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971.
In this paper we introduce the crossed product construction for a discrete group action on an operator system. In analogy to the work of E. Katsoulis and C. Ramsey, we describe three canonical crossed products arising from such a dynamical system. We describe how these crossed product constructions behave under G-equivariant maps, tensor products, and the canonical -covers. We show that hyperrigidity is preserved under two of the three crossed products. Finally, using A. Kavruk's notion of an operator system that detects -nuclearity, we give a negative answer to a question on operator algebra crossed products posed by Katsoulis and Ramsey. 相似文献
972.
Abdolraouf Samadi-Maybodi Robin K. Harris S. Naser Azizi Alan M. Kenwright 《Magnetic resonance in chemistry : MRC》2001,39(8):443-446
Silicon-29 NMR spectra were obtained for more than 20 aqueous alkaline silicate solutions containing methanol. A signal assigned to CH3OSi(OH)3 or one of its deprotonated congeners was studied in detail for the first time for the solution conditions involved. Its appearance was monitored as a function of the solution compositions. The pseudo-equilibrium constant for its formation is of the order of 0.65. Copyright © 2001 John Wiley & Sons, Ltd. 相似文献
973.
P.R. Shearing L.E. Howard P.S. Jørgensen N.P. Brandon S.J. Harris 《Electrochemistry communications》2010,12(3):374-377
The 3-dimensional microstructure of a porous electrode from a lithium-ion battery has been characterized for the first time. We use X-ray tomography to reconstruct a 43 × 348 × 478 μm sample volume with voxel dimensions of 480 nm, subsequent division of the reconstructed volumes into sub-volumes of different sizes allow us to determine microstructural parameters as a function of sub-division size. We show that the minimum size for a representative volume element is about 43 × 60 × 60 μm for volume-specific surface area, but as large as the full sample volume for porosity and tortuosity. 相似文献
974.
Tanja Radu Simon Gallagher Brian Byrne Paul Harris Seamus Coveney Stephen McCarron 《光谱学快报》2013,46(7):516-526
Case studies from two sites demonstrate how concentration distributions of hazardous contaminants can be rapidly measured and visualized using portable XRF (X-ray fluorescence) coupled with geostatistical interpolation tools. In this study, lead is used as an exemplar due to its well-known detrimental effect on human health through long-term exposure. A portable Thermo Scientific NITON X-ray fluorescence (XRF) instrument was used for real-time in-situ concentration measurements, which were linked to GPS coordinates of the sampling locations. A 52 point mixed sampling density survey was performed at a site near Maynooth, Co. Kildare, and a second 58 survey undertaken at Dublin City University (DCU). At Maynooth, high concentrations of Pb (above 110 mg/kg) were found close to the site where a local canal meets a road. At the DCU site, results indicate high Pb concentrations (above 160 mg/kg) near a busy main road. Geostatistical techniques were used to generate concentration prediction and critical threshold contour surfaces for both sites. Linked with GPS coordinates for each sampling location, this technology enables the distribution of multiple elements to be mapped over wide areas in a relatively short time. Supplemental materials are available for this article. Go to the publisher's online edition of Spectroscopy Letters to view the supplemental file. 相似文献
975.
976.
Applications of quantum cascade lasers for sensitive trace gas measurements of CO, CH4, N2O and HCHO 总被引:1,自引:0,他引:1
C.L. Schiller H. Bozem C. Gurk U. Parchatka R. Königstedt G.W. Harris J. Lelieveld H. Fischer 《Applied physics. B, Lasers and optics》2008,92(3):419-430
We describe here a sensitive quantum cascade laser absorption spectrometer (QCLAS) employed for aircraft based measurements
during the GABRIEL 2005 and HOOVER 2006 and 2007 campaigns. This 3-channel instrument measures CO, HCHO, CH4 and N2O using a 64-m path double corner cube White cell. Performance of the instrument was examined for the four species and precisions
for CO, N2O and CH4 were measured in the field to be 0.5, 0.5 and 0.7% respectively (2σ). The 1σ detection limit for HCHO was ∼500 pptv for a
2 s average, while signal averaging of the HCHO over a 2 min time interval resulted in a 150 pptv detection limit with a duty
cycle of 60%.
PACS 82.80.Gk; 07.88.+y; 42.62.-b; 92.60.H- 相似文献
977.
Lomont JP Nguyen SC Schlegel JP Zoerb MC Hill AD Harris CB 《Journal of the American Chemical Society》2012,134(6):3120-3126
We report the observation of a solvent-dependent spin state equilibrium in the 16-electron photoproduct CpCo(CO). Time-resolved infrared spectroscopy has been used to observe the concurrent formation of two distinct solvated monocarbonyl photoproducts, both of which arise from the same triplet CpCo(CO) precursor. Experiments in different solvent environments, combined with electronic structure theory calculations, allow us to assign the two solvated photoproducts to singlet and triplet CpCo(CO)(solvent) complexes. These results add to our previous picture of triplet reactivity for 16-electron organometallic photoproducts, in which triplets were not believed to interact strongly with solvent molecules. In the case of this photoproduct, it appears that spin crossover does not present a significant barrier to reactivity, and relative thermodynamic stabilities determine the spin state of the CpCo(CO) photoproduct in solution on the picosecond time scale. While the existence of transition metal complexes with two thermally accessible spin states is well-known, this is, to our knowledge, the first observation of a transient photoproduct that exhibits an equilibrium between two stable spin states, and also the first observed case in which a solvent has been able to coordinate as a token ligand to two spin states of the same photoproduct. 相似文献
978.
Mechanochemistry: opportunities for new and cleaner synthesis 总被引:2,自引:0,他引:2
James SL Adams CJ Bolm C Braga D Collier P Friščić T Grepioni F Harris KD Hyett G Jones W Krebs A Mack J Maini L Orpen AG Parkin IP Shearouse WC Steed JW Waddell DC 《Chemical Society reviews》2012,41(1):413-447
The aim of this critical review is to provide a broad but digestible overview of mechanochemical synthesis, i.e. reactions conducted by grinding solid reactants together with no or minimal solvent. Although mechanochemistry has historically been a sideline approach to synthesis it may soon move into the mainstream because it is increasingly apparent that it can be practical, and even advantageous, and because of the opportunities it provides for developing more sustainable methods. Concentrating on recent advances, this article covers industrial aspects, inorganic materials, organic synthesis, cocrystallisation, pharmaceutical aspects, metal complexes (including metal-organic frameworks), supramolecular aspects and characterization methods. The historical development, mechanistic aspects, limitations and opportunities are also discussed (314 references). 相似文献
979.
Adsorption of 11-mercaptoundecanoic acid (MUA) on silver from methanol and aqueous solutions was monitored in situ by surface-enhanced Raman scattering (SRES) spectroscopy. While adsorption of MUA from methanol is a one-step formation of a thiol-bound monolayer, SERS spectra reveal that monolayer formation from aqueous solution involves interactions of both carboxylate and thiol groups of MUA with the silver surface. Several Raman scattering bands, including the ν(C-S), ν(s)(COO(-)), and ν(C-C), were used to investigate the evolution of the structure of adsorbed MUA on silver surfaces. The time-dependent profiles of these bands for assembly from aqueous solution indicate a multistep process, which is initiated by the binding of both carboxylate and thiol groups to silver, producing a mixture of gauche and trans conformations. In a subsequent step, the COO-Ag interactions are displaced by stronger S-Ag bonds, leading to ordering of the resulting monolayer with formation of a complete SAM with all-trans conformations. The results also showed that the adsorption process depended strongly on the solution pH and surface potential of the metal. These factors can significantly affect the participation and displacement of -COO(-) during self-assembly of MUA from aqueous solution. 相似文献
980.
Jiani Ma Adam C. Rea Dr. Huiying An Dr. Chensheng Ma Dr. Xiangguo Guan Dr. Ming‐De Li Tao Su Chi Shun Yeung Kyle T. Harris Dr. Yue Zhu Jameil L. Nganga Dr. Olesya D. Fedoryak Dr. Timothy M. Dore Dr. David Lee Phillips 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(22):6854-6865
Photoremovable protecting groups (PPGs) when conjugated to biological effectors forming “caged compounds” are a powerful means to regulate the action of physiologically active messengers in vivo through 1‐photon excitation (1PE) and 2‐photon excitation (2PE). Understanding the photodeprotection mechanism is important for their physiological use. We compared the quantum efficiencies and product outcomes in different solvent and pH conditions for the photolysis reactions of (8‐chloro‐7‐hydroxyquinolin‐2‐yl)methyl acetate (CHQ‐OAc) and (8‐bromo‐7‐hydroxyquinolin‐2‐yl)methyl acetate (BHQ‐OAc), representatives of the quinoline class of phototriggers for biological use, and conducted nanosecond time‐resolved spectroscopic studies using transient emission (ns‐EM), transient absorption (ns‐TA), transient resonance Raman (ns‐TR2), and time‐resolved resonance Raman (ns‐TR3) spectroscopies. The results indicate differences in the photochemical mechanisms and product outcomes, and reveal that the triplet excited state is most likely on the pathway to the product and that dehalogenation competes with release of acetate from BHQ‐OAc, but not CHQ‐OAc. A high fluorescence quantum yield and a more efficient excited‐state proton transfer (ESPT) in CHQ‐OAc compared to BHQ‐OAc explain the lower quantum efficiency of CHQ‐OAc relative to BHQ‐OAc. 相似文献