全文获取类型
收费全文 | 936篇 |
免费 | 82篇 |
专业分类
化学 | 890篇 |
晶体学 | 3篇 |
力学 | 18篇 |
数学 | 53篇 |
物理学 | 54篇 |
出版年
2023年 | 13篇 |
2022年 | 17篇 |
2021年 | 35篇 |
2020年 | 32篇 |
2019年 | 41篇 |
2018年 | 20篇 |
2017年 | 16篇 |
2016年 | 39篇 |
2015年 | 40篇 |
2014年 | 45篇 |
2013年 | 37篇 |
2012年 | 84篇 |
2011年 | 73篇 |
2010年 | 51篇 |
2009年 | 39篇 |
2008年 | 74篇 |
2007年 | 50篇 |
2006年 | 52篇 |
2005年 | 49篇 |
2004年 | 37篇 |
2003年 | 21篇 |
2002年 | 31篇 |
2001年 | 19篇 |
2000年 | 13篇 |
1999年 | 10篇 |
1998年 | 10篇 |
1997年 | 15篇 |
1996年 | 12篇 |
1995年 | 5篇 |
1994年 | 12篇 |
1993年 | 6篇 |
1992年 | 1篇 |
1991年 | 7篇 |
1990年 | 1篇 |
1989年 | 4篇 |
1987年 | 1篇 |
1984年 | 1篇 |
1980年 | 1篇 |
1977年 | 1篇 |
1973年 | 1篇 |
1972年 | 1篇 |
1966年 | 1篇 |
排序方式: 共有1018条查询结果,搜索用时 31 毫秒
961.
962.
963.
Reaction of 2,5‐bis(dibromoboryl)thiophene ( 4 ) or 1,4‐bis(dibromoboryl)benzene ( 6 ) with two equivalents of N,N′‐dilithiated 2,3‐diaminopyridine ( 3 ) led to the generation of the pyridodiazaboroles 5 and 7 in which the two diazaborole rings are linked by 2,5‐thiophen‐diyl or 1,4‐phenylene units via the boron atom. The novel compounds were characterized by elemental analyses and spectroscopy (1H‐, 11B‐, 13C‐NMR, MS, and UV‐VIS). The molecular structure of 5 was elucidated by X‐ray diffraction. Cyclovoltammograms of 5 and 7 show two irreversible oxidation waves at 0.76 and 0.73 V, respectively vs Fc/Fc+. The novel compounds display intense blue luminescence with Stokes shifts of 76 and 74 nm and relative quantum yields of 39 and 43 % vs Coumarin 120 (Φ = 50 %). 相似文献
964.
965.
Matthijs de Geus Linda Schormans Anja R. A. Palmans Cor E. Koning Andreas Heise 《Journal of polymer science. Part A, Polymer chemistry》2006,44(14):4290-4297
The synthetic parameters for the chemoenzymatic cascade synthesis of block copolymers combining enzymatic ring‐opening polymerization (EROP) and atom transfer radical polymerization (ATRP) in one pot were investigated. A detailed analysis of the mutual interactions between the single reaction components revealed that the ATRP catalyst system could have a significant inhibiting effect on the enzyme activity. The inhibition of the enzyme was less pronounced in the presence of multivalent ligands such as dinonyl bipyridine, which thus could be used in this reaction as an ATRP catalyst. Moreover, the choice of the ATRP monomer was investigated. Methyl methacrylate interfered with EROP by transesterification, whereas t‐butyl methacrylate was inert. Block copolymers were successfully synthesized with this cascade approach by the activation of ATRP after EROP by the addition of the ATRP catalyst and, with lower block copolymer yields, by the mixing of all the components before the copolymerization. Adetailed kinetic analysis of the reactions and the structure of the block copolymers showed that the first procedure proceeded smoothly to high block copolymer yields, whereas in the latter a noteworthy amount of the poly(t‐butyl methacrylate) homopolymer was detected. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4290–4297, 2006 相似文献
966.
In this paper we propose several goodness-of-fit tests based on robust measures of skewness and tail weight. They can be seen
as generalisations of the Jarque–Bera test (Bera and Jarque in Econ Lett 7:313–318, 1981) based on the classical skewness
and kurtosis, and as an alternative to the approach of Moors et al. (Stat Neerl 50:417–430, 1996) using quantiles. The power
values and the robustness properties of the different tests are investigated by means of simulations and applications on real
data. We conclude that MC-LR, one of our proposed tests, shows the best overall power and that it is moderately influenced
by outlying values. 相似文献
967.
968.
Frank Waiblinger Anja P. Fluegge Juergen Keck Martin Stein Horst E. A. Kramer David Leppard 《Research on Chemical Intermediates》2001,27(1-2):5-20
2-(2-Hydroxyphenyl)-4,6-diaryl-1,3,5-triazines (HPTs) bearing one or more intramolecular hydrogen bonds (IMHBs) show phosphorescence in polar solvents at 77 K which increases in intensity with UV-irradiation time (λirr = 333 nm) until an equilibrium value is reached (phosphorescence evolution). Phosphorescence emission is produced from open conformers of the molecules with intermolecular rather than intramolecular hydrogen bonds, which are formed in polar solvents under the influence of UV radiation. All IMHBs of an individual molecule must be broken to enable triplet state population. Reformation of the closed form is observed for HPTs after dark periods resulting in a lower initial phosphorescence intensity upon renewed irradiation (relaxation). The methoxy derivatives (MPTs), where the OH groups are replaced by methoxy groups, can be employed as spectroscopic models for the open form; they emit phosphorescence independent of irradiation time. For the equilibrium between open and closed form of M-OH-P (2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine) under constant irradiation (λirr = 333 nm, 100 W-HBO lamp) a proportion of 5% of open form was evaluated. 相似文献
969.
Katharina J. Hock Anja Knorrscheidt Ren Hommelsheim Junming Ho Martin J. Weissenborn Rene M. Koenigs 《Angewandte Chemie (International ed. in English)》2019,58(11):3630-3634
The functionalization of C?H bonds with non‐precious metal catalysts is an important research area for the development of efficient and sustainable processes. Herein, we describe the development of iron porphyrin catalyzed reactions of diazoacetonitrile with N‐heterocycles yielding important precursors of tryptamines, along with experimental mechanistic studies and proof‐of‐concept studies of an enzymatic process with YfeX enzyme. By using readily available FeTPPCl, we achieved the highly efficient C?H functionalization of indole and indazole heterocycles. These transformations feature mild reaction conditions, excellent yields with broad functional group tolerance, can be conducted on gram scale, and thus provide a unique streamlined access to tryptamines. 相似文献
970.
Chiara Mazzoni Rasmus Due Jacobsen Jacob Mortensen Jacob Rune Jrgensen Lukas Vaut Jette Jacobsen Carsten Gundlach Anette Müllertz Line Hagner Nielsen Anja Boisen 《Macromolecular bioscience》2019,19(5)
Oral delivery of proteins and peptides is one of the main challenges in pharmaceutical drug development. Microdevices have the possibility to protect the therapeutics until release is desired, avoiding losses by degradation. One type of microdevice is polymeric microcontainers. In this study, lysozyme is chosen as model protein and loaded into microcontainers with the permeation enhancer sodium decanoate (C10). The loaded microcontainers are sealed and functionalized by applying polymeric lids onto the cavity of the devices. The first lid is poly(lactic‐co‐glycolic) acid (PLGA) and on top of this either polyethylene glycol (PEG) or chitosan is applied (PLGA+PEG or PLGA+chitosan, respectively). The functionalization is evaluated in vitro for morphology, drug release, and mucoadhesive properties. These are coupled with in vitro and ex vivo studies using Caco‐2 cells, Caco‐2/HT29‐MTX‐E12 co‐cultures, and porcine intestinal tissue. PLGA+chitosan shows slower release compared to PLGA+PEG or only PLGA in buffer and the transport of lysozyme across cell cultures is not enhanced compared to the bulk powder. Microcontainers coated with chitosan or PEG demonstrate a three times stronger adhesion during ex vivo mucoadhesion studies compared to samples without coatings. Altogether, functionalized microcontainers with mucoadhesive properties and tunable release for oral protein delivery are developed and characterized. 相似文献