The strong and specific interactions present between the amine groups of the dendrimer (PAMAM) and the carboxylic acid residues of PAA in the copolymer have a strong influence on the structure formation. The PAMAM concentration as well as the character of the terminal groups of the dendrimer influence the strength of these interactions and consequently affect the structure formation process. As shown by fluorescence quenching experiments, on all supramolecular hierarchical structure levels, and specifically in vesicles, the dendrimer is coated by the PAA chains of the block copolymer due to the strong interactions; since the PAA blocks are connected to the PS blocks, which form the corona, the dendrimer is surrounded by PS chains and is thus encapsulated into the hydrophobic regions of the block copolymer aggregates. A high-resolution transmission electron microscopy image of a micelle is shown, in which the individual dendrimer cores are seen to be localized in the center of these aggregates, and thus, the structure proposed in the previous publication (Kroeger, A.; Li, X.; Eisenberg, A. Langmuir 2007, 23, 10732) is confirmed. Furthermore, the sizes of the resulting aggregates depend on the relative concentration of dendrimer, expressed as RAm/Ac (the ratio of amine to acid groups). With increasing RAm/Ac values, not only the sizes of the micelles but also the vesicle dimensions, especially vesicle wall thicknesses, increase, and this effect suggests the encapsulation of the dendrimer into the vesicle walls. Thus, the constitution of the vesicle structure is determined precisely. This feature allows the potential incorporation of a wide range of species into the vesicle walls or the center of the micelle cores.     

Dendrimer building toolkit: Model building and characterization of various dendrimer architectures

We have developed a graphical user interface based dendrimer builder toolkit (DBT) which can be used to generate the dendrimer configuration of desired generation for various dendrimer architectures. The validation of structures generated by this tool was carried out by studying the structural properties of two well known classes of dendrimers: ethylenediamine cored poly(amidoamine) (PAMAM) dendrimer, diaminobutyl cored poly(propylene imine) (PPI) dendrimer. Using full atomistic molecular dynamics (MD) simulation we have calculated the radius of gyration, shape tensor and monomer density distribution for PAMAM and PPI dendrimer at neutral and high pH. A good agreement between the available simulation and experimental (small angle X‐ray and neutron scattering; SAXS, SANS) results and calculated radius of gyration was observed. With this validation we have used DBT to build another new class of nitrogen cored poly(propyl ether imine) dendrimer and study it's structural features using all atomistic MD simulation. DBT is a versatile tool and can be easily used to generate other dendrimer structures with different chemistry and topology. The use of general amber force field to describe the intra‐molecular interactions allows us to integrate this tool easily with the widely used molecular dynamics software AMBER. This makes our tool a very useful utility which can help to facilitate the study of dendrimer interaction with nucleic acids, protein and lipid bilayer for various biological applications. © 2012 Wiley Periodicals, Inc.     

PAMAM树形分子与Cd2＋的配位作用研究及CdS/PAMAM纳米复合材料的制备与表征

CdS半导体纳米簇具有独特的光、电性能, 如何制备均匀分散的、能够稳定存在的CdS纳米簇是目前的研究热点之一. 以聚酰胺-胺(PAMAM)树形分子为模板, 原位合成了CdS纳米簇. 首先用UV-Vis分光光度法研究了与树形分子的配位机理, 得出G4.5和G5.0的平均饱和配位数分别为16和34, 并发现在G4.5PAMAM树形分子中Cd^2＋主要与最外层叔胺基配位, 在G5.0PAMAM树形分子中Cd^2＋主要与最外层伯胺基配位. 酯端基的G4.5的模板作用要明显优于胺端基的G5.0. 通过改变Cd^2＋与G4.5树形分子的摩尔比可以得到不同粒径的CdS纳米簇. 溶液的pH值对CdS纳米簇影响很大, pH在7.0左右制备的CdS纳米簇粒径小而均匀, 且溶液稳定性高. 用UV-Vis分光光度计和TEM对CdS纳米簇的大小和形貌进行了表征. 结果表明TEM观测CdS纳米簇的粒径要大于用Brus公式的估算值.     

Template Mediated Hybrid from Dendrimer

Novel dendrimer-titania hybrids were prepared in this work from hydroxy and amine terminated polyamidoamine dendrimer (PAMAM generation 4) and titanium alkoxide by an in-situ sol-gel process in presence of a ligand. Dendritic polymers are chosen because of their unique architectural features. Such dendrimer nanocomposite (DNC) can then be used for optical, catalytic, biomedical applications. The hybrid material formed in situ is found to be transparent, brittle and yellow in colour. The hybrids show higher thermal stability than their organic precursors. This is due to enhanced interaction of the inorganic material with the dendrimer through hydrogen bonding as evidenced by PA-FTIR. XPS studies show predominantly the existence of tetravalent titanium due to titania formation.     

Dendrimer polyaluminosilicates as a matrix for filled coatings

Sol-gel synthesis of filled polyaluminosilicates with macromolecules having a dendrimer morphology (M _calc ≈ 480 000) was developed. The software package Gaussian B3LYP/6-31G(d) was used to assess the possible mechanism by which nuclei of dendrimer molecules are created, with the subsequent generation of crowns of branched ensembles capable of accommodating up to 70 wt % nano-Al₂O₃ as a filler. The data furnished by transmission electron microscopy of the samples are in agreement with the suggested mechanism of generation and growth of dendrimers. The main results were obtained on filled aluminosilicate samples that contain 70 wt % nano-Al₂O₃ and exhibit a high wear resistance in tribological tests.     

含有咪唑生色团系列树型有机分子二阶非线性光学性质的密度泛函理论研究

应用密度泛函理论(DFT)B3LYP/6-31G*方法计算研究了系列树型含有咪唑生色团的有机分子的结构和非线性光学性质.计算结果表明:该系列分子具有A- -D- -A(A:受体,D:给体)结构,分子基态的偶极矩、极化率、二阶NLO系数( )随共轭链的增长及吸电子基的增强而增大;同时,前线轨道能级差值越小此类分子的二阶极化率总有效值( )越大.计算的吸收光谱显示此系列树型分子在低能区域247.79nm-419.87nm都有一个最强吸收,并且均是最高占据轨道与最低空轨道之间的跃迁.     

Amphiphilic Dendrimer as Reverse Micelle: Synthesis,Characterization and Application as Homogeneous Organocatalyst

The core and surface terminal groups are the two main catalytic sites in a dendrimer. In most of the reported examples, the catalytic sites in dendritic catalysis are the surface terminal functional groups. This perspective article concerned with the dendrimer based catalysis, involving these two catalytic sites and the dendrimer cavities. The interior cavities provide the nanoscale reactor sites, by creating reverse micelle like appearance for catalysis. In exploring the significant achievements in this area, a low generation PAMAM dendrimer with amphiphilic nature, having a polymeric core with large number of pendent amino groups was synthesized and concentrated its catalytic activity. The key features with respect to positive and/or negative catalytic activity was highlighted by synthesizing various aryl and heteroaryl 2-substituted benzimidazoles. The synthesized dendritic organocatalyst was proved to be amazingly reactive and gave high yield of products within a few minutes at room temperature with low catalyst loading. Here, a new stable hemiaminal, the species rarely been detected and much less isolated in bulk, was obtained during the synthesis of benzimidazoles. Moreover, this is the first reported method for the synthesis of benzimidazoles, using the homogeneous PAMAM dendrimer as a basic organocatalyst.     

Nanostructured Crosslinkable Micropatterns by Amphiphilic Dendrimer Stamping

Summary: Microcontact printing was used to deposit stable, nanostructured, amphiphilic and crosslinkable patterns of poly(amidoamine organosilicon) (PAMAMOS)‐dimethoxymethylsilyl (DMOMS) dendrimer multilayers onto silicon wafers, glass, and polyelectrolyte multilayers. The effects of dendrimer ink concentration, contact time, and inking method, on the thickness, uniformity, and stability of the resulting patterns were studied using optical microscopy, fluorescence microscopy, atomic force microscopy (AFM), and contact‐angle analysis. Microarrayed dendrimer film thickness was found to be controllable by conditions used during spin self‐assembly.

Optical micrograph of the circular patterns, obtained from a 0.5% PAMAMOS dendrimer solution, on a glass substrate.     

Effect of Mass Transport in the Synthesis of Partially Acetylated Dendrimer: Implications for Functional Ligand-Nanoparticle Distributions

Partial acetylation of the amine-terminated poly(amidoamine) dendrimer has been used in the preparation of dendrimer particles conjugated with a wide variety of functional ligands including targeting moieties, therapeutic agents, and dye molecules. The effectiveness of mass transport during the partial acetylation reaction was found to have a major effect on subsequent distributions of dendrimer-ligand components and to be a major source of inconsistency between batches. This study has broad implications for a wide range of nanoparticle-ligand systems because it demonstrates that conjugates with the same mean ligand-particle ratios can have completely different distribution profiles.     

Second‐Generation Supramolecular Dendrimer with a Defined Structure due to Orthogonal Binding

A second‐generation supramolecular dendrimer has been prepared by orthogonal multiple hydrogen bonding. In the first (inner) recognition domain, the interaction of one bis‐isocyanuric acid ( 25 ) with two branching units ( 21 ) that carry complementary Hamilton receptors has been exploited. In the second (outer) generation, the two ADDA (A=hydrogen‐bond acceptor, D=donor) receptors of each branching unit ( 21 ) have bound complementary DAAD units ( 4 ). The problem of limited solubility of the building blocks has been overcome by the introduction of branched ethylhexyl residues and by the use of flexible alkylene or oligo(ethylene glycol) linking chains. The orthogonal binding of the two hydrogen‐bonding pairs was elucidated by chemical induced shift NMR titrations, which proved that the two pairs, isocyanuric acid with the Hamilton receptor and ADDA with DAAD, bind preferentially. The formation of the supramolecular self‐assembled 1:2:4 dendrimer with a molecular weight of 5065 g mol^?1 was investigated by diffusion NMR spectroscopy.     

荧光性聚酰胺-胺树形分子在潜指纹显现中的应用研究

本文系统研究了不同条件(树形分子代数、浓度、浸泡时间等)下荧光性聚酰胺-胺树形分子(PAMAM)水溶液作为荧光探针对锡纸、透明胶带等基底上油印潜指纹的显现效果.结果发现PAMAM树形分子可以和指纹残留物进行靶向结合.结合到指纹纹线上的该荧光性纳米材料在暗室中365 nm紫外光的激发下发出明亮的蓝色荧光,指印纹线与基底反差大、指纹易于辨认,且操作简单,试剂完全环保无污染.这些结果表明PAMAM水溶液是一种潜在的优良的指纹显现试剂.最后,把PAMAM树形分子水溶液对指纹的显现效果进行量化处理,乳突纹与基底间的灰度对比度达到90%以上.     

Hexameric MnII Dendrimer as MRI Contrast Agent

A Mn^II chelating dendrimer was prepared as a contrast agent for MRI applications. The dendrimer comprises six tyrosine‐derived [Mn(EDTA)(H₂O)]^2? moieties coupled to a cyclotriphosphazene core. Variable temperature ¹⁷O NMR spectroscopy revealed a single water co‐ligand per Mn^II that undergoes fast water exchange (k_ex=(3.0±0.1)×10⁸ s^?1 at 37 °C). The 37 °C per Mn^II relaxivity ranged from 8.2 to 3.8 mM ^?1 s^?1 from 0.47 to 11.7 T, and is sixfold higher on a per molecule basis. From this field dependence a rotational correlation time was estimated as 0.45(±0.02) ns. The imaging and pharmacokinetic properties of the dendrimer were compared to clinically used [Gd(DTPA)(H₂O)]^2? in mice at 4.7 T. On first pass, the higher per ion relaxivity of the dendrimer resulted in twofold greater blood signal than for [Gd(DTPA)(H₂O)]^2?. Blood clearance was fast and elimination occurred through both the renal and hepatobiliary routes. This Mn^II containing dendrimer represents a potential alternative to Gd‐based contrast agents, especially in patients with chronic kidney disease where the use of current Gd‐based agents may be contraindicated.     

Size and Structure of Empty and Filled Nanocontainer Based on Peptide Dendrimer with Histidine Spacers at Different pH

Novel peptide dendrimer with Lys-2His repeating units was recently synthesized, studied by NMR (Molecules, 2019, 24, 2481) and tested as a nanocontainer for siRNA delivery (Int. J. Mol. Sci., 2020, 21, 3138). Histidine amino acid residues were inserted in the spacers of this dendrimer. Increase of their charge with a pH decrease turns a surface-charged dendrimer into a volume-charged one and should change all properties. In this paper, the molecular dynamics simulation method was applied to compare the properties of the dendrimer in water with explicit counterions at two different pHs (at normal pH with neutral histidines and at low pH with fully protonated histidines) in a wide interval of temperatures. We obtained that the dendrimer at low pH has essentially larger size and size fluctuations. The electrostatic properties of the dendrimers are different but they are in good agreement with the theoretical soft sphere model and practically do not depend on temperature. We have shown that the effect of pairing of side imidazole groups is much stronger in the dendrimer with neutral histidines than in the dendrimer with protonated histidines. We also demonstrated that the capacity of a nanocontainer based on this dendrimer with protonated histidines is significantly larger than that of a nanocontainer with neutral histidines.