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991.
Ka-Man Cheung Ka-Wang Chan Ian D. Williams 《Journal of organometallic chemistry》2005,690(12):2913-2921
Treatment of [Ir(ppy)2(μ-Cl)]2 and [Ir(ppy)2(dtbpy)][OTf] (ppy = 2-(2′-pyridyl)phenyl; dtbpy = 4,4′-di-tert-butyl-2,2′-bipyridine; OTf = triflate) with pyridinium tribromide in the presence of Fe powder led to isolation of [Ir(4-Br-ppy)(μ-Br)]2 (1) and [Ir(4-Br-ppy)2(dtbpy)][OTf] (2), respectively. Pd-catalyzed cross-coupling of 2 with RB(OH)2 afforded [Ir(4-R-ppy)2(dtbpy)][OTf] (R = 4′-FC6H4 (3)), 4′-PhC6H4 (4), 2′-thienyl (5), 4′-C6H4CH2OH (6). Treatment of 4 with B2(pin)2 (pin = pinacolate) afforded [Ir{4-(pin)B-ppy}2(dtbpy)][OTf] (7). The alkynyl complexes [Ir(4-PhCC-ppy)2(dtbpy)][OTf] (8) and [Ir{4-Me2(OH)CC-ppy}(4-Br-ppy)(dtbpy)][OTf] (9) were prepared by cross-coupling of 2 with PhCCSnMe3 and Me2C(OH)CCH, respectively. Ethynylation of [Ir(fppy)2(dtbpy)][OTf] (fppy = 5-formyl-2-(2′-pyridyl)phenyl) with Ohira’s reagent MeCOC(N2)P(O)(OEt)2 afforded [Ir{5-HCC-ppy}2(dtbpy)][OTf] (10). The solid-state structures of 2, 5, 7, and 10 have been determined. 相似文献
992.
Nicholas E. Leadbeater Sharon J. Pillsbury Erik Shanahan Victoria A. Williams 《Tetrahedron》2005,61(14):3565-3585
In the light of the controversy in the area and since reports using simultaneous cooling in conjunction with microwave heating are appearing in the literature, we were keen to assess the methodology, looking at temperature measurement issues as well as the use of the technique in three classes of reaction, namely a Heck coupling, a Diels-Alder cycloaddition and a Michael addition. We present our initial findings here. 相似文献
993.
The effect of sintering dispersed dispersion and nano-emulsion particles of high molecular weight polytetrafluoroethylene (PTFE) on a substrate as a function of "melt" time and temperature is described. Folded chain single crystals parallel to the substrate and as ribbons on-edge (with double striations), as well as bands, are produced for longer sintering times; particle merger and diffusion of individual molecules, crystallizing as folded chain, single (or few) molecule,single crystals when "trapped" on the substrate by cooling occur for shorter sintering times. It is suggested the observed structures develop with sintering time, in a mesomorphic melt. The structure of the nascent particles is also discussed. 相似文献
994.
Andreas Dorian Emily J. Landgreen Hayley R. Petras Prof. James J. Shepherd Prof. Florence J. Williams 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(42):10839-10843
The facile production of ArCF2X and ArCX3 from ArCF3 using catalytic iron(III)halides is reported, which constitutes the first iron-catalyzed halogen exchange for non-aromatic C−F bonds. Theoretical calculations suggest direct activation of C−F bonds by iron coordination. ArCX3 and ArCF2X products of the reaction are synthetically valuable due to their diversification potential. In particular, chloro- and bromodifluoromethyl arenes (ArCF2Cl, ArCF2Br respectively) provide access to a myriad of difluoromethyl arene derivatives (ArCF2R). To optimize for mono-halogen exchange, a statistical method called Design of Experiments was used. Optimized parameters were successfully applied to electron rich and electron deficient aromatic substrates, and to the late stage diversification of flufenoxuron, a commercial insecticide. These methods are highly practical, being run at convenient temperatures and using inexpensive common reagents. 相似文献
995.
Vladimir Gubala Jonathan Siegrist Ruairi Monaghan Brian O’Reilly Ram Prasad Gandhiraman Stephen Daniels David E. Williams Jens Ducrée 《Analytica chimica acta》2013
Herein a simple analytical method is presented for the characterization of biomolecule adsorption on cyclo olefin polymer (COP, trade name: Zeonor®) substrates which are widely used in microfluidic lab-on-a-chip devices. These Zeonor® substrates do not possess native functional groups for specific reactions with biomolecules. Therefore, depending on the application, such substrates must be functionalized by surface chemistry methods to either enhance or suppress biomolecular adsorption. This work demonstrates a microfluidic method for evaluating the adsorption of antibodies and oligonucleotides surfaces. The method uses centrifugal microfluidic flow-through chips and can easily be implemented using common equipment such as a spin coater. The working principle is very simple. The user adds 40 L of the solution containing the sample to the starting side of a microfluidic channel, where it is moved through by centrifugal force. Some molecules are adsorbed in the channel. The sample is then collected at the other end in a small reservoir and the biomolecule concentration is measured. As a pilot application, we characterized the adsorption of goat anti-human IgG and a 20-mer DNA on Zeonor®, and on three types of functionalized Zeonor: 3-aminopropyltriethoxysilane (APTES) modified surface with mainly positive charge, negatively charged surface with immobilized bovine serum albumin (BSA), and neutral, hydrogel-like film with polyethylene glycol (PEG) characteristics. This simple analytical approach adds to the fundamental understanding of the interaction forces in real, microfluidic systems. This method provides a straightforward and rapid way to screen surface compositions and chemistry, and relate these to their effects on the sensitivity and resistance to non-specific binding of bioassays using them. In an additional set of experiments, the surface area of the channels in this universal microfluidic chip was increased by precision milling of microscale trenches. This modified surface was then coated with APTES and tested for its potential to serve as a unique protein dilution feature. 相似文献
996.
J. P. Waltho J. G. Vinter A. Davis D. H. Williams 《Journal of computer-aided molecular design》1988,2(1):31-41
Summary NMR studies of the rotation barrier of the disaccharide of the glycopeptide antibiotic vancomycin have been used to test the performance of computer simulation techniques using molecular mechanics. In the absence of any solvated water, no correlation could be found between experiment and calculation. By introducing solvent water molecules into the binding region of the antibiotic, the NMR results could be simulated both qualitatively and quantitatively within experimental error without using massive computational resources. 相似文献
997.
David P. Clark Philip R. Cunningham Stephen G. Reams Fairoz Mat-Jan Raafat Mohammedkhani Charling R. Williams 《Applied biochemistry and biotechnology》1988,17(1-3):163-173
Wild typeE. coli ferments glucose to a mixture of ethanol and acetic, lactic, formic, and succinic acids. Mutants defective in acid production have now been isolated, including those defective in lactate dehydrogenase (LDH) or with excess alcohol dehydrogenase. These mutations had no phenotype without apfl mutation. Novel mutants affecting acetate metabolism were isolated by insertion of the fusion vector Mudl. TheseaceG mutants cannot grow anaerobically on glucose or aerobically on acetate yet lack the pleiotropic growth defects of previously knownpta/ack mutants. In some genetic backgrounds acetate negative mutations suppress the growth defects ofadh mutations. These results are discussed in terms of redox balance. 相似文献
998.
999.
1000.
Serenella Medici Marcella Gagliardo ScottB. Williams PrestonA. Chase Serafino Gladiali Martin Lutz AnthonyL. Spek GerardP.M. vanKlink Gerard vanKoten 《Helvetica chimica acta》2005,88(3):694-705
Achiral P‐donor pincer‐aryl ruthenium complexes ([RuCl(PCP)(PPh3)]) 4c , d were synthesized via transcyclometalation reactions by mixing equivalent amounts of [1,3‐phenylenebis(methylene)]bis[diisopropylphosphine] ( 2c ) or [1,3‐phenylenebis(methylene)]bis[diphenylphosphine] ( 2d ) and the N‐donor pincer‐aryl complex [RuCl{2,6‐(Me2NCH2)2C6H3}(PPh3)], ( 3 ; Scheme 2). The same synthetic procedure was successfully applied for the preparation of novel chiral P‐donor pincer‐aryl ruthenium complexes [RuCl(P*CP*)(PPh3)] 4a , b by reacting P‐stereogenic pincer‐arenes (S,S)‐[1,3‐phenylenebis(methylene)]bis[(alkyl)(phenyl)phosphines] 2a , b (alkyl=iPr or tBu, P*CHP*) and the complex [RuCl{2,6‐(Me2NCH2)2C6H3}(PPh3)], ( 3 ; Scheme 3). The crystal structures of achiral [RuCl(equation/tex2gif-sup-3.gifPCP)(PPh3)] 4c and of chiral (S,S)‐[RuCl(equation/tex2gif-sup-6.gifPCP)(PPh3)] 4a were determined by X‐ray diffraction (Fig. 3). Achiral [RuCl(PCP)(PPh3)] complexes and chiral [RuCl(P*CP*)(PPh3)] complexes were tested as catalyst in the H‐transfer reduction of acetophenone with propan‐2‐ol. With the chiral complexes, a modest enantioselectivity was obtained. 相似文献