全文获取类型
收费全文 | 1032篇 |
免费 | 21篇 |
国内免费 | 3篇 |
专业分类
化学 | 622篇 |
晶体学 | 9篇 |
力学 | 15篇 |
数学 | 108篇 |
物理学 | 302篇 |
出版年
2020年 | 7篇 |
2019年 | 7篇 |
2018年 | 5篇 |
2017年 | 6篇 |
2016年 | 16篇 |
2015年 | 22篇 |
2014年 | 22篇 |
2013年 | 38篇 |
2012年 | 40篇 |
2011年 | 48篇 |
2010年 | 24篇 |
2009年 | 23篇 |
2008年 | 43篇 |
2007年 | 47篇 |
2006年 | 46篇 |
2005年 | 60篇 |
2004年 | 36篇 |
2003年 | 43篇 |
2002年 | 26篇 |
2001年 | 31篇 |
2000年 | 30篇 |
1999年 | 28篇 |
1998年 | 15篇 |
1997年 | 9篇 |
1996年 | 23篇 |
1995年 | 30篇 |
1994年 | 19篇 |
1993年 | 19篇 |
1992年 | 32篇 |
1991年 | 10篇 |
1990年 | 15篇 |
1989年 | 6篇 |
1988年 | 6篇 |
1987年 | 23篇 |
1986年 | 12篇 |
1985年 | 19篇 |
1984年 | 8篇 |
1983年 | 10篇 |
1982年 | 5篇 |
1981年 | 9篇 |
1980年 | 12篇 |
1978年 | 8篇 |
1977年 | 7篇 |
1976年 | 12篇 |
1975年 | 10篇 |
1974年 | 13篇 |
1973年 | 21篇 |
1972年 | 5篇 |
1970年 | 5篇 |
1969年 | 8篇 |
排序方式: 共有1056条查询结果,搜索用时 31 毫秒
71.
The structure of the complex, [Fe2(II)Fe2(III)(HCOO)10(C6H7N6)n, (1) exhibits a neutral two-dimensional layer network of alternating iron(II) and iron(III) ions, bridged equatorially by formate groups. All iron atoms are octahedrally coordinated, with iron(III) coordinating axially to one gamma-picoline and one formate group, while the iron(II) centers interact axially with two gamma-picoline groups, above and below the layer plane. The complex crystallizes in the triclinic space group P1 at all studied temperatures [at 120 K, the cell dimensions are: a = 10.228(1), b = 12.071(1), c = 12.072(1) A, alpha = 89.801(2), beta = 71.149(2), gamma = 73.371(2) degrees]. An intralayer antiferromagnetic exchange interaction of J = -2.8 cm(-1) between iron(II) and iron(III) was observed in the magnetic studies. Decreasing the temperature to close to 20 K causes a magnetic-ordering phenomenon to occur and a low-temperature phase with a long-range antiferromagnetic spin orientation appears. The magnetic phase transition was confirmed by M?ssbauer spectroscopic studies at temperatures above and below the critical temperature. Structural information of 1 from synchrotron X-ray diffraction data collected at room temperature and 16 K suggests that the antiferromagnetic ordering is caused by an enhanced pi-pi interaction between chi-picoline groups from adjacent layers. 相似文献
72.
Petersson B Nielsen BB Rasmussen H Larsen IK Gajhede M Nielsen PE Kastrup JS 《Journal of the American Chemical Society》2005,127(5):1424-1430
The X-ray structure of a partly self-complementary peptide nucleic acid (PNA) decamer (H-GTAGATCACT-l-Lys-NH(2)) to 2.60 A resolution is reported. The structure is mainly controlled by the canonical Watson-Crick base pairs formed by the self-complementary stretch of four bases in the middle of the decamer (G(4)A(5)T(6)C(7)). One right- and one left-handed Watson-Crick duplex are formed. The two PNA units C(9)T(10) change helical handedness, so that each PNA strand contains both a right- and a left-handed section. The changed handedness in C(9)T(10) allows formation of Hoogsteen hydrogen bonding between C(9)T(10) and G(4)A(5) of a PNA strand in an adjacent Watson-Crick double helix of the same handedness. Thereby, a PNA-PNA-PNA triplex is formed. The PNA unit A(3) forms a noncanonical base pair with A(8) in a symmetry-related strand of opposite handedness; the base pair is of the A-A reverse Hoogsteen type. The structural diversity of this PNA demonstrates how the PNA backbone is able to adapt to structures governed by the stacking and hydrogen-bonding interactions between the nucleobases. The crystal structure further shows how PNA oligomers containing limited sequence complementarity may form complex hydrogen-bonding networks. 相似文献
73.
Bond AD Derossi S Jensen F Larsen FB McKenzie CJ Nelson J 《Inorganic chemistry》2005,44(17):5987-5989
Treatment of cryptand L(1) with Cu(II) generates a H3O2(-)-bridged dicopper(II) cryptate, 2, where the guest anion has responded to steric constraint by a significant shortening of the O-O distance to 2.325(9) A; computational optimization at the B3LYP/6-31(d) level suggests that the bridging O-H...O H-bond is bent (approximately 157 degrees) but that the barrier to interchange of the bridging H atom is low (<4 kJ mol(-1)). This cryptate, rather than the [Cu2L(1)muCN]3+ species recently claimed to derive from cleavage of the C-C bond of the solvent, is the product of acetonitrile recrystallization of the initially formed reaction product, 1. 相似文献
74.
Øystein Stakkestad Anja CV Larsen Anne-Katrine Kvissel Sissel Eikvar Sigurd Ørstavik Bjørn S Skålhegg 《BMC biochemistry》2011,12(1):7
Background
Protein kinase A type I (PKAI) and PKAII are expressed in most of the eukaryotic cells examined. PKA is a major receptor for cAMP and specificity is achieved partly through tissue-dependent expression and subcellular localization of subunits with different biochemical properties. In addition posttranslational modifications help fine tune PKA activity, distribution and interaction in the cell. In spite of this the functional significance of two forms of PKA in one cell has not been fully determined. Here we have tested the ability of PKAI and PKAII formed by expression of the regulatory (R) subunits RIα or RIIα in conjunction with Cα1 or Cβ2 to activate a co-transfected luciferace reporter gene, controlled by the cyclic AMP responsive element-binding protein (CREB) in vivo. 相似文献75.
76.
Hill MP Carroll EC Vang MC Addington TA Toney MD Larsen DS 《Journal of the American Chemical Society》2010,132(47):16953-16961
The mechanisms of pyridoxal 5'-phosphate (PLP)-dependent enzymes require substrates to form covalent "external aldimine" intermediates, which absorb light strongly between 410 and 430 nm. Aspartate aminotransferase (AAT) is a prototypical PLP-dependent enzyme that catalyzes the reversible interconversion of aspartate and α-ketoglutarate with oxalacetate and glutamate. From kinetic isotope effects studies, it is known that deprotonation of the aspartate external aldimine C(α)-H bond to give a carbanionic quinonoid intermediate is partially rate limiting in the thermal AAT reaction. We show that excitation of the 430-nm external aldimine absorption band increases the steady-state catalytic activity of AAT, which is attributed to the photoenhancement of C(α)-H deprotonation on the basis of studies with Schiff bases in solution. Blue light (250 mW) illumination gives an observed 2.3-fold rate enhancement for WT AAT activity, a 530-fold enhancement for the inactive K258A mutant, and a 58600-fold enhancement for the PLP-Asp Schiff base in water. These different levels of enhancement correlate with the intrinsic reactivities of the C(α)-H bond in the different environments, with the less reactive Schiff bases exhibiting greater enhancement. Time-resolved spectroscopy, ranging from femtoseconds to minutes, was used to investigate the nature of the photoactivation of C(α)-H bond cleavage in PLP-amino acid Schiff bases both in water and bound to AAT. Unlike the thermal pathway, the photoactivation pathway involves a triplet state with a C(α)-H pK(a) that is estimated to be between 11 and 19 units lower than the ground state for the PLP-Val Schiff base in water. 相似文献
77.
The scope of the palladium-catalyzed carboamination reaction for the synthesis of 2-substituted pyrrolidines, piperidines, and morpholines was investigated. Formation of a 2,4-disubstituted pyrrolidine proceeded in high yield but with a diastereoisomeric ratio of only 2:5, favoring the cis-isomer. The diastereoselectivity is hence significantly smaller than that observed previously in the formation of 2,3- and 2,5-disubstituted pyrrolidines. The yields of substituted piperidines and morpholines were lowered by competing Heck arylation reactions. Both the N-substituent and the choice of phosphine ligand for the palladium-catalyzed reaction were determining for the outcome. 相似文献
78.
Poulsen RD Jørgensen MR Overgaard J Larsen FK Morgenroth W Graber T Chen YS Iversen BB 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(35):9775-9790
Three high-quality single-crystal X-ray diffraction data sets have been measured under very different conditions on a structurally simple, but magnetically complex, coordination polymer, [Mn(HCOO)(2)(H(2)O)(2)](infinity) (1). The first data set is a conventional 100(2) K Mo(Kalpha) data set, the second is a very high resolution 100(2) K data set measured on a second-generation synchrotron source, while the third data set was measured with a tiny crystal on a high brilliance third-generation synchrotron source at 16(2) K. Furthermore, the magnetic susceptibility (chi) and the heat capacity (C(p)) have been measured from 2 to 300 K on pressed powder. The charge density of 1 was determined from multipole modeling of the experimental structure factors, and overall there is good agreement between the densities obtained separately from the three data sets. When considering the fine density features, the two 100 K data sets agree well with each other, but show small differences to the 16 K data set. Comparison with ab initio theory suggests that the 16 K APS data set provides the most accurate density. Topological analysis of the metal-ligand bonding, experimental 3d orbital populations on the Mn atoms, and Bader atomic charges indicate quite ionic, high-spin metal atoms. This picture is supported by the effective moment estimated from the magnetization measurements (5.840(2) mu(B)), but it is at variance with earlier spin density measurements from polarized neutron diffraction. The magnetic ordering originates from superexchange involving covalent interactions with the ligands, and non-ionic effects are observed in the static deformation density maps as well as in plots of the valence shell charge concentrations. Overall, the present study provides a benchmark charge density that can be used in comparison with future metal formate dihydrate charge densities. 相似文献
79.
Andersen D Storz T Liu P Wang X Li L Fan P Chen X Allgeier A Burgos A Tedrow J Baum J Chen Y Crockett R Huang L Syed R Larsen RD Martinelli M 《The Journal of organic chemistry》2007,72(25):9648-9655
Melanin-concentrating hormone (MCH) is implicated in the feeding behavior in mammals affording a potential target to control overeating in people. Compound 1 (AMG 076) has been identified as a potent MCHr1 antagonist for the treatment of obesity. A synthesis suitable for the large-scale preparation of this lead candidate was developed to support preclinical studies. A Robinson annulation of benzylpiperidone and resolution of the desired enone from a mixture of the diastereomers afforded key intermediate 6 after a stereoselective hydrogenation. Subsequent Fischer indole synthesis with hydrazine 5 then provided the advanced intermediate, indole 2. Two complementary reductive amination strategies employing either aldehyde 3 or lactol 4 led to the synthesis of title compound 1. 相似文献
80.
[chemical reaction: see text]. Prior to detachment of compounds synthesized on sulfonamide based safety-catch linkers, the molecular anchor has to be activated. This is achieved by alkylation of the nitrogen atom of the N-acylsulfonamide using different established protocols. As an addition to the existing repertoire of activating reagents, we suggest the use of O,N,N'-trialkylisoureas. Besides the demonstration of the feasibility of these mild alkylating agents for this purpose, custom-tailored novel O,N,N'-trialkylisoureas prepared from electron-deficient alcohols are reported. 相似文献