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51.
Proton relaxation time measurements are performed for 6m aqueous solutions of7LiI and6LiI in D2O containing small amounts of H2O. The measurements are done at low temperatures and yield maxima of the relaxation rate plotted against 1/T. From the maxima of the relaxation rates, proteon-I– and proton-Li+ distances in the first coordination sphere of the ions are determined, and from the knowledge of the ion-water oxygen distance it is shown that for iodide a somewhat broadened H-bonded configuration is valid and that for Li+ the electric dipole orientation deviates from the radial direction. In order to test the reliability of the method a proton-127I interaction study is also performed in KI solution in glycerol. The I-H distance obtained is in satisfactory agreement with that found in the aqueous system. 相似文献
52.
Novak P Tepes P Cindrić M Ilijas M Dragojević S Mihaljević K 《Journal of chromatography. A》2004,1033(2):299-303
Directly coupled LC-MS and LC-NMR were applied to identify and structurally characterize an acarbose degradation product A in acidic media. A comparative analysis of the stop-flow LC-NMR (1H and TOCSY) and LC-MS data provided evidence that A is structurally related to acarbose, differing from the parent compound in a number of subunits present in the molecule. Spectral analysis revealed that A was the alpha-glucosidase inhibitor amylostatin XG. Complementary information obtained from the two methods led to the structural elucidation of A which was later corroborated by high-resolution NMR spectroscopy of the isolated molecule. 相似文献
53.
Jos R. Ascenso Maria de Deus Carvalho Alberto R. Dias Carlos C. Romo Maria J. Calhorda Luis F. Veiros 《Journal of organometallic chemistry》1994,470(1-2):147-152
The metallocene thioether derivatives [Cp2M(MeSCH2CH2SMe)][PF6]2 (1, M = MO; 2, M = W), [Cp2Mo(SCH2CH2SMe)][PF6] (3) and [Cp2M(SCH2CH2S)] (4, M = Mo; 5, M = W) exhibit temperature-dependent fluxional behavior in solution, owing to the pyramidal sulfur inversion process. The activation energies for this process were determined from proton band-shape analysis in the cases of 1 (54.9 ± 2 kJ mol−1), 2 (51.2 ± 4.6 kJ mol−1) and 3 (30.0 ± 3.1 kJ mol−1). Extended Hückel calculations on related model complexes suggest that local inversion at the sulfur atoms, rather that an inversion of the complete S---C---C---S chain, is responsible for the observed fluxional behaviour. 相似文献
54.
K.B. Helean S.V. Ushakov A. Navrotsky J. Lian J.M. Farmer 《Journal of solid state chemistry》2004,177(6):1858-1866
High-temperature oxide melt solution calorimetry and Rietveld refinements of powder X-ray diffraction data were used to investigate the structure (Fd3m; Z=8) and energetics of a series of RE2Ti2O7 (RE=Sm-Lu) compounds with the pyrochlore structure as well as La2Ti2O7 with a layered perovskite-type structure. All of the RE-titanates were found to be stable in enthalpy with respect to their oxides. In the pyrochlore series, Lu2Ti2O7 was least stable in enthalpy (ΔHf-ox at 298 K=−56.0±4.0 kJ/mol); the most stable materials were Gd-, Eu-, and Sm2Ti2O7 with ΔHf-ox at 298 K=−113.4±2.7, −106.1±4.2, −115.4±4.2 kJ/mol, respectively. In general, as the radius ratio of the A- to B-site cations, RA/RB, decreases, the pyrochlore structure becomes less stable. The trend of ionic radius of the RE3+ cation vs. ΔHf-ox at 298 K is non-linear and approximately parallels the increasing “resistance” to ion-beam-induced amorphization as RA/RB decreases. 相似文献
55.
Daniel Carmona Joaquina Ferrer María Pilar Lamata Luis A. OroHans-Heinrich Limbach Gerd SchererJos Elguero María Luisa Jimeno 《Journal of organometallic chemistry》1994,470(1-2):271-274
The Arrhenius equation corresponding to the process P---Ag+P*---Ag*→---P---Ag*+P*---Ag has been determined for [(η6-p-cymene)Ru(μ-pz)3Ag(PPh3)] (1) by complete line-shape analysis of the 31P NMR spectra between −40°C and +30°C. It has the form K = 1011.8± e(−46±5 kJ mol−1/RT). The preexponential term, log A = 11.8 corresponds to a small activation entropy, whereas the activation energy, 46 kJ mol−1 is comparable to those determined for other phosphorus—metal compounds. 相似文献
56.
《应用光谱学评论》2013,48(1):19-55
ABSTRACT This review is intended to present an introduction to the use of thermal neutron activation analysis (TNAA) as an analytical technique for the determination of elements in almost all kinds of matrices. This method of analysis is generally multi-element and experimental conditions can be designed to be nondestructive to the sample. This review will focus on thermal neutron activation as this technique allows determination of approximately two-thirds of the elements on the periodic chart. There are also more and wider spread facilities in the United States that offer these services. The available facilities are located across the United States and are generally accessible to everyone. The review will also detail the advantages and disadvantages of TNAA compared to other common spectroscopic methods. An outline of the general procedure for performing the analysis of the elements using activation analysis is presented to emphasize the ease of using this technique. The outline is divided into sections that give the general procedure, how to choose the correct nuclear reaction and reaction product, and the main sources of errors that can affect the results of the study. These sources of error are subdivided into general types of errors. The general types of errors are divided into those related to pre-chemistry, problems associated with the irradiation of the samples, errors associated with the use of nuclear constants (cross sections, half-lives, transition probabilities, etc.), the choice of the correct reaction and reaction product, and those associated with the counting of the irradiated samples. The general theory of activation analysis is presented and summarizes the derivation of the equations used and the development of the comparator method of analysis. The comparator method is used to simplify the method by irradiating samples along with standards. This reduces the need for using the nuclear constants and thus reducing errors. The use of radiochemical separations to isolate analytes of choice from the radioactive matrix is also described. Some current literature is also included to give a feel for current applications of the use of thermal neutron activation analyses. The summary also describes some of the different matrices that have been used for analyses. 相似文献
57.
《International journal of environmental analytical chemistry》2013,93(3):123-132
Heating a suspension of Bisphenol A diglycidyl ether (BADGE) in 20 : 80 tetrahydrofuran/water at 70°C and subsequent passage of the resulting solution through C18 columns allowed isolation and purification to > 97% of each of the two hydrolysis products 2-[4-(2,3-dihydroxypropoxy) phenyl]-2-[4-(2,3-epoxypropoxy)phenyl]propane (1HP) and 2,2-bis[4-(2,3-dihydroxypropoxy)phenyl] propane (2HP), which were characterized by UV, IR, 1H and I3C NMR spectroscopy and mass spectrometry. 相似文献
58.
Nuclear counting is a challenging task for nuclear instrumentation because of the stochastic nature of radioactivity. Event counting has to be processed and filtered to determine a stable count rate value and perform variation monitoring of the measured event. An innovative approach for nuclear counting is presented in this study, improving response time and maintaining count rate stability. Some nonlinear filters providing a local maximum likelihood estimation of the signal have been recently developed, which have been tested and compared with conventional linear filters. A nonlinear filter thus developed shows significant performance in terms of response time and measurement precision. The filter also presents the specificity of easy embedment into digital signal processor (DSP) electronics based on field-programmable gate arrays (FPGA) or microcontrollers, compatible with real-time requirements. © 2001 Elsevier Science. All rights reserved. 相似文献
59.
《Analytical letters》2012,45(16):2613-2625
Caloric restriction increases the life-span of a number of organisms. The relationship between the increase in life-span and the extent of caloric restriction, however, varies among species. The underlying mechanisms are yet unknown, but appear to be related to changes in metabolism. In order to investigate the metabolic response of caloric restriction of rats, here is presented the first nuclear magnetic resonance (NMR) spectroscopy-based study of how blood metabolite profiles are influenced by graded levels of caloric restriction. The study involved three groups of obese rats exposed to 0, 20, and 40 percent caloric restriction for five days. Blood serum from each individual was analyzed by 1H NMR and the resulting spectra were subjected to multivariate analysis by unsupervised principal component analysis and supervised orthogonal-partial least square discriminant analysis. The analyses revealed that a response to caloric restriction was present at 20 percent caloric restriction. The metabolites that distinguished the profiles at 20 percent restriction deviated from those at 40 percent restriction. The changes induced by caloric restriction were most clearly observed as an increased level of 3-hydroxybutyrate, and decreased levels of lipids and pyruvate. The metabolic responses of rats exposed to caloric restriction are in good agreement with a switch in metabolism from anabolic pathways towards fatty acid catabolism and gluconeogenesis, which is consistent with previous observations for mice. 相似文献
60.
The thermal evolution of the energies and free energies of a set of spherical and near-spherical nuclei spanning the whole periodic table are calculated in the subtracted finite-temperature Thomas–Fermi framework with the zero-range Skyrme-type KDE0 and the finite-range modified Seyler–Blanchard interaction. The calculated energies are subjected to a global fit in the spirit of the liquid-drop model. The extracted parameters in this model reflect the temperature dependence of the volume symmetry and surface symmetry coefficients of finite nuclei, in addition to that of the volume and surface energy coefficients. The temperature dependence of the surface symmetry energy is found to be very substantial whereas that of the volume symmetry energy turns out to be comparatively mild. 相似文献