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1.
2.
A simple high-performance liquid chromatographic method, using photodiode array detection was developed for the determination
of propylene glycol in human plasma and in the fluid retreived after continuous veno-venous hemofiltration. The method entailed
alkaline derivatization with benzoyl chloride and ethylene glycol as internal standard. The separation of the compounds, after
extraction with pentane, was carried out on a Pursuit C8 column with UV-detection at 230 nm. Validation samples were analyzed
with an accuracy between 95 and 105%, and intra- and inter-day coefficients of variation of less than 8%. The calibration
curve was linear over a concentration range of 5–100 mg L−1 with a detection limit of 1 mg L−1. Blood plasma samples of several patients were analysed by using the prescribed method with propylene glycol concentrations
varying from 5 to 98 mg L−1. Compared to previously described LC methods, this method is ten times more sensitive and thus suitable for use in pharmacokinetic
studies of propylene glycol. 相似文献
3.
Density functional theory (BPW91/TZ2P) is used to explore the nature of cation-cation interactions (CCIs) that exist between two actinyl cations in solution. Solvation, which is modeled using COSMO, favors the complexes (ONpO-ONpO)2+ and (ONpO-OUO)3+ over separated NpO2+(aq) and UO2(2+)(aq) cations because of the quadratic dependence of solvation on charge. For (OUO-OUO)4+, solvation effects, even though very large, are unable to overcome intrinsic electrostatic repulsion between the units. The actinyl-actinyl complexes are T-shaped, with the oxygen of one unit coordinated to the actinide metal of the other unit. The association free energies of (ONpO-ONpO)2+ and (ONpO-OUO)3+ are calculated as -42.1 and -29.2 kcal/mol. Explicit consideration of the first solvation shell at the B3LYP/LANL2DZ level suggests that the free energies of binding may be overestimated. The Hg2(2+) dication, though not considered a "traditional" CCI, is very similar to the actinyl-actinyl interaction. The binding free energy of Hg2(2+) in solution is calculated as -16.0 kcal/mol. 相似文献
4.
Swart M Fonseca Guerra C Bickelhaupt FM 《Journal of the American Chemical Society》2004,126(51):16718-16719
Recently, Vakonakis and LiWang (J. Am. Chem. Soc. 2004, 126, 5688) reported experimental evidence for stronger hydrogen bonds in RNA A:U than in DNA A:T base pairs, which was based on differences in NMR shielding for adenine C2. We have analyzed the proposed correlation between NMR shielding and hydrogen-bond strength using density functional theory. Although we agree with the conclusion that A:U is more strongly bound, we find no correlation between the hydrogen-bond strength and the NMR shielding of C2. Our study shows that NMR merely probes the presence/absence of the methyl group in thymine/uracil, without any relation to the strength of the hydrogen bonds involved. In other words, one cannot infer the Watson-Crick hydrogen-bond strength from the NMR shielding constant of adenine C2. 相似文献
5.
Köcher T Pichler P Mazanek M Swart R Mechtler K 《Analytical and bioanalytical chemistry》2011,400(8):2339-2347
The Mascot search algorithm is one of the most commonly used tools for protein identification. Tandem mass spectrometry data
searched against a protein sequence database is utilized for identifying peptides and proteins, each reported with a score.
Higher Mascot scores are associated with lower chances of random hits. The process of peak selection performed by the search
engine prior to the search is a critical aspect of the process. Here, we show that Mascot divides the MS/MS spectrum into
fixed m/z regions for peak selection, starting at the lowest m/z value of the peak list. Therefore, modifying the m/z range of the peak lists by insertion of a dummy peak with low m/z value changes the ensemble of peaks used for searching. As a consequence, Mascot peptide scores and search results are altered
significantly and a different subset of the peptides present in the sample is identified after processing. We further show
that the effect can be exploited and additional proteins and peptides can be identified by repeating the search with a combined
set of differently processed files, even when applying identical false-positive rates. 相似文献
6.
J. K. Klahn J. J. M. Janssen G. E. J. Vaessen R. de Swart W. G. M. Agterof 《Colloids and surfaces. A, Physicochemical and engineering aspects》2002,210(2-3):167-181
This paper deals with a phenomenon which plays an important role in the phase inversion process of emulsions. This process is governed by the interplay of coalescence of droplets, often leading to double emulsions, and the escape of those internal droplets. The latter process retards the inversion process. Coalescence has been the subject of many studies, contrary to the escape event. This paper addresses the escape process both theoretically and experimentally. The model developed analyses the rate of the escape of internal droplets from the mother droplet via a coalescence process, where the internal flow, as generated by the external flow, generates the viscous force for coalescence. Incomplete mixing in the droplet has been assumed. Experimental data on the escape rate of oil droplets from O/W/O emulsions have been analysed using a Computational Fluid Dynamics approach, where the model as indicated above has been incorporated. Experimental data and simulations compare very well. Data have been compared on varying the size of the inner droplets and the rotational speed of the vessel where the double emulsion has been formed and where the escape took place. 相似文献
7.
JM Fonville M Swart Z Vokáčová V Sychrovský JE Sponer J Sponer CW Hilbers FM Bickelhaupt SS Wijmenga 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(39):12372-12387
NMR chemical shifts are highly sensitive probes of local molecular conformation and environment and form an important source of structural information. In this study, the relationship between the NMR chemical shifts of nucleic acids and the glycosidic torsion angle, χ, has been investigated for the two commonly occurring sugar conformations. We have calculated by means of DFT the chemical shifts of all atoms in the eight DNA and RNA mono-nucleosides as a function of these two variables. From the DFT calculations, structures and potential energy surfaces were determined by using constrained geometry optimizations at the BP86/TZ2P level of theory. The NMR parameters were subsequently calculated by single-point calculations at the SAOP/TZ2P level of theory. Comparison of the (1) H and (13) C?NMR shifts calculated for the mono-nucleosides with the shifts determined by NMR spectroscopy for nucleic acids demonstrates that the theoretical shifts are valuable for the characterization of nucleic acid conformation. For example, a clear distinction can be made between χ angles in the anti and syn domains. Furthermore, a quantitative determination of the χ angle in the syn domain is possible, in particular when (13) C and (1) H chemical shift data are combined. The approximate linear dependence of the C1' shift on the χ angle in the anti domain provides a good estimate of the angle in this region. It is also possible to derive the sugar conformation from the chemical shift information. The DFT calculations reported herein were performed on mono-nucleosides, but examples are also provided to estimate intramolecularly induced shifts as a result of hydrogen bonding, polarization effects, or ring-current effects. 相似文献
8.
M.A. Lephoto O.M. Ntwaeaborwa Shreyas S. Pitale H.C. Swart J.R. Botha B.M. Mothudi 《Physica B: Condensed Matter》2012,407(10):1603-1606
Combustion method was used in this study to prepare BaAl2O4:Eu2+ phosphors co-doped with different trivalent rare-earths (Re3+=Dy3+, Nd3+, Gd3+, Sm3+, Ce3+, Er3+, Pr3+ and Tb3+) ions at an initiating temperature of 600 °C. The phosphors were annealed at 1000 °C for 3 h. As confirmed from the X-ray diffraction (XRD) data, both as prepared and post annealed samples crystallized in the well known hexagonal structure of BaAl2O4. All samples exhibited bluish-green emission associated with the 4f65d1→4f7 transitions of Eu2+ at ∼500 nm. Although the highest intensity was observed from Er3+ co-doping, the longest afterglow (due to trapping and detrapping of charge carriers) was observed from Nd3+ followed by Dy3+ co-doping. The traps responsible for the long afterglow were studied using thermoluminescence (TL) spectroscopy. 相似文献
9.
P.S. Mbule G.H. Mhlongo Shreyas S. Pitale H.C. Swart O.M. Ntwaeaborwa 《Physica B: Condensed Matter》2012,407(10):1607-1610
In this study, red cathodoluminescence (CL) (λemission=614 nm) was observed from Pr3+ ions in a glassy (amorphous) SiO2 host. This emission was enhanced considerably when ZnO quantum dots (QDs) were incorporated in the SiO2:Pr3+ suggesting that the ZnO QDs transferred excitation energy to Pr3+ ions. That is, ZnO QDs acted to sensitize the Pr3+ emission. The sol–gel method was used to prepare ZnO–SiO2:Pr3+ phosphors with different molar ratios of Zn to Si. The effects of the ZnO QDs concentration and the possible mechanisms of energy transfer from ZnO to Pr3+ are discussed. In addition, the electronic states and the chemical composition of the ZnO–SiO2:Pr3+ phosphors were analyzed using X-ray photoelectron spectroscopy (XPS). 相似文献
10.
Arno Swart Gerard L.G. Sleijpen Leo R.M. Maas Jan Brandts 《Journal of Computational and Applied Mathematics》2007
This paper deals with numerical approximation of the two-dimensional Poincaré equation that arises as a model for internal wave motion in enclosed containers. Inspired by the hyperbolicity of the equation we propose a discretisation particularly suited for this problem, which results in matrices whose size varies linearly with the number of grid points along the coordinate axes. Exact solutions are obtained, defined on a perturbed boundary. Furthermore, the problem is seen to be ill-posed and there is need for a regularisation scheme, which we base on a minimal-energy approach. 相似文献