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W.R.C. Somerville B. Auguié E.C. Le Ru 《Journal of Quantitative Spectroscopy & Radiative Transfer》2012,113(7):524-535
A severe loss of precision is unravelled in the numerical calculation of surface integrals that appear in the Extended Boundary Condition Method (EBCM), to calculate the T-matrix elements of axisymmetric particles. We systematically study the occurrence of numerical cancellations for three basic particle shapes, namely cylinders, spheroids, and offset spheres, with typical sizes, aspect ratios and materials often studied as benchmark examples in the literature. The cancellations are evidenced both for spheroids and offset spheres, and are particularly pronounced in the latter case. The resulting loss of precision is independent from the commonly asserted problems of matrix inversion. We show that the origin of these severe cancellations can be further studied and understood by numerical investigations of the scaling of the integrands and integrals with respect to the particle size parameter. This allows us to develop a detailed mathematical proof of these cancellations. The results suggest that the EBCM method, in its usual formulation, suffers important numerical instabilities which reduce the domain of convergence for specific particle shapes that are commonly used for testing and benchmarking the method. 相似文献
33.
SL Mironov E Skorova G Taschenberger N Hartelt VO Nikolaev MJ Lohse S Kügler 《BMC neuroscience》2009,10(1):29-11
Background
cAMP is an ubiquitous second messenger mediating various neuronal functions, often as a consequence of increased intracellular Ca2+ levels. While imaging of calcium is commonly used in neuroscience applications, probing for cAMP levels has not yet been performed in living vertebrate neuronal tissue before. 相似文献34.
Rosie J. Somerville Andryj M. Borys Marina Perez-Jimenez Ainara Nova David Balcells Lorraine A. Malaspina Simon Grabowsky Ernesto Carmona Eva Hevia Jesús Campos 《Chemical science》2022,13(18):5268
More than four decades ago, a complex identified as the planar homoleptic lithium nickelate “Li3NiPh3(solv)3” was reported by Taube and co-workers. This and subsequent reports involving this complex have lain dormant since; however, the absence of an X-ray diffraction structure leaves questions as to the nature of the Ni–PhLi bonding and the coordination geometry at Ni. By systematically evaluating the reactivity of Ni(COD)2 with PhLi under different conditions, we have found that this classical molecule is instead a unique octanuclear complex, [{Li3(solv)2Ph3Ni}2(μ-η2:η2-C6H4)] (5). This is supported by X-ray crystallography and solution-state NMR studies. A theoretical bonding analysis from NBO, QTAIM, and ELI perspectives reveals extreme back-bonding to the bridging C6H4 ligand resulting in dimetallabicyclobutane character, the lack of a Ni–Ni bond, and pronounced σ-bonding between the phenyl carbanions and nickel, including a weak σC–Li → sNi interaction with the C–Li bond acting as a σ-donor. Employing PhNa led to the isolation of [Na2(solv)3Ph2NiCOD]2 (7) and [Na2(solv)3Ph2(NaC8H11)Ni(COD)]2 (8), which lack the benzyne-derived ligand. These findings provide new insights into the synthesis, structure, bonding and reactivity of heterobimetallic nickelates, whose prevalence in organonickel chemistry and catalysis is likely greater than previously believed.We disclose the actual octanuclear nature of the major compound from reacting Ni(COD)2 and PhLi, assigned for more than four decades as ‘Li3NiPh3(solv)3’. We provide a thorough bonding analysis and discuss its potential implications in catalysis. 相似文献
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Van Bael MJ Bekaert J Temst K Van Look L Moshchalkov VV Bruynseraede Y Howells GD Grigorenko AN Bending SJ Borghs G 《Physical review letters》2001,86(1):155-158
A scanning Hall probe microscope is used to study flux pinning in a thin superconducting Pb film covering a square array of single-domain Co dots with in-plane magnetization. We show that single flux quanta of opposite sign thread the superconducting film below T(c) at the opposite poles of these dipoles. Depending on the polarity of the applied field, flux lines are attracted to a specific pole of the dipoles, due to the direct interaction with the vortexlike structures induced by the local stray field. 相似文献
38.
A. Colin-Russ J. H. Highberger C. E. Retzsch F. H. Small A. Fritsch W. R. Atkin L. Goldman F. C. Thompson W. F. Barker E. H. Rohwer S. G. Shuttleworth W. F. Barker H. G. Turley I. C. Somerville und F. P. Cronin 《Fresenius' Journal of Analytical Chemistry》1942,123(1-2):47-49
Ohne Zusammenfassung 相似文献
39.
This work describes an integrated method of enzymatic digestion, heteroduplex analysis (HA) and electrophoretic sizing on a microfluidic chip. HA techniques based on microchip electrophoresis are capable of the high sensitivity detection of subtle mutations such as single nucleotide polymorphisms (SNPs) but are not readily able to detect homozygous mutant genotypes. Such homozygous conditions are commonly encountered with the gene implicated in hereditary haemochromatosis, HFE. We employed the restriction fragment length polymorphism (RFLP) method of mutation detection to complement the HA method in a rapid novel on-chip procedure that separated digested PCR fragments to reliably determine the presence or absence of the most important mutations associated with haemochromatosis. This method was able to distinguish the homozygous mutant, heterozygous and homozygous wildtype genotypes. The mutations investigated here (C282Y, H63D and S65C) are often the mutation targets used in the genetic testing for haemochromatosis. This method provides the extremely specific digestion methods needed for the analysis of the known and relatively common mutations that have a significant probability of occurring in a homozygous form. However, the high sensitivity of the HA method is useful in detecting other mutations of lesser likelihood which, by virtue of their rarity, are likely to be present only in a heterozygous form. Although the conventional methods of analysing these mutations require as much as a day to perform, this microchip method, even without robotics or multiplexed operation, can be performed in about 10 min per sample. 相似文献
40.
MJ Lazaro AA Herod M Domin Y Zhuo CA Islas R Kandiyoti 《Rapid communications in mass spectrometry : RCM》1999,13(14):1401-1412
Three methods for determining a 'safe' estimate for high-mass limits of MALDI spectra of coal derived liquids were explored, using a sample of coal-tar pitch and its pyridine-insoluble fraction. Co-addition of increasing numbers of single-shot spectra (10, 30, 50 and 100 pulses) showed visually observable reductions in noise levels, consistent with robust and statistically meaningful signals. Three separate types of post-acquisition calculation were used to identify high-mass limits of the spectra. (i) A literature method indicated high-mass limits similar to those observed visually-as a shift from baseline at the highest masses, nearly 350 000 u for the coal tar pitch and about 390 000 u for its pyridine insoluble fraction. (ii) Comparing instrument signal with pre-selected multiples of the standard deviation, upper mass estimates of between 40-60 000 u for the coal-tar pitch and about 95 000 u for its pyridine-insoluble fraction were found. (iii) Calculation of the slope was used to identify 'lift-off' of the spectrum from baseline. The angle between the smoothed spectrum and the baseline was matched to a pre-selected value (e.g. 0.5 degrees and 1 degrees ). However, the arbitrary specification of the key parameter did not establish this last method on a firm basis. The choice of a criterion for estimating high-mass limits of MALDI spectra remains a semi-quantitative procedure; a reasonably conservative high-mass limit may be estimated by comparison of signal with five times the standard deviation. However, evaluation of size exclusion chromatograms of the present samples using polystyrene standards suggests that molecular mass distributions of pitch samples arrived at by MALDI mass spectrometry are, at least partly, determined by the limitations of available instruments. Copyright 1999 John Wiley & Sons, Ltd. 相似文献