全文获取类型
收费全文 | 509篇 |
免费 | 21篇 |
国内免费 | 3篇 |
专业分类
化学 | 387篇 |
晶体学 | 6篇 |
力学 | 11篇 |
数学 | 69篇 |
物理学 | 60篇 |
出版年
2023年 | 4篇 |
2022年 | 8篇 |
2021年 | 7篇 |
2020年 | 8篇 |
2019年 | 6篇 |
2018年 | 10篇 |
2017年 | 6篇 |
2016年 | 9篇 |
2015年 | 12篇 |
2014年 | 18篇 |
2013年 | 31篇 |
2012年 | 35篇 |
2011年 | 36篇 |
2010年 | 32篇 |
2009年 | 19篇 |
2008年 | 35篇 |
2007年 | 38篇 |
2006年 | 34篇 |
2005年 | 29篇 |
2004年 | 18篇 |
2003年 | 11篇 |
2002年 | 18篇 |
2001年 | 9篇 |
2000年 | 4篇 |
1999年 | 6篇 |
1998年 | 5篇 |
1997年 | 7篇 |
1996年 | 5篇 |
1994年 | 4篇 |
1993年 | 3篇 |
1992年 | 2篇 |
1991年 | 3篇 |
1989年 | 5篇 |
1985年 | 6篇 |
1982年 | 2篇 |
1981年 | 2篇 |
1979年 | 2篇 |
1976年 | 4篇 |
1975年 | 6篇 |
1933年 | 2篇 |
1932年 | 1篇 |
1930年 | 4篇 |
1929年 | 1篇 |
1927年 | 2篇 |
1926年 | 1篇 |
1925年 | 1篇 |
1923年 | 1篇 |
1922年 | 1篇 |
1912年 | 1篇 |
1901年 | 1篇 |
排序方式: 共有533条查询结果,搜索用时 46 毫秒
21.
In an attempt to generate antibodies for the development of an immunoanalysis method for potassium and caesium ions, new 1,3-alternate calix[4]arenes-crown-5 and -6 bearing either carboxylic or hydroxyl functions were synthesized in good yields. Their complexation properties towards potassium and caesium ions were investigated using 1H NMR spectroscopy and the usual properties proved to be preserved in the presence of the anchoring arms. 相似文献
22.
Dr. Agnes Kütt Prof. Dr. Gunnar Jeschke Dr. Lauri Toom Dr. Jaak Nerut Prof. Christopher A. Reed 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(41):8871-8874
Hydride abstraction from diarylamines with the trityl ion is explored in an attempt to generate a stable diarylnitrenium ion, Ar2N+. Sequential H-atom abstraction reactions ensue. The first H-atom abstraction leads to intensely colored aminium radical cations, Ar2NH.+, some of which are quite stable. However, most undergo a second H-atom abstraction leading to ammonium ions, Ar2NH2+. In the absence of a ready source of H-atoms, a unique self-abstraction reaction occurs when Ar=Me5C6, leading to a novel iminium radical cation, Ar=N.+Ar, which decays via a second self H-atom abstraction reaction to give a stable iminium ion, Ar=N+HAr. These products differ substantially from those derived via photochemically produced diarylnitrenium ions. 相似文献
23.
Agnes M Modro Tom A Modro P. Bernatowicz Wojciech Schilf Lech Stefaniak 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1)
Abstract A series of phosphoric amidodiesters, diamidoesters and triamides was prepared and their 31P and15 N NMR spectra were recorded in order to evaluate the major structural factors that determine the chemical shifts and coupling contants values. Considering the equation expressing the structural effects on shielding[1]. 相似文献
24.
Dr. Debangshu Chaudhuri Dr. Eva Sigmund Annemarie Meyer Lisa Röck Philippe Klemm Sebastian Lautenschlager Agnes Schmid Shane R. Yost Prof. Dr. Troy Van Voorhis Dr. Sebastian Bange Prof. Dr. Sigurd Höger Prof. Dr. John M. Lupton 《Angewandte Chemie (International ed. in English)》2013,52(50):13449-13452
25.
Szabolcs Fekete Jean-Luc Veuthey Sebastiaan Eeltink Davy Guillarme 《Analytical and bioanalytical chemistry》2013,405(10):3137-3151
Various recent wide-pore reversed-phase stationary phases were studied for the analysis of intact monoclonal antibodies (mAbs) of 150 kDa and their fragments possessing sizes between 25 and 50 kDa. Different types of column technology were evaluated, namely, a prototype silica-based inorganic monolith containing mesopores of ~250 Å and macropores of ~?1.1 μm, a column packed with 3.6 μm wide-pore core-shell particles possessing a wide pore size distribution with an average around 200 Å and a column packed with fully porous 1.7 μm particles having pore size of ~300 Å. The performance of these wide-pore materials was compared with that of a poly(styrene–divinyl benzene) organic monolithic column, with a macropore size of approximately 1 μm but without mesopores (stagnant pores). A systematic investigation was carried out using model IgG1 and IgG2 mAbs, namely rituximab, panitumumab, and bevacizumab. Firstly, the recoveries of intact and reduced mAbs were compared on the two monolithic phases, and it appeared that adsorption was less pronounced on the organic monolith, probably due to the difference in chemistry (C18 versus phenyl) and the absence of mesopores (stagnant zones). Secondly, the kinetic performance was investigated in gradient elution mode for all columns. For this purpose, peak capacities per meter as well as peak capacities per time unit and per pressure unit (PPT) were calculated at various flow rates, to compare performance of columns with different dimensions. In terms of peak capacity per meter, the core-shell 3.6 μm and fully porous 1.7 μm columns outperformed the two monolithic phases, at a temperature of 60 °C. However, when considering the PPT values, the core-shell 3.6 μm column remained the best phase while the prototype silica-based monoliths became very interesting, mostly due to a very high permeability compared with the organic monolith. Therefore, these core-shell and silica-based monolith provided the fastest achievable separation. Finally, at the maximal working temperature of each column, the core-shell 3.6 μm column was far better than the other one, because it is the only one stable up to 90 °C. Lastly, the loading capacity was also measured on these four different phases. It appeared that the organic monolith was the less interesting and rapidly overloaded, due to the absence of mesopores. On the other hand, the loading capacity of prototype silica-based monolith was indeed reasonable. 相似文献
26.
Karine Vuignier Szabolcs Fekete Pierre‐Alain Carrupt Jean‐Luc Veuthey Davy Guillarme 《Journal of separation science》2013,36(14):2231-2243
In the present study, three types of silica‐based monoliths, i.e. the first and second generations of commercial silica monolithic columns and a wide‐pore prototype monolith were compared for the analysis of large biomolecules. These molecules possess molecular weights between 1 and 66 kDa. The gradient kinetic performance of the first‐generation monolith was lower than that of the second generation, for large biomolecules (>14 kDa) but very close with smaller ones (1.3–5.8 kDa). In contrast, the wide‐pore prototype column was particularly attractive with proteins larger than 19 kDa (higher peak capacity). Among these three columns, the selectivity and retention remained quite similar but a possible larger number of accessible and charged residual silanols was noticed on the wide‐pore prototype material, which led to unpredicted small changes in selectivity and slightly broader peaks than expected. The peak shapes attained with the addition of 0.1% formic acid in the mobile phase remained acceptable for MS coupling, particularly for biomolecules of less than 6 kDa. It was found that one of the major issues with all of these silica‐based monoliths is the possible poor recovery of large biomolecules (principally with monoclonal antibody fragments of more than 25 kDa). 相似文献
27.
An efficient method for the oxidation of alcohols is presented. The use of catalytic amounts of sodium chloride in combination with oxone allows the conversion primary aliphatic alcohols to symmetric esters. Secondary alcohols can be easily oxidized to ketones, and benzylic alcohols are converted to the corresponding aldehydes. The method is cost effective and enviromentally benign. 相似文献
28.
Lead Structures for New Antibacterials: Stereocontrolled Synthesis of a Bioactive Muraymycin Analogue 下载免费PDF全文
Daniel Wiegmann Dr. Stefan Boettcher Agnes Mihalyi Prof. Timothy D. H. Bugg Prof. Christian Ducho 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(47):15292-15297
Naturally occurring muraymycin nucleoside antibiotics represent a promising class of novel antibacterial agents. The structural complexity suggests the investigation of simplified analogues as potential lead structures, which can then be further optimized towards highly potent antimicrobials. Herein we report studies on muraymycin‐derived potential lead structures lacking an aminoribose motif found in most naturally occurring muraymycins. We have identified a 5′‐defunctionalized motif to be ideal in terms of stability and chemical accessibility and have synthesized a full‐length muraymycin analogue based on this structure using a novel fully stereocontrolled route. The obtained 5′‐deoxy analogue of the natural product muraymycin C4 showed good inhibitory properties towards the bacterial target protein MraY, sufficient pharmacokinetic stability and no cytotoxicity against human cells, thus making it a promising lead for antibacterial drug development. 相似文献
29.
Dr. Santosh K. Singh Jesse La Jeunesse Vasant Vuppuluri Prof. Steven F. Son Dr. Bing-Jian Sun Mr. Yue-Lin Chen Prof. Agnes H. H. Chang Prof. Alexander M. Mebel Prof. Dr. Ralf I. Kaiser 《Chemphyschem》2020,21(9):837-842
Understanding of the fundamental mechanisms involved in the decomposition of 1,3,5-trinitro-1,3,5-triazinane (RDX) still represents a major challenge for the energetic materials and physical (organic) chemistry communities mainly because multiple competing dissociation channels are likely involved and previous detection methods of the products are not isomer selective. In this study we exploited a microsecond pulsed infrared laser to decompose thin RDX films at 5 K under mild conditions to limit the fragmentation channels. The subliming decomposition products during the temperature programed desorption phase are detected using isomer selective single photoionization time-of-flight mass spectrometry (PI-ReTOF-MS). This technique enables us to assign a product signal at m/z=42 to ketene (H2CCO), but not to diazomethane (H2CNN; 42 amu) as speculated previously. Electronic structure calculations support our experimental observations and unravel the decomposition mechanisms of RDX leading eventually to the elusive ketene (H2CCO) via an exotic, four-membered ring intermediate. This study highlights the necessity to exploit isomer-selective detection schemes to probe the true decomposition products of nitramine-based energetic materials. 相似文献
30.
Christophe Ferrari Agnes Roche Veronique Jacob Panayotis Foster Patrick Baussand 《国际化学动力学杂志》1996,28(8):609-614
The rate constants of the isopropyl acetate, n-propyl acetate, isopropenyl acetate, n-propenyl acetate, n-butyl acetate, and ethyl butyrate reactions with OH radicals were determined in purified air under atmospheric conditions, at 750 torr and (295 ± 2) K. A relative rate experimental method was used; n-heptane, n-octane, and n-nonane were the reference compounds, with, respectively, rate constants for the reaction with OH of 7.12 × 10−12, 8.42 × 10−12, and 9.70 × 10−12 molecule−1 cm3s−1. The following rate constants were obtained in units of 10−12 molecule−1 cm3s−1; isopropyl acetate, (3.12 ± 0.29); n-propyl acetate, (1.97 ± 0.24); isopropenyl acetate, (62.53 ± 1.24); n-propenyl acetate, (24.57 ± 0.24); n-butyl acetate, (3.29 ± 0.35); and ethyl butyrate, (4.37 ± 0.42). Tertiary butyl acetate has a low reactivity with OH radicals (<1 × 10−12 molecule−1 cm3s−1). © 1996 John Wiley & Sons, Inc. 相似文献