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1.
Wu L Lemr K Aggerholm T Cooks RG 《Journal of the American Society for Mass Spectrometry》2003,14(2):152-160
The kinetic method is applied to differentiate and quantify mixtures of isomeric tripeptides based on the competitive dissociations of divalent metal ion-bound clusters in an ion trap mass spectrometer. This methodology is extended further to determine compositions of ternary mixtures of the isomers Gly-Gly-Ala (GGA), Ala-Gly-Gly (AGG), and Gly-Ala-Gly (GAG). This procedure also allows to perform chiral quantification of a ternary mixture of optical isomers. The divalent metal ion Ca(II) is particularly appropriate for isomeric distinction and quantification of the isobaric tripeptides Gly-Gly-Leu/Gly-Gly-Ile (GGL/GGI). Among the first-row transition metal ions, Cu(II) yields remarkably effective isomeric differentiation for both the isobaric tripeptides, GGI/GGL using GAG as the reference ligand, and the positional isomers GAG/GGA using GGI as the reference ligand. This is probably due to agostic bonding: alpha-agostic bonding occurs between Cu(II) and GAG and beta-agostic bonding between Cu(II) and GGI, each produces large but different steric effects on the stability of the Cu(II)-bound dimeric clusters. These data form the basis for possible future quantitative analyses of mixtures of larger peptides such as are generated, for example, in combinatorial synthesis of peptides and peptide mimics. 相似文献
2.
Karel Obruba 《Mikrochimica acta》1961,49(5):801-805
Zusammenfassung Es wurde eine Mikromethode für die Bestimmung von Oxyäthylengruppen ausgearbeitet. Das Prinzip der Methode beruht darauf, daß Äthylenoxydverbindungen beim Sieden mit Jodwasserstoffsäure neben anderen Produkten eine äquivalente Menge Jod liefern, die durch Titration mit Natriumthiosulfat bestimmt wird.Es wurde eine einfache Apparatur erprobt, die selbst geringe Jodverluste verhindert.
Herrn Dipl.-Ing.J. Simandl danken wir für die anregende Diskussion und die Überlassung von oxyäthylierten Aminen. Herrn Dipl.-Ing.J. Kami danken wir für die Überlassung von Proben reiner Polyglykoläther. Die Wasserbestimmung nachK. Fischer führte HerrZ. Netuil aus. 相似文献
Summary A micromethod has been worked out for the determination of oxyethylene groups. Its principle is based on the fact that on boiling with hydriodic acid, the ethylene oxide compounds yield, along with other products, an equivalent quantity of iodine, which can be measured by titration with sodium thiosulfate.A simple apparatus has been tested, which prevents the loss of even slight amounts of iodine.
Résumé On a mis au point une microméthode pour doser les groupes oxéthyles. Le principe de la méthode repose sur le fait que les composés de l'oxyde d'éthylène, portés à l'ébullition avec de l'acide iodhydrique, libèrent, à côté d'autres produits, une quantité équivalente d'iode que l'on titre par le thiosulfate de sodium.On a expérimenté un appareil simple qui empêche les pertes en iode, même faibles.
Herrn Dipl.-Ing.J. Simandl danken wir für die anregende Diskussion und die Überlassung von oxyäthylierten Aminen. Herrn Dipl.-Ing.J. Kami danken wir für die Überlassung von Proben reiner Polyglykoläther. Die Wasserbestimmung nachK. Fischer führte HerrZ. Netuil aus. 相似文献
3.
Optimal assay conditions were established for the previously described method used to determine the activity ofSaccharomyces cerevisiae pore-forming killer toxin K1. The method is based on cell staining with bromocresol purple. Sensitive cells ofS. cerevisiae from the early exponential phase under nongrowth conditions and in the presence of glucose were the most convenient for determining the killer toxin activity. Maximum killing war reached when the suspension was buffered with 10 mM citrate-phosphate at pH 4.6. 相似文献
4.
We explore two- and three-state Markov models driven out of thermal equilibrium by non-potential forces, to demonstrate basic properties of the steady heat capacity based on the concept of quasistatic excess heat. It is shown that large enough driving forces can make the steady heat capacity negative. For both the low- and high-temperature regimes we propose an approximative thermodynamic scheme in terms of “dynamically renormalized” effective energy levels. 相似文献
5.
Lenka Kubíčková Jaroslav Kohout Petr Brázda Miroslav Veverka Tomáš Kmječ Denisa Kubániová Petr Bezdička Mariana Klementová Eva Šantavá Karel Závěta 《Hyperfine Interactions》2016,237(1):159
Magnetic nanoparticles have found broad applications in medicine, especially for cell targeting and transport, and as contrast agents in MRI. Our samples of ??-Fe2O3 nanoparticles were prepared by annealing in silica matrix, which was leached off and the bare particles were then coated with amorphous silica layers of various thicknesses. The distribution of particle sizes was determined from the TEM pictures giving the average size ~20 nm and the thickness of silica coating ~5; 8; 12; 19 nm. The particles were further characterized by the XRPD and DC magnetic measurements. The nanoparticles consisted mainly of ??-Fe2O3 with admixtures of ~1 % of the α phase and less than 1 % of the γ phase. The hysteresis loops displayed coercivities of ~2 T at room temperature. The parameters of hyperfine interactions were derived from transmission Mössbauer spectra. Observed differences of hyperfine fields for nanoparticles in the matrix and the bare ones are ascribed to strains produced during cooling of the composite. This interpretation is supported by slight changes of their lattice parameters and increase of the elementary cell volume deduced from XRD. The temperature dependence of the magnetization indicated a two-step magnetic transition of the ??-Fe2O3 nanoparticles spread between ~85 K and ~150 K, which is slightly modified by remanent tensile stresses in the case of nanoparticles in the matrix. The subsequent coating of the bare particles by silica produced no further change in hyperfine parameters, which indicates that this procedure does not modify magnetic properties of nanoparticles. 相似文献
6.
We explain the (non-)validity of close-to-equilibrium entropy production principles in the context of linear electrical circuits.
Both the minimum and the maximum entropy production principles are understood within dynamical fluctuation theory. The starting
point are Langevin equations obtained by combining Kirchoff’s laws with a Johnson-Nyquist noise at each dissipative element
in the circuit. The main observation is that the fluctuation functional for time averages, that can be read off from the path-space
action, is in first order around equilibrium given by an entropy production rate.
That allows to understand beyond the schemes of irreversible thermodynamics (1) the validity of the least dissipation, the
minimum entropy production, and the maximum entropy production principles close to equilibrium; (2) the role of the observables’
parity under time-reversal and, in particular, the origin of Landauer’s counterexample (1975) from the fact that the fluctuating
observable there is odd under time-reversal; (3) the critical remark of Jaynes (1980) concerning the apparent inappropriateness
of entropy production principles in temperature-inhomogeneous circuits. 相似文献
7.
Helena ?těpánková Karel Kou?il Vojtěch Chlan Peter G?rnert Robert Müller Josef ?těpánek 《Journal of magnetism and magnetic materials》2010,322(9-12):1323-1326
57Fe nuclear magnetic resonance (NMR) spectra of hexaferrite BaFe12O19 powder samples prepared by glass crystallization method were measured at 4.2 K and analyzed in comparison to spectra of single crystals. Samples with various mean particle dimensions were tested. NMR spectral lines corresponding to individual iron sublattices showed pronounced frequency shifts of their positions and a significant line broadening compared to single crystals. The significant contribution to the line shifts and line shape had a uniform macroscopic origin giving identical absolute value of shifts and the same line shapes for all measured lines of a particular sample. Estimations of demagnetization fields based on mean particle dimensions reasonably corresponded to the observed frequency shifts for particle mean diameter 67 nm, or had a higher value for a sample with mean diameter of 340 nm, for which a presence of domain walls was detected by NMR. In the spectrum of a sample with the smallest particles (~16 nm), an additional contribution having broader lines and faster spin-spin relaxations was found. It could be assigned to weaker exchange interactions or deviations of magnetic moment directions from the hexagonal axis in a surface layer. 相似文献
8.
9.
Proteoliposomes carrying reconstituted yeast plasma membrane H+-ATPase in their lipid membrane or plasma membrane vesicles are model systems convenient for studying basic electrochemical
processes involved in formation of the proton electrochemical gradient (ΔμH
+) across the microbial or plant cell membrane. Δψ- and pH-sensitive fluorescent probes were used to monitor the gradients
formed between inner and outer volume of the reconstituted vesicles. The Δψ-sensitive fluorescent ratiometric probe oxonol
VI is suitable for quantitative measurements of inside-positive Δψ generated by the reconstituted H+-ATPase. Its Δψ response can be calibrated by the K+/valinomycin method and ratiometric mode of fluorescence measurements reduces undesirable artefacts. In situ pH-sensitive fluorescent probe pyranine was used for quantitative measurements of pH inside the proteoliposomes. Calibration
of pH-sensitive fluorescence response of pyranine entrapped inside proteoliposomes was performed with several ionophores combined
in order to deplete the gradients passively formed across the membrane. Presented model system offers a suitable tool for
simultaneous monitoring of both components of the proton electrochemical gradient, Δψ and ΔpH. This approach should help in
further understanding how their formation is interconnected on biomembranes and even how transport of other ions is combined
to it. 相似文献
10.
Shivaji S. Kadam Lukáš Maier Tomáš Šolomek Marek Nečas Karel Šmejkal Jiří Dostál Vladimír Sklenář Radek Marek 《Journal of Physical Organic Chemistry》2013,26(10):814-821
We report a preparation of new 6‐substituted‐5,6‐dihydrobenzo[c]phenanthridines by the reaction of azoles with quaternary benzo[c]phenanthridine alkaloids sanguinarine and chelerythrine. The prepared compounds have been characterized by NMR spectroscopy, mass spectrometry, and single‐crystal X‐ray diffraction. Conformational behaviors of carbazole derivatives in solution have been investigated by low‐temperature NMR experiments. Barriers to rotation around newly formed C6–N bonds were determined to be 12–13 kcal/mol. Quantum chemical calculations have been used to reproduce the experimental observations. Large structural effects on several 1H NMR resonances were observed experimentally, analyzed by Density Functional Theory (DFT) calculations at B3LYP/6‐311+G(d,p)/PCM level, and interpreted by ring‐current effects of the benzo[c]phenanthridine and carbazole units. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献