全文获取类型
收费全文 | 6105篇 |
免费 | 386篇 |
国内免费 | 15篇 |
专业分类
化学 | 4840篇 |
晶体学 | 36篇 |
力学 | 74篇 |
数学 | 701篇 |
物理学 | 855篇 |
出版年
2024年 | 10篇 |
2023年 | 58篇 |
2022年 | 83篇 |
2021年 | 107篇 |
2020年 | 197篇 |
2019年 | 187篇 |
2018年 | 77篇 |
2017年 | 98篇 |
2016年 | 268篇 |
2015年 | 252篇 |
2014年 | 301篇 |
2013年 | 327篇 |
2012年 | 466篇 |
2011年 | 499篇 |
2010年 | 289篇 |
2009年 | 242篇 |
2008年 | 376篇 |
2007年 | 352篇 |
2006年 | 320篇 |
2005年 | 261篇 |
2004年 | 245篇 |
2003年 | 200篇 |
2002年 | 194篇 |
2001年 | 109篇 |
2000年 | 86篇 |
1999年 | 75篇 |
1998年 | 70篇 |
1997年 | 79篇 |
1996年 | 68篇 |
1995年 | 73篇 |
1994年 | 89篇 |
1993年 | 51篇 |
1992年 | 49篇 |
1991年 | 43篇 |
1990年 | 36篇 |
1989年 | 45篇 |
1988年 | 30篇 |
1987年 | 24篇 |
1986年 | 19篇 |
1985年 | 12篇 |
1984年 | 14篇 |
1983年 | 10篇 |
1982年 | 12篇 |
1981年 | 15篇 |
1980年 | 20篇 |
1979年 | 13篇 |
1978年 | 17篇 |
1977年 | 14篇 |
1976年 | 8篇 |
1975年 | 3篇 |
排序方式: 共有6506条查询结果,搜索用时 5 毫秒
91.
Mes*‐substituted 2,3‐dimethyl‐1,4‐diphosphabuta‐1,3‐diene, 1,2‐diphenyl‐3,4‐diphosphinidenecyclobutene, 2,2‐bis(methylsulfanyl)‐1‐phosphaethene, and 3,3‐diphenyl‐1,3‐diphosphapropenes (Mes*=2,4,6‐tri‐tert‐butylphenyl) were employed as P ligands of gold(I) complexes. The (E,E)‐2,3‐dimethyl‐1,4‐diphosphabuta‐1,3‐diene functioned as a P2 ligand for digold(I) complex formation with or without intramolecular Au–Au contact, which depends on the conformation of the 1,3‐diphosphabuta‐1,3‐diene. The 1,2‐diphenyl‐3,4‐diphosphinidenecyclobutene, which has a rigid s‐cis P?C? C?P skeleton, afforded the corresponding digold(I) complexes with a slight distortion of the planar diphosphinidenecyclobutene framework and intramolecular Au–Au contact. In the case of the 2,2‐bis(methylsulfanyl)‐1‐phosphaethene, only the phosphorus atom coordinated to gold, and the sulfur atom showed almost no intra‐ or intermolecular coordination to gold. On the other hand, the 1,3‐diphosphapropenes behaved as nonequivalent P2 ligands to afford the corresponding mono‐ and digold(I) complexes. Some phosphaalkene–gold(I) complexes showed catalytic activity for 1,6‐enyne cycloisomerization without cocatalysts such as silver hexafluoroantimonate. 相似文献
92.
The reaction of dimethylzinc and tri(tert‐butyl)silylphosphane in toluene yielded dimeric methylzinc tri(tert‐butyl)silylphosphanide ( 1 ) which crystallized tetrameric. Compound 1 was deprotonated with sodium in DME and the solvent‐separated dimeric ion pair [(dme)3Na]+ [(dme)Na(MeZn)2(μ‐PSitBu3)2]? ( 2 ) was isolated. The reaction of 1 in THF with two equivalents of potassium and one equivalent of tri(tert‐butyl)silylphosphane gave dimeric [{tBu3Si(H)P}{(thf)2K}2(MeZn)(PSitBu3)]2 ( 3 ). Both of these phosphanylzincates contain Zn2P2 cycles with Zn‐P bond lengths of approximately 237 pm, whereas in 1 larger Zn‐P bond lengths of 248.5 pm were found due to the larger coordination numbers of the phosphorus and zinc atoms. 相似文献
93.
Matthias HeydenreichAndreas Koch László LázárIstván Szatmári Reijo SillanpääErich Kleinpeter Ferenc Fülöp 《Tetrahedron》2003,59(11):1951-1959
Starting from the 1′- or 2′-phenyl-substituted 1-(2′-hydroxyethyl)-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinoline diastereomers 3 and 6, 4-unsubstituted and 4-(p-nitrophenyl)- and 4-oxo-substituted 1-phenyl- and 2-phenyl-9,10-dimethoxy-2H,4H-1,6,7,11b-tetrahydro-1,3-oxazino[4,3-a]isoquinolines (7-12) were prepared. The relative configurations and the predominant conformations of the products were determined by NMR spectroscopy, by quantum chemical calculations and, for (2R∗,4S∗,11bR∗)-9,10-dimethoxy-4-(p-nitrophenyl)-2-phenyl-2H,4H-1,6,7,11b-tetrahydro-1,3-oxazino[4,3-a]isoquinoline (11), by X-ray diffraction. 相似文献
94.
The complexes (RN=CH-CH=NR)Co(NO)(CO) with R = isopropyl, 2,6-diisopropylphenyl, or p-tolyl are chemically and electrochemically reducible to radical anions at potentials which strongly depend on R. The DFT calculated structure for the neutral compound with R = iPr agrees with the experiment, and the computed structure of the anion radical reveals changes according to a reduction of the R-DAB ligand. EPR results confirm an (R-DAB)-based singly occupied molecular orbital in [(RNCHCHNR)Co(NO)(CO)](.-), with minor but detectable contributions from NO as supported by IR spectroelectrochemistry and as quantified by DFT spin density calculations. The calculations indicate increasingly stabilized CO, NO, and RNCHCHNR pi* acceptor orbitals, in that order. On the basis of TD-DFT (time-dependent density functional theory) calculations, the lowest-lying excited states are assigned to metal-to-(R-DAB) charge transfer transitions while bands due to the metal-to-nitrosyl charge transfer occur at higher energies but still in the visible region. Resonance Raman studies were used to probe these assignments. 相似文献
95.
Lipophilic trifluoroacetophenone derivatives incorporated in plasticized PVC membranes are able to selectively extract water and alcohols from the sample solution into the organic membrane phase, reversibly forming hydrates and hemi-acetals, respectively. Since this is accompanied by a change in the absorption spectrum of the acetophenone isologue, the chemical recognition process can directly be translated into an optical signal. With N-acetyl-N-dodecyl-4-trifluoroacetylaniline (ETH 6022) as the electrically neutral, lipophilized carrier ethanol can be determined from 0.5 to 35% (v/v) in aqueous solutions. The calibration curve for different ethanol-water mixtures shows a good correlation with the mathematically derived formalism and thus confirms the theoretically expected behavior. Besides high reproducibility of the optical signals, very short response times of less than 30 s were realized. The optode membrane presented exhibits a preference for ethanol compared to water by a factor greater than 11. The selectivities for several primary alcohols, such as methanol, ethanol, 1-propanol and 1-n-butanol, are comparable, but isopropanol and tert.-butanol are rejected by a factor of about 10. The alcohol concentration in different beverages was determined to evaluate the reliability of the system. The values obtained for wine, beer and different spirits show an excellent correlation with those obtained by a conventional approach involving distillation and density measurements. A residual standard deviation of ± 0.27% (v/v) over the 0.7–40% (v/v) range was found. 相似文献
96.
Bickelhaupt FM DeKock RL Baerends EJ 《Journal of the American Chemical Society》2002,124(7):1500-1505
Exceptionally short N [bond] F bond distances of only 1.217 A (crystal) and 1.246 A (gas phase) have been reported for N(2)F(+), making it the shortest N [bond] F bond ever observed. To trace the origin of this structural phenomenon, we have analyzed the model systems N(2)X(+), NF(3)X(+), and NH(3)X(+) (X [double bond] F, H) using generalized gradient approximation density functional theory at BP86/TZ2P. In good agreement with experiment, the computations yield an extremely short N [bond] F bond for N(2)F(+): we find N [bond] F bond distances in N(2)F(+), NF(4)(+), and NH(3)F(+) of 1.245, 1.339, and 1.375 A, respectively. The N [bond] X bonding mechanisms are quantitatively analyzed in the framework of Kohn-Sham MO theory. At variance with the current hypothesis, reduced steric and other Pauli repulsion (of substituents or lone pairs at N with F) rather than the extent of s [bond] p hybridization of N (i.e., sp versus sp(3)) are responsible for the much shorter N [bond] F distance in N(2)F(+) compared to NF(4)(+). The results for our nitrogen compounds are furthermore discussed in the more general context of how bond lengths are determined by both bonding and repulsive orbital interactions. 相似文献
97.
Single crystal EPR studies of the reduced active site of [NiFe] hydrogenase from Desulfovibrio vulgaris Miyazaki F 总被引:1,自引:0,他引:1
Foerster S Stein M Brecht M Ogata H Higuchi Y Lubitz W 《Journal of the American Chemical Society》2003,125(1):83-93
In the catalytic cycle of [NiFe] hydrogenase the paramagnetic Ni-C intermediate is of key importance, since it is believed to carry the substrate hydrogen, albeit in a yet unknown geometry. Upon illumination at low temperatures, Ni-C is converted to the so-called Ni-L state with markedly different spectroscopic parameters. It is suspected that Ni-L has lost the "substrate hydrogen". In this work, both paramagnetic states have been generated in single crystals obtained from the [NiFe] hydrogenase from Desulfovibrio vulgaris Miyazaki F. Evaluation of the orientation dependent spectra yielded the magnitudes of the g tensors and their orientations in the crystal axes system for both Ni-C and Ni-L. The g tensors could further be related to the atomic structure by comparison with the X-ray crystallographic structure of the reduced enzyme. Although the g tensor magnitudes of Ni-C and Ni-L are quite different, the orientations of the resulting g tensors are very similar but differ from those obtained earlier for Ni-A and Ni-B (Trofanchuk et al. J. Biol. Inorg. Chem. 2000, 5, 36-44). The g tensors were also calculated by density functional theory (DFT) methods using various structural models of the active site. The calculated g tensor of Ni-C is, concerning magnitudes and orientation, in good agreement with the experimental one for a formal Ni(III) oxidation state with a hydride (H(-)) bridge between the Ni and the Fe atom. Satisfying agreement is obtained for the Ni-L state when a formal Ni(I) oxidation state is assumed for this species with a proton (H(+)) removed from the bridge between the nickel and the iron atom. 相似文献
98.
99.
Photoelectron Spectra and Molecular Properties. 133. Trifluoromethyldisulfane and Derivates F3CSSX (X?CF3, F, Cl, Br) The He(I) photoelectron spectra of trifluoromethyldisulfane F3CSSH and its derivatives F3CSSX (X?CF3, F, Cl, Br) are assigned by Koopmans correlations, IE = ?ε, with MNDO eigenvalues and by radical cation state comparison. Of special interest are the n/n splittings, which amount to 1.15 eV F3C? SS? F or 0.87 eV in F3? SS? Cl, and the dependance of which on the dihedral angle ω(XS? SX), on the SS bond length and on the acceptor effect of the F3C substituents is discussed. 相似文献
100.
Matthias Bauer Christoph Gastl Christoph Köppl Guido Kickelbick Helmut Bertagnolli 《Monatshefte für Chemie / Chemical Monthly》2006,137(5):567-581
Summary. The molecular structure of the transition metal alkoxide Zr(OnBu)4 in toluene and its modification by addition of i-propanol, tetrahydrofurane, and the coordinating ligand pentane-1,3-dione (Hacac) were investigated by extended X-ray absorption fine structure (EXAFS) and X-ray absorption near edge structure (XANES) spectroscopy.
Zr(OnBu)4 dissolved in toluene forms dimers. It was proved that cluster size is a function of the number of added equivalents ligand.
In contrast, the addition of i-propanol or tetrahydrofurane caused no structural changes observable by EXAFS spectroscopy. A detailed discussion of the
structural models is given in terms of possible alternatives and errors within the EXAFS analysis. 相似文献