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61.
[reaction: see text]. (-)-PF1163B, a new macrocyclic antifungal antibiotic isolated from Streptomyces sp., has been prepared in eight steps from (S)-citronellene. The key step is a ring-closing metathesis reaction of an ester and amide derivative obtained from a substituted N-methyl-l-tyrosine. 相似文献
62.
Mireia Morell Brigitte Voit Xavier Ramis Àngels Serra Albena Lederer 《Journal of polymer science. Part A, Polymer chemistry》2011,49(14):3138-3151
Well‐defined multiarm star block copolymers poly(glycidol)‐b‐poly(methyl methacrylate) (PGOHBr‐b‐PMMAx) with an average number of PMMA arms of 85, 55, and 45 have been prepared. The core‐first approach has been selected as the methodology using atom transfer radical polymerization (ATRP) of MMA from an activated hyperbranched poly(glycidol) as the core. These activated hyperbranched macroinitiators were prepared by esterification of hyperbranched poly(glycidol) (PGOH) with 2‐bromoisobutyryl bromide. The effect of monomer/initiator ratio, catalyst concentration, time, temperature, and solvent on the growing of the arms has been studied in detail in order to optimize the process and to diminish the radical‐radical coupling. The final products and intermediates were characterized by means of size exclusion chromatography (SEC), nuclear magnetic resonance (NMR) and Fourier transform‐infrared (FTIR) spectroscopy. The length of PMMA arms was determined by SEC after cleavage of ester bond linked to PGOH core. Glass transition temperature (Tg), thermal stability and rheological properties of the multiarm star copolymers were also studied. Finally, tapping mode atomic force microscopy (TMAFM) allowed the clear visualization of nano‐sized particles (80–200 nm) corresponding to individual star molecules. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011 相似文献
63.
Christine Bressy Minh Ngoc NGuyen Brigitte Tanguy Van Giang Ngo André Margaillan 《Polymer Degradation and Stability》2010,95(7):1260-9117
Polymers containing hydrolytically labile trialkylsilyl ester side groups were synthesised via a conventional and a controlled radical polymerization. The trialkylsilyl methacrylate monomer unit was chosen for its capacity to hydrolyse into basic, acid or sea water varying the hydrophilic character of the resulting polymer backbone with time. The hydrolysis or saponification reaction of the ester bond of the trialkylsilyl methacrylate was monitored through a 1H NMR study showing the formation of siloxane side-products. Several copolymers and polymer blends were prepared as matrixes for controlled erodible systems. Their capacity to hydrolyse was demonstrated through SEM investigations with selective dissolution of free films containing hydrolysable copolymers and PMMA blends. Well-defined random and diblock copolymers with methyl methacrylate were investigated to show the effect of the microstructure on the erosion properties of the corresponding coatings. Poly(methyl methacrylate-b-tert-butyldimethylsilyl methacrylate) diblock copolymers synthesised through the RAFT process showed a better control of the erosion with a constant erosion rate over a long-time service in sea water at pH = 8.2. In addition, experiments showed that the erosion rate could be modulated by varying the molar proportion of hydrolysable side groups onto the copolymer backbone and the weight amount of copolymers mixed with PMMA in toluene solution. 相似文献
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Sarah W. Kamau Chapman Paul O. Hassa Sabine Koch-Schneidemann Brigitte von Rechenberg Margarethe Hofmann-Amtenbrink Benedikt Steitz Alke Petri-Fink Heinrich Hofmann Michael O. Hottiger 《Journal of magnetism and magnetic materials》2008
Primary cell lines are more difficult to transfect when compared to immortalized/transformed cell lines, and hence new techniques are required to enhance the transfection efficiency in these cells. We isolated and established primary cultures of synoviocytes, chondrocytes, osteoblasts, melanocytes, macrophages, lung fibroblasts, and embryonic fibroblasts. These cells differed in several properties, and hence were a good representative sample of cells that would be targeted for expression and delivery of therapeutic genes in vivo. The efficiency of gene delivery in all these cells was enhanced using polyethylenimine-coated polyMAG magnetic nanoparticles, and the rates (17–84.2%) surpassed those previously achieved using other methods, especially in cells that are difficult to transfect. The application of permanent and pulsating magnetic fields significantly enhanced the transfection efficiencies in synoviocytes, chondrocytes, osteoblasts, melanocytes and lung fibroblasts, within 5 min of exposure to these magnetic fields. This is an added advantage for future in vivo applications, where rapid gene delivery is required before systemic clearance or filtration of the gene vectors occurs. 相似文献
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In this paper we give upper and lower bounds for each eigenvalue λ
n
of Hill's differential equation. We apply the results to toroidal surfaces of revolution in order to get estimates for the
eigenvalues of the Laplacian in terms of curvature expressions; they are sharp for the flat torus. As an example, we investigate
the standard torus in IR3; here, the bounds depend on the radii only. 相似文献
70.
The spectroscopic, electronic, and DNA-binding characteristics of two novel ruthenium complexes based on the dialkynyl ligands 2,3-bis(phenylethynyl)-1,4,8,9-tetraaza-triphenylene (bptt, 1) and 2,3-bis(4-tert-butyl-phenylethynyl)-1,4,8,9-tetraaza-triphenylene (tbptt, 2) have been investigated. Electronic structure calculations of bptt reveal that the frontier molecular orbitals are localized on the pyrazine-dialkynyl portion of the free ligand, a property that is reflected in a red shift of the lowest energy electronic transition (1: λ(max) = 393 nm) upon substitution at the terminal phenyl groups (2: λ(max) = 398 nm). Upon coordination to ruthenium, the low-energy ligand-centered transitions of 1 and 2 are retained, and metal-to-ligand charge transfer transitions (MLCT) centered at λ(max) = 450 nm are observed for [Ru(phen)(2)bptt](2+)(3) and [Ru(phen)(2)tbptt](2+)(4). The photophysical characteristics of 3 and 4 in ethanol closely parallel those observed for [Ru(bpy)(3)](2+) and [Ru(phen)(3)](2+), indicating that the MLCT excited state is primarily localized within the [Ru(phen)(3)](2+) manifold of 3 and 4, and is only sparingly affected by the extended conjugation of the bptt framework. In an aqueous environment, 3 and 4 possess notably small luminescence quantum yields (3: ?(H(2)O) = 0.005, 4: ?(H(2)O) = 0.011) and biexponential decay kinetics (3: τ(1) = 40 ns, τ(2) = 230 ns; 4: τ(1) ~ 26 ns, τ(2) = 150 ns). Addition of CT-DNA to an aqueous solution of 3 causes a significant increase in the luminescence quantum yield (?(DNA) = 0.045), while the quantum yield of 4 is relatively unaffected (?(DNA) = 0.013). The differential behavior demonstrates that tert-butyl substitution on the terminal phenyl groups inhibits the ability of 4 to intercalate with DNA. Such changes in intrinsic luminescence demonstrate that 3 binds to DNA via intercalation (K(b) = 3.3 × 10(4) M(-1)). The origin of this light switch behavior involves two competing (3)MLCT states similar to that of the extensively studied light switch molecule [Ru(phen)(2)dppz](2+). The solvent- and temperature-dependence of the luminescence of 3 reveal that the extended ligand aromaticity lowers the energy of the (3)ππ* excited state into competition with the emitting (3)MLCT state. Interconversion between these two states plays a significant role in the observed photophysics and is responsible for the dual emission in aqueous environments. 相似文献