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531.
We investigate the consistency of the labeling and assignments of the vibrations of the monosubstituted benzenes in the electronic ground state. In doing so, we also identify some inconsistencies in the labeling of the benzene modes. We commence by investigating the behavior of the benzene vibrations as one hydrogen is replaced by an artificial atomic substituent of increasing mass via quantum chemical calculations; the wavenumber variations with mass give insight into the assignments. We also examine how well the monohalobenzene vibrations can be described in terms of the benzene ones: consistent with some recent studies, we conclude that this is futile in a significant number of cases. We then show that "isotopic wavenumbers" obtained by artificially changing the mass of the fluorine atom in fluorobenzene are in very good agreement with the wavenumbers obtained via explicit calculation for the relevant monohalobenzene (chlorobenzene, bromobenzene, and iodobenzene) vibrations. As a consequence, we propose that the vibrations of monofluorobenzene be used as the basis for labelling the vibrational assignments of monosubstituted benzenes. As well as the four monohalobenzenes, we also apply this approach to the vibrations of aniline, toluene, benzonitrile, phenylacetylene, phenylphosphine, and nitrobenzene. This has allowed a much more consistent picture of the vibrational assignments to be obtained across ten monosubstituted benzenes. 相似文献
532.
Gardner AM Gutsmiedl KA Wright TG Lee EP Breckenridge WH Rajbhandari S Chapman CY Viehland LA 《The journal of physical chemistry. A》2011,115(25):6979-6985
We present potential energy curves calculated at the CCSD(T) level of theory for Ga(+)-RG and In(+)-RG complexes (RG = He-Rn). Spectroscopic parameters have been derived from these potentials and compared to previously calculated parameters for the Al(+)-RG and Tl(+)-RG complexes. Additionally, for some cases, we compare these parameters with those obtained from electronic spectroscopic studies on excited states of the neutral species, arising from atomic-based d ← p excitations. The Ga(+)-RG and In(+)-RG potentials have also been used to calculate the transport coefficients for M(+) traveling through a bath of RG atoms. 相似文献
533.
The CEARXRF GUI‐Based Monte Carlo–Library Least‐Squares (MCLLS) Code is demonstrated with results from a micro‐focused EDXRF analyzer, which can be used to calculate elemental weight fractions in metal alloys or rock samples accurately by library least‐squares regression of the measured X‐ray spectrum with computer‐generated elemental library spectra. An elemental stratified sampling variance reduction technique has been implemented in the CEARXRF5 code, which equalizes the statistical precision of the elemental libraries within the measured sample independent of the relative elemental amounts that are present. Also, an improved Si(Li) detector response function (DRF) has been obtained for micro‐focused X‐ray fluorescence (XRF) analyzers, and the DRF parameters are obtained based on regression from pure elemental experimental spectra. It is demonstrated that the resulting MCLLS approach can greatly improve the accuracy of elemental XRF analysis results. Copyright © 2011 John Wiley & Sons, Ltd. 相似文献
534.
Han-Seung Yang Alper Kiziltas Douglas J. Gardner 《Journal of Thermal Analysis and Calorimetry》2013,113(2):673-682
The isothermal and non-isothermal decompositions of cellulose nanofiber (CNF) and microfibrillated cellulose (MFC)-filled polypropylene (PP) composites were evaluated and compared with microcrystalline cellulose (MCC)-filled composites by means of thermogravimetric analysis (TG). X-ray diffraction was employed to evaluate crystallinity of the composites. The degree of maximum thermal degradation (ultimate DTG peak value) increased and thermal degradation onset temperature decreased as the cellulose content increased because the thermal stability of cellulose fillers is lower than that of neat PP, but the thermal degradation of the composite was hindered at higher temperature conditions because of the increased residual mass content of the cellulose nanofibril fillers compared to the matrix polymer. The isothermal residual mass of the cellulose nanofibril-filled PP composites under melt blending and injection molding temperatures was decreased marginally by incorporation of the cellulose reinforcement but still exhibited considerable isothermal stability. The raw materials and composites examined in this study were not affected by the manufacturing process temperatures utilized to produce the composites. The MCC decreased the composite crystallinity while the nano-sized cellulose (CNF and MFC) did not appear to have an effect on crystallinity. 相似文献
535.
Amy Gardner Kevin Sheridan William Groom Nicolas Seymour-Smith Matthias Keller 《Applied physics. B, Lasers and optics》2014,117(2):755-762
In this paper , we present a technique for the precise measurement of electric dipole-allowed transitions in trapped ions. By applying a probe and a cooling laser in quick succession, the full transition can be probed without causing distortion from heating the ion. In addition, two probes can be utilized to measure a dispersion-like signal, which is well suited to stabilizing the laser to the transition. We have fully characterized the parameters for the measurement and find that it is possible to measure the line center to better than 100 kHz with an interrogation time of 30 s. The long-term stability of the spectroscopy signal is determined by employing two independent ion trap systems. The first ion trap is used to stabilize the spectroscopy laser. The second ion trap is then employed to measure the stability by continuously probing the transition at two frequencies. From the Allan variance, we obtained a frequency instability of \(1\cdot 10^{-10}\) for an interrogation time of 1,000 s. 相似文献
536.
Yilei Wu Dr. Marco Frasconi Daniel M. Gardner Dr. Paul R. McGonigal Dr. Severin T. Schneebeli Prof. Michael R. Wasielewski Prof. J. Fraser Stoddart 《Angewandte Chemie (International ed. in English)》2014,53(36):9476-9481
Investigating through‐space electronic communication between discrete cofacially oriented aromatic π‐systems is fundamental to understanding assemblies as diverse as double‐stranded DNA, organic photovoltaics and thin‐film transistors. A detailed understanding of the electronic interactions involved rests on making the appropriate molecular compounds with rigid covalent scaffolds and π–π distances in the range of ca. 3.5 Å. Reported herein is an enantiomeric pair of doubly‐bridged naphthalene‐1,8:4,5‐bis(dicarboximide) (NDI) cyclophanes and the characterization of four of their electronic states, namely 1) the ground state, 2) the exciton coupled singlet excited state, 3) the radical anion with strong through‐space interactions between the redox‐active NDI molecules, and 4) the diamagnetic diradical dianion using UV/Vis/NIR, EPR and ENDOR spectroscopies in addition to X‐ray crystallography. Despite the unfavorable Coulombic repulsion, the singlet diradical dianion dimer of NDI shows a more pronounced intramolecular π–π stacking interaction when compared with its neutral analog. 相似文献
537.
Sghaier Chriki Graham E Gardner Catherine Jurie Brigitte Picard Didier Micol Jean-Paul Brun Laurent Journaux Jean-Francois Hocquette 《BMC biochemistry》2012,13(1):1-11
Background
Unsaturated fatty acids are susceptible to oxidation and damaged chains are removed from glycerophospholipids by phospholipase A2. De-acylated lipids are then re-acylated by lysophospholipid acyltransferase enzymes such as LPCAT1 which catalyses the formation of phosphatidylcholine (PC) from lysoPC and long-chain acyl-CoA.Results
Activity of LPCAT1 is inhibited by Ca2+, and a Ca2+-binding motif of the EF-hand type, EFh-1, was identified in the carboxyl-terminal domain of the protein. The residues Asp-392 and Glu-403 define the loop of the hairpin structure formed by EFh-1. Substitution of D392 and E403 to alanine rendered an enzyme insensitive to Ca2+, which established that Ca2+ binding to that region negatively regulates the activity of the acyltransferase amino-terminal domain. Residue Cys-211 of the conserved motif III is not essential for catalysis and not sufficient for sensitivity to treatment by sulfhydryl-modifier agents. Among the several active cysteine-substitution mutants of LPCAT1 generated, we identified one to be resistant to treatment by sulfhydryl-alkylating and sulfhydryl-oxidizer agents.Conclusion
Mutant forms of LPCAT1 that are not inhibited by Ca2+ and sulfhydryl-alkylating and ?Coxidizing agents will provide a better understanding of the physiological function of a mechanism that places the formation of PC, and the disposal of the bioactive species lysoPC, under the control of the redox status and Ca2+ concentration of the cell. 相似文献538.
Oseback SN Shim SW Kumar M Greer SM Gardner SR Lemar KM DeGregory PR Papish ET Tierney DL Zeller M Yap GP 《Dalton transactions (Cambridge, England : 2003)》2012,41(9):2774-2787
The tris(3-phenyl-5-methyl-1,2,4-triazolyl)borate (Ttz(Ph,Me)) ligand provides intermediate steric bulk and forms predominantly bis(ligand) complexes of the form M(Ttz(Ph,Me))(2) with first row divalent transition metals (1(M), M = Zn, Cu, Ni, Co, Fe, Mn). Due to ligand field effects that are greatest with Ni and Cu, ligand rearrangement is favored with these metals and Cu(Ttz(Ph,Me)*)(2) (1(Cu)*) and (Ttz(Ph,Me)*)Ni(Ttz(Ph,Me)) (1(Ni)*) were isolated by selective recrystallization and fully characterized (* indicates a rearranged Ttz ligand with Ph and Me in swapped positions in one triazole ring). For comparison with Co(Ttz(Ph,Me))(2), the less bulky analogs (Ttz(H,H))(2)Co (4) and (Ttz(Me,Me))(2)Co (5) were studied by NMR and EPR spectroscopy, and 5 was crystallographically characterized. These complexes allow for a study of how slight changes in structure and electron donor properties (for Ni and Cu), as well as dramatic changes in steric bulk (for Co), influence the physical properties; specifically there are significant changes in the UV-Vis, EPR and NMR spectra. Bis(ligand) complexes predominate with all metals, but (Ttz(Ph,Me))Ni(OH(2))Cl (2) and (Ttz(Ph,Me))ZnBr (3) were also isolated and these show that Ttz(Ph,Me) is coordinatively flexible. 相似文献
539.
M. Gail Jones Grant E. Gardner Amy R. Taylor Jennifer H. Forrester Thomas Andre 《School science and mathematics》2012,112(3):171-178
This study examined students' accuracy of measurement estimation for linear distances, different units of measure, task context, and the relationship between accuracy estimation and logical thinking. Middle school students completed a series of tasks that included estimating the length of various objects in different contexts and completed a test of logical thinking ability. Results found that the students were not able to give accurate estimations for the lengths of familiar objects. Students were also less accurate in estimating in metric units as compared to English or novel units. Estimation accuracy was dependent on the task context. There were significant differences in estimation accuracy for two‐ versus three‐dimensional estimation tasks. There were no significant differences for estimating objects with different orientations or embedded objects. For the tasks requiring the students to estimate in English units, the embedded task and the three‐dimensional tasks were correlated with logical thinking. For estimation tasks with novel units, three‐dimensional and two‐dimensional estimation tasks were significantly correlated with the logical thinking. In order to interact effectively with our environment it is essential to possess an intuitive grasp of both dimension and scale and to be able to manipulate such information. Estimation, approximating and measuring are all components of such intuition ( Forrester, Latham, & Shire, 1990 , p. 283). 相似文献
540.
Rule KC Ruff JP Gaulin BD Dunsiger SR Gardner JS Clancy JP Lewis MJ Dabkowska HA Mirebeau I Manuel P Qiu Y Copley JR 《Physical review letters》2006,96(17):177201
High resolution time-of-flight neutron scattering measurements on Tb(2)Ti(2)0(7) reveal a rich low temperature phase diagram in the presence of a magnetic field applied along [110]. In zero field at T = 0.4 K, Tb(2)Ti(2)0(7) is a highly correlated cooperative paramagnet with disordered spins residing on a pyrochlore lattice of corner-sharing tetrahedra. Application of a small field condenses much of the magnetic diffuse scattering, characteristic of the disordered spins, into a new Bragg peak characteristic of a polarized paramagnet. At higher fields, a magnetically ordered phase is induced, which supports spin wave excitations indicative of continuous, rather than Ising-like, spin degrees of freedom. 相似文献