树状大分子/金属纳米复合物的制备与催化作用

综述了一类新的有机/无机杂化纳米材料———树状大分子/金属纳米复合物的制备及其催化作用。树状大分子/金属纳米复合物是以树状大分子为模板或稳定剂,通过还原树状大分子内或树状大分子间螯合金属离子制备。讨论了树状大分子/金属纳米复合物在水、有机溶剂、氟/有机两相溶剂和超临界CO2中的催化作用。     

可双固化树枝形聚酰胺-胺树脂的合成及其涂膜性能研究

探讨了以乙二胺与丙烯酸甲酯交替反应，制备了1．5，2．5代树枝形聚酰胺一胺树脂（PAMAM），对其用甲基丙烯酸缩水甘油酯（GMA）和γ-氨丙基三乙氧基硅烷进行了改性，使其能够紫外光固化和潮气固化。热分析考查了玻璃化温度和热稳定性，并进行了硬度、光泽、光固化速度、潮气固化速度、附着力、柔韧性等测试。     

Organolithium route to poly(arylsilane)s

Various poly(arylsilane)s The poly(carbosilane)s prepared in this way are of higher molecular weight than when prepared by the Wurtz-type condensation route previously reported. TG shows 40–50% overll weight loss attained at 500–600°C.     

树枝状荧光探针设计制备及荧光特性初步研究

树枝状荧光探针是将荧光染料引入树枝状化合物（dendrimer）端基的一类化合物,具有良好的稳定性及光谱特性．笔者以2,2-二甲氧基乙胺为核,采用发散合成法合成了一端含活性氨基的扇形树枝状化合物,并将羧基噻唑橙染料（TO—COOH）引入树枝状化合物的端基,制备出树枝状荧光分子．初步研究了其荧光特性,讨论了反应温度、反应时间等条件对反应收率的影响．     

聚酰胺胺树状大分子与Cu2+、Co2+配位作用的比较

用发散法合成了G3．5和G4．0的聚酰胺胺（PAMAM）树状大分子，研究了聚酰胺胺树状大分子的代数、溶液的pH值、反应时间对聚酰胺胺树状大分子与Cu^2＋、Co^2＋配位作用的影响。结果表明，当G4．0的聚酰胺胺树状大分子存在时，Cu^2＋和Co^2＋的配合物水溶液的最大吸收波长都出现了蓝移。当G3．5的聚酰胺胺树状大分子存在时，G3．5的聚酰胺胺树状大分子几乎不和Co^2＋发生配位作用。延长反应时间，Co^2＋／G4．0PAMAM的吸收强度增加，但是Cu^2＋／G4．0PAMAM的吸收曲线几乎没有变化。溶液的pH值对G4．0的聚酰胺胺树状分子与Cu^2＋，Co^2＋配位作用有很大的影响，这为其循环使用提供了理论基础。     

Preparation, optical properties and cell staining of water soluble amine-terminated PAMAM G 2.0-Au nanocomposites

The solution chemical and optical characteristics of formation of amine-terminated polyamidoamine dendrimer G2.0(NH₂-PAMAM G2.0)-Au nanocomposites in the aqueous solution of NH₂-PAMAM G2.0 at various mole ratios of Au(III) to NH₂-PAMAM G2.0 were studied by both UV-visible spectrometry and fluorospectrometry. The NH₂-PAMAM G2.0-Au nanocomposites, with a type of structure in which one Au nanoparticle is surrounded by several NH₂-PAMAM G2.0 dendrimers, emit strong bluish violet fluorescence, and are uniform, water soluble and biocompatible as well as very stable in frozen conditions. The size of gold nanoparticles in the nanocomposites is about 2.5 nm and decreases with the increase of NH₂-PAMAM G2.0 concentration. The NH₂-PAMAM G2. 0 plays an important role in acting as host or micro-reactor for Au(III) before Au(III) reduction and acting as dispersant and stabilizer for gold nanoparticles after Au(III) reduction. Preliminary experiments of cells staining to human embryonic lung fibroblast cell lines show that the NH₂-PAMAM G2.0-Au nanocomposites can be used as optical imaging markers for bioanalyses and medical diagnoses.     

Sub‐5 nm Dendrimer Directed Self‐Assembly with Large‐Area Uniform Alignment by Graphoepitaxy

Directed self‐assembly (DSA) using soft materials is an important method for producing periodic nanostructures because it is a simple, cost‐effective process for fabricating high‐resolution patterns. Most of the previously reported DSA methods exploit the self‐assembly of block copolymers, which generates a wide range of nanostructures. In this study, cylinders obtained from supramolecular dendrimer films with a high resolution (<5 nm) exhibit planar ordering over a macroscopic area via guiding topographical templates with a high aspect ratio (>10) and high spatial resolution (≈20 nm) of guiding line patterns. Theoretical and experimental studies reveal that this property is related to geometrical anchoring on the meniscus region and physical surface anchoring on the sidewall. Furthermore, this DSA of dendrimer cylinders is demonstrated by the non‐regular geometry of the patterned template. The macroscopic planar alignment of the dendrimer nanostructure reveals an extremely small feature size (≈4.7 nm) on the wafer scale (>16 cm²). This study is expected to open avenues for the production of a large family of supramolecular dendrimers with different phases and feature dimensions oriented by the DSA approach.     

Dendritic Nanotheranostic for the Delivery of Infliximab: A Potential Carrier in Rheumatoid Arthritis Therapy

Antibodies are macromolecules that specifically recognize their target, making them good candidates to be employed in various therapies. The possibility of attaching a drug to an immunoglobulin makes it possible to release it specifically into the affected tissue as long as it overexpresses the target. However, chemical coupling could affect the functionality (specificity and affinity) of the antibody. It has been observed that the use of intermediaries, such as dendrimers, could resolve this issue. Because carbosilane dendrimers have aroused great interest in the field of biomedicine, this report describes the synthesis of an anionic carbosilane dendrimer with a fluorochrome on its surface that then forms a conjugate with an antibody. It has been used as immunoglobulin and infliximab, whose target is TNF-α, which is a cytokine that is overexpressed in the inflamed area or even in the blood of patients with autoimmune diseases, such as rheumatoid arthritis. In addition, the integrity and functionality of the antibody has been studied to see if they have been affected after the chemical coupling process.     

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.     

聚酰胺-胺型树枝状水性聚氨酯的合成与表征

为了提高水性聚氨酯耐水性等性能,以异佛尔酮二异氰酸酯(IPDI)、聚四亚甲基醚二醇(PTMG)、二羟甲基丙酸(DMPA)、1,4-丁二醇(BDO)等为原料,二月桂酸二丁基锡(DBTDL)为催化剂,通过预聚体法合成了单端封闭的聚氨酯预聚体(PPU),然后以一代端羟基树枝状聚合物(PAMAM-OH)为核,通过接枝共聚法制备了树枝状水性聚氨酯(HWPU)。通过单因素分析法优化出PPU的最佳合成条件:反应时间为2 h,反应温度为80℃,n(NCO)∶n(OH)为6∶1。采用FIIR、XRD和纳米粒度表面电位分析仪对产物的结构和性能进行了表征,并对胶膜的耐水性、表面粗糙度和力学性能进行了测试。结果表明:HWPU乳液粒径为43.56 nm,胶膜结晶度为1.59%,胶膜24 h的吸水率为4.8%,拉伸强度为39.2 MPa,断裂伸长率为376.4%,胶膜表面粗糙度降低。与未加PAMAM-OH的水性聚氨酯(WPU)相比,HWPU的吸水率降低了67.1%,拉伸强度提高了74.2%,耐水性和拉伸强度得到明显提高。