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81.
Schierbeek H Te Braake F Godin JP Fay LB van Goudoever JB 《Rapid communications in mass spectrometry : RCM》2007,21(17):2805-2812
A novel analytical method using liquid chromatography coupled to isotope ratio mass spectrometry (LC/IRMS) was developed for measuring the fractional synthesis rate (FSR) of glutathione (GSH) in neonates after infusion of [1-(13)C]-glycine as a tracer. After transformation of GSH into GSSG, its dimeric form, the intra-erythrocytic concentration and (13)C-isotopic enrichment of GSH were determined using 200 microL of blood. The results showed that, using LC/IRMS, the concentration (range of micromol/mL) was reliably measured using norvaline as internal standard with precision better than 0.1 micromol/mL. In addition, the (13)C-isotopic enrichment measured in the same run gave reliable values with excellent precision (with standard deviation (sd) lower than 0.3 per thousand) and accuracy (measured between 0 and 2 Atom % Excess (APE)). The inter-assay repeatability of delta(13)C of norvaline used as internal standard with in vivo samples was assessed at -26.07 +/- 0.28 per thousand with coefficient of variance (CV) at 1.1%. The FSR calculated either with GSH or GSSG showed similar results with slightly higher values for GSSG (41.6 +/- 4.7 and 46.5 +/- 4.4, respectively). The slightly lower FSR of GSH is probably due to interfering compounds in the biological matrix. Successfully used in a clinical study, this rapid and reliable method opens up a variety of kinetic studies with relatively low administration of tracer infusates, reducing the total cost of the study design. The small volume of blood needed enables studies even in extremely small subjects, such as premature infants, as reported in this study. 相似文献
82.
The ionization of 46 anabolic steroids has been studied. The absence of basic or acidic moieties in most of these analytes makes their direct ionization as [M + H]+ by atmospheric pressure interfaces difficult. The formation of adducts with different components of the mobile phase has been found to be an efficient way to ionize anabolic steroids by electrospray. Different mobile phases using methanol (MeOH) or acetonitrile as organic solvent and HCOOH, Na+ or NH4+ as additives have been tested to favor the adduct formation. A direct correlation between the chemical structure of the anabolic steroid and the possibility to ionize it in a particular chromatographic condition has been found. According to their ionization, anabolic steroids can be divided into seven different groups depending on both the nature and the relative position of their functional groups. The formation of different adducts such as [M + Na + MeOH]+ or [M + H + CH3 CN - H2O]+ is required in order to ionize some of these groups and the optimal mobile phase composition for each group of anabolic steroids is proposed. Despite the ionization limitations due to their chemical structure, most of tested anabolic steroids could be ionized using the adduct formation approach. 相似文献
83.
Alexander M. Skvortsov Leonid I. Klushin Frans A. M. Leermakers 《Macromolecular Symposia》2006,237(1):73-80
Summary: Upon compression between two pistons an end-tethered polymer chain undergoes an abrupt transition from a confined coil state to an inhomogeneous flower-like conformation that is partially escaped from the gap. In the thermodynamic limit the system demonstrates a first-order phase transition. A rigorous analytical theory of this phenomenon for a Gaussian chain is presented in two ensembles: a) the H-ensemble, in which the distance H between pistons plays the role of the control parameter, and b) the conjugate f-ensemble in which the external compression force f is the independent parameter. A loop region for 〈f(H)〉 with negative compressibility exists in the H-ensemble, while in the f-ensemble 〈H(f)〉 is strictly monotonic. The average lateral forces taken as functions of H (or 〈H〉, respectively) have distinctly different behavior in the two ensembles. This result is a clear counterexample of the main principles of statistical mechanics stating that all ensembles are equivalent in the thermodynamic limit. Another theorem states that the thermodynamic potential as a function of volume must be concave everywhere. We demonstrated that the exact free energy in the H-ensemble contradicts this statement. Inapplicability of these fundamental theorems to a macromolecule undergoing the escape transition is clearly related to the fact that phase coexistence in the present system is strictly impossible. This is a direct consequence of the tethering and the absence of global translational degrees of freedom of the polymer chain. 相似文献
84.
85.
It is shown that one of the two conjugate solutions compatible with the AB part of an ABX system can easily be eliminated, at an early stage of the analysis, by considering intensity ratios in the X region. 相似文献
86.
We construct two types of twists for the SU(N→∞) twisted-Eguchi-Kawai model, which mimic a periodic boundary condition in the temporal direction only and over an arbitrary extent N0. In this way we introduce finite temperature (T=N0?1 in lattice units) in the single-point model. In weak coupling one gets the correct planar expansion. 相似文献
87.
Gerhard Hilgers 《Radiation measurements》2010,45(10):1228-1232
In nanodosimetry, the track structure of ionizing radiation is characterized by the probability distribution of the number of ionizations produced by an ionizing particle in a target volume. By Monte-Carlo simulations of the track structure, this so called ionization cluster size distribution can be determined for nanometric cylindrical water targets used as substitute for the radiation sensitive biological target, namely a DNA-segment of about 20 base pairs length. Measurements of ionization cluster size distributions are carried out in an ion-counting nanodosimeter filled with an appropriate working gas at low pressure. A scaling procedure was proposed by Grosswendt (2006) to derive an operating pressure depending on the working gas for which the measured ionization cluster size distribution becomes equivalent to the ionization cluster size distribution within a nanometric target of liquid water. This scaling procedure was previously tested by means of Monte-Carlo simulations and is now tested experimentally.Ionization cluster size distributions produced by mono-energetic proton and alpha particle beams in the energy range between 0.1 MeV and 20 MeV were measured at the accelerator facilities of the PTB. The working gases used in this experiment were C3H8 and N2. According to the NIST databases for stopping power and mean ionization energy (NIST, 2009), equivalent cluster size distributions for protons and alpha particles should be obtained for pressures of 0.25 mbar C3H8 and 1.2 mbar N2. Measurements reveal the best agreement with pressures of 0.425 mbar C3H8 and 1.2 mbar N2 for protons and 0.46 mbar C3H8 and 1.2 mbar N2 for alpha particles. 相似文献
88.
Engelkamp H Hatzakis NS Hofkens J De Schryver FC Nolte RJ Rowan AE 《Chemical communications (Cambridge, England)》2006,(9):935-940
Single-enzyme studies suggest that dynamic disorder is a general characteristic of enzyme catalysis. 相似文献
89.
Anthony JM Garrett 《Contemporary Physics》2013,54(2):163-165
The dynamic electronic structure of atoms and molecules can be directly observed by means of the (e, 2e) reaction, which measures the distribution of energies and momenta of two electrons in coincidence after a knockout reaction initiated by an electron beam of known momentum incident on a molecular gas target. The molecular state for each event is identified by the electron separation energy. The recoil momentum for each event is known from the difference of measured initial and final momenta. It has been verified that values of this momentum are equal under suitable conditions to the momentum of the electron in the target immediately before knockout. Thus the spherically-averaged electron momentum distribution for each molecular orbital is measured. This is directly related to molecular orbitals calculated by the methods of quantum chemistry. Properties obtained by this method for different types of molecules are discussed. 相似文献
90.
Denis D. Arslanov Marius Spunei Julien Mandon Simona M. Cristescu Stefan T. Persijn Frans J. M. Harren 《Laser u0026amp; Photonics Reviews》2013,7(2):188-206
Over the past 10 years, with the advent of new crystals designs and a new generation of pump lasers, continuous‐wave (cw) optical parametric oscillators (OPOs) have developed into mature monochromatic light sources. Nowadays, cw OPOs can fulfill a wide variety of criteria for sensitive molecular gas sensing. It can access the mid‐infrared wavelength region, where many molecules have their fundamental rotational‐vibrational transitions, with high power. This high power combined with wide wavelength tuning and narrow linewidth creates excellent conditions for sensitive, high‐resolution spectroscopy. OPOs combined with robust methods, such as photoacoustic spectroscopy and cavity‐enhanced spectroscopy, are well suited for field measurements and remote‐sensing applications. The wide tunability of cw OPOs allows detection of larger molecules with broad absorption band structures, and its fast scanning capabilities allow rapid detection of trace gases, the latter is a demand for life‐science applications. After a short introduction about the physical principle of cw OPOs, with its most recent physical developments, this review focuses on sensitive molecular gas sensing with a variety of spectroscopic applications in atmospheric and life sciences. 相似文献