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排序方式: 共有111条查询结果,搜索用时 31 毫秒
1.
Ahmed M. Rozza Marcell Papp Neil R. McFarlane Prof. Jeremy N. Harvey Dr. Julianna Oláh 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(49):e202200930
The binding of small gas molecules such as NO and CO plays a major role in the signaling routes of the human body. The sole NO-receptor in humans is soluble guanylyl cyclase (sGC) – a histidine-ligated heme protein, which, upon NO binding, activates a downstream signaling cascade. Impairment of NO-signaling is linked, among others, to cardiovascular and inflammatory diseases. In the present work, we use a combination of theoretical tools such as MD simulations, high-level quantum chemical calculations and hybrid QM/MM methods to address various aspects of NO binding and to elucidate the most likely reaction paths and the potential intermediates of the reaction. As a model system, the H-NOX protein from Shewanella oneidensis (So H-NOX) homologous to the NO-binding domain of sGC is used. The signaling route is predicted to involve NO binding to form a six-coordinate intermediate heme-NO complex, followed by relatively facile His decoordination yielding a five-coordinate adduct with NO on the distal side with possible isomerization to the proximal side through binding of a second NO and release of the first one. MD simulations show that the His sidechain can quite easily rotate outward into solvent, with this motion being accompanied in our simulations by shifts in helix positions that are consistent with this decoordination leading to significant conformational change in the protein. 相似文献
2.
An integral equation formulation for buoyancy-driven convection problems is developed and illustrated. Buoyancy-driven convection in a bounded cylindrical geometry with a free surface is studied for a range of aspect ratios and Nusselt numbers. The critical Rayleigh number, the nature of the cellular motion, and the heat transfer enhancement are computed using linear theory. Green's functions are used to convert the linear problem into linear Fredholm integral equations. Theorems are proved which establish the properties of the eigenvalues and eigenfunctions of the linear integral operator which appears in these equations. 相似文献
3.
A series of terminal alkynes has been reacted with sodium perborate and mercuric acetate catalyst in acetic acid to produce 1-acetoxyalkan-2-ones in good yield. The reaction constitutes a mild and convenient method for the oxidation of terminal triple bonds. 相似文献
4.
EI Rodriguez Martinez CI Barriga-Paulino MI Zapata CC Chinchilla AM López-Jiménez CM Gómez 《BMC neuroscience》2012,13(1):104-23
ABSTRACT: BACKGROUND: The peri-adolescent period is a crucial developmental moment of transition from childhood to emergent adulthood. The present report analyses the differences in Power Spectrum (PS) of the Electroencephalogram (EEG) between late childhood (24 children between 8 and 13 years old) and young adulthood (24 young adults between 18 and 23 years old). RESULTS: The narrow band analysis of the Electroencephalogram was computed in the frequency range of 0--20 Hz. The analysis of mean and variance suggested that six frequency ranges presented a different rate of maturation at these ages, namely: low delta, delta-theta, low alpha, high alpha, low beta and high beta. For most of these bands the maturation seems to occur later in anterior sites than posterior sites. Correlational analysis showed a lower pattern of correlation between different frequencies in children than in young adults, suggesting a certain asynchrony in the maturation of different rhythms. The topographical analysis revealed similar topographies of the different rhythms in children and young adults. Principal Component Analysis (PCA) demonstrated the same internal structure for the Electroencephalogram of both age groups. Principal Component Analysis allowed to separate four subcomponents in the alpha range. All these subcomponents peaked at a lower frequency in children than in young adults. CONCLUSIONS: The present approaches complement and solve some of the incertitudes when the classical brain broad rhythm analysis is applied. Children have a higher absolute power than young adults for frequency ranges between 0-20 Hz, the correlation of Power Spectrum (PS) with age and the variance age comparison showed that there are six ranges of frequencies that can distinguish the level of EEG maturation in children and adults. The establishment of maturational order of different frequencies and its possible maturational interdependence would require a complete series including all the different ages. 相似文献
5.
D. Cozzi A. A. Kolessnik W. D. McFarlane A. J. Sutherland K. Halaka P. Meunier Ch. Mentzer L. S. Lanke C. Gatti und A. Kñalinsky 《Fresenius' Journal of Analytical Chemistry》1943,126(4):153-155
Ohne Zusammenfassung 相似文献
6.
Andrew Mills Pauline Grosshans Michael McFarlane 《Journal of photochemistry and photobiology. A, Chemistry》2009,201(2-3):136-141
A novel UV dosimeter is described comprising a tetrazolium dye, neotetrazolium chloride (NTC), dissolved in a film of polymer, polyvinyl alcohol (PVA). The dosimeter is pale yellow/colourless in the absence of UV light, and turns red upon exposure to UV light. The spectral characteristics of a typical UV dosimeter film and the mechanism through which the colour change occurs are detailed. The NTC UV dosimeter films exhibit a response to UV light that is related to the intensity and duration of UV exposure, the level of dye present in the films and the thickness of the films themselves. The response of the dosimeter is temperature independent over the range 20–40 °C and, like most UV dosimeters, exhibits a cosine-like response dependence upon irradiance angle. The introduction of a layer of a UV-screening compound which slows the rate at which the dosimeter responds to UVR enables the dosimeter response to be tailored to different UV doses. The possible use of these novel dosimeters to measure solar UV exposure dose is discussed. 相似文献
7.
The lead-lead nuclear spin-spin coupling constant determined by heteronuclear double resonance in hexamethyldilead has the surprisingly small value of +290 Hz which suggests that the s-overlap integral for the metal-metal bond is low. 相似文献
8.
Randall C. McFarlane Park M. Reilly Kenneth F. O'driscoll 《Journal of polymer science. Part A, Polymer chemistry》1980,18(1):251-257
Six recently proposed methods for analyzing copolymerization composition data have been compared to a nonlinear least-squares analysis to ascertain the precision of the six methods in determining reactivity ratios. Data used were simulated for five hypothetical monomer pairs with three different types of experiment design and contained error structures similar to those observed experimentally. The results of the comparisons suggest that retrospective analyses of existing copolymerization data should only be done with a nonlinear least-squares analysis. For new data, the design of experiments is of great importance, and when done properly allows the use of some of the linear least-squares methods of analysis. 相似文献
9.
10.
Synthesis and conductivities of the apatite-type systems, La9.33+xSi6−yMyO26+z (M=Co, Fe, Mn) and La8Mn2Si6O26 总被引:1,自引:1,他引:0
Apatite-type oxides of formula (La/Sr)10−xSi6O26+y have been attracting significant interest recently, because of their high oxide ion conductivity. In this paper we report
the synthesis and conductivities of phases based on doping La9.33Si6O26 with Co, Fe, Mn on the Si site, according to the formula La9.33+x/3Si6−xMxO26 (M=Co, Fe, Mn). Substitution limits observed were x≤1.5 (Co), x≤1.25 (Fe), x≤0.5 (Mn). Higher Mn levels could be achieved
by substituting onto the La site, with it being possible to prepare the phase La8Mn2Si6O26. The highest conductivities were observed for the Co doped samples, although investigations into the dependence of conductivity
on p(O2) (0.2–10−5 atm.) indicated that the conductivity was dominated by the electronic component in these cases. In contrast, the conductivities
for the Fe and Mn doped samples were mainly ionic in the same p(O2) range. Experiments into varying the oxygen content of these doped phases indicated that increasing the oxygen content above
the nominally stoichiometric O26 appears to increase the oxide ion conductivity.
Preliminary studies of the reactivity of the electrolyte La9.33Si6O26 with potential SOFC cathode materials (La1−xSrxMO3; M=Co, Fe, Mn) suggests that reaction can occur at high temperatures leading to the incorporation of the transition metal
into the apatite electrolyte. However, the fact that these doped phases exhibit high conductivities suggests that this may
limit any problems caused by such a reaction at the electrolyte-electrode interface.
Paper presented at the 8th EuroConference on Ionics, Carvoeiro, Algarve, Portugal, Sept. 16–22, 2001. 相似文献