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271.
Park SH Prytulla S De Angelis AA Brown JM Kiefer H Opella SJ 《Journal of the American Chemical Society》2006,128(23):7402-7403
Solid-state NMR spectra with single-site resolution of CXCR1, a G protein-coupled receptor (GPCR), were obtained in magnetically aligned phospholipid bicelles. These results demonstrate that GPCRs in phospholipid bilayers are suitable samples for structure determination by solid-state NMR. The spectra also enable studies of drug-receptor interactions. 相似文献
272.
BJ Mason SJ King RE Miles KM Manfred AM Rickards J Kim JP Reid AJ Orr-Ewing 《The journal of physical chemistry. A》2012,116(33):8547-8556
The ability of two techniques, aerosol cavity ring down spectroscopy (A-CRDS) and optical tweezers, to retrieve the refractive index of atmospherically relevant aerosol was compared through analysis of supersaturated sodium nitrate at a range of relative humidities. Accumulation mode particles in the diameter range 300-600 nm were probed using A-CRDS, with optical tweezer measurements performed on coarse mode particles several micrometers in diameter. A correction for doubly charged particles was applied in the A-CRDS measurements. Both techniques were found to retrieve refractive indices in good agreement with previously published results from Tang and Munkelwitz, with a precision of ±0.0012 for the optical tweezers and ±0.02 for the A-CRDS technique. The coarse mode optical tweezer measurements agreed most closely with refractive index predictions made using a mass-weighted linear mixing rule. The uncertainty in the refractive index retrieved by the A-CRDS technique prevented discrimination between predictions using both mass-weighted and volume-weighted linear mixing rules. No efflorescence or kinetic limitations on water transport between the particle and the gas phase were observed at relative humidities down to 14%. The magnitude of the uncertainty in refractive index retrieved using the A-CRDS technique reflects the challenges in determining particle optical properties in the accumulation mode, where the extinction efficiency varies steeply with particle size. 相似文献
273.
Organolithium-induced alkylative ring opening of aziridines: synthesis of unsaturated amino alcohols and ethers 总被引:1,自引:0,他引:1
Hodgson DM Stefane B Miles TJ Witherington J 《The Journal of organic chemistry》2006,71(22):8510-8515
Organolithium-induced alkylative ring opening of N-sulfonyl-protected aziridinyl ethers is described. The reactions were efficiently carried out with a variety of organolithiums, providing a promising new strategy to unsaturated amino alcohols and ethers. Cis- and trans-1,4-dimethoxybut-2-ene-derived aziridines were prepared, and their propensity to undergo organolithium- induced alkylative desymmetrization is detailed. Use of a single enantiomer of the latter aziridine provides a route to enantiopure unsaturated amino ethers. 相似文献
274.
Ten acyclic and monocyclic delta,epsilon-unsaturated ketones, with and without methyl substituents on the double bond, underwent halide-terminated Prins (halo-Prins) cyclizations under anhydrous conditions in the presence of Lewis acids. TiCl4, TiBr4, BCl3, and BBr3 promoted syn-selective cyclizations to sterically congested chloro- and bromohydrins, while SnCl4, SnBr4, InCl3, ZrCl4, and several other Lewis acids effected highly anti-selective reactions to furnish the corresponding trans halohydrins. The stronger Lewis acids (TiX4 and BX3) favor the syn process that involves axial delivery of a halide ligand. Competition experiments showed that substitution at the delta carbon (methallyl enones) led to increased rates (40-50-fold), while substitution at the epsilon position (cis and trans crotyl enones) retarded the rate and eroded the selectivity of the cyclizations. The trends in syn vs anti selectivity, reactivity, and effects of different Lewis acidic metal halides are rationalized by competitive reaction pathways proceeding through syn carbocation-halide ion pairs and a higher order transition state that leads to inversion of configuration and formation of trans halohydrins, along with cyclic olefins arising from proton elimination. 相似文献
275.
276.
Richard Miles 《Monatshefte für Mathematik》2006,147(2):155-164
This paper gives an algebraic characterization of expansive actions of countable abelian groups on compact abelian groups.
This naturally extends the classification of expansive algebraic
-actions given by Schmidt using complex varieties. Also included is an application to a natural class of examples arising
from unit subgroups of integral domains.
The author is very grateful for the helpful advice and comments of Tom Ward. 相似文献
277.
Miles DR Mesfin M Mody TD Stiles M Lee J Fiene J Denis B Boswell GW 《Analytical and bioanalytical chemistry》2006,385(2):345-356
Liquid chromatography–fluorescence (LC–FLS), liquid chromatography–tandem mass spectrometry (LC–MS/MS) and inductively coupled
plasma–mass spectrometry (ICP-MS) methods were developed and validated for the evaluation of motexafin gadolinium (MGd, Xcytrin)
pharmacokinetics and biodistribution in plasma and tissues. The LC–FLS method exhibited the greatest sensitivity (0.0057 μg
mL−1), and was used for pharmacokinetic, biodistribution, and protein binding studies with small sample sizes or low MGd concentrations.
The LC–MS/MS method, which exhibited a short run time and excellent selectivity, was used for routine clinical plasma sample
analysis. The ICP–MS method, which measured total Gd, was used in conjunction with LC methods to assess MGd stability in plasma.
All three methods were validated using human plasma. The LC–FLS method was also validated using plasma, liver and kidneys
from mice and rats. All three methods were shown to be accurate, precise and robust for each matrix validated. For three mice,
the mean (standard deviation) concentration of MGd in plasma/tissues taken 5 hr after dosing with 23 mg kg−1 MGd was determined by LC–FLS as follows: plasma (0.025±0.002 μg mL−1), liver (2.89±0.45 μg g−1), and kidney (6.09±1.05 μg g−1). Plasma samples from a subset of patients with brain metastases from extracranial tumors were analyzed using both LC–MS/MS
and ICP–MS methods. For a representative patient, ≥90% of the total Gd in plasma was accounted for as MGd over the first hour
post dosing. By 24 hr post dosing, 63% of total Gd was accounted for as MGd, indicating some metabolism of MGd. 相似文献
278.
Drew SC Leong SL Pham CL Tew DJ Masters CL Miles LA Cappai R Barnham KJ 《Journal of the American Chemical Society》2008,130(24):7766-7773
The interaction of the small (140 amino acid) protein, alpha-synuclein (alphaS), with Cu(2+) has been proposed to play a role in Parkinson's disease (PD). While some insight from truncated model complexes has been gained, the nature of the corresponding Cu(2+) binding modes in the full length protein remains comparatively less well characterized. This work examined the Cu(2+) binding of recombinant human alphaS using Electron Paramagnetic Resonance (EPR) spectroscopy. Wild type (wt) alphaS was shown to bind stoichiometric Cu(2+) via two N-terminal binding modes at physiological pH. An H50N mutation isolated one binding mode, whose g parallel, A parallel, and metal-ligand hyperfine parameters correlated well with a {NH2, N(-), beta-COO(-), H2O} mode previously identified in truncated model fragments. Electron spin-echo envelope modulation (ESEEM) studies of wt alphaS confirmed the second binding mode at pH 7.4 involved coordination of His50 and its g parallel and A parallel parameters correlated with either {NH2, N(-), beta-COO(-), N(Im)} or {N(Im), 2 N(-)} coordination observed in alphaS fragments. At pH 5.0, His50-anchored Cu(2+) binding was greatly diminished, while {NH2, N(-), beta-COO(-), H2O} binding persisted in conjunction with another two binding modes. Metal-ligand hyperfine interactions from one of these indicated a 1N3O coordination sphere, which was ascribed to a {NH2, CO} binding mode. The other was characterized by a spectrum similar to that previously observed for diethylpyrocarbonate-treated alphaS and was attributed to C-terminal binding centered on Asp121. In total, four Cu(2+) binding modes were identified within pH 5.0-7.4, providing a more comprehensive picture of the Cu(2+) binding properties of recombinant alphaS. 相似文献
279.
Miles EW 《Chemical record (New York, N.Y.)》2001,1(2):140-151
Tryptophan synthase is a classic enzyme that channels a metabolic intermediate, indole. The crystal structure of the tryptophan synthase alpha2beta2 complex from Salmonella typhimurium revealed for the first time the architecture of a multienzyme complex and the presence of an intramolecular tunnel. This remarkable hydrophobic tunnel provides a likely passageway for indole from the active site of the alpha subunit, where it is produced, to the active site of the beta subunit, where it reacts with L-serine to form L-tryptophan in a pyridoxal phosphate-dependent reaction. Rapid kinetic studies of the wild type enzyme and of channel-impaired mutant enzymes provide strong evidence for the proposed channeling mechanism. Structures of a series of enzyme-substrate intermediates at the alpha and beta active sites are elucidating enzyme mechanisms and dynamics. These structural results are providing a fascinating picture of loops opening and closing, of domain movements, and of conformational changes in the indole tunnel. Solution studies provide further evidence for ligand-induced conformational changes that send signals between the alpha and beta subunits. The combined results show that the switching of the enzyme between open and closed conformations couples the catalytic reactions at the alpha and beta active sites and prevents the escape of indole. 相似文献
280.