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111.
McLellan R Boag NM Dodds K Ellis D Macgregor SA McKay D Masters SL Noble-Eddy R Platt NP Rankin DW Robertson HE Rosair GM Welch AJ 《Dalton transactions (Cambridge, England : 2003)》2011,40(27):7181-7192
The molecular structures of 1,2-closo-P(2)B(10)H(10) (1) and 1,2-closo-As(2)B(10)H(10) (2) have been determined by gas electron diffraction and the results obtained compared with those from computation at the MP2/6-31G** level of theory. The level of agreement is good for 2 (root-mean-square [rms] misfit for As and B atoms 0.0297 ?) and very good for 1 (rms misfit for P and B atoms 0.0082 ?). In comparing the structures of 1 and 2 with that of 1,2-closo-C(2)B(10)H(12) (I) it is evident that expansion of the polyhedron from I to 1 to 2 is restricted only to the heteroatom vertices and the B(6) face to which these are bound. Following deboronation (at B3) and subsequent metallation, compounds 1 and 2 have been converted into the new metalladiheteroboranes 3-(η-C(9)H(7))-3,1,2-closo-CoAs(2)B(9)H(9) (4), 3-(η-C(10)H(14))-3,1,2-closo-RuAs(2)B(9)H(9) (5), 3-(η-C(5)H(5))-3,1,2-closo-CoP(2)B(9)H(9) (6), 3-(η-C(9)H(7))-3,1,2-closo-CoP(2)B(9)H(9) (7) and 3-(η-C(10)H(14))-3,1,2-closo-RuP(2)B(9)H(9) (8), the last three constituting the first examples of metalladiphosphaboranes. Together with the known compound 3-(η-C(5)H(5))-3,1,2-closo-CoAs(2)B(9)H(9) (3), compounds 4-8 have been analysed by NMR spectroscopy and (except for 8) single-crystal X-ray diffraction. The (11)B NMR spectra of analogous pairs of metalladiphosphaborane and metalladiarsaborane (6 and 3, 7 and 4, 8 and 5) reveal a consistently narrower (9-10 ppm) chemical shift range for the metalladiarsaboranes, the combined result of a deshielding of the lowest frequency resonance (B6) and an increased shielding of the highest frequency resonance (B8) via an antipodal effect. In crystallographic studies, compounds 3 and 5B (one of two crystallographically-independent molecules) suffer As/B disorder, but in both cases it was possible to refine distinct, ordered, components of the disorder, the first time this has been reported for metalladiarsaboranes. Moreover, whilst the Cp compounds 6 and 3 are disordered, their indenyl analogues 7 and 4 are either ordered or significantly less disordered, a consequence of both the reduced symmetry of an indenyl ligand compared to a Cp ligand and the preference of the former for a distinct conformation relative to the cage heteroatoms. Unexpectedly, whilst this conformation in the cobaltadiphosphaborane 7 is cis-staggered (similar to that previously established for the analogous cobaltadicarborane), in the cobaltadiarsaborane 4 the conformation is close to cis-eclipsed. 相似文献
112.
Kennedy DC McKay CS Tay LL Rouleau Y Pezacki JP 《Chemical communications (Cambridge, England)》2011,47(11):3156-3158
Silver nanoparticles bonded to terminal alkynes form stable particles in aqueous solution, produce strong SERS signals for molecular imaging that arise from the carbon-metal bond, and expand the scope of molecules that can be used to stably functionalize plasmonic particles for mammalian cell imaging applications. β-Lactams represent a class of biologically important molecules that can be adapted to SERS studies in this manner. 相似文献
113.
McKay D Frey AS Green JC Cloke FG Maron L 《Chemical communications (Cambridge, England)》2012,48(34):4118-4120
Calculations reveal a multistep pathway towards formation of linear [U](2)-(μ-η(1):η(1)-C(2)O(2)); [U] = U(η-C(8)H(6){SiH(3)-1,4}(2))(η-Cp). However formation of deltate-bridged [U](2)-(μ-η(1):η(2)-C(3)O(3)) requires an alternative mechanism, involving a side-on [U](2)-(μ-η(2):η(2)-CO) complex and whereby the bridging units of [U](2)-(μ-η(2):η(2)-C(n)O(n)) intermediates (n = 1, 2) react directly with free CO. 相似文献
114.
Crozet D McKay D Bijani C Gual A Godard C Claver C Maron L Urrutigoïty M Kalck P 《Dalton transactions (Cambridge, England : 2003)》2012,41(12):3369-3373
Reaction of [Rh(CO)(2){(R,R)-Ph-BPE}][BF(4)] 1 under 7 bar H(2) provides the dihydride [Rh(H)(2)(CO)(2){(R,R)-Ph-BPE}][BF(4)] 3, which reacts with the neutral hydride [Rh(H)(CO){(R,R)-Ph-BPE}] 2 arising from 3 in THF. The resulting complex is the dimeric monocationic Rh((I))-Rh((III)) complex [Rh(H)(2)(CO)(2){(R,R)-Ph-BPE}][BF(4)] 4. 相似文献
115.
A McAnaw M Elena Lopez G Scott D Ellis D McKay GM Rosair AJ Welch 《Dalton transactions (Cambridge, England : 2003)》2012,41(36):10957-10969
Reduction of the tethered carborane 1,2-μ-(CH(2)SiMe(2)CH(2))-1,2-closo-C(2)B(10)H(10) followed by metallation with {CpCo} or {(p-cymene)Ru} fragments affords both C,C'-dimethyl 4,1,2-MC(2)B(10) and 4,1,6-MC(2)B(10) species. DFT calculations indicate that the barriers to isomerisation of both 4-Cp-4,1,2-closo-CoC(2)B(10)H(12) and 4-(η-C(6)H(6))-4,1,2-closo-RuC(2)B(10)H(12) to their respective 4,1,6-isomers are too high for this to be the origin of the unexpected formation of 4,1,6-MC(2)B(10) products (in marked contrast to the related isomerisation of 1,2-closo-C(2)B(11)H(13) to 1,6-closo-C(2)B(11)H(13)), and, indeed, the 4,1,2-species are recovered unchanged from refluxing toluene. Equally, the DFT-calculated profile for the isomerisation of [7,8-nido-C(2)B(10)H(12)](2-) to [7,9-nido-C(2)B(10)H(12)](2-) suggests that the unexpected formation of 4,1,6-metallacarboranes is unlikely to result from isomerisation of a reduced (nido) carborane following desilylation. Instead, the source of the 4,1,6-MC(2)B(10) compounds is traced to desilylation of 1,2-μ-(CH(2)SiMe(2)CH(2))-1,2-closo-C(2)B(10)H(10) by Li or Na prior to reduction. The supraicosahedral metallacarboranes 1,8-Me(2)-4-Cp-4,1,8-closo-CoC(2)B(10)H(10), 1,12-Me(2)-4-Cp-4,1,12-closo-CoC(2)B(10)H(10) and 1,12-Me(2)-4-(p-cymene)-4,1,12-closo-RuC(2)B(10)H(10) are also reported with all new species characterised both spectroscopically and crystallographically. 相似文献
116.
Nicholas P. McKay David L. Dettman Robert T. Downs Jonathan T. Overpeck 《Journal of Raman spectroscopy : JRS》2013,44(3):469-474
The potential for using Raman spectroscopy to measure stable oxygen isotope ratios (18O/16O) in carbonates is evaluated by measuring the Raman spectra and isotope ratios of a suite of 60 synthesized, 18O‐enriched calcite crystals ranging in composition from natural abundance (0.2 mole‐% 18O) to 1.2 mole‐% 18O. We determined the Raman‐inferred isotopic ratios (RRaman) by fitting curves to the ν1 symmetric stretching peak at 1086 cm−1 and the smaller satellite peak, associated with the ν1 stretching mode of singly substituted carbonate groups (C16O218O) at 1065 cm−1. The ratio of the two peak areas shows a 1:1 correspondence with the 18O/16O ratios derived from standard mass spectrometry methods, confirming that the relative intensities of the ν1 symmetric stretching peaks is a direct measure of the isotopic ratio in the carbonates. The 1‐sigma uncertainties of the RRaman values of the individual crystals were 0.00079 (384‰ PDB) and 0.00043 (210‰ PDB) for the four‐crystal sample means. This level of uncertainty is much too high to provide significant estimates of natural variability; however, there are multiple prospects for improving the accuracy and precision of the technique. Carbon isotope ratios in carbonates cannot be measured by our approach, but our results highlight the potential of Raman‐based isotope ratio measurement for C and other elements in minerals and organic compounds. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
117.
We discuss the transport of a tracer particle through the Bose?CEinstein condensate of a Bose gas. The particle interacts with the atoms in the Bose gas through two-body interactions. In the limiting regime where the particle is very heavy and the Bose gas is very dense, but very weakly interacting (??mean-field limit??), the dynamics of this system corresponds to classical Hamiltonian dynamics. We show that, in this limit, the particle is decelerated by emission of gapless modes into the condensate (Cerenkov radiation). For an ideal gas, the particle eventually comes to rest. In an interacting Bose gas, the particle is decelerated until its speed equals the propagation speed of the Goldstone modes of the condensate. This is a model of ??Hamiltonian friction??. It is also of interest in connection with the phenomenon of ??decoherence?? in quantum mechanics. This note is based on work we have carried out in collaboration with D Egli, I M Sigal and A Soffer. 相似文献
118.
Aparna Dixit Pankaj Jain Douglas W. McKay Parama Mukherjee 《The European Physical Journal C - Particles and Fields》2010,68(3-4):573-580
We explore the possibility that a new-physics interaction can provide an explanation for the knee just above 106 GeV in the cosmic ray spectrum. We model the new-physics modifications to the total proton–proton cross section with an incoherent term that allows for missing energy above the scale of new physics. We add the constraint that the new physics must also be consistent with published pp cross section measurements, using cosmic ray observations, an order of magnitude and more above the knee. We find that the rise in cross section required at energies above the knee is radical. The increase in cross section suggests that it may be more appropriate to treat the scattering process in the black disc limit at such high energies. In this case there may be no clean separation between the standard model and new-physics contributions to the total cross section. We model the missing energy in this limit and find a good fit to the Tibet III cosmic ray flux data. We comment on testing the new-physics proposal for the cosmic ray knee at the Large Hadron Collider. 相似文献
119.
All-glass endless single-mode photonic crystal fibers 总被引:1,自引:0,他引:1
Endless single-mode fibers, which remain single mode over their entire range of guidance, are, to the best of our knowledge, the first reported unique application of photonic crystal fibers. These endless single-mode fibers are made by omitting a single air hole in a periodic array of small air holes in a background silica glass. The feasibility of all-glass endless single-mode photonic crystal fibers where the air holes are replaced by a glass with vanishingly small refractive index contrast relative to silica is first studied theoretically and then demonstrated experimentally. This new all-glass design enables not only ease and consistency of fabrication but also the convenience to be handled and spliced like conventional fibers. 相似文献
120.
DC magnetization, neutron depolarization and neutron diffraction (with both polarized and unpolarized neutrons) measurements
have been reported for the Co1.1−x
Zn
x
Ge0.1Fe1.2O1 spinels with x=0.5, 0.6 and 0.7. Neutron depolarization and neutron diffraction measurements confirm the presence of a long range ferrimagnetic
ordering of the local canted spins in these ferrite samples. The observed features of low field magnetization have been explained
under the framework of thermally activated domain wall movement of ferrimagnetic arrangement of local canted spins. An important
role of magnetic anisotropy (due to the presence of Co2+ ions) in establishing the magnetic ordering and domain kinetics in these ferrites has been observed. 相似文献