全文获取类型
收费全文 | 5151篇 |
免费 | 206篇 |
国内免费 | 14篇 |
专业分类
化学 | 3597篇 |
晶体学 | 182篇 |
力学 | 58篇 |
数学 | 754篇 |
物理学 | 780篇 |
出版年
2023年 | 40篇 |
2021年 | 73篇 |
2020年 | 94篇 |
2019年 | 97篇 |
2018年 | 47篇 |
2017年 | 44篇 |
2016年 | 122篇 |
2015年 | 141篇 |
2014年 | 143篇 |
2013年 | 229篇 |
2012年 | 296篇 |
2011年 | 292篇 |
2010年 | 170篇 |
2009年 | 155篇 |
2008年 | 204篇 |
2007年 | 209篇 |
2006年 | 227篇 |
2005年 | 202篇 |
2004年 | 216篇 |
2003年 | 169篇 |
2002年 | 137篇 |
2001年 | 87篇 |
2000年 | 63篇 |
1999年 | 65篇 |
1998年 | 60篇 |
1997年 | 63篇 |
1996年 | 53篇 |
1995年 | 61篇 |
1994年 | 72篇 |
1993年 | 50篇 |
1992年 | 47篇 |
1991年 | 47篇 |
1990年 | 31篇 |
1989年 | 52篇 |
1988年 | 32篇 |
1987年 | 39篇 |
1985年 | 43篇 |
1984年 | 29篇 |
1983年 | 35篇 |
1982年 | 39篇 |
1980年 | 41篇 |
1979年 | 52篇 |
1978年 | 45篇 |
1977年 | 38篇 |
1959年 | 70篇 |
1958年 | 65篇 |
1957年 | 44篇 |
1956年 | 80篇 |
1955年 | 57篇 |
1954年 | 90篇 |
排序方式: 共有5371条查询结果,搜索用时 163 毫秒
81.
Herein we report our investigation on the oxidation of solid-support-bound amino alcohols to their corresponding aldehydes. These aldehydes were converted into diastereomerically pure (>10:1) 2,4-cis-2-aminoalkyl-3-sulfonyl-1,3-oxazolidines using optically pure 1,2-amino alcohols. The relative configuration was determined using the nuclear Overhauser effect (NOE). The synthesized oxazolidines, which were obtained in high purities, represent a new, diverse scaffold for the solid-phase synthesis of libraries directed toward a pharmacological target. 相似文献
82.
We have demonstrated that a bipyrimidinylplatinum-polyoxometalate, [Pt(Mebipym)Cl2]+[H4PV2Mo10O40]-, supported on silica is an active catalyst for the aerobic oxidation of methane to methanol in water under mild reaction conditions. Further oxidation of methanol yields acetaldehyde. The presence of the polyoxometalate is presumed to allow the facile oxidation of a Pt(II) intermediate to a Pt(IV) intermediate and to aid in the addition of methane to the Pt catalytic center. 相似文献
83.
A phenanthroline ligand has been covalently modified at the 2 and 9 positions by an aminophenylhexamolybdate substituent. The 1H NMR spectrum indicated a strong electron-withdrawing effect of the hexamolybdate (Mo6O19(2-)) moiety on the phenanthroline ligand. UV-vis and cyclic voltammetry showed extended conjugation of the hybrid phenanthroline-polyoxometalate compound and the possibility of easy oxidation of the extended phenanathroline ligand. Further EPR experiments provided strong evidence for an intramolecular charge-transfer process with the formation of a phenanthroline cation radical and a reduced hexamolybdate. 相似文献
84.
Helmut Simon Johann Bader Helmut Günther Stefan Neumann Jordanes Thanos 《Angewandte Chemie (International ed. in English)》1985,24(7):539-553
It has been known for many decades that chiral compounds can be obtained by stereospecific biocatalytic reduction. Further significant methodological developments in this field have, however, only been made during the past ten years; they include the application of previously unused microorganisms and electron donors, the discovery of additional substrates for the known reductases, the development of methods for regenerating reduced pyridine nucleotides, and the discovery of new reductases which were sought for specific preparative purposes. Many chiral compounds can now be synthesized by microbial hydrogenation using H2 and hydrogenase-containing microorganisms as well as by electromicrobial or electroenzymatic reduction. In the two latter methods, anaerobic or aerobic organisms are supplied with electrons from electrochemically reduced, artificial mediators, e.g., methyl viologen. Reductases that do not require pyridine nucleotides and can accept electrons directly from reduced viologens are especially useful. Two examples of this type of enzyme are described which are of preparative interest. Many cells contain methyl viologen-dependent NAD(P) reductases, a large number of which have still not been characterized. A productivity number is proposed which allows different methods of bioconversion with microorganisms to be compared. The productivity numbers of compounds synthesized by the methods described in this review are often 10- to 100-fold higher than those of substances obtained by conventional techniques. 相似文献
85.
Authentic samples of whisky produced in Scotland and USA and counterfeit whisky samples commercialized in Brazil have been directly submitted to electrospray ionization mass spectrometry (ESI-MS) analysis in both the negative and positive ion modes to assess the potential of this technique for simple and rapid quality control and proof of authenticity of whisky samples. ESI in the negative ion mode yields the most characteristic whisky fingerprinting mass spectra in just a few seconds by direct infusion of the samples, detecting the most polar or acidic components of each sample in their deprotonated anionic forms. No pre-treatment of the sample, such as extraction or derivatization or even dilution, is required. The analysis of the ESI(-)-MS data both by simple visual inspection but more particularly by chemometric data treatment enables separation of the whisky samples into three unequivocally distinct groups: Scotch, American and counterfeit whisky, whereas single malt and blended Scotch whiskies are also distinguished to some extent. As indicated by ESI-MS/MS analysis, the diagnostic anions are simple sugars, disaccharides and phenolic compounds. Direct infusion ESI-MS therefore provides immediate chemical fingerprinting of whisky samples for type, origin and quality control, as demonstrated herein for American, Scottish and counterfeit samples, whereas ESI-MS/MS analysis of diagnostic ions adds a second dimension of fingerprinting characterization when improved selectivity is desired. 相似文献
86.
87.
In NMR spectroscopy, homonuclear scalar couplings normally lead to modulations of spin echoes that tend to interfere with the accurate determination of transverse relaxation rates by Carr-Purcell-Meiboom-Gill (CPMG) multiple refocusing experiments. Surprisingly, the echo modulations are largely cancelled when the refocusing pulses applied to the coupling partner deviate slightly from ideal pi rotations due to tilted effective radio-frequency (RF) fields, even at offsets that are much smaller than the radio-frequency amplitude. Experiments and simulations illustrate these effects for two-spin IS systems containing donor and acceptor (15)N nuclei I=N (D) and S=N(A) in RNA Watson-Crick base pairs with homonuclear scalar couplings J(IS)=(2h)J(N(D), N(A)) across the hydrogen bonds. 相似文献
88.
Palladium[0]-mediated Ullmann cross-coupling of 1-bromo-2-nitrobenzene (1 R = H) and its derivatives with a range of beta-halo-enals, -enones, or -esters readily affords the corresponding beta-aryl derivatives, which are converted into the corresponding quinolines, 2-quinolones, phenanthridines, or 6(5H)-phenanthridinones on reaction with dihydrogen in the presence of Pd on C or with TiCl(3) in aqueous acetone. [reaction: see text] 相似文献
89.
Jens Hartig Andreas Schnepf L. Jos de Jongh David Bono Hansgeorg Schnöckel Prof. Dr. 《无机化学与普通化学杂志》2007,633(1):63-76
Towards the Understanding of the Unexpected Properties of the Metalloid Cluster Compound [Ga84(N(SiMe3)2)20][Li6Br2(THF)20]·2Toluol In several short communications we have recently reported on the electrical and superconducting properties of the crystalline title compound 1 which contains anionic Ga84R20‐moieties. Here we present a collection of these results, complemented and interpreted by using DFT‐calculations on model clusters (Ga84(NH2)20?). These calculations allow a) a first insight into the dynamics of the Ga84‐moieties (e.g. a rotation of the central Ga2‐dumbbell) and thus an explanation of the temperature‐dependent Ga‐NMR‐spectra described recently, and b) estimations on the lattice energy of 1 and its resulting unexpected energetic stabilization compared to metallic gallium. A possible contribution of the cations in the electrical conduction mechanism of 1 can also be made feasible with model calculations. The basis for all the results presented is to be found in the “perfect” arrangement of nanoscopic Ga84‐clusters in the crystal. This theoretically predicted condition for superconductivity in a “chain” of identical metal cluster molecules is a requirement which can hardly be realized by means of physical fabrication methods. Therefore, on the one hand the results presented here make for some disillusionment in the field of nanoscience, but on the other hand, especially in the field of synthetic chemistry, they present rewarding challenges for fundamental work in the future. 相似文献
90.
The application of solid layer crystallization techniques in industry is arousing ever more interest. One reason is the increasing demand for ultrapure products, and another is the energysaving potential of this separation technology.This article examines solid layer melt crystallization as concerns its purification efficiency. The crystallization process was carried out in two different modes, whereby the process parameters were varied and post-crystallization treatments were additionally applied. The experimental results were used as the basis for a mathematical fit of a semi-empirical expression which predicts the purification efficiency. It was used for a design of different multistage plants, which operate with different crystallization strategies. One result is that a comparable product quality is attainable with a simple process technique in combination with post-crystallization treatments, instead of a more complicated and therefore more expensive process technique.The authors wish to acknowledge support by the EU (JOULE program), which helped attainment of some results presented here. 相似文献