全文获取类型
收费全文 | 1510篇 |
免费 | 57篇 |
国内免费 | 8篇 |
专业分类
化学 | 1132篇 |
晶体学 | 9篇 |
力学 | 42篇 |
数学 | 175篇 |
物理学 | 217篇 |
出版年
2023年 | 12篇 |
2022年 | 7篇 |
2021年 | 14篇 |
2020年 | 16篇 |
2019年 | 26篇 |
2018年 | 19篇 |
2017年 | 8篇 |
2016年 | 29篇 |
2015年 | 38篇 |
2014年 | 23篇 |
2013年 | 80篇 |
2012年 | 76篇 |
2011年 | 79篇 |
2010年 | 53篇 |
2009年 | 36篇 |
2008年 | 84篇 |
2007年 | 92篇 |
2006年 | 86篇 |
2005年 | 88篇 |
2004年 | 86篇 |
2003年 | 58篇 |
2002年 | 57篇 |
2001年 | 21篇 |
2000年 | 19篇 |
1999年 | 21篇 |
1998年 | 18篇 |
1997年 | 16篇 |
1996年 | 27篇 |
1995年 | 13篇 |
1994年 | 16篇 |
1993年 | 11篇 |
1992年 | 12篇 |
1991年 | 10篇 |
1990年 | 18篇 |
1989年 | 14篇 |
1988年 | 15篇 |
1987年 | 7篇 |
1986年 | 12篇 |
1985年 | 27篇 |
1984年 | 21篇 |
1983年 | 20篇 |
1982年 | 41篇 |
1981年 | 23篇 |
1980年 | 28篇 |
1979年 | 16篇 |
1978年 | 15篇 |
1977年 | 11篇 |
1976年 | 14篇 |
1975年 | 10篇 |
1974年 | 10篇 |
排序方式: 共有1575条查询结果,搜索用时 15 毫秒
41.
Andrew F. Kuntz Andrew W. Boynton Geoffrey A. David Kathryn E. Colyer John C. Poutsma 《Journal of the American Society for Mass Spectrometry》2002,13(1):72-81
The proton affinity of proline analogs, L-azetidine-2-carboxylic acid (Aze), L-proline (Pro), and L-pipecolic acid (Pip), have been measured using the Armentrout modification of the extended kinetic method in a quadrupole ion trap instrument. Experimental values of 223.0 +/- 1.5, 224.9 +/- 1.6, and 225.6 +/- 1.6 kcal/mol have been determined for the 298K proton affinities of Aze, Pro, and Pip respectively. High level theoretical calculations using both MP2 and B3LYP methods at a variety of basis sets were carried out in order to give theoretical predictions for the 298 K proton affinity and gas phase basicity of all three analogs. Recommended values for the gas phase basicity and proton affinity for proline based on our work and other recent determinations are 216 +/- 2 and 224 +/- 2 kcal/mol. 相似文献
42.
The preparation of the η4-4-2,3,5,6-tetramethyl-1,4-benzoquinonecomplex [CO(C5Me5)(C10H12O2)] (I) is reported. Complex I undergoesreversible protonation to yield the 2-6-η-4-hydroxy-1-oxo-2,3,5,6-tetramethylcyclohexadienyl complex [Co(C5Me5)(C10H13O2)BF4 (II) and diprotonation to yield the η6-6-1,4-dihydroxy-2,3,5,6-tetramethylbenzene complex [Co(C5Me5)(C10H14O2)] (BF4)2 (III). Methylation of complex I with MeI/AgPF6 gives the 2---6-η-4-methoxy-1-oxo-2,3,5,6-tetramethylcyclohexadienyl complex [Co(C5Me5)(C11H15O2])PF6 (IV). In trifluoroacetic acid solution complex IV is protonated to form the η6-1-hydroxy-4-methoxy-2,3,5,6-tetramethylbenzene cation [Co(C5Me5)-(C11H16O2)]2+ 相似文献
43.
William J. Orts Geoffrey A. R. Nobes Gregory M. Glenn Gregory M. Gray Syed Imam Bor‐Sen Chiou 《先进技术聚合物》2007,18(8):629-635
Blends of thermoplastic starch with poly(ethylene‐co‐vinyl alcohol) copolymer (EVOH) were melt extruded with water/glycerol as plasticizer and a series of amino acid additives. The biggest factor in end‐use mechanical properties proved to be the relative humidity (RH) during storage. Plasticized starch‐EVOH blends stored at 0 and 50% RH changed significantly over time, with, for example, the tensile strength (TS) of the glycerol‐plasticized blend increasing from 4.7 to 26.3 MPa over 8 weeks when maintained at 0% RH. In contrast, the TS of this same sample stored at 75% RH remained unchanged for 8 weeks. Amino acids provided relatively minor, but significant changes in mechanical properties with time. Based on TS, elongation‐to‐break, and modulus, it may be concluded that β‐alanine, sarcosine, and L ‐proline were more effective than glycerol at maintaining strong flexible blends. Increases in crystallinity and changes in morphology with time, as described by modulated DSC were correlated to these changes in mechanical properties. Published in 2007 by John Wiley & Sons, Ltd. 相似文献
44.
Self-assembled monolayers (SAMs) obtained from 1-(10-acetylsulfanyldecyl)-4-[2-(4-dimethylaminophenyl)vinyl]quinolinium iodide exhibit asymmetric current-voltage (I-V) characteristics. The rectification may be reversibly switched: it is suppressed when the film is exposed to HCl vapor, the intramolecular charge-transfer axis being inhibited by protonation, but restored when exposed to NH(3). The behavior is intrinsic to the donor-(pi-bridge)-acceptor moiety, and ambiguity in the assignment has been excluded by matching the alkyl tails on the substrate and contacting STM tip to locate the chromophore midway between the electrodes: Au-S-C(10)H(21)//D-pi-A-C(10)H(20)-S-Au. Films contacted by gold tips exhibit rectification ratios of ca. 18 at +/-1 V, whereas those contacted by pentanethiolate (Au-S-C(5)H(11))- and decanethiolate (Au-S-C(10)H(21))-coated tips have corresponding ratios of ca. 11 and 5, respectively. The I-V curves are different, but when adjusted for thickness the current versus electric field dependence is indistinguishable. Seven dyes are reported: SAMs with sterically hindered D-pi-A moieties, in which the donor and acceptor are twisted out of plane, exhibit rectification, whereas those that are planar or have a weak donor-acceptor combination do not. 相似文献
45.
46.
David J. Barsky Geoffrey R. Grimmett Charles M. Newman 《Probability Theory and Related Fields》1991,90(1):111-148
Renormalization arguments are developed and applied to independent nearest-neighbor percolation on various subsets of
d
,d2, yielding:
Corollaries of these results include uniqueness of the infinite cluster for such 's and sufficiency of the following for proving continuity of the full-space phase transition: showing that percolation in the full-space at densityp implies percolation in the half-space at thesame density. 相似文献
| Equality of the critical densities,p c (), for a half-space, quarter-space, etc., and (ford>2) equality with the limit of slab critical densities. |
| Continuity of the phase transition for the half-space, quarter-space, etc.; i.e., vanishing of the percolation probability, (p), atp=p c (). |
47.
The rationale for a new class of HMG CoA reductase inhibitors, represented by ,ga-difluoroketones 3 and 4, is described. The syntheses of 3, 4, and their nonfluorinated analogue 5 are presented. 相似文献
48.
Plieger PG Burrell AK Jameson GB Officer DL 《Dalton transactions (Cambridge, England : 2003)》2004,(2):319-326
A new series of meso-substituted diaryl free-base and metalloporphyrins have been prepared. Each arene has been substituted with both a methyl group in the ortho position and a formyl group in the meta position. Rotation of the arene units is prevented at room temperature due to the steric restrictions imposed by the flanking methyl groups at the porphyrin beta-pyrrolic positions on the methyl groups at the ortho position on the meso-substituted arene unit. This allowed the alpha alpha and alpha beta atropisomers of this porphyrin to be separated and characterised. X-Ray crystallographic determination of the structure of the free-base porphyrin revealed a very flat porphyrin core. Metallation resulted in the isolation and characterisation of the nickel, zinc and copper derivatives. The assignments of the alpha alpha and alpha beta isomers are confirmed by X-ray crystallographic determination of the structures of the Cu(II) analogues. The copper alpha alpha structure exhibits a very twisted porphyrin core, the copper alpha beta structure is also distorted, but to a lesser degree. The activation energy for rotation has been calculated for each of the 2H, Ni and Zn derivatives. The energy required to rotate the arene ring increases in the order Ni < Zn approximately 2H. No significant difference in the free energy of rotation was observed between experiments carried out with the alpha alpha and small alpha beta isomers. 相似文献
49.
α-Oxo-carboxylic acids undergo photo-oxidative decarboxylation from both C-1 and C-2 positions, and reaction does not involve singlet oxygen: a mechanism involving an electron transfer reaction is postulated. 相似文献
50.
Hui Yang Xing Chen Guoxiang Hu Wan-Ting Chen Siobhan J. Bradley Weijie Zhang Gaurav Verma Thomas Nann De-en Jiang Paul E. Kruger Xiangke Wang He Tian Geoffrey I. N. Waterhouse Shane G. Telfer Shengqian Ma 《Chemical science》2020,11(13):3523
Optimizing interfacial contacts and thus electron transfer phenomena in heterogeneous electrocatalysts is an effective approach for enhancing electrocatalytic performance. Herein, we successfully synthesized ultrafine β-Mo2C nanoparticles confined within hollow capsules of nitrogen-doped porous carbon (β-Mo2C@NPCC) and found that the surface layer of molybdenum atoms was further oxidized to a single Mo–O surface layer, thus producing intimate O–Mo–C interfaces. An arsenal of complementary technologies, including XPS, atomic-resolution HAADF-STEM, and XAS analysis clearly reveals the existence of O–Mo–C interfaces for these surface-engineered ultrafine nanostructures. The β-Mo2C@NPCC electrocatalyst exhibited excellent electrocatalytic activity for the hydrogen evolution reaction (HER) in water. Theoretical studies indicate that the highly accessible ultrathin O–Mo–C interfaces serving as the active sites are crucial to the HER performance and underpinned the outstanding electrocatalytic performance of β-Mo2C@NPCC. This proof-of-concept study opens a new avenue for the fabrication of highly efficient catalysts for HER and other applications, whilst further demonstrating the importance of exposed interfaces and interfacial contacts in efficient electrocatalysis.Ultrafine β-Mo2C nanostructures encapsulated in N-doped carbon capsules featuring O–Mo–C interfaces as the active sites for HER have been unveiled. 相似文献