全文获取类型
收费全文 | 1411篇 |
免费 | 36篇 |
国内免费 | 1篇 |
专业分类
化学 | 654篇 |
晶体学 | 14篇 |
力学 | 41篇 |
数学 | 131篇 |
物理学 | 608篇 |
出版年
2020年 | 23篇 |
2019年 | 14篇 |
2018年 | 8篇 |
2016年 | 30篇 |
2015年 | 24篇 |
2014年 | 38篇 |
2013年 | 55篇 |
2012年 | 66篇 |
2011年 | 54篇 |
2010年 | 39篇 |
2009年 | 41篇 |
2008年 | 51篇 |
2007年 | 37篇 |
2006年 | 37篇 |
2005年 | 30篇 |
2004年 | 38篇 |
2003年 | 28篇 |
2002年 | 26篇 |
2001年 | 38篇 |
2000年 | 39篇 |
1999年 | 34篇 |
1998年 | 16篇 |
1997年 | 18篇 |
1996年 | 38篇 |
1995年 | 15篇 |
1994年 | 26篇 |
1993年 | 33篇 |
1992年 | 18篇 |
1991年 | 25篇 |
1990年 | 8篇 |
1989年 | 31篇 |
1988年 | 23篇 |
1987年 | 23篇 |
1986年 | 22篇 |
1985年 | 21篇 |
1984年 | 23篇 |
1983年 | 12篇 |
1982年 | 21篇 |
1981年 | 23篇 |
1980年 | 13篇 |
1979年 | 18篇 |
1978年 | 22篇 |
1977年 | 22篇 |
1976年 | 19篇 |
1975年 | 9篇 |
1974年 | 17篇 |
1973年 | 13篇 |
1972年 | 10篇 |
1971年 | 13篇 |
1970年 | 12篇 |
排序方式: 共有1448条查询结果,搜索用时 203 毫秒
1.
2.
Dr. Yujia Qing Mira D. Liu Denis Hartmann Dr. Linna Zhou Dr. William J. Ramsay Prof. Hagan Bayley 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(36):15841-15846
We report a single-molecule mechanistic investigation into 2-cyanobenzothiazole (CBT) chemistry within a protein nanoreactor. When simple thiols reacted reversibly with CBT, the thioimidate monoadduct was approximately 80-fold longer-lived than the tetrahedral bisadduct, with important implications for the design of molecular walkers. Irreversible condensation between CBT derivatives and N-terminal cysteine residues has been established as a biocompatible reaction for site-selective biomolecular labeling and imaging. During the reaction between CBT and aminothiols, we resolved two transient intermediates, the thioimidate and the cyclic precursor of the thiazoline product, and determined the rate constants associated with the stepwise condensation, thereby providing critical information for a variety of applications, including the covalent inhibition of protein targets and dynamic combinatorial chemistry. 相似文献
3.
4.
5.
6.
7.
H. Sucipto J. H. Sahner E. Prusov S. C. Wenzel R. W. Hartmann J. Koehnke R. Müller 《Chemical science》2015,6(8):5076-5085
Myxopyronins are α-pyrone antibiotics produced by the terrestrial bacterium Myxococcus fulvus Mx f50 and possess antibacterial activity against Gram-positive and Gram-negative pathogens. They target the bacterial RNA polymerase (RNAP) “switch region” as non-competitive inhibitors and display no cross-resistance to the established RNAP inhibitor rifampicin. Recent analysis of the myxopyronin biosynthetic pathway led to the hypothesis that this secondary metabolite is produced from two separate polyketide parts, which are condensed by the stand-alone ketosynthase MxnB. Using in vitro assays we show that MxnB catalyzes a unique condensation reaction forming the α-pyrone ring of myxopyronins from two activated acyl chains in form of their β-keto intermediates. MxnB is able to accept thioester substrates coupled to either N-acetylcysteamine (NAC) or a specific carrier protein (CP). The turnover rate of MxnB for substrates bound to CP was 12-fold higher than for NAC substrates, demonstrating the importance of protein–protein interactions in polyketide synthase (PKS) systems. The crystal structure of MxnB reveals the enzyme to be an unusual member of the ketosynthase group capable of binding and condensing two long alkyl chains bound to carrier proteins. The geometry of the two binding tunnels supports the biochemical data and allows us to propose an order of reaction, which is supported by the identification of novel myxopyronin congeners in the extract of the producer strain. Insights into the mechanism of this unique condensation reaction do not only expand our knowledge regarding the thiolase enzyme family but also opens up opportunities for PKS bioengineering to achieve directed structural modifications. 相似文献
8.
This paper proposes a method to improve the reliability of construction schedules by optimizing schedule robustness of construction projects. The schedule robustness is measured by a criterion evaluating the impact of deviations from the initial schedule on the makespan, which arise during the realization phase of a construction project. (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
9.
Dr. Selina Beatrice van der Meer Theresa Seiler Christin Buchmann Georgia Partalidou Dr. Sophia Boden Dr. Kateryna Loza Dr. Marc Heggen Dr. Jürgen Linders Dr. Oleg Prymak Prof. Dr. Cristiano L. P. Oliveira Prof. Dr. Laura Hartmann Prof. Dr. Matthias Epple 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(4):1451-1464
Ultrasmall gold nanoparticles (diameter about 2 nm) were surface-functionalized with cysteine-carrying precision macromolecules. These consisted of sequence-defined oligo(amidoamine)s (OAAs) with either two or six cysteine molecules for binding to the gold surface and either with or without a PEG chain (3400 Da). They were characterized by 1H NMR spectroscopy, 1H NMR diffusion-ordered spectroscopy (DOSY), small-angle X-ray scattering (SAXS), and high-resolution transmission electron microscopy. The number of precision macromolecules per nanoparticle was determined after fluorescent labeling by UV spectroscopy and also by quantitative 1H NMR spectroscopy. Each nanoparticle carried between 40 and 100 OAA ligands, depending on the number of cysteine units per OAA. The footprint of each ligand was about 0.074 nm2 per cysteine molecule. OAAs are well suited to stabilize ultrasmall gold nanoparticles by selective surface conjugation and can be used to selectively cover their surface. The presence of the PEG chain considerably increased the hydrodynamic diameter of both dissolved macromolecules and macromolecule-conjugated gold nanoparticles. 相似文献
10.
Matthias Ermer Julian Mehler Björn Rosenberger Dr. Marcus Fischer Dr. Peter S. Schulz Prof. Martin Hartmann 《ChemistryOpen》2021,10(2):233-242
Using ionic liquids (ILs) as linker precursors, the well-known metal-organic framework (MOF) UiO-66 (Universitetet i Oslo) and the recently reported MOF hcp UiO-66 (hexagonal closed packed) have been successfully synthesized and characterized. The advantage of the applied novel synthesis approach is an economically and environmentally benign work-up procedure, due to the better solubility of the IL. Additionally, the reactivity of the terephthalate anions is increased compared to terephthalic acid, resulting in faster MOF formation with an increased amount of defects in the MOF structure. In order to explore to the influence of defects on the catalytic performance, the cyclisation of citronellal to isopulegol was employed as test reaction. The activity of hcp UiO-66 and fcc UiO-66 (face centered cubic) is improved compared to other MOF or zeolite based catalysts, while the selectivity is similar. 相似文献