Design,Synthesis, and Self-Assembly Studies of a Suite of Monodisperse,Facially Amphiphilic,Protein–Dendron Conjugates

The custom design of protein–dendron amphiphilic macromolecules is at the forefront of macromolecular engineering. Macromolecules with this architecture are very interesting because of their ability to self-assemble into various biomimetic nanoscopic structures. However, to date, there are no reports on this concept due to technical challenges associated with the chemical synthesis. Towards that end, herein, a new chemical methodology for the modular synthesis of a suite of monodisperse, facially amphiphilic, protein–dendron bioconjugates is reported. Benzyl ether dendrons of different generations (G1–G4) are coupled to monodisperse cetyl ethylene glycol to form macromolecular amphiphilic activity-based probes (AABPs) with a single protein reactive functionality. Micelle-assisted protein labeling technology is utilized for site-specific conjugation of macromolecular AABPs to globular proteins to make monodisperse, facially amphiphilic, protein–dendron bioconjugates. These biohybrid conjugates have the ability to self-assemble into supramolecular protein nanoassemblies. Self-assembly is primarily mediated by strong hydrophobic interactions of the benzyl ether dendron domain. The size, surface charge, and oligomeric state of protein nanoassemblies could be systematically tuned by choosing an appropriate dendron or protein of interest. This chemical method discloses a new way to custom-make monodisperse, facially amphiphilic, protein–dendron bioconjugates.     

Segmented polymer networks containing amino‐dendrimers

Polymer networks in which poly(propylene imine) dendrimers (Astramol?) are connected to each other by linear polytetrahydrofuran (polyTHF) segments, were prepared by two methods. The first method was a one‐step procedure in which bifunctionally living polyTHF, obtained by initiation of the THF polymerization with trifluoromethane sulfonic anhydride (triflic anhydride), was reacted with an amino‐dendrimer. This reaction was very fast but did not allow formation of the end products. The second method was a two‐step procedure. In a first step, living polyTHF, prepared with acryloyloxybutyl triflate as initiator, was grafted on an amino‐dendrimer, to form a star‐like, acrylate‐terminated polyTHF multi‐macromonomer with the dendrimer as core. In a second step, networks were obtained by Michael addition between the acrylate end‐groups and unreacted amino‐groups of the dendrimer. This cross‐linking reaction occurred spontaneously upon heating of the solution of the multi‐macromonomer with gelation times varying from a few minutes to a few hours, depending on the temperature and the composition of the prepolymers. With this method it was possible to prepare networks in the form of coatings or films. © 2003 Society of Chemical Industry     

基于树枝型聚合物的膜与膜过程研究进展

树枝型聚合物是具有内部疏松、外部致密、端基官能团众多等结构的高度支化聚合物,这些特点使得树枝型聚合物具有多种不同于线性聚合物的特性,与膜和膜技术相结合有特殊意义.介绍了树枝型聚合物气体分离膜、支撑液膜、离子交换膜、膜表面改性以及树枝型聚合物参与的膜过程等方面的研究进展,简要展望了基于树枝型聚合物的分离膜与膜技术的发展趋势.     

国外有机硅树枝状化合物的应用进展

有机硅树枝状化合物是以Si-O、Si-C、Si-Si等键为骨架，具有三维立体结构类似于树枝形状的化合物。结合当今国外该领域的最新进展系统地介绍了国外有机硅树枝状化合物的最新应用。     

A structure/function study of polyaminoamide dendrimers as silica scale growth inhibitors

Dendrimers have attracted immense attention during the last decade due to their interesting properties both from a basic and an applied research viewpoint. Encapsulation of metal nanoparticles for catalysis, drug delivery and light harvesting are only some applications of dendrimers that are breaking new ground. A novel application of dendrimer technology is described in the present paper that relates to industrial water treatment. Industrial water systems often suffer from undesirable inorganic deposits. These can form either in the bulk or on metallic surfaces, such as heat exchangers or pipelines. Silica (SiO₂) scale formation and deposition is a major problem in high‐silica‐containing cooling waters. Scale prevention rather than removal is highly desired. In this paper, benchtop screening tests on various silica inhibition chemistries are reported, with emphasis on materials with a dendrimeric structure. Specifically, the inhibition properties of commercially available STARBURST^® polyaminoamide (PAMAM) dendrimers generations 0.5, 1, 1.5, 2, and 2.5 are investigated in detail together with other commonly‐used scale inhibitors. Experimental results show that inhibition efficiency largely depends on structural features of PAMAM dendrimers such as generation number and nature of the end groups. PAMAM dendrimers are effective inhibitors of silica scale growth at 40 ppm dosage levels. PAMAM dendrimers also act as silica nucleators, forming SiO₂–PAMAM composites. This occurs because the SiO₂ formed by incomplete inhibition interacts with cationic PAMAM‐1 and ‐2. The general scope of silica formation and inhibition in industrial waters is also discussed. Copyright © 2005 Society of Chemical Industry     

Engineering of Janus-Like Dendrimers with Peptides Derived from Glycoproteins of Herpes Simplex Virus Type 1: Toward a Versatile and Novel Antiviral Platform

Novel antiviral nanotherapeutics, which may inactivate the virus and block it from entering host cells, represent an important challenge to face viral global health emergencies around the world. Using a combination of bioorthogonal copper-catalyzed 1,3-dipolar alkyne/azide cycloaddition (CuAAC) and photoinitiated thiol–ene coupling, monofunctional and bifunctional peptidodendrimer conjugates were obtained. The conjugates are biocompatible and demonstrate no toxicity to cells at biologically relevant concentrations. Furthermore, the orthogonal addition of multiple copies of two different antiviral peptides on the surface of a single dendrimer allowed the resulting bioconjugates to inhibit Herpes simplex virus type 1 at both the early and the late stages of the infection process. The presented work builds on further improving this attractive design to obtain a new class of therapeutics.     

紫外光快速固化的树枝状丙烯酸酯齐聚物的制备和性能

通过乙二胺(EDA)和三羟甲基丙烷三丙烯酸酯(TMPTA)，以甲醇为催化剂，在30℃进行6小时Michael加成反应，可制得含多个双键的树枝状丙烯酸酯齐聚物(DAO)．与相似分子量的线性丙烯酸酯齐聚物相比，DAO粘度低，用作紫外光固化树脂，其固化速度快，且固化产物硬度好，耐溶剂性好．     

Investigation of allyl‐capped carbosilane dendrimers used as crosslinker for silicone rubber

High‐temperature vulcanized silicone rubber was prepared by using allyl‐capped carbosilane dendrimers, in which the core molecules were Si(CH₂CH?CH₂)₄ and Ph₂Si(CH₂CH?CH₂)₂ as crosslinker and nanoscale reinforcing filler, respectively. Allyl‐capped carbosilane dendrimers improved the mechanical properties of silicone rubber. The optimum tensile strength and tear strength were 9.6 MPa and 31.0 kN/m, respectively, when using SiG_n(allyl)m as the crosslinker and 10.1 MPa and 32.0 kN/m, respectively, when using Ph₂SiG_n(allyl)m as the crosslinker. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1772–1775, 2006     

以聚酰胺-胺树形分子为模板制备AgI纳米簇

本文以聚酰胺-胺(PAMAM)树形分子为模板,原位制备AgI纳米簇.系统地研究了AgI纳米簇制备过程中各种反应条件如树形分子端基、反应时间、Ag 与PAMAM摩尔比等对AgI纳米簇粒径的影响,分别用紫外-可见光谱、荧光光谱、透射电镜等对所制备的纳米簇进行表征.在相同的条件下,以G4.5-COOH3为模板较以G5.0-NH2为模板制备的AgI纳米簇粒径小、分布均匀,这主要取决于G4.5-COOCH3PAMAM树形分子所起的“内模板”作用.G4·5-COOH3树形分子浓度为1×10-5mol/L,Ag 与树形分子摩尔比为30∶1时所制备的AgI纳米簇的粒径分布均匀、稳定性好,室温避光可稳定存在两个月以上.     

Polyamidoamine dendrimers as curing agents: The optimum polyamidoamine concentration selected by dynamic torsional vibration method and thermogravimetric analyses

Polyamidoamine (PAMAM) dendrimers were investigated as curing agents in bisphenol A epoxy resin systems. The cure behavior of epoxy resin/PAMAM at varying components was investigated by a dynamic torsional vibration method (DTVM); the thermal behavior of the materials was characterized by means of thermogravimetric (TGA) analyses. The DTVM results show that 10/100 parts of the resin (phr) PAMAM was the optimum concentration for 1.0, 3.0, and 5.0 G PAMAM dendrimers/resin systems in our experiment. Also, the TGA results agreed with the conclusions made by the DTVM. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1430–1434, 2007