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141.
Parenty AD Smith LV Pickering AL Long DL Cronin L 《The Journal of organic chemistry》2004,69(18):5934-5946
A new class of phenanthridinium derivative has been isolated from the reaction of 2-bromoethyl-phenanthridinium bromide with a range of primary amines in excellent yields. The reaction pathway is unprecedented and proceeds via three cascade steps: nucleophilic attack of a primary amine on the iminium moiety of a heteroaromatic ring system and cyclization to form a five-membered ring, followed by hydride loss to yield a rearomatized dihydro-1H-imidazo[1,2-f]phenanthridinium derivative. A range of NMR phase transfer experiments were carried out to elucidate the mechanistic pathway, and the methodology has been further developed by means of a biphasic system using N-bromosuccinimide as a co-oxidizing agent. The method has also been extended to other N-heterocyclic cation derivatives such as quinolinium and quinazolinium. 相似文献
142.
Feick JD Chukwumah N Noel AE Velegol D 《Langmuir : the ACS journal of surfaces and colloids》2004,20(8):3090-3095
Charge nonuniformity (sigmazeta) was altered on individual polystyrene latex particles and measured using the novel experimental technique of rotational electrophoresis. It has recently been shown that unaltered sulfated latices often have significant charge nonuniformity (sigmazeta = 100 mV) on individual particles. Here it is shown that anionic polyelectrolytes and surfactants reduce the native charge nonuniformity on negatively charged particles by 80% (sigmazeta = 20 mV), even while leaving the average surface charge density almost unchanged. Reduction of charge uniformity occurs as large domains of nonuniformity are minimized, giving a more random distribution of charge on individual particle surfaces. Targeted reduction of charge nonuniformity opens new opportunities for the dispersion of nanoparticles and the oriented assembly of particles. 相似文献
143.
Gallagher A Aduse-Opoku J Rangarajan M Slaney JM Curtis MA 《Current protein & peptide science》2003,4(6):427-441
Post-translational modification of proteins by covalent attachment of sugars to the protein backbone (protein glycosylation) is the most common post-translational modification in the eucaryotic cell. However, the addition of carbohydrates to proteins of Eubacteria and Archaea has been demonstrated and accepted only recently. There is now a rapidly expanding list of bacterial glycoproteins that have been characterised from a variety of different organisms including many important pathogens. The Arg-gingipains of Porphyromonas gingivalis are recent additions to this list. In this review we present a summary of our investigations on the structure of the glycan additions to these proteolytic enzymes, the genetics of the glycosylation process and some of the effects on enzyme function and recognition. These findings are placed in the context of the current status of understanding of glycoconjugate structure and synthesis in other bacteria. Given the importance of glycosylation of eucaryotic proteins to their stability, structure, resistance to proteolysis and recognition, the modifications to the proteases described in the present report are likely to have a functional role in the properties of these enzymes in periodontal disease. 相似文献
144.
145.
Roth KM Yasseri AA Liu Z Dabke RB Malinovskii V Schweikart KH Yu L Tiznado H Zaera F Lindsey JS Kuhr WG Bocian DF 《Journal of the American Chemical Society》2003,125(2):505-517
Redox kinetics were measured for two electroactive molecules attached to Si(100) surfaces, a ferrocene (Fc-BzOH) and a Zn(II) trimesitylporphyrin (Por-BzOH). Each molecule was derivatized with a benzyl alcohol linker for attachment to the Si surface via the formation of a Si-O bond. A complete protocol was developed for the preparation of stable Si(100) surfaces derivatized with the electroactive molecules. The redox-kinetic measurements were performed on the resulting Fc-BzOH and Por-BzOH monolayers to probe (1) the rate of electron transfer (k0) for oxidation in the presence of applied potentials and (2) the rate of charge dissipation after the applied potential is disconnected (in the form of a charge-retention half-life t1/2). The k0 values for the two types of monolayers were found to be similar to one another as were the t1/2 values. Perhaps more importantly, the electron-transfer rates for both the Fc-BzOH and the Por-BzOH monolayers differ from the charge-dissipation rates by approximately 6 orders of magnitude and are strongly dependent on the surface concentration of the electroactive species. For the Por-BzOH monolayers on Si(100), the k0 and t1/2 values and their trends as a function of surface coverage were determined to be similar to those previously measured for the analogous thiol-derivatized molecule assembled on Au(111). In contrast, the Fc-BzOH monolayers on Si(100) were found to exhibit much slower electron-transfer and charge-dissipation rates than those in the corresponding thiol-Au(111) case. Two alternative hypotheses are advanced to explain both the diminution in rates with increased surface coverage and the contrasting behavior with the analogous thiols on Au, one based on space-charge effects at the monolayer-solution interface, and a second relying on changes in distance of the redox centers from the surface as modulated by the orientation of the linking chains. Collectively, the ability to prepare and study stable, electroactive molecular media on Si(100) is likely to be key in the development of hybrid molecular/semiconductor devices. 相似文献
146.
[reaction: see text] A new one-pot tandem aldol process is described in which a secondary epoxy silyl ether is converted into the 1,5-bis-silyloxy-3-alkanone in good yield. Thus, treatment of the epoxy silyl ether 8 with TBSOTf and base affords the silyl enol ether 9 via non-aldol aldol rearrangement and addition of benzaldehyde and TBSOTf gives the ketone 10 with 4:1 syn selectivity. The diastereoselectivity changes to an anti preference for most aldehydes. This anti selectivity overwhelms the normal Felkin-Ahn preference; namely, the 1,5-anti isomer predominates even when it is anti-Felkin-Ahn. 相似文献
147.
McCarroll AJ Sandham DA Titcomb LR Lewis AK Cloke FG Davies BP de Santana AP Hiller W Caddick S 《Molecular diversity》2003,7(2-4):115-123
The palladium catalysed coupling of aryl chlorides and amines can be readily achieved with short reaction times when carried out at high temperatures under thermal or microwave conditions. These coupling protocols are successful using two co-ordinate palladium-N-heterocyclic carbene complexes, or imidazolium salt protocols. 相似文献
148.
Orietta León Alexandra Muñoz‐Bonilla Vanesa Bordegé Manuel Sánchez‐Chaves Marta Fernández‐García 《Journal of polymer science. Part A, Polymer chemistry》2011,49(12):2627-2635
In this work the synthesis of poly(butyl acrylate)‐b‐poly(2‐{[(D ‐glucosamin‐2‐N‐yl)carbonyl]oxy}ethyl methacrylate) (PBA‐b‐PHEMAGl) diblock glycopolymer and poly(2‐{[(D ‐glucosamin‐2‐N‐yl)carbonyl]oxy}ethyl methacrylate)‐b‐poly(butyl acrylate)‐b‐poly(2‐{[(D ‐glucosamin‐2‐N‐yl)carbonyl]oxy}ethyl methacrylate) (PHEMAGl‐b‐PBA‐b‐PHEMAGl) was performed via atom transfer radical polymerization. Monofunctional and difunctional poly(butyl acrylate) macroinitiators were used to synthesize the well‐defined diblock and triblock glycopolymers by chain extension reaction with the glycomonomer HEMAGl. The self‐assembly of these glycopolymers in aqueous solution was studied by dynamic light scattering and transmission electron microcopy, showing the coexistence of spherical micelles and polymeric vesicles. In addition, the biomolecular recognition capacity of these micelles and vesicles, containing glucose moieties in their coronas, was investigated using the lectin Concanavalin A, Canavalia Ensiformis, which specifically interacts with glucose groups. The binding capacity of Concanavalin A with glycopolymer is influenced by the copolymer composition, increasing with the length of HEMAGl glycopolymer segment in the block copolymer. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011 相似文献
149.
Alexandra Fidalgo Tessy M. Lopez Laura M. Ilharco 《Journal of Sol-Gel Science and Technology》2009,49(3):320-328
Wet sol–gel silica matrices produced under different hydrolysis conditions were used as delivery devices to the active principle
of an antiepileptic drug (phenytoin sodium), encapsulated during the condensation stage. Post-incorporation into dry silica
powder was an alternative loading procedure. It was proven by infrared spectroscopy that neither the silica network nor the
drug loose integrity by encapsulation. The kinetics of in vitro drug release was studied at 37 °C, to water and to artificial
cerebrospinal fluid (ACSF). Emphasis has been given to the release to ACSF under dynamic conditions (with fluid renovation,
emulating what occurs in the brain). Different delivery regimes were identified and correlated with the loading method and
the matrix structure. Matrices with lower total porosity and smaller average pore size proved to be better for a long term
release. Renovation of ACSF is relevant to assure a constant concentration of phenytoin in the vicinity of the device. 相似文献
150.
In the present work, we compare the influence introduced by the variation of water-to-cement ratio and the presence of different superplasticizers on the hydration process of gray cement using the low-field nuclear magnetic resonance relaxometry. The stages of hydration are identified and a relationship between the ettringite formation during hydration process and the transverse relaxation time is established. It is also demonstrated that the addition of small amounts of superplasticizer in the cement paste significantly expands the dormant period while the hardening period is reduced. On the other side, the increase in the water-to-cement ratio has little influence on the dormant period but can instead increase the porosity of the sample and consequently reduce its strength. 相似文献