全文获取类型
收费全文 | 312篇 |
免费 | 7篇 |
专业分类
化学 | 232篇 |
晶体学 | 2篇 |
力学 | 4篇 |
数学 | 10篇 |
物理学 | 71篇 |
出版年
2019年 | 2篇 |
2018年 | 2篇 |
2017年 | 4篇 |
2016年 | 6篇 |
2014年 | 5篇 |
2013年 | 12篇 |
2012年 | 11篇 |
2011年 | 6篇 |
2010年 | 8篇 |
2009年 | 4篇 |
2008年 | 24篇 |
2007年 | 19篇 |
2006年 | 13篇 |
2005年 | 16篇 |
2004年 | 9篇 |
2003年 | 10篇 |
2002年 | 6篇 |
2001年 | 13篇 |
2000年 | 19篇 |
1999年 | 8篇 |
1997年 | 4篇 |
1996年 | 9篇 |
1995年 | 7篇 |
1994年 | 6篇 |
1993年 | 4篇 |
1992年 | 8篇 |
1991年 | 5篇 |
1990年 | 4篇 |
1989年 | 3篇 |
1988年 | 5篇 |
1987年 | 7篇 |
1986年 | 4篇 |
1985年 | 5篇 |
1984年 | 3篇 |
1983年 | 3篇 |
1982年 | 2篇 |
1981年 | 4篇 |
1980年 | 3篇 |
1979年 | 2篇 |
1978年 | 2篇 |
1977年 | 2篇 |
1976年 | 6篇 |
1974年 | 4篇 |
1973年 | 7篇 |
1972年 | 2篇 |
1969年 | 2篇 |
1968年 | 2篇 |
1955年 | 1篇 |
1929年 | 2篇 |
1866年 | 1篇 |
排序方式: 共有319条查询结果,搜索用时 15 毫秒
21.
Garcia Ruano JL Alemparte C Martin Castro AM Adams H Rodriguez Ramos JH 《The Journal of organic chemistry》2000,65(23):7938-7943
The behavior of (Z)-3-p-tolylsulfinylacrylonitrile (1) as a chiral dienophile has been evaluated from its reactions with furan and acyclic dienes. Electrostatic interactions of the cyano group with the sulfinyl one restrict the conformational mobility around the C-S bond, thus controlling the pi-facial selectivity, which is almost complete in all cases, the approach of the diene from the less-hindered face of the dienophile (that bearing the lone electron pair) in the predominant rotamer being the favored one. The regioselectivity is also completely controlled by the cyano group. Additionally, the reactivity of compound 1 as well as its endo-selectivity are both higher than those observed for the corresponding (Z)-3-sulfinylacrylates, thus proving the potential of sulfinylnitriles as chiral dienophiles. 相似文献
22.
There is widespread acceptance that singlet oxygen is a key intermediate on one of the pathways leading to the phenomenon of photodynamic action. However, the identification of this moiety within a particular biological system and the determination of a direct link between its presence and a particular photodynamic effect is a goal which photobiologists have hitherto failed to achieve. The aim of this review is to assess the problems associated with such a goal and methods whereby they might be overcome. Initially the general photochemical and environmental factors which govern the ability of a photosensitizer to promote photodynamic action via the intermediacy of singlet oxygen are introduced and the fundamental parameters defining the formation, decay and reactivity of this species summarized. The experimental requirements for relating a particular photodynamic effect to singlet oxygen intermediacy are then analysed and the intrinsic properties of singlet oxygen which will influence this goal are discussed. Having concluded that the singlet oxygen detection method of choice for this purpose is that in which the IR emission at 1269 nm of this molecule is monitored, the advantages and disadvantages of pulsed and continuous wave photoexcitation of cellular systems are analysed. It becomes evident that, no matter what the future improvements in instrumentation are likely to be, the inherent natures of singlet oxygen and the biological system lead to a kinetic situation which will preclude a successful time-resolved solution to this problem. In contrast, experimentation with continuous wave systems holds out significant hope for the future. In particular, the use of phase modulation techniques to overcome background emission problems, the enhancement of photosensitizer optical densities as a consequence of higher extinction coefficients and/or improved photosensitizer delivery systems and the use of high power lasers and/or improved light delivery systems can, at least in principle, lead to the solution of the problem addressed herein. 相似文献
23.
Linder DP Rodgers KR Banister J Wyllie GR Ellison MK Scheidt WR 《Journal of the American Chemical Society》2004,126(43):14136-14148
Recent years have seen dramatic growth in our understanding of the biological roles of nitric oxide (NO). Yet, the fundamental underpinnings of its reactivities with transition metal centers in proteins and enzymes, the stabilities of their structures, and the relationships between structure and reactivity remains, to a significant extent, elusive. This is especially true for the so-called ferric heme nitrosyls ([FeNO](6) in the Enemark-Feltham scheme). The Fe-CO and C-O bond strengths in the isoelectronic ferrous carbonyl complexes are widely recognized to be inversely correlated and sensitive to structural, environmental, and electronic factors. On the other hand, the Fe-NO and N-O bonds in [FeNO](6) heme complexes exhibit seemingly inconsistent behavior in response to varying structure and environment. This report contains resonance Raman and density functional theory results that suggest a new model for FeNO bonding in five-coordinate [FeNO](6) complexes. On the basis of resonance Raman and FTIR data, a direct correlation between the nu(Fe)(-)(NO) and nu(N)(-)(O) frequencies of [Fe(OEP)NO](ClO(4)) and [Fe(OEP)NO](ClO(4)).CHCl(3) (two crystal forms of the same complex) has been established. Density functional theory calculations show that the relationship between Fe-NO and N-O bond strengths is responsive to FeNO electron density in three molecular orbitals. The highest energy orbital of the three is sigma-antibonding with respect to the entire FeNO unit. The other two comprise a lower-energy, degenerate, or nearly degenerate pair that is pi-bonding with respect to Fe-NO and pi-antibonding with respect to N-O. The relative sensitivities of the electron density distributions in these orbitals are shown to be consistent with all published indicators of Fe-N-O bond strengths and angles, including the examples reported here. 相似文献
24.
Threshold collision-induced dissociation of M(+)(adenine) with xenon is studied using guided ion beam mass spectrometry. M(+) includes all 10 first-row transition metal ions: Sc(+), Ti(+), V(+), Cr(+), Mn(+), Fe(+), Co(+), Ni(+), Cu(+), and Zn(+). For the systems involving the late metal ions, Cr(+) through Cu(+), the primary product corresponds to endothermic loss of the intact adenine molecule, whereas for Zn(+), this process occurs but to form Zn + adenine(+). For the complexes to the early metal ions, Sc(+), Ti(+), and V(+), intact ligand loss competes with endothermic elimination of purine and of HCN to form MNH(+) and M(+)(C(4)H(4)N(4)), respectively, as the primary ionic products. For Sc(+), loss of ammonia is also a prominent process at low energies. Several minor channels corresponding to formation of M(+)(C(x)H(x)N(x)), x = 1-3, are also observed for these three systems at elevated energies. The energy-dependent collision-induced dissociation cross sections for M(+)(adenine), where M(+) = V(+) through Zn(+), are modeled to yield thresholds that are directly related to 0 and 298 K bond dissociation energies for M(+)-adenine after accounting for the effects of multiple ion-molecule collisions, kinetic and internal energy distributions of the reactants, and dissociation lifetimes. The measured bond energies are compared to those previously studied for simple nitrogen donor ligands, NH(3) and pyrimidine, and to results for alkali metal cations bound to adenine. Trends in these results and theoretical calculations on Cu(+)(adenine) suggest distinct differences in the binding site propensities of adenine to the alkali vs transition metal ions, a consequence of s-dsigma hybridization on the latter. 相似文献
25.
Bo Yang R. R. Wu N. C. Polfer G. Berden J. Oomens M. T. Rodgers 《Journal of the American Society for Mass Spectrometry》2013,24(10):1523-1533
The gas-phase structures of alkali metal cation-cytosine complexes generated by electrospray ionization are probed via infrared multiple photon dissociation (IRMPD) action spectroscopy and theoretical calculations. IRMPD action spectra of five alkali metal cation–cytosine complexes exhibit both similar and distinctive spectral features over the range of ~1000–1900 cm-1. The IRMPD spectra of the Li+(cytosine), Na+(cytosine), and K+(cytosine) complexes are relatively simple but exhibit changes in the shape and shifts in the positions of several bands that correlate with the size of the alkali metal cation. The IRMPD spectra of the Rb+(cytosine) and Cs+(cytosine) complexes are much richer as distinctive new IR bands are observed, and the positions of several bands continue to shift in relation to the size of the metal cation. The measured IRMPD spectra are compared to linear IR spectra of stable low-energy tautomeric conformations calculated at the B3LYP/def2-TZVPPD level of theory to identify the conformations accessed in the experiments. These comparisons suggest that the evolution in the features in the IRMPD action spectra with the size of the metal cation, and the appearance of new bands for the larger metal cations, are the result of the variations in the intensities at which these complexes can be generated and the strength of the alkali metal cation-cytosine binding interaction, not the presence of multiple tautomeric conformations. Only a single tautomeric conformation is accessed for all five alkali metal cation–cytosine complexes, where the alkali metal cation binds to the O2 and N3 atoms of the canonical amino-oxo tautomer of cytosine, M+(C1). Figure
? 相似文献
26.
27.
28.
29.
The thermal, unimolecular elimination of HF from CH3CF3 was studied by three different groups over the temperature range 1000° to 1800°K. While the reported kinetic parameters varied greatly, it is shown here that these data may be satisfactorily correlated in terms of a four-center transition state. This correlation results in ΔE = 69.2 kcal/mol, and log (k/s?1) = 14.6 – 72.6/θ. These results may then be combined with the kinetics of the chemically activated elimination of HF from CH3CF3 formed by the recombination of methyl and trifluoromethyl radicals. The data from three different laboratories are shown to be in excellent agreement. These data, combined with extant thermal data, yield as a best value DH(CH3? CF3) = 99.6 ± 1.1 kcal/mol. This gives the unexpectedly high value of DH298°(CH3? CF3) = 101.2 ± 1.1 kcal/mol. It is suggested that dipoledipole interactions, primarily in CH3CF3, account for this surprisingly strong C? C bond dissociation energy. These results also yield δH(CH3CF3; g, 298) = ?178.6 ± 1.5 kcal/mol. 相似文献
30.
Predicting and characterizing the crystal structure of materials is a key problem in materials research and development. It is typically addressed with highly accurate quantum mechanical computations on a small set of candidate structures, or with empirical rules that have been extracted from a large amount of experimental information, but have limited predictive power. In this Letter, we transfer the concept of heuristic rule extraction to a large library of ab initio calculated information, and we demonstrate that this can be developed into a tool for crystal structure prediction. 相似文献