Structure and photochromism of polyoxometalates nanoparticles in cross-linked polymer networks

Cross-linked polymer (P(VP-MB)) based on N-vinylpyrrolidone (VP) and N, N′-methylene-bis-acrylamide (MB) was used as polymer matrix to construct photochromic nanocomposite thin films with entrapping the Keggin-type polyoxometalates (POM). The microstructure, photochromic behavior, and mechanism of the films were studied with transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), ultraviolet-visible spectra (UV-vis), and electron resonance spectra (ESR). The transparent films changed from colorless to blue under UV irradiation. The films showed good reversible photochromism and could recover the colorless state gradually in the air, where oxygen plays an important role during the bleaching process. The heteropolyanions dispersed in composite films uniformly and exhibited strong coulombic interaction with cross-linked polymer. Composite films contained molybdenum had higher photochromic efficiency and slower bleaching reaction than films contained tungsten. According to ESR, the photochromic mechanism was followed by charge-transfer happened between POM and cross-linked polymer.     

Preparation and photochromic behavior of crosslinked polymer thin films containing polyoxometalates

A series of reversible photochromic nanocomposite films were prepared by entrapping phosphotungstic acid (PWA) and molybdenumphsophoric acid (PMoA) into P(VP-BVA), which was a crosslinked polymer based on N-vinylpyrrolidone (VP) and bisvinyl-A (BVA). The microstructure, photochromic behavior and mechanism of the films were studied with transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), ultraviolet-visible spectra (UV-vis) and electron resonance spectra (ESR). The TEM image showed that the polyoxometalates particles had regular microstructure with narrow size distribution (average diameter of 30 nm) in hybrid films. FT-IR results showed that the Keggin geometry of polyoxometalates (POM) was still preserved inside the composites and strong coulombic interaction between POM and crosslinked polymer matrix was built. Irradiated with ultraviolet light, the transparent films changed from colorless to blue and showed reversible photochromism. Oxygen plays an important role during the bleaching process. PMoA/P(VP-BVA) film had higher photochromic efficiency and slower bleaching reaction than PWA/P(VP-BVA) film. The characteristic signals of W (V) or Mo (V) in ESR spectra indicated that electron transfer occurred between the organic substrates and heteropolyanions under UV irradiation, which induced heteropolyanions to heteropolybules with simultaneous oxidation of the organic substrates.     

以树形分子为模板制备金纳米簇及其表征

利用酯端基聚酰胺-胺（PAMAM）树形分子为模板,以N,N-二甲基甲酰胺（DMF）为溶剂,用硼氢化钠还原氯化金制备了树形分子封装的金纳米簇复合物.UV-vis光谱和TEM表征研究表明,分子代数越大,制备的金纳米粒子直径越小,粒径分布越均匀,在DMF溶剂中越稳定.     

碳硅烷树形分子的合成与应用

从一个含有烯基的中心核分子开始,重复进行硅氢化作用和烯基化作用的过程可以获得以硅原子作为支化点的碳硅烷树形分子。碳硅烷树形分子在催化化学、主客体化学、电化学、液晶高分子化学等领域有着广泛的应用。     

Rheology of polybenzyl ether dendrimers their copolymer and blends

The dynamic rheological behavior of pure polybenzyl ether dendrimers and their copolymers have been studied in the molten state. The pure polybenzyl ether dendrimer generation 4 and generation 5 show Newtonian behavior whilst the generation 3 appears to be a very slightly shear-thinning within the deformation rates investigated, the behavior also being a function of thermal pretreatment. When the dendrimer component was included as a dendritic polystyrene copolymer (covalently attached), the viscosity was much lower compared to corresponding polystyrene of similar molecular weight. The same concentration of dendrimer could be physically blended into the polystyrene forming an immiscible mixture, which also reduced viscosity. However, if the dendritic component was covalently attached, it had a lower viscosity than if physically blended at the same concentration. Electronic Publication     

Potentiometric response characteristics of polycation-sensitive membrane electrodes toward poly(amidoamine) and poly(propylenimine) dendrimers

The potentiometric response characteristics of polycation-sensitive membrane electrodes toward two classes of polycationic dendrimers are examined. Using appropriately formulated polymer membrane electrodes composed of a dinonylnaphthalenesulfonate (DNNS) salt in a plasticized polyurethane matrix, it is shown that poly(amidoamine) (PAMAM) and poly(propylenimine) (PPI) dendrimers are readily detected at submicrogram per milliliter levels via a nonequilibrium response mechanism. The relationship between the total EMF response (at equilibrium) and the specific dendrimer structure is also examined. For both the PAMAM and PPI species, it is shown that the total EMF response does not change significantly with dendrimer generation number; however, the nonequilibrium analytically useful response curves are shifted to higher mass concentrations as the generation number is increased. The relative contributions of the terminal primary amines and the interior tertiary amines of the dendrimers to the observed EMF response are investigated by synthesis of various dendrimer derivatives (acetylated, quaternized, etc.). By comparing the total EMF responses for these derivatives as a function of sample pH, it is demonstrated that the lipophilic cation exchanger (DNNS) within the membrane phase can likely interact electrostatically with both protonated forms of the terminal primary amines and interior tertiary amines of the dendrimer structures. The practical application of the nonequilibrium potentiometric detection of dendrimers for monitoring their interaction with DNA is also demonstrated.     

Controlled Microstructure and Photochromism of Inorganic-organic Thin Films by Ultrasound

A series of inorganic-organic thin films based on uniformly dispersed nanoparticles of polyoxometalates （POM）entrapped in polyacrylamide （PAM） matrix were prepared by ultrasonic method with different irradiation time.The microstructure, photochromic behavior and mechanism of the films were studied by transmission electron microscopy （TEM）, ultraviolet-visible spectra （UV-VIS） and Fourier transform-infrared spectroscopy （FT-IR）.The microstructure and photochromic properties of the hybrid thin films could be controlled by ultrasound.TEM image revealed that the average size of phosphotungstic acid （PWA） nanoparticles decreased from 20 to 10 nm with the ultrasound irradiation time from 30 to 60 min. After irradiated with ultraviolet light,the transparent films changed from colorless to blue and showed reversible photochromism. The hybrid film, with ultrasound irradiation for 60 min had higher photochromic efficiency and faster bleaching reaction than the one with ultrasound irradiation for 30 min. FT-IR spectra showed that the Keggin geometry of heteropolyoxometalate was still preserved inside the composites, and the interactions between polyanions and polymer matrix increased as the ultrasound time prolonged. It is suggested that the mechanism of the different photochromic properties for the inorganic-organic thin films is the variation of the microstructure and interfacial interactions induced by ultrasound.     

Spectroscopic investigations of poly(propyleneimine)dendrimers using the solvatochromic probe phenol blue and comparisons to poly(amidoamine) dendrimers.

The physical and chemical properties of PPI dendrimers' interior were investigated using the fluorescent, solvatochromic probe phenol blue. In aqueous solutions of each generation studied, two discrete dye populations were clearly observed. PPI dendrimers were shown to form a tight, nonpolar association with the vast majority of available dye, within the dendrimer interior, near the core. In the steady-state fluorescence emission spectra, a microenvironment of decreasing polarity in increasingly larger-generation PPI dendrimers (up to G3) was seen for the associated probe. Each of the remaining larger-generation dendrimers provided a microenvironment of essentially equal polarity. Fluorescence anisotropy values for phenol blue in the PPI dendrimers demonstrated the dye's sensitivity to the changing molecular volumes of the dendrimer generations. Model compounds that mimicked PPI's surface groups and branching moieties were used to better define the associated dye's location. The mimics further confirmed that phenol blue was associated inside the dendrimer, where it did not interact with the dendrimer surface groups. The comparison of amine-terminated PPI and PAMAM dendrimers clearly demonstrated the effects of their structural differences and the ability of phenol blue to have sensed those differences, including the initiator core length, branching unit length, and branching unit chemical composition.     

Silver/dendrimer nanocomposites as biomarkers: fabrication, characterization, in vitro toxicity, and intracellular detection

We have synthesized water-soluble, biocompatible, fluorescent, and stable silver/dendrimer nanocomposites that exhibit a potential for in vitro cell labeling. Amino-, hydroxyl-, and carboxyl-terminated ethylenediamine core generation 5 poly(amidoamine) dendrimers were utilized to prepare aqueous silver(I)-dendrimer complexes (with the molar ratio of 25 Ag+ per dendrimer) at the biologic pH of 7.4. Conversion of silver(I)-dendrimer complexes into dendrimer nanocomposites was achieved by irradiating the solutions with UV light to reduce the bound Ag+ cations to zerovalent Ag0 atoms, which were simultaneously trapped in the dendrimer network, resulting in the formation of {(Ag0)25-PAMAM_E5.NH2}, {(Ag0)25-PAMAM_E5.NGly}, and {(Ag0)25-PAMAM_E5.NSAH} dendrimer nanocomposites (DNC), respectively. The silver-DNCs were characterized by means of UV-vis, fluorescence spectroscopy, dynamic light-scattering, zeta potential measurements, high-resolution transmission electron microscopy, X-ray energy dispersive spectroscopy, and selected area electron diffraction. The cytotoxicity of dendrimers and related silver nanocomposites was evaluated using an XTT colorimetric assay of cellular viability. The cellular uptake of nanoparticles was examined by transmission electron and confocal microscopy. Results indicate that {(Ag0)25-PAMAM_E5.NH2}, {(Ag0-)25-PAMAM_E5.NGly}, and {(Ag0)25-PAMAM_E5.NSAH} form primarily single particles with diameters between 3 and 7 nm. The dendrimer nanocomposites are fluorescent, and their surface charge, cellular internalization, toxicity, and cell labeling capabilities are determined by the surface functionalities of dendrimer templates. The {(Ag0)25-PAMAM_E5.NH2} and {(Ag0)25-PAMAM_E5.NSAH} nanocomposites exhibit potential application as cell biomarkers.     

Development and characterization of triazine based dendrimers for delivery of antitumor agent

In the present study we developed the novel kind of triazine dendrimers by utilizing differential reactivity of the cyanuric chloride (triazine trichloride) which overcome the limitations associated with the others classes of dendrimers like toxicity, low yield, high synthesis cost etc. Triazine dendrimers were synthesized by divergent method using triazine trichloride as core and diethanolamine as branching unit to avoid the use of protecting group and functional group interconversion up to third generation. These hydroxyl terminated dendrimers were characterized by FTIR, 1HNMR, 13CNMR, ES mass spectroscopy, and by elemental analysis. The yield of pure G3 dendrimers was 63%. This novel dendrimers increases the aqueous solubility of hydrophobic drug Paclitaxel up to 0.562 mg/ml as well as showed control release behavior. Hemolytic and toxicology studies of this dendrimer in mice showed no adverse toxicity to the kidneys and the liver up to 200 mg/kg dose (i.p). Triazine being a hydrophobic compound, the core of this dendrimer is hydrophobic and supposed to easily incorporate the hydrophobic guest while presence of hydroxyl group on periphery increases its water solubility and reduces its toxicity; and thus it is useful in various fields like gene delivery, MRI contrasting agents, vaccines or as solubilization tool.     

Improved tumor targetability of Tat-conjugated PAMAM dendrimers as a novel nanosized anti-tumor drug carrier

The generation 4-poly-amidoamine-dendrimers (PAMAM G4 dendrimer, P) was conjugated to Tat peptide (Tat, T), a cell-penetrating peptide, in search of an efficient anti-tumor drug delivery vehicle for cancer therapy. In this study, we synthesized BODIPY-labeled Tat-Conjugated PAMAM dendrimers (BPTs) as a novel nanosized anticancer drug carriers and systemically investigated their biodistribution and the tumor accumulation in Sarcoma 180-bearing mice. In addition, the uptake and the cytotoxicity to S180 cells of BPTs thereof were evaluated. The unmodified dendrimer (BP) showed a soon clearance from the blood stream and nonspecific accumulation in tumor. In contrast, the Tat-modified dendrimer, BPT(64) with appropriate particle size showed a better retention in blood and could be accumulated effectively in tumor tissue via the enhanced permeability and retention (EPR) effect. Moreover, BPTs with a high Tat modification rate was accumulated more effectively in tumor tissue. In vitro experiments, these BPTs displayed low cytotoxicity on S180 cells and high uptake to S180 cells. These findings indicate that the nanoparticulate system on the basis of Tat-conjugated PAMAM dendrimers is safer and effective in the concentration range (below 20?μg/ml) to be used as a carrier of anti-tumor drugs for tumor targeting by intravenous administration.     

Amine-terminated TEG-derived PAMAM dendrimer as template for preparation of gold nanoparticles in water

Nano-sized monodisperse gold particles (AuNPs) have received significant attention in the past decade, due to their unique physical properties and good chemical stability, which can lead to a wide variety of potential applications. In this work, TEG-derived PAMAM dendrimers with amine-terminating groups were synthesized and characterized by ¹H NMR and FT-IR. These dendrimers were investigated as the templates for preparation of gold nanoparticles through the reduction of HAuCl₄ by NaBH₄ in water. Stable gold nanoparticles with diameters around 10 nm were obtained in the presence of G2.0 – G5.0 dendrimers and characterized by UV-Vis spectroscopy, transmission electron microscopy (TEM) and dynamic light scattering (DLS). The particle size of the produced AuNPs decreased with increasing dendrimer generations. A dendrimer of higher generation has a rigid structure with many end groups on the surface and may play a powerful role in the growth of the AuNPs, as well as having a solid stabilization effect on the AuNPs.     

石墨/树状大分子复合材料的分子动力学模拟

在COMPASS(Condensed-phase optimized molecular potentials for atomistic simulation studies)力场下, 对以氨(Amine)、 丁二胺(Butanediamine)为核的1代~3代(1G~3G)石墨/树状大分子纳米复合材料进行了分子动力学模拟(Molecular dynamics simulation)。介绍了复合体系的构建过程及分子动力学模拟细节, 从微观构形、 能量变化研究了正则系综(恒定的NVT)中6种插层复合物的稳定性及其机理, 最后利用径向分布函数(Radial distribution function)对能量变化结果进行了分析。结果表明, 当树状大分子体积较小时, 石墨层容易弯曲, 体系能量较高, 导致复合体系不稳定; 随着树状大分子代数的增加, 石墨层形变减小, 体系能量降低, 3代时树状大分子体系最稳定。      

金属簇/树形高分子纳米复合材料的制备及应用

分类综述了金属簇／树形高分子蚋米复合材料的制备方法，包括直接化学还原法、光还原法、置换法和成盐法等，以及其在催化、指纹识别、阻燃等领域的应用。     

Preparation of dendrimer SAM on Au substrate and adsorption/desorption of poly-L-glutamate on the SAM

A self-assembled monolayer (SAM) of a dendrimer has been fabricated by covalent bonding of amine-terminated dendrimers to 3-mercaptopropionic acid SAM on an Au substrate, where an amide bond was formed between the amine and the carboxylic acid using amide-coupling reagents. Each reaction step was inspected by transmission surface-enhanced infrared absorption spectroscopy. Reaction was affected by solvents of the coupling reagents and concentrations of the coupling reagents and dendrimers. The pH-dependent adsorption/desorption behavior of sodium poly-L-glutamate (PGA) has been examined on the dendrimer SAM prepared. The adsorbed amount was abundant at acid pH below the pK(a) of carboxylate, while desorption from PGA-adsorbed dendrimer SAM prepared at acid pH proceeded as the pH was raised. The reaction was reversible and reproducible within 30 min under controlled pH, although the carboxylic acid species adsorbed at pH 4.2 was deprotonated to a carboxylate species after more than 30 min of desorption at pH 9.4.     

Dilute Solution Behavior of Dendrimers and Polysaccharides: SEC, ESI-MS, and Computer Modeling

Dendrimers, the most highly branched structures achievable, have found numerous uses in the chemical, biological, and pharmaceutical fields. We have employed size exclusion chromatography (SEC) with universal calibration to determine molecular weight averages, distributions, intrinsic viscosities, and structural parameters of Starburst dendrimers, dextrans, and the starch degradation polysaccharides known as maltodextrins. Comparisons have been made in the dilute solution behavior of dendrimers and polysaccharides with equivalent weight-average molecular weights. Intrinsic viscosities decreased in the order [η](dextran) > [η](dextrin) > [η](dendrimer). While the difference between dendrimer and polysaccharides may be attributed to the higher branching of the former, which leads to a higher chain density in solution, the difference between dextran and dextrin is likely a result of the variation in solution behavior of α-(1→6) vs α-(1→4) linked carbohydrates. The solution behavior of the maltodextrins studied indicates that debranching in their manufacture appears to have been more thorough than in that of β-limiting dextrins studied by other groups. Comparison of molecular radii obtained from SEC data to radii from molecular dynamics studies show Starburst dendrimers behave as θ-stars with functionality between 1 and 4. Additionally, electrospray ionization mass spectrometry was employed to determine M(w), M(n), and PD of Astramol dendrimers.     

Immobilization of dendrimers on Si-C linked carboxylic acid-terminated monolayers on silicon(111)

Poly(amidoamine) dendrimers were attached to activated undecanoic acid monolayers, covalently linked to smooth silicon surfaces via Si-C bonds. The resulting ultra-thin dendrimer films were characterized by X-ray photoelectron spectroscopy (XPS), X-ray reflectometry (XR) and atomic force microscopy (AFM). XPS results suggested amide bond formation between the dendrimer and the surface carboxylic acid groups. XR yielded thicknesses of 10 Å for the alkyl region of the undecanoic acid monolayer and 12 Å for the dendrimer layer, considerably smaller than the diameter of these spherical macromolecules in solution. This was consistent with AFM images showing collapsed dendrimers on the surface. It was concluded that the deformation arose from a large number of amine groups on the surface of each dendrimer reacting efficiently with the activated surface, whereby the dendrimers can deform to fill voids while spreading over the activated surface to form a homogeneous macromolecular layer.     

Preparation and in vitro characterization of pluronic-attached polyamidoamine dendrimers for drug delivery

Context: Polyamidoamine (PAMAM) dendrimers have attracted lots of interest as drug carriers. And little study about whether pluronic-attached PAMAM dendrimers could be potential drug delivery systems has been carried on.

Objective: Pluronic F127 (PF127) attached PAMAM dendrimers were designed as novel drug carriers.

Methods: Two conjugation ratios of PF127-attached PAMAM dendrimers were synthesized. ¹H nuclear magnetic resonance (¹H-NMR), Fourier transform infrared spectrum (FTIR), element analysis and ninhydrin assay were used to characterize the conjugates. Size, zeta potential and critical micelle concentrations (CMC) were also detected. And DOX was incorporated into the hydrophobic interior of the conjugates. Studies on their drug loading and drug release were carried on. Furthermore, hemolysis and cytotoxicity assay were used to evaluate the toxicity of the conjugates.

Results and discussion: PF127 was successfully conjugated to the fifth generation PAMAM dendrimer at two molar ratios of 19% and 57% (PF127 to surface amine per PAMAM dendrimer molecular). The conjugates showed an increased size and a reduced zeta potential. And higher CMC values were obtained than pure PF127. Compared with unconjugated PAMAM dendrimer, PF127 conjugation significantly reduced the hemolytic toxicity and cytotoxicity of PAMAM dendrimer in vitro. The encapsulation results showed that the ability to encapsulate DOX by the conjugate of 19% conjugation ratio was better than that of 57% conjugation ratio. And the maximum is ～12.87 DOX molecules per conjugate molecule. Moreover, the complexes showed a sustained release behavior compared to pure DOX.

Conclusion: Findings from the in vitro study show that the PF127-attached PAMAM dendrimers may be potential carriers for drug delivery.     

Glucose biosensors based on dendrimer monolayers

The peculiarities of glucose biosensors based on different generation of dendrimers (G0, G1 and G4) have been studied by amperometry and QCM techniques. It is shown that stable glucose biosensor can be obtained with low generation of dendrimers. The sensor sensitivity, however considerable, increased with increasing number of generation of dendrimers. This can be due to the increased volume of the dendrimer interior as well as with increased number of binding sites for glucose oxidase (GOX). QCM experiments showed that immobilization of GOX resulted in formation of enzyme multilayers on a dendrimer surface. The enzyme turnover for this system (0.1-0.01 s(-1)) was lower then that for immobilization of GOX onto a supported lipid films by means of avidin-biotin technology (1.1 s(-1)). However, dendrimer based biosensors are more stable in comparison with sBLM based sensors and could be stored in a refrigerator in dry conditions over 15 days without substantial loss of sensitivity.     

Bioactive multilayer thin films of charged N,N-disubstituted hydrazine phosphorus dendrimers fabricated by layer-by-layer self-assembly

Charged N,N-disubstituted hydrazine phosphorus-containing dendrimers are deposited either as alternate all-dendrimers multilayers or alternating with linear polymers on 3-mercaptopropionic acid or 3-aminopropyldimethylethoxysilane coated surfaces via electrostatic layer-by-layer self-assembly. The behavior of the film formation is investigated by surface plasmon resonance spectroscopy and ellipsometry. Fetal cortical rat neurons were cultured on the dendrimer films in order to investigate the influence of the surface charge of the outermost layer on their adhesion and maturation. It was found that neurons attached preferentially and matured slightly faster on film surfaces terminated with positively charged dendrimers than on negatively charged surfaces.