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1.
Yu‐Hsiang Hu Chuh‐Yung Chen Chen‐Chien Wang Yao‐Hui Huang Shao‐Ping Wang 《Journal of polymer science. Part A, Polymer chemistry》2004,42(19):4976-4993
The bulk polymerization of styrene initiated by ?‐caprolactam (CL) and n‐dodecyl mercaptan (RSH) has been explored. This novel polymerization system shows living characteristics. For example, the molecular weight of the resulting polymers increases with conversion, and the system has the ability to form diblock copolymers and so forth. The polymer chain end contains thiol and lactam structures, which we have investigated with Fourier transform infrared, 1H NMR, and 13C NMR techniques. Electron spin resonance spectra and theoretical calculations by the Hartree–Fock methods have been used to examine the mechanism. The results reveal that the initial polymerization starts from thiol via a chain‐transfer reaction, and the propagation proceeds by the insertion of a monomer between the terminal group and the intermediate structure of lactam. Finally, the polymerization kinetics have been examined. The polymerization rate varies linearly with the concentration of CL and RSH, and this confirms the mechanism. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4976–4993, 2004 相似文献
2.
The effects of instanton-anti-instanton interactions in high-temperature QCD with colour SU(2) are studied with and without quarks. The instanton potential proves to have no repulsive core, thus creating troubles with the definition of nonperturbative contributions to physical quantities. Also the chiral condensate is calculated, and it is shown to vanish if number of quark flavoursN f≧2, whereas forN f=1 it is nonzero for the arbitrary high temperature. 相似文献
3.
4.
We performed ab initio quantum-chemical studies for the development of intra- and intermolecular interaction potentials for formic acid for use in molecular-dynamics simulations of formic acid molecular crystal. The formic acid structures considered in the ab initio studies include both the cis and trans monomers which are the conformers that have been postulated as part of chains constituting liquid and crystal phases under extreme conditions. Although the cis to trans transformation is not energetically favored, the trans isomer was found as a component of stable gas-phase species. Our decomposition scheme for the interaction energy indicates that the hydrogen-bonded complexes are dominated by the Hartree-Fock forces while parallel clusters are stabilized by the electron correlation energy. The calculated three-body and higher interactions are found to be negligible, thus rationalizing the development of an atom-atom pair potential for formic acid based on high-level ab initio calculations of small formic acid clusters. Here we present an atom-atom pair potential that includes both intra- and inter molecular degrees of freedom for formic acid. The newly developed pair potential is used to examine formic acid in the condensed phase via molecular-dynamics simulations. The isothermal compression under hydrostatic pressure obtained from molecular-dynamics simulations is in good agreement with experiment. Further, the calculated equilibrium melting temperature is found to be in good agreement with experiment. 相似文献
5.
S. F. Biagi M. Bourquin R. M. Brown H. J. Burckhart P. Extermann M. Gailloud C. N. P. Gee W. M. Gibson P. Jacot-Guillarmod J. Perrier K. J. Ragan Ph. Rosselet P. Schirato H. W. Siebert V. J. Smith K. P. Streit J. J. Thresher A. T. Wood C. Yanagisawa 《Zeitschrift fur Physik C Particles and Fields》1987,34(2):175-185
In an experiment at the CERN-SPS charged hyperon beam, we have investigated the inclusive \(\Lambda \bar K^0 \) and \(\Sigma ^0 \bar K^0 \) final states formed in Ξ? Be interactions. In the \(\Lambda \bar K^0 \) channel, we observe a signal at 1826 MeV/c2 which can be identified with the known Ξ(1820) resonance. We determine its mass and width to be:M=1826±4 MeV/c2, Г=12±14 MeV/c2. A moment analysis is consistent with a spin of 3/2 and indicates a negative parity for this spin assignment. Also in the \(\Lambda \bar K^0 \) channel, we observe a 3.6σ signal with the following parameters:M=1963±5 MeV/c2, Г=25±15 MeV/c2. This state, which we call Ξ(1960), is not observed in the \(\Sigma ^0 \bar K^0 \) channel, leading to an upper limit on the ratio of partial widths \(\Sigma \bar K/\Lambda \bar K\) of 2.3 (90% confidence level). A moment analysis of the \(\Lambda \bar K^0 \) final state indicates a spin of 5/2 or greater in the natural spin-parity series 5/2+, 7/2?, etc. 相似文献
6.
Kim HG Lee CW Yun S Hong BH Kim YO Kim D Ihm H Lee JW Lee EC Tarakeshwar P Park SM Kim KS 《Organic letters》2002,4(22):3971-3974
[formula: see text] A new molecular system, 2,11-dithio[4,4]metametaquinocyclophane containing a quinone moiety, was designed and synthesized. As the quinone moiety can readily be converted into an aromatic pi-system (hydroquinone) upon reduction, the nanomechanical molecular cyclophane system exhibits a large flapping motion like a molecular flipper from the electrochemical redox process. The conformational changes upon reduction and oxidation are caused by changes of nonbonding interaction forces (devoid of bond formation/breaking) from the edge-to-face to face-to-face aromatic interactions and vice versa, respectively. 相似文献
7.
The products of the reaction of OClO with NO3 were investigated between 220 and 298 K using a flow reactor and infrared, visible, and ultraviolet analysis. At temperatures below 250 K new infrared and ultraviolet absorption features were observed and assigned to the novel compound chloryl nitrate (O2ClONO2). Additionally, ClO and NO2 were observed as reaction products, indicating the existence of a second reaction channel. O2ClONO2 formation predominates at temperatures below 230 K. The reaction rate constant at 220 K is estimated to be on the order of 10(-14) cm3 molecule-1 s-1 in 1-5 Torr of helium. These observations suggest that O2ClONO2 may exist in the terrestrial stratosphere. 相似文献
8.
Seo YJ Jeon MH Lee JH Lee YJ Youn HJ Ko JH Lee JH 《Experimental & molecular medicine》2005,37(6):624-630
Bis (Bag-3, CAIR), a Bcl-2-interacting protein, promotes the anti-apoptotic activity of Bcl-2 and increased levels of Bis have been observed in several disease models. The involvement of Bcl-2 and some Bcl-2-binding proteins in differentiation has recently been reported. However, the relevance of Bis to cellular differentiation remains unknown. The findings herein show that Bis expression is up-regulated during the differentiation of HL-60 cells. To investigate the effect of Bis expression on differentiation, we established Bis-overexpressing HL-60 cells (HL-60-bis). HL-60-bis cells have a low nuclear: cytoplasmic ratio and indented nucleus in Wright- Giemsa staining, and an increased expression of CD11b in immunofluorescence study, indicating the promotion of differentiation. The overexpression of Bis also resulted in a retarded cell growth rate, accompanied by the accumulation of HL-60 cells at the G0/G1 phase of the cell cycle, which was sustained during the differentiation process. Western blot analysis revealed that the expression of p27, a representative inducer of cell cycle arrest at the G1 phase, was increased 2.5-fold in HL-60-bis cells compared to HL-60-neo cells. These results suggest that the Bis induced growth inhibition of HL-60 cells promotes G0/G1 phase arrest via up-regulation of p27, which seems to be a prerequisite for differentiation. Further studies will be required to define the exact roles of Bis on cellular differentiation more precisely. 相似文献
9.
Myron S. Huzan Manuel Fix Matteo Aramini Peter Bencok J. Frederick W. Mosselmans Shusaku Hayama Franziska A. Breitner Leland B. Gee Charles J. Titus Marie-Anne Arrio Anton Jesche Michael L. Baker 《Chemical science》2020,11(43):11801
Large single-ion magnetic anisotropy is observed in lithium nitride doped with iron. The iron sites are two-coordinate, putting iron doped lithium nitride amongst a growing number of two coordinate transition metal single-ion magnets (SIMs). Uniquely, the relaxation times to magnetisation reversal are over two orders of magnitude longer in iron doped lithium nitride than other 3d-metal SIMs, and comparable with high-performance lanthanide-based SIMs. To understand the origin of these enhanced magnetic properties a detailed characterisation of electronic structure is presented. Access to dopant electronic structure calls for atomic specific techniques, hence a combination of detailed single-crystal X-ray absorption and emission spectroscopies are applied. Together K-edge, L2,3-edge and Kβ X-ray spectroscopies probe local geometry and electronic structure, identifying iron doped lithium nitride to be a prototype, solid-state SIM, clean of stoichiometric vacancies where Fe lattice sites are geometrically equivalent. Extended X-ray absorption fine structure and angular dependent single-crystal X-ray absorption near edge spectroscopy measurements determine FeI dopant ions to be linearly coordinated, occupying a D6h symmetry pocket. The dopant engages in strong 3dπ-bonding, resulting in an exceptionally short Fe–N bond length (1.873(7) Å) and rigorous linearity. It is proposed that this structure protects dopant sites from Renner–Teller vibronic coupling and pseudo Jahn–Teller distortions, enhancing magnetic properties with respect to molecular-based linear complexes. The Fe ligand field is quantified by L2,3-edge XAS from which the energy reduction of 3dz2 due to strong 4s mixing is deduced. Quantification of magnetic anisotropy barriers in low concentration dopant sites is inhibited by many established methods, including far-infrared and neutron scattering. We deduce variable temperature L3-edge XAS can be applied to quantify the J = 7/2 magnetic anisotropy barrier, 34.80 meV (∼280 cm−1), that corresponds with Orbach relaxation via the first excited, MJ = ±5/2 doublet. The results demonstrate that dopant sites within solid-state host lattices could offer a viable alternative to rare-earth bulk magnets and high-performance SIMs, where the host matrix can be tailored to impose high symmetry and control lattice induced relaxation effects.Taking advantage of synchrotron light source methods, we present the geometric and electronic structure of iron doped in lithium nitride. 相似文献
10.
M. Kashiwara T. Miwa J. -U. H. Petersen C. M. Yung 《Selecta Mathematica, New Series》1996,2(3):415-499
In [S], [KMS] the semi-infinite wedge construction of level 1U
q
(A
n
(1)
) Fock spaces and their decomposition into the tensor product of an irreducibleU
q
(A
n
(1)
)-module and a bosonic Fock space were given. Here a general scheme for the wedge construction ofq-deformed Fock spaces using the theory of perfect crystals is presented.LetU
q
(g) be a quantum affine algebra. LetV be a finite-dimensionalU
q
(g)-module with a perfect crystal base of levell. LetV
aff V [z,z
–1] be the affinization ofV, with crystal base (L
aff,B
aff). The wedge spaceV
aff V
aff is defined as the quotient ofV
aff V
aff by the subspace generated by the action ofU
q
(g) [z
a
z
b
+z
b
z
a
]a,b onv v (v an extremal vector). The wedge space r
V
aff (r ) is defined similarly. Normally ordered wedges are defined by using the energy functionH :B
aff B
aff . Under certain assumptions, it is proved that normally ordered wedges form a base of r
V
aff.Aq-deformed Fock space is defined as the inductive limit of r
V
aff asr , taken along the semi-infinite wedge associated to a ground state sequence. It is proved that normally ordered wedges form a base of the Fock space and that the Fock space has the structure of an integrableU
q
(g)-module. An action of the bosons, which commute with theU
q
(g)-action, is given on the Fock space. It induces the decomposition of theq-deformed Fock space into the tensor product of an irreducibleU
q
(g)-module and a bosonic Fock space.As examples, Fock spaces for typesA
2n
(2)
,B
n
(1)
,A
2n
–1/(2)
,D
n
(1)
andD
n
+1/(2)
at level 1 andA
1
(1)
at levelk are constructed. The commutation relations of the bosons in each of these cases are calculated, using two point functions of vertex operators. 相似文献