全文获取类型
收费全文 | 1090篇 |
免费 | 47篇 |
国内免费 | 1篇 |
专业分类
化学 | 732篇 |
晶体学 | 7篇 |
力学 | 25篇 |
数学 | 228篇 |
物理学 | 146篇 |
出版年
2023年 | 5篇 |
2022年 | 11篇 |
2021年 | 14篇 |
2020年 | 16篇 |
2019年 | 22篇 |
2018年 | 20篇 |
2017年 | 21篇 |
2016年 | 40篇 |
2015年 | 43篇 |
2014年 | 44篇 |
2013年 | 50篇 |
2012年 | 88篇 |
2011年 | 73篇 |
2010年 | 52篇 |
2009年 | 39篇 |
2008年 | 75篇 |
2007年 | 81篇 |
2006年 | 71篇 |
2005年 | 69篇 |
2004年 | 38篇 |
2003年 | 26篇 |
2002年 | 32篇 |
2001年 | 14篇 |
2000年 | 16篇 |
1999年 | 14篇 |
1998年 | 9篇 |
1997年 | 9篇 |
1996年 | 9篇 |
1995年 | 6篇 |
1994年 | 11篇 |
1993年 | 6篇 |
1992年 | 5篇 |
1990年 | 5篇 |
1989年 | 6篇 |
1988年 | 10篇 |
1986年 | 4篇 |
1985年 | 10篇 |
1984年 | 9篇 |
1983年 | 7篇 |
1982年 | 5篇 |
1981年 | 11篇 |
1980年 | 4篇 |
1979年 | 2篇 |
1978年 | 4篇 |
1976年 | 6篇 |
1975年 | 7篇 |
1974年 | 4篇 |
1973年 | 2篇 |
1968年 | 3篇 |
1927年 | 2篇 |
排序方式: 共有1138条查询结果,搜索用时 0 毫秒
111.
Wout De Nolf Jakub Jaroszewicz Roberto Terzano Ole Christian Lind Brit Salbu Bart Vekemans Koen Janssens Gerald Falkenberg 《Spectrochimica Acta Part B: Atomic Spectroscopy》2009,64(8):775
The performance of a combined microbeam X-ray fluorescence/X-ray powder diffraction (XRF/XRPD) measurement station at Hamburger Synchrotronstrahlungslabor (HASYLAB) Beamline L is discussed in comparison to that at European Synchrotron Radiation Facility (ESRF) ID18F/ID22. The angular resolution in the X-ray diffractograms is documented when different combinations of X-ray source, optics and X-ray diffraction detectors are employed. Typical angular resolution values in the range 0.3–0.5° are obtained at the bending magnet source when a ‘pink’ beam form of excitation is employed. A similar setup at European Synchrotron Radiation Facility beamlines ID18F and ID22 allows to reach angular resolution values of 0.1–0.15°. In order to document the possibilities and limitations for speciation of metals in environmental materials by means of Hamburger Synchrotronstrahlungslabor Beamline L X-ray fluorescence/X-ray powder diffraction setup, two case studies are discussed, one involved in the identification of the crystal phases in which heavy metals such as chromium, iron, barium and lead are present in polluted soils of an industrial site (Val Basento, Italy) and another involved in the speciation of uranium in depleted uranium particles (Ceja Mountains, Kosovo). In the former case, the angular resolution is sufficient to allow identification of most crystalline phases present while in the latter case, it is necessary to dispose of an angular resolution of ca. 0.2° to distinguish between different forms of oxidized uranium. 相似文献
112.
Dr. Alexander G. Shtukenberg Prof. Yurii O. Punin Ankit Gujral Prof. Bart Kahr 《Angewandte Chemie (International ed. in English)》2014,53(3):672-699
Crystals of a variety of substances including elements, minerals, simple salts, organic molecular crystals, and high polymers forgo long‐range translational order by twisting and bending as they grow. These deviations have been observed in crystals ranging in size from nanometers to centimeters. How and why so many materials choose dramatic non‐crystallographic distortions is analyzed, with an emphasis on crystal chemistries that give rise to stresses operating either on surfaces of crystallites or within the bulk. 相似文献
113.
A simple method for the synthesis of sugar-derived imines by a Schwartz's reagent reduction of easily available sugar lactams has been described. A direct addition of nucleophiles to the generated in situ cyclic imines and subsequent deprotection of hydroxyl function allows to convert sugar lactams in polyhydroxylated pyrrolidines and piperidines. 相似文献
114.
Bart SC Lobkovsky E Bill E Chirik PJ 《Journal of the American Chemical Society》2006,128(16):5302-5303
Treatment of the iron bis(dinitrogen) complex, (iPrPDI)Fe(N2)2 (iPrPDI = (2,6-iPr2C6H3N=CMe)2C5H3N), with a series of aryl azides resulted in loss of 3 equiv of N2 and formation of the corresponding four-coordinate iron imide compounds, (iPrPDI)Fe(NAr). These complexes, two of which (Ar = 2,6-iPr2-C6H3 and 2,4,6-Me3-C6H2) have been characterized by X-ray diffraction, are significantly distorted from planarity. The metrical parameters in combination with M?ssbauer spectroscopic and SQUID magnetic data suggest an intermediate spin iron(III) center antiferromagnetically coupled to a ligand-centered radical. Nitrene group transfer has been accomplished by addition of 1 atm of CO, yielding aryl isocyanates, ArNCO, and (iPrPDI)Fe(CO)2. Hydrogenation of the more sterically hindered members of the series furnished free aniline and the previously reported iron dihydrogen complex. Catalytic aryl azide hydrogenation has also been achieved, and the observed relative rates are consistent with N-H bond formation as the rate-determining step in aniline formation. 相似文献
115.
116.
Ghesquière B Goethals M Van Damme J Staes A Timmerman E Vandekerckhove J Gevaert K 《Rapid communications in mass spectrometry : RCM》2006,20(19):2885-2893
Nitrated tyrosines are easily converted into their aminotyrosine equivalents by a reduction step. We here show that this conversion can be exploited to readily discern 3-aminotyrosine peptides in a background of non-nitrated peptides. Furthermore, aminotyrosine peptides are more stable in single mass spectrometry (MS) mode rendering peptide mass maps easier to interpret. One significant caveat of both 3-nitrotyrosine and 3-aminotyrosine peptides is their lack of efficient fragmentation upon collision-induced dissociation (CID) which, in the case of the latter peptides, also produces unexpected, deviating isotopic patterns of fragment ions containing the aminotyrosine residue. The net result is that sequence database searching becomes daunting as the correct peptide is frequently missed since insufficient and/or inaccurate peptide fragments are used. We show that a simple acetylation step, blocking all amines (including aminotyrosine), produces peptides that undergo extensive backbone fragmentation by CID and are thus easily identifiable in databases. Our procedure is additionally illustrated by doubling the number of nitration events mapped in tetranitromethane-nitrated bovine serum albumin (BSA) as compared to a direct analysis of the nitrated peptides using the same amount of material. In conclusion, we here illustrate that this two-step process, heme-mediated reduction and acetylation, can be used for more efficient characterization of protein-bound nitrated tyrosines. 相似文献
117.
Van der Bruggen B Jansen JC Figoli A Geens J Boussu K Drioli E 《The journal of physical chemistry. B》2006,110(28):13799-13803
The large diversity of membrane separation processes results in a different optimization of membrane materials and structures for each process. In this article, the extent to which a single membrane type can be used in gas separation, pervaporation, and nanofiltration has been investigated. Interpretation of transport and separation properties has led to the conclusion that the membrane SolSep 3360 is a multifunctional membrane fulfilling all requirements for the three separation processes. This can be achieved by keeping a good balance between the thickness of the top layer, sterical hindrance during transport, and the effect of hydrophobicity/hydrophilicity. 相似文献
118.
Crespo-Biel O Lim CW Ravoo BJ Reinhoudt DN Huskens J 《Journal of the American Chemical Society》2006,128(51):17024-17032
The multivalent binding of a supramolecular complex at a multivalent host surface by combining the orthogonal beta-cyclodextrin (CD) host-guest and metal ion-ethylenediamine coordination motifs is described. As a heterotropic, divalent linker, an adamantyl-functionalized ethylenediamine derivative was used. This was complexed with Cu(II) or Ni(II). The binding of the complexes to a CD self-assembled monolayer (SAM) was studied as a function of pH by means of surface plasmon resonance (SPR) spectroscopy. A heterotropic, multivalent binding model at interfaces was used to quantify the multivalent enhancement at the surface. The Cu(II) complex showed divalent binding to the CD surface with an enhancement factor higher than 100 relative to the formation of the corresponding divalent complex in solution. Similar behavior was observed for the Ni(II) system. Although the Ni(II) system could potentially be trivalent, only divalent binding was observed at the CD SAMs, which was confirmed by desorption experiments. 相似文献
119.
A bifunctional biaryl lactone has been synthesized that should be capable of iterative unidirectional aryl-aryl bond rotation via: (1) a diastereoselective lactone ring opening, (S)-1 to (P,S)-2 or (M,S)-2; (2) a chemoselective lactonization, (P,S)-2 or (M,S)-2 to (S)-3; and (3) a chemoselective hydrolysis, (S)-3 to (S)-1. Preliminary results of a racemic sample have indicated unidirectional 180 degrees rotation with very high directional selectivity per individual artificial molecular motor molecule through the first two steps of this sequence. [reaction: see text] 相似文献
120.
Marcin Śnieżek Sebastian Stecko Irma Panfil Bartłomiej Furman Zofia Urbańczyk-Lipkowska Marek Chmielewski 《Tetrahedron: Asymmetry》2013,24(2-3):89-103
The stereoselectivity of 1,3-dipolar cycloaddition reactions of C-phenyl open-chain nitrones and α,β-unsaturated γ- and δ-lactones was investigated under thermal and catalytic conditions. It was found that under thermal conditions, the endo approach of the reactants was preferred leading to the thermodynamic product. In the presence of Sc(OTf)3 the exo adduct was obtained in high yield and selectivity. The energies of the cycloaddition reactions were investigated by means of molecular orbital calculations at the B3LYP/6-31+G(d,p) and MP3/6-31+G(d,p) theory level. Different reaction channels and reactant approaches, fitting the individual regio- and stereochemical preferences, are discussed. The computational results were compared with the corresponding experimental data and found to be in good agreement. 相似文献