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91.
Chris D. Geddes Peter Douglas Christopher P. Moore Trevor J. Wear Peter L. Egerton 《Journal of fluorescence》1999,9(3):163-171
Fourteen thin-film optical sensors in which halide-sensitive fluorophores are immobilized in a thin copolymer film (50 m, dry) have been developed and characterized. The sensor films use rhodamine, 6-methoxyquinoline, and harmane dyes which have been functionalized and bound to a hydrophilic copolymer. The sensor films are reversibly capable of determining aqueous bromide and iodide with 4 and 2% accuracy, respectively, at concentrations of around 10–3 mol dm–3, and are more sensitive than previous plastic sensor fabrications. The 90% response time to molar iodide is 30–60 s. A combination of sensor films allows the simultaneous determination of both I– and Br– in a mixed-halide solution. The interference of several ions, including pseudo-halides, on the sensor films has been studied. 相似文献
92.
We consider four-dimensional variational data assimilation (4DVar) and show that it can be interpreted as Tikhonov or L2-regularisation, a widely used method for solving ill-posed inverse problems. It is known from image restoration and geophysical problems that an alternative regularisation, namely L1-norm regularisation, recovers sharp edges better than L2-norm regularisation. We apply this idea to 4DVar for problems where shocks and model error are present and give two examples which show that L1-norm regularisation performs much better than the standard L2-norm regularisation in 4DVar. (© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
93.
Dejian Fu Keeyoon Sung Chris D. Boone Kaley A. Walker Peter F. Bernath 《Journal of Quantitative Spectroscopy & Radiative Transfer》2008,109(12-13):2219-2243
Carbon cycle science by Fourier transform spectroscopy (CC-FTS) is an advanced study for a future satellite mission. The goal of the mission is to obtain a better understanding of the carbon cycle in the Earth's atmosphere by monitoring total and partial columns of CO2, CH4, N2O, and CO in the near infrared. CO2, CH4, and N2O are important greenhouse gases, and CO is produced by incomplete combustion. The molecular O2 column is also needed to obtain the effective optical path of the reflected sunlight and is used to normalize the column densities of the other gases. As part of this advanced study, ground-based Fourier transform spectra are used to evaluate the spectral region and resolution needed. Spectra in the 3950–7140 cm?1 region with a spectral resolution of 0.0042 cm?1 recorded at Kiruna (67.84°N, 20.41°E, and 419 m above sea level), Sweden, on 1 April 1998, were degraded to the resolutions of 0.01, 0.1, and 0.3 cm?1. The effect of spectral resolution on the retrievals has been investigated with these four Kiruna spectra. To obtain further information on the spectral resolution, optical components and spectroscopic parameters required by the future mission, high-resolution solar absorption spectra between 2000 and 15000 cm?1 were recorded using Fourier transform spectrometers at Kitt Peak (31.9°N, 111.6°W, and 2.1 km above sea level), Arizona, on 25 July 2005 and Waterloo (43.5°N, 80.6°W, and 0.3 km above sea level), Ontario, on 22 November 2006 with spectral resolutions of 0.01 and 0.1 cm?1, respectively. Dry air volume mixing ratios (VMRs) of CO2 and CH4 were retrieved from these ground-based observations. The HITRAN 2004 spectroscopic parameters are used with the SFIT2 package for the spectral analysis. The measurement precisions for CO2 and CH4 total columns are better than 1.07% and 1.13%, respectively, for our observations. Based on these results, a Fourier transform spectrometer (maximum spectral resolution of 0.1 cm?1 or 5 cm maximum optical path difference (MOPD)) operating between 2000 and 15000 cm?1 is suggested as the primary instrument for the mission. Further progress in improving the atmospheric retrievals for CO2, CH4, and O2 requires new laboratory measurements of the spectroscopic line parameters. 相似文献
94.
Dr. Massimo Rigo Evi R. M. Habraken Dr. Koyel Bhattacharyya Manuela Weber Dr. Andreas W. Ehlers Dr. Nicolas Mézailles Dr. J. Chris Slootweg Prof. Dr. Christian Müller 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(37):8769-8779
A series of substituted phosphinines, 1-phosphabarrelenes and 5-phosphasemibullvalenes were synthesized and evaluated for their potential application as ligands in homogeneous catalytic reactions. While their buried volume (%Vbur) was calculated to get insight into the steric properties, [LNi(CO)3] complexes were prepared in order to determine the corresponding Tolman electronic parameter. ETS-NOCV (extended-transition-state natural orbital for chemical valence) calculations on [LAuCl] complexes further allowed an estimation of the σ- and π-contributions to the L− M interaction. AuI coordination compounds of selected examples were prepared and characterized by single crystal X-ray diffraction. Finally, the three classes of PIII compounds were successfully used in the AuI-catalyzed cycloisomerization of N-2-propyn-1-ylbenzamide, showing very good activities and selectivities, which are comparable with the reported data of cationic phosphorus-based gold catalysts. 相似文献
95.
Etienne A. Lapierre Prof. Warren E. Piers Jian-Bin Lin Chris Gendy 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(17):4305-4308
Isolable cationic PtII and PtIV alkylidenes, proposed intermediates in catalytic organic transformations, are reported. The bonding in these species was probed by experimental, structural, spectroscopic, electrochemical and computational methods, providing direct evidence for π-bonding, the often-theorized relativistic stabilization of these species, and the influence of oxidation state. 相似文献
96.
Science China Chemistry - 相似文献
97.
Julia Leitl Dr. Andrew R. Jupp Dr. Evi R. M. Habraken Verena Streitferdt Dr. Peter Coburger Dr. Daniel J. Scott Prof. Dr. Ruth M. Gschwind Prof. Dr. Christian Müller Dr. J. Chris Slootweg Prof. Dr. Robert Wolf 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(35):7788-7800
Salt metathesis of 1-methyl-2,4,6-triphenylphosphacyclohexadienyl lithium and chlorobis(pentafluorophenyl)borane affords a 1-phospha-7-bora-norbornadiene derivative 2 . The C≡N triple bonds of nitriles insert into the P−B bond of 2 with concomitant C−B bond cleavage, whereas the C≡C bonds of phenylacetylenes react with 2 to form λ4-phosphabarrelenes. Even though 2 must formally be regarded as a classical Lewis adduct, the C≡N and C≡C activation processes observed (and the mild conditions under which they occur) are reminiscent of the reactivity of frustrated Lewis pairs. Indeed, NMR and computational studies give insight into the mechanism of the reactions and reveal the labile nature of the phosphorus–boron bond in 2 , which is also suggested by detailed NMR spectroscopic studies on this compound. Nitrile insertion is thus preceded by ring opening of the bicycle of 2 through P−B bond splitting with a low energy barrier. By contrast, the reaction with alkynes involves formation of a reactive zwitterionic methylphosphininium borate intermediate, which readily undergoes alkyne 1,4-addition. 相似文献
98.
Annals of the Institute of Statistical Mathematics - 相似文献
99.
Prof. Volker L. Deringer Prof. Chris J. Pickard Prof. Davide M. Proserpio 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(37):16014-16019
The discovery of materials is increasingly guided by quantum-mechanical crystal-structure prediction, but the structural complexity in bulk and nanoscale materials remains a bottleneck. Here we demonstrate how data-driven approaches can vastly accelerate the search for complex structures, combining a machine-learning (ML) model for the potential-energy surface with efficient, fragment-based searching. We use the characteristic building units observed in Hittorf's and fibrous phosphorus to seed stochastic (“random”) structure searches over hundreds of thousands of runs. Our study identifies a family of hierarchically structured allotropes based on a P8 cage as principal building unit, including one-dimensional (1D) single and double helix structures, nanowires, and two-dimensional (2D) phosphorene allotropes with square-lattice and kagome topologies. These findings yield new insight into the intriguingly diverse structural chemistry of phosphorus, and they provide an example for how ML methods may, in the long run, be expected to accelerate the discovery of hierarchical nanostructures. 相似文献
100.
Renny Mathew Karolina A. Uchman Lydia Gkoura Chris J. Pickard Maria Baias 《Magnetic resonance in chemistry : MRC》2020,58(11):1018-1025
A combined experimental and computational approach was used to distinguish between different polymorphs of the pharmaceutical drug aspirin. This method involves the use of ab initio random structure searching (AIRSS), a density functional theory (DFT)-based crystal structure prediction method for the high-accuracy prediction of polymorphic structures, with DFT calculations of nuclear magnetic resonance (NMR) parameters and solid-state NMR experiments at natural abundance. AIRSS was used to predict the crystal structures of form-I and form-II of aspirin. The root-mean-square deviation between experimental and calculated 1H chemical shifts was used to identify form-I as the polymorph present in the experimental sample, the selection being successful despite the large similarities between the molecular environments in the crystals of the two polymorphs. 相似文献