全文获取类型
收费全文 | 805篇 |
免费 | 34篇 |
国内免费 | 8篇 |
专业分类
化学 | 495篇 |
晶体学 | 5篇 |
力学 | 12篇 |
数学 | 147篇 |
物理学 | 188篇 |
出版年
2023年 | 3篇 |
2022年 | 9篇 |
2021年 | 10篇 |
2020年 | 19篇 |
2019年 | 18篇 |
2018年 | 15篇 |
2017年 | 13篇 |
2016年 | 20篇 |
2015年 | 22篇 |
2014年 | 26篇 |
2013年 | 46篇 |
2012年 | 55篇 |
2011年 | 80篇 |
2010年 | 44篇 |
2009年 | 29篇 |
2008年 | 47篇 |
2007年 | 54篇 |
2006年 | 76篇 |
2005年 | 57篇 |
2004年 | 62篇 |
2003年 | 50篇 |
2002年 | 27篇 |
2001年 | 13篇 |
2000年 | 4篇 |
1999年 | 8篇 |
1998年 | 9篇 |
1997年 | 7篇 |
1996年 | 5篇 |
1995年 | 5篇 |
1994年 | 5篇 |
1993年 | 5篇 |
1992年 | 1篇 |
1991年 | 1篇 |
1990年 | 1篇 |
1985年 | 1篇 |
排序方式: 共有847条查询结果,搜索用时 10 毫秒
111.
Unusually intense near-infrared (near-IR) photoluminescence has been observed from mixed solutions of C70 and palladium octaethylporphyrin (PdOEP). The novel emission has a spectrum similar to C70 phosphorescence and an intensity that is approximately 20 times greater than that of C70 fluorescence. The emitting species is identified as a noncovalently bound, short-lived triplet exciplex of C70 with PdOEP. The emission is essentially C70 phosphorescence intensified by spin-orbit coupling from the Pd atom in the nearby metalloporphyrin. This supramolecular heavy atom effect increases the C70 emissive quantum yield to approximately 1 x 10(-2) in degassed hexane solution at room temperature. The radiative rate constant is enhanced by a factor of 10(5), to approximately 7 x 10(4) s(-1), which is a value that exceeds the phosphorescence rate constant of PdOEP. Comparative studies in a rigid poly(methyl methacrylate) (PMMA) matrix show that the excited state of the static C70-PdOEP complex decays in approximately 150 ns. A Job's plot analysis shows that the complex has a 1:1 stoichiometry. It forms dynamically in solution and is relatively weakly bound, with an estimated equilibrium constant near 100 M(-1). Qualitatively similar supramolecular heavy atom effects were also observed for complexes of PdOEP with C60 and fullerene derivatives. 相似文献
112.
113.
We report on the glass-forming ability and devitrification behavior of Zr60Cu30Al10, Zr60Cu25Al10Fe5 and Zr62.5Cu22.5Al10Fe5 bulk glass-forming alloys on heating. The effect of Fe addition on the structure of Zr–Al–Cu alloys is also discussed. Crystallization kinetics and structural changes in the glassy alloys were studied using X-ray diffraction, transmission electron microscopy, differential scanning and isothermal calorimetry methods. The results indicate that good glass-formers, such as Zr62.5Cu22.5Al10Fe5, are located somewhat beyond the equilibrium eutectic point. Possible phase separation in the supercooled liquid on heating and electron beam-induced in situ crystallization are observed and discussed. 相似文献
114.
115.
Dr. Stefan van der Vorm Thomas Hansen Dr. Erwin R. van Rijssel Rolf Dekkers Jerre M. Madern Prof. Dr. Herman S. Overkleeft Dr. Dmitri V. Filippov Prof. Dr. Gijsbert A. van der Marel Dr. Jeroen D. C. Codée 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(29):7149-7157
The 3D shape of glycosyl oxocarbenium ions determines their stability and reactivity and the stereochemical course of SN1 reactions taking place on these reactive intermediates is dictated by the conformation of these species. The nature and configuration of functional groups on the carbohydrate ring affect the stability of glycosyl oxocarbenium ions and control the overall shape of the cations. We herein map the stereoelectronic substituent effects of the C2-azide, C2-fluoride and C4-carboxylic acid ester on the stability and reactivity of the complete suite of diastereoisomeric furanoses by using a combined computational and experimental approach. Surprisingly, all furanosyl donors studied react in a highly stereoselective manner to provide the 1,2-cis products, except for the reactions in the xylose series. The 1,2-cis selectivity for the ribo-, arabino- and lyxo-configured furanosides can be traced back to the lowest-energy 3E or E3 conformers of the intermediate oxocarbenium ions. The lack of selectivity for the xylosyl donors is related to the occurrence of oxocarbenium ions adopting other conformations. 相似文献
116.
Alex van der Ham Thomas Hansen Dr. Gerrit Lodder Dr. Jeroen D. C. Codée Dr. Trevor A. Hamlin Dr. Dmitri V. Filippov 《Chemphyschem》2019,20(16):2103-2109
Lithium ion selective crown ethers have been the subject of much research for a multitude of applications. Current research is aimed at structurally rigidifying crown ethers, as restructuring of the crown ether ring upon ion binding is energetically unfavorable. In this work, the lithium ion binding ability of the relatively rigid 8-crown-4 was investigated both computationally by density functional theory calculations and experimentally by 1H and 7Li NMR spectroscopy. Although both computational and experimental results showed 8-crown-4 to bind lithium ion, this binding was found to be weak compared to larger crown ethers. The computational analysis revealed that the complexation is driven by enthalpy rather than entropy, illustrating that rigidity is only of nominal importance. To elucidate the origin of the favorable interaction of lithium ion with crown ethers, activation strain analyses and energy decomposition analyses were performed pointing to the favorable interaction being mainly electrostatic in nature. 8-crown-4 presents the smallest crown ether reported to date capable of binding lithium ion, possessing two distinct conformations from which it is able to do so. 相似文献
117.
We extract the bulk viscosity of hot quark–gluon matter in the presence of light quarks from the recent lattice data on the QCD equation of state. For that purpose we extend the sum rule analysis by including the contribution of light quarks. We also discuss the universal properties of bulk viscosity in the vicinity of a second-order phase transition, as it might occur in the chiral limit of QCD at fixed strange quark mass and most likely does occur in two-flavor QCD. We point out that a chiral transition in the O(4) universality class at zero baryon density as well as the transition at the chiral critical point which belongs to the Z(2) universality class both lead to the critical behavior of bulk viscosity. In particular, the latter universality class implies the divergence of the bulk viscosity, which may be used as a signature of the critical point. We discuss the physical picture behind the dramatic increase of bulk viscosity seen in our analysis, and devise possible experimental tests of related phenomena. 相似文献
118.
We establish an analogue of the Ikehara theorem for positive non-increasing functions convergent to zero. In particular, this provides a complete proof of the results formulated in Diekmann & Kaper (1978) [5] and Carr & Chmaj (2004) [1], which are widely used nowadays to prove the uniqueness of traveling waves for various reaction–diffusion equations. 相似文献
119.
A General Approach Towards Triazole‐Linked Adenosine Diphosphate Ribosylated Peptides and Proteins 下载免费PDF全文
Qiang Liu Dr. Hans A. V. Kistemaker Dr. Sagar Bhogaraju Prof. Dr. Ivan Dikic Prof. Dr. Herman S. Overkleeft Prof. Dr. Gijsbert A. van der Marel Prof. Dr. Huib Ovaa Dr. Gerbrand J. van der Heden van Noort Dr. Dmitri V. Filippov 《Angewandte Chemie (International ed. in English)》2018,57(6):1659-1662
Current methods to prepare adenosine diphosphate ribosylated (ADPr) peptides are not generally applicable due to the labile nature of this post‐translational modification and its incompatibility with strong acidic conditions used in standard solid‐phase peptide synthesis. A general strategy is presented to prepare ADPr peptide analogues based on a copper‐catalyzed click reaction between an azide‐modified peptide and an alkyne‐modified ADPr counterpart. The scope of this approach was expanded to proteins by preparing two ubiquitin ADPr analogues carrying the biological relevant α‐glycosidic linkage. Biochemical validation using Legionella effector enzyme SdeA shows that clicked ubiquitin ADPr is well‐tolerated and highlights the potential of this strategy to prepare ADPr proteins. 相似文献
120.
Dmitri A. Shmel'kin 《Geometriae Dedicata》1998,72(2):189-216
In order to describe explicitly the algebra of invariants for a non-connected reductive subgroup G GL(V) we apply the method of strata. For this we describe codimension 1 strata of the quotient V//G and study the normality property of their closures. We find some criteria for k[V]G to be polynomial or a hypersurface. Then we apply these results to complete the classification [Sh] of nonconnected simple groups G such that k[V]G is polynomial. 相似文献