Structure control within poly(amidoamine) dendrimers: size, shape and regio-chemical mimicry of globular proteins

This work describes the syntheses of a new poly(amidoamine) (PAMAM) dendrimer family possessing a disulfide function (cystamine) in its core. Traditional redox-chemistry associated with the disulfide core in these dendrimer structures, provides a versatile strategy for designing unique sizes, shapes and controlling the regio-disposition of chemical groups on the surface of these dendrimers. Various single site, sulfhydryl functionalized dendron reactants may be generated in situ, under standard reducing conditions (i.e. dithiothreitol (DTT)). Facile control of size, shape and chemical functionality placement involves covalent hybridization of these single point, sulfhydryl reactive dendron components. This is accomplished by re-oxidation in the presence of air, to yield generation/surface chemistry differentiated cross-over products which may be isolated by preparative thin layer or column chromatography. Differentiated cystamine core dendrimers derived from combination and permutation of lower generation (i.e. Gen.=0-3) sulfhydryl functionalized dendrons possessing amino, hydroxyl, acetamido or dansyl surface groups, were synthesized and isolated. They were characterized by a variety of methods including; ¹³C NMR, capillary electrophoresis (CE), gel electrophoresis (PAGE), thin layer chromatography (TLC) and electrospray (ES) or matrix assisted laser desorption ionization (MALDI-TOF) mass spectrometry. This general strategy has broad implications for the systematic size, shape and regio-chemical control of a wide range of dendritic nanostructures, many of which may be designed to mimic the sizes, shapes and regio specific chemo-domains observed for globular proteins.     

Synthesis of dendritic polyamide with protected amino functional groups in the periphery

A homologous series of first-to third-generation dendritic polyamides 2a, 3, and 5 with tris(aminoethyl) amine (TREA) as the core and the protected amino functional groups at the periphery were synthesized via active ester route from “Schlüter” type dendron 1a. Their structures were characterized by ¹H-NMR and mass spectra. Based on the efficient synthesis of the first generation dendrimer 2a (yield 75%), the synthesis of second-generation dendrimer 3 was found to be more efficient via the convergent method (yield 69%), while the mixed strategy was applied efficiently for the synthesis of the higher generation dendrimer 5 (yield 37%). The overall yield for the third generation dendrimer 5 from Schlüter dendron is 12%. __________ Translated from Huaxue Tongbao (Chemistry), 2005, 68(12) (in Chinese)     

Linear‐dendritic block copolymer hosts for the encapsulation of electro‐optic chromophores via H‐Bonding

Linear‐dendritic block copolymer hosts were synthesized by end‐functionalizing poly(methylmethacrylate) with dendrons that acted as hydrogen‐bonding acceptors for nonlinear optical chromophores. Second harmonic generation experiments indicate that the d₃₃ coefficients and maximum chromophore loading are increased in linear‐dendritic block copolymer hosts over comparable homopolymer hosts. Transmission electron microscopy shows 5–10 nm chromophore domains, confirming the effective spatial dispersion of the chromophores. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5017–5026, 2009     

Synthesis and thermoreversible gelation of dendron‐like polypeptide/linear poly(ε‐caprolactone)/dendron‐like polypeptide triblock copolymers

Dendron‐like poly(γ‐benzyl‐L ‐glutamate)/linear poly(ε‐caprolactone)/dendron‐like poly(γ‐benzyl‐L ‐glutamate) triblock copolymers having 2^{m + 1} PBLG branches (denoted as PBLG‐Dm‐PCL‐Dm‐PBLG, m = 0, 1, 2, and 3) were for the first time synthesized by utilizing ring‐opening polymerization (ROP) and click chemistry. The bifunctional azide‐terminated PCL (N₃‐PCL‐N₃) was click conjugated with propargyl focal point PAMAM‐typed dendrons Dm to generate Dm‐PCL‐Dm, which was then used as macroinitiator for the ROP of BLG‐NCA monomer to produce the targeted PBLG‐Dm‐PCL‐Dm‐PBLG triblock copolymers. Their molecular structures and physical properties were characterized in detail by FTIR, NMR, gel permeation chromatography, differential scanning calorimetry, and wide angle X‐ray diffraction (WAXD). The crystallinity of the central PCL segment within these copolymers is increasingly suppressed by the flanking PBLG wedges, whereas the PBLG segments gradually changed from a β‐sheet conformation to an α‐helix conformation with the increasing PBLG branches. These triblock copolymers formed thermoreversible organogels in toluene, and the dendritic topology of PBLG wedges controlled their critical gelation concentrations. The self‐assembled structure of organogels was further characterized by means of transmission electron microscopy, WAXD, and small‐angle X‐ray scattering. The fibers with flat ribbon morphology were clearly shown, and the gelation occurred through a self‐assembled nanoribbon mechanism. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 709–718, 2010     

Van Douwen's problem on 0-dimensional images of ordered compacta

A compact 0-dimensional space has a -separating rank 1 family of clopen sets iff it is the continuous image of a compact 0-dimensional linearly ordered space.

     

Regioselective Dendritic Functionalization of Cellulose

Summary: A series of regioselectively dendronized cellulose derivatives has been prepared by the treatment of cellulose in a N,N‐dimethylacetamide/LiCl solvent system with dendrons possessing isocyanate focal substituents. These new materials were characterized using FT‐IR and ¹³C NMR spectroscopies, and thermogravimetric analysis; the products were highly soluble in a wide range of organic solvents.

Substitution pattern of the dendronized cellulose.     

两亲性树形-线团大单体的合成及其丙烯酸共聚乳液的流变行为

将3,4,5-三(十六烷基氧基)苯甲酰氯先后与分子量为1000的聚乙二醇、甲基丙烯酰氯反应合成了一种新的可聚合两亲性树形-线团大单体——3,4,5-三(十六烷氧基)苯甲酰氧基聚氧乙烯甲基丙烯酸酯(6).通过核磁、红外、元素分析等对产物进行了表征.然后将其与甲基丙烯酸、丙烯酸乙酯进行乳液共聚合,制备了一种疏水树形侧链改性...     

Amphiphilic water soluble cationic ring opening metathesis copolymer as an antibacterial agent

Bacterial infection is a global problem, especially resistance acquired by bacteria against to antibiotics; there is urgent need for the development of antibiotics. Here, we proposed dendron-grafted polymers via ring opening metathesis polymerization (ROMP) featuring different with tailored hydrophobicity/hydrophilicity and cationic charges. Dendritic oxanorbornene derivatives were synthesized having two and six carbon linkers and their corresponding random and block copolymers were prepared having pendant pyridinium salt moieties via ROMP. In total, 12 different water-soluble dendronized cationic polymers featuring hexyl pyridinium moieties were prepared and investigated. Six carbon linker possessing triple charge density and hexyl pyridinium functionality each repeating unit copolymers exhibited high antibacterial activity against Gram-positive bacteria (S. aureus). However, all the polymers were inactive against Gram-negative bacteria (E. coli). Most of the copolymers are non-hemolytic (>HC ₅₀ = 1,000 μg/ml). It was also observed that, there is no significant effect between block copolymers and random copolymers keeping hydrophobicity and cationic charge density constant. Zeta potential was measured to investigate the mechanism in solution via the interaction of polymers with S. aureus, while scanning electron microscope (SEM) measurements image confirms damage of the bacterial cell wall after implementation of biocidal polymer.     

Synthesis of carbon dendron nano-chains with π-extended conjugation based on linear 1,4-phenylethynyl and 1,5-naphthylethynyl subunits

A convenient and efficient synthesis of 3,5-di(trimethylsilylethynyl)phenylacetylene and p-[3,5-di(trimethylsilylethynyl)-1-phenylethynyl]phenylacetylene and the naphthylethynyl homologues terminal acetylenes of 5-(N,N-dimethylamino)naphthylethyne have been carried out. These terminal acetylene compounds serve to prepare nanometer-sized conjugated 1,3,5-tri(ethynylphenyl)benzene and 1,3,5-tri(ethynylnaphthyl)benzene oligomers, by means of heterocoupling with 1,3,5-triiodobenzene, catalysed by palladium, in excellent yields. Both the ethynylphenyl or ethynylnaphthyl homologues chains show fluorescence emission radiation, with important quantum yield.     

Efficient synthesis of immolative carbamate dendrimer with olefinic periphery

An efficient synthetic strategy for immolative carbamate dendrons and dendrimers is described that requires no protection/deprotection in the convergent growth step. 1,3-Diamino-2-propanol was used as AB₂ building block and 4-nitrophenyl chloroformate as carbamate forming reagent. The method was demonstrated with a G3-dendron. A combination of convergent and divergent growth method was used to couple G2-dendrons to a G2-core or G3-dendrons to a tetrahedral G1-core with amine functional groups to form a spherical carbamate dendrimer (G4) possessing an olefinic periphery.