全文获取类型
收费全文 | 7639篇 |
免费 | 203篇 |
国内免费 | 24篇 |
专业分类
化学 | 5774篇 |
晶体学 | 41篇 |
力学 | 70篇 |
数学 | 1115篇 |
物理学 | 866篇 |
出版年
2020年 | 77篇 |
2019年 | 73篇 |
2016年 | 147篇 |
2015年 | 146篇 |
2014年 | 114篇 |
2013年 | 258篇 |
2012年 | 244篇 |
2011年 | 324篇 |
2010年 | 183篇 |
2009年 | 192篇 |
2008年 | 293篇 |
2007年 | 301篇 |
2006年 | 274篇 |
2005年 | 306篇 |
2004年 | 285篇 |
2003年 | 231篇 |
2002年 | 199篇 |
2001年 | 112篇 |
2000年 | 103篇 |
1999年 | 110篇 |
1998年 | 109篇 |
1997年 | 129篇 |
1996年 | 129篇 |
1995年 | 124篇 |
1994年 | 112篇 |
1993年 | 123篇 |
1992年 | 109篇 |
1991年 | 108篇 |
1990年 | 85篇 |
1989年 | 109篇 |
1988年 | 119篇 |
1987年 | 105篇 |
1986年 | 113篇 |
1985年 | 139篇 |
1984年 | 107篇 |
1983年 | 109篇 |
1982年 | 112篇 |
1981年 | 97篇 |
1980年 | 106篇 |
1979年 | 93篇 |
1978年 | 86篇 |
1977年 | 83篇 |
1976年 | 82篇 |
1974年 | 93篇 |
1973年 | 86篇 |
1971年 | 74篇 |
1961年 | 142篇 |
1960年 | 196篇 |
1959年 | 102篇 |
1958年 | 115篇 |
排序方式: 共有7866条查询结果,搜索用时 15 毫秒
991.
992.
993.
LC-NMR coupling technology: recent advancements and applications in natural products analysis 总被引:4,自引:0,他引:4
Exarchou V Krucker M van Beek TA Vervoort J Gerothanassis IP Albert K 《Magnetic resonance in chemistry : MRC》2005,43(9):681-687
An overview of recent advances in nuclear magnetic resonance (NMR) coupled with separation technologies and their application in natural product analysis is given and discussed. The different modes of LC-NMR operation are described, as well as how technical improvements assist in establishing LC-NMR as an important tool in the analysis of plant-derived compounds. On-flow, stopped-flow and loop-storage procedures are mentioned, together with the new LC-SPE-NMR configuration. The implementation of mass spectrometry in LC-NMR is also useful on account of the molecular weight and fragmentation information that it provides, especially when new plant species are studied. Cryogenic technology and capillary LC-NMR are the other important recent developments. Since the plant kingdom is endless in producing potential drug candidates, development and optimization of LC-NMR techniques convert the study of natural products to a less-time-consuming task, speeding up identification. 相似文献
994.
995.
Hitzeroth G Vater J Franke P Gebhardt K Fiedler HP 《Rapid communications in mass spectrometry : RCM》2005,19(20):2935-2942
Streptocidins, a family of tyrocidine-like cyclic decapeptides, are an ideal demonstration object for the detection and in situ structure analysis of natural compounds directly in microbial cells using whole cell matrix-assisted laser desorption/ionization time-of-flight-mass spectrometry (MALDI-TOFMS), an emerging technique that can be used for rapid sensitive metabolic profiling of microorganisms. Five main members of the streptocidin family (A-E) were detected in Brevibacillus cells picked from agar plates and identified by in situ structure analysis with post-source decay MALDI-TOFMS. This efficient modern method allows the precise detection of metabolites within minutes without the need to isolate and purify the target compounds. The generated mass spectra are of similar quality to those obtained for the purified peptides. In addition, surface extracts were prepared by treating Brevibacillus cells with 70% acetonitrile in the presence of 0.1% trifluoroacetic acid and fractionated by high-resolution reversed-phase high-performance liquid chromatography (HPLC). In this way ten minor streptocidins were detected demonstrating the full biosynthetic variety of streptocidin production on the cellular level. The streptocidins differ from the well-known tyrocidines essentially in position 3 of the decapeptide chain by replacement of the aromatic amino acid (F/W) found in tyrocidines by L-leucine or L-valine. 相似文献
996.
Schottenberger H Wurst K Griesser UJ Jetti RK Laus G Herber RH Nowik I 《Journal of the American Chemical Society》2005,127(18):6795-6801
X-ray structure determinations of two different single crystals of octamethylferrocenium tetrafluoroborate (OMFc(+)BF(4)(-)) revealed conformational polymorphism with ligand twist angles of 180 degrees and 108 degrees , respectively. Their concomitant occurrence could be explained by the small lattice energy difference of 3.2 kJ mol(-1). Temperature-dependent Moessbauer spectroscopy of (57)Fe-labeled OMFc(+)BF(4)(-) over the range 90 < T < 370 K did not show the anomalous sudden increase in the motion of the metal atom as observed in neutral OMFc. Broadened absorption curves characteristic of relaxation spectra were obtained with an isomer shift of 0.466(6) mm s(-1) at 90 K. The temperature dependence of the isomer shift corresponded to an effective vibrating mass of 79 +/- 10 Da and, in conjunction with the temperature dependence of the recoil-free fraction, to a Moessbauer lattice temperature of 89 K. The spin relaxation rate could be better described by an Orbach rather than a Raman process. At 400 K, a reversible solid-solid transition to a plastic crystalline mesophase was noted. 相似文献
997.
Single chains of the conjugated polymer polyfluorene are shown to exist in two distinct conformational arrangements. Planarization of the chain to the single molecule beta-phase leads to a red shift in the emission and a strong modification of the vibronic progression. Most importantly, this structural rearrangement dramatically affects the photophysical stability on the single molecule level. Single molecule beta-phase emission displays a vastly improved lifetime and much less noise on both the emission intensity and the spectral position. In the absence of signatures of multichromophoric emission on the single molecule level, we propose that the effective conjugation length accounts for most of the physical chain length of the beta-phase. 相似文献
998.
Maspoch D Domingo N Ruiz-Molina D Wurst K Hernández JM Vaughan G Rovira C Lloret F Tejada J Veciana J 《Chemical communications (Cambridge, England)》2005,(40):5035-5037
A metal-organic open-framework with an unprecedented (6,3)-helical topology, large channels and mixed ferro- and antiferromagnetic interactions has been synthesized using a three-connecting tricarboxylic polychlorotriphenylmethyl radical and Co(ii) ions. 相似文献
999.
Selle H Lamerz J Buerger K Dessauer A Hager K Hampel H Karl J Kellmann M Lannfelt L Louhija J Riepe M Rollinger W Tumani H Schrader M Zucht HD 《Combinatorial chemistry & high throughput screening》2005,8(8):801-806
The objective of this work was the application of peptidomics technologies for the detection and identification of reliable and robust biomarkers for Alzheimer's disease (AD) contributing to facilitate and further improve the diagnosis of AD. Using a new method for the comprehensive and comparative profiling of peptides, the differential peptide display (DPD), 312 cerebrospinal fluid (CSF) samples from AD patients, cognitively unimpaired subjects and from patients suffering from other primary dementia disorders were analysed as four independent analytical sets. By combination with a cross validation procedure, candidates were selected from a total of more than 6,000 different peptide signals based on their discriminating power. Twelve candidates were identified using mass-spectrometric techniques as fragments of the possibly neuroprotective neuroendocrine protein VGF and another one as the complement factor C3 descendent C3f. The combination of peptide profiling and cross validation resulted in the detection of novel potential biomarkers with remarkable robustness and a close relation to AD pathophysiology. 相似文献
1000.