全文获取类型
收费全文 | 468篇 |
免费 | 20篇 |
国内免费 | 2篇 |
专业分类
化学 | 307篇 |
晶体学 | 1篇 |
力学 | 21篇 |
数学 | 85篇 |
物理学 | 76篇 |
出版年
2023年 | 4篇 |
2022年 | 8篇 |
2021年 | 9篇 |
2020年 | 17篇 |
2019年 | 9篇 |
2018年 | 11篇 |
2017年 | 10篇 |
2016年 | 15篇 |
2015年 | 9篇 |
2014年 | 16篇 |
2013年 | 32篇 |
2012年 | 47篇 |
2011年 | 54篇 |
2010年 | 23篇 |
2009年 | 18篇 |
2008年 | 40篇 |
2007年 | 19篇 |
2006年 | 26篇 |
2005年 | 31篇 |
2004年 | 17篇 |
2003年 | 8篇 |
2002年 | 10篇 |
2001年 | 5篇 |
2000年 | 3篇 |
1999年 | 4篇 |
1998年 | 4篇 |
1996年 | 1篇 |
1995年 | 2篇 |
1994年 | 1篇 |
1993年 | 2篇 |
1990年 | 1篇 |
1989年 | 1篇 |
1985年 | 3篇 |
1984年 | 2篇 |
1983年 | 1篇 |
1982年 | 2篇 |
1981年 | 1篇 |
1979年 | 3篇 |
1978年 | 2篇 |
1977年 | 3篇 |
1976年 | 2篇 |
1974年 | 2篇 |
1972年 | 2篇 |
1971年 | 1篇 |
1970年 | 1篇 |
1968年 | 2篇 |
1955年 | 1篇 |
1931年 | 1篇 |
1910年 | 2篇 |
1909年 | 1篇 |
排序方式: 共有490条查询结果,搜索用时 15 毫秒
81.
The first general synthesis of boron-substituted 1,2-dihydro-1,2-azaborines is described. The versatile 1,2-dihydro-1,2-azaborine precursor 4 is synthesized through a ring-closing metathesis-oxidation sequence. Treatment of 4 with a wide range of anionic nucleophiles furnishes the desired adducts 5 in good yields. The scope includes hydrogen- and a variety of carbon- and heteroatom-based nucleophiles. Furthermore, the boron-containing isostere (7) of the potent hypolipidemic agent, methyl 2-ethylphenoxyacetate (8), is readily prepared through our method. 相似文献
82.
83.
The interaction of the nitric oxide ions NO+ and NO- with benzene (C6H6) and the aromatic R-groups of the amino acids phenylalanine (Phe), tyrosine (Tyr), histidine (His), and tryptophan (Trp) have been examined using the DFT method B3LYP and the conventional electron correlation method MP2. In particular, the structures and complexation energies of the resulting half-sandwich Ar...NO+/- and sandwich [Ar...NO...Ar]+/- complexes have been considered. For the Ar...NO+ complexes, the presence of an electron rich heteroatom within or attached to the ring is found to not preclude the cation...pi bound complex from being the most stable. Furthermore, unlike the anionic complexes, the pi...cation...pi ([Ar...NO...Ar]+) complexes do not correspond to a "doubling" of the parent half-sandwich. 相似文献
84.
Jesse Hoey 《Entropy (Basel, Switzerland)》2021,23(11)
In this paper, I investigate a connection between a common characterisation of freedom and how uncertainty is managed in a Bayesian hierarchical model. To do this, I consider a distributed factorization of a group’s optimization of free energy, in which each agent is attempting to align with the group and with its own model. I show how this can lead to equilibria for groups, defined by the capacity of the model being used, essentially how many different datasets it can handle. In particular, I show that there is a “sweet spot” in the capacity of a normal model in each agent’s decentralized optimization, and that this “sweet spot” corresponds to minimal free energy for the group. At the sweet spot, an agent can predict what the group will do and the group is not surprised by the agent. However, there is an asymmetry. A higher capacity model for an agent makes it harder for the individual to learn, as there are more parameters. Simultaneously, a higher capacity model for the group, implemented as a higher capacity model for each member agent, makes it easier for a group to integrate a new member. To optimize for a group of agents then requires one to make a trade-off in capacity, as each individual agent seeks to decrease capacity, but there is pressure from the group to increase capacity of all members. This pressure exists because as individual agent’s capacities are reduced, so too are their abilities to model other agents, and thereby to establish pro-social behavioural patterns. I then consider a basic two-level (dual process) Bayesian model of social reasoning and a set of three parameters of capacity that are required to implement such a model. Considering these three capacities as dependent elements in a free energy minimization for a group leads to a “sweet surface” in a three-dimensional space defining the triplet of parameters that each agent must use should they hope to minimize free energy as a group. Finally, I relate these three parameters to three notions of freedom and equality in human social organization, and postulate a correspondence between freedom and model capacity. That is, models with higher capacity, have more freedom as they can interact with more datasets. 相似文献
85.
We say a 0–1 matrix A avoids a matrix P if no submatrix of A can be transformed into P by changing some ones to zeroes. We call P an m-tuple permutation matrix if P can be obtained by replacing each column of a permutation matrix with m copies of that column. In this paper, we investigate n×n matrices that avoid P and the maximum number ex(n,P) of ones that they can have. We prove a linear bound on ex(n,P) for any 2-tuple permutation matrix P, resolving a conjecture of Keszegh [B. Keszegh, On linear forbidden matrices, J. Combin. Theory Ser. A 116 (1) (2009) 232–241]. Using this result, we obtain a linear bound on ex(n,P) for any m-tuple permutation matrix P. Additionally, we demonstrate the existence of infinitely many minimal non-linear patterns, resolving another conjecture of Keszegh from the same paper. 相似文献
86.
Simple synthetic di-iron dithiolate complexes provide good models of the composition of the active site of the iron-iron hydrogenase enzymes. However, the formally Fe(I)Fe(I) complexes synthesized to date fail to reproduce the precise orientation of the diatomic ligands about the iron centers that is observed in the molecular structure of the reduced form of the enzyme active site. This structural difference is often used to explain the fact that the synthetic di-iron complexes are generally poor catalysts when compared to the enzyme. Herein, density functional theory computations are used for the rational design of synthetic complexes as structural models of the reduced form of the enzyme active site. These computations suggest several possible synthetic targets. The synthesis of complexes containing five-atom S-to-S linkers of the form S(CH2)2X(CH2)2S (X = CH2, NH, or O) or pendant functionalities attached to the three-carbon framework is one method. Another approach is the synthesis of asymmetrically substituted complexes, in which one iron center has strongly electron donating ligands and the adjacent iron center has strongly electron accepting ligands. The combination of a sterically demanding S-to-S linker and asymmetric substitution of the CO ligands is predicted to be a particularly effective synthetic target. 相似文献
87.
The dihydrogen adsorption isotherms of eight metal-organic frameworks (MOFs), measured at 77 K up to a pressure of 1 atm, have been examined for correlations with their structural features. All materials display approximately Type I isotherms with no hysteresis, and saturation was not reached for any of the materials under these conditions. Among the six isoreticular MOFs (IRMOFs) studied, the catenated materials exhibit the largest capacities on a molar basis, up to 9.8 H(2) per formula unit. The addition of functional groups (-Br, -NH(2), -C(2)H(4)-) to the phenylene links of IRMOF-1 (MOF-5), or their replacement with thieno[3,2-b]thiophene moieties in IRMOF-20, altered the adsorption behavior by a minor amount despite large variations in the pore volumes of the resulting materials. In contrast, replacement of the metal oxide units with those containing coordinatively unsaturated metal sites resulted in greater H(2) uptake. The enhanced affinities of these materials, MOF-74 and HKUST-1, were further demonstrated by calculation of the isosteric heats of adsorption, which were larger across much of the range of coverage examined, compared to those of representative IRMOFs. The results suggest that under low-loading conditions, the H(2) adsorption behavior of MOFs can be improved by imparting larger charge gradients on the metal oxide units and adjusting the link metrics to constrict the pore dimensions; however, a large pore volume is still a prerequisite feature. 相似文献
88.
The bicyclic core of octosyl acid A has been prepared using a diastereoselective acetylide addition and 6-endo selenoetherification as key steps. A detailed study of the selenoetherification reaction and difficulties encountered in the conversion of a phenyl group to a carboxylic acid will be discussed. 相似文献
89.
This paper examines unexplored correlations in the parameter spaces probed by recent ATLAS analyses for gluinos and squarks, addressing various shortcomings in the literature. Six 13 TeV ATLAS analyses based on 3.2 fb\(^{-1}\) of integrated luminosity are interpreted in the 19-parameter R-parity conserving phenomenological minimal supersymmetric extension to the Standard Model (pMSSM). The distinct regions covered by each search are independent of prior, and we reveal particularly striking complementarity between the 2–6 jets and Multi-b searches. In the leptonic searches, we identify better sensitivity to models than those used for analysis optimisation, notably a squark–slepton–wino scenario for the SS/3L search. Further, we show how collider searches for coloured states probe the structure of the pMSSM dark sector more extensively than the Monojet analysis alone, with sensitivity to parameter spaces that are challenging for direct detection experiments. 相似文献
90.
JH Engel Y Surendranath AP Alivisatos 《Journal of the American Chemical Society》2012,134(32):13200-13203
Semiconductor nanocrystal solids are attractive materials for active layers in next-generation optoelectronic devices; however, their efficient implementation has been impeded by the lack of precise control over dopant concentrations. Herein we demonstrate a chemical strategy for the controlled doping of nanocrystal solids under equilibrium conditions. Exposing lead selenide nanocrystal thin films to solutions containing varying proportions of decamethylferrocene and decamethylferrocenium incrementally and reversibly increased the carrier concentration in the solid by 2 orders of magnitude from their native values. This application of redox buffers for controlled doping provides a new method for the precise control of the majority carrier concentration in porous semiconductor thin films. 相似文献