全文获取类型
收费全文 | 114篇 |
免费 | 6篇 |
专业分类
化学 | 88篇 |
晶体学 | 2篇 |
力学 | 2篇 |
数学 | 2篇 |
物理学 | 26篇 |
出版年
2022年 | 2篇 |
2021年 | 2篇 |
2020年 | 3篇 |
2019年 | 1篇 |
2017年 | 1篇 |
2016年 | 4篇 |
2015年 | 1篇 |
2014年 | 5篇 |
2013年 | 6篇 |
2012年 | 6篇 |
2011年 | 9篇 |
2010年 | 5篇 |
2009年 | 2篇 |
2008年 | 8篇 |
2007年 | 6篇 |
2006年 | 9篇 |
2005年 | 4篇 |
2004年 | 5篇 |
2003年 | 3篇 |
2002年 | 6篇 |
2001年 | 2篇 |
2000年 | 2篇 |
1998年 | 2篇 |
1997年 | 3篇 |
1995年 | 1篇 |
1994年 | 2篇 |
1993年 | 2篇 |
1992年 | 2篇 |
1990年 | 1篇 |
1987年 | 1篇 |
1983年 | 1篇 |
1980年 | 1篇 |
1975年 | 1篇 |
1969年 | 1篇 |
1934年 | 1篇 |
1925年 | 1篇 |
1923年 | 2篇 |
1920年 | 2篇 |
1908年 | 2篇 |
1907年 | 1篇 |
1893年 | 1篇 |
排序方式: 共有120条查询结果,搜索用时 31 毫秒
1.
Yuji Naruse Atsushi Takamori Itsuki Nagasawa 《Phosphorus, sulfur, and silicon and the related elements》2020,195(7):523-525
AbstractWe previously designed and prepared the first molecules to exhibit observable CD spectra by n-σ* excitation, 2,6-dithiaspiro[3.3]heptane 2,6-dioxide. Spiro[3.3]heptane frameworks possess axial asymmetry due to puckering of 2 four-membered rings; the ring bonds are rich in p-character due to acute bond angles, which lowers the σ* energy levels. In contrast, the lone pairs are rich in s-character, which results in a good donor with conformational fixation. We expected that, instead of lone pairs as donating orbitals, the use of σ-electron-donating Si-Si bonds should result in UV absorption in the observable range (>180?nm), so that the Cotton effect could appear, at least partially, in that range. We designed 2,6-disilyl-2,6-disilaspiro[3.3]heptanes as models, and performed theoretical calculations to confirm our idea. 相似文献
2.
Fukuyama Y Minami H Matsuo A Kitamura K Akizuki M Kubo M Kodama M 《Chemical & pharmaceutical bulletin》2002,50(3):368-371
New five seven-membered vibsane-type diterpenes named 5-epi-vibsanin C, 5-epi-vibsanin H, 5-epi-vibsanin K, 18-O-methyl-5-epi-vibsanin K and 5-epi-vibsanin E have been isolated from the leaves of Viburnum awabuki (Caplifoliaceae). Their structures have been elucidated by analyses of spectroscopic data and comparison of their spectral data with those of the previously known seven-membered vibsane-type diterpenes. The occurrence of these seven-membered vibsane-type diterpenes with a cis relationship on the C-5 and C-10 positions in nature have been predicted by conformational analysis of vibsanin B, an eleven-membered vibsane-type diterpene. Vibsanin C, 5-epi-vibsanin C and 5-epi-vibsanin H exhibited moderate cytotoxic activities on KB cells. 相似文献
3.
Yoshitomo Kashiwagi Yumiko Takamori Kentaro Yoshida Tetsuya Ono 《Electroanalysis》2013,25(12):2575-2577
This paper describes the electrocatalytic oxidation of amines on TEMPO (2,2,6,6‐tetramethylpiperidine‐1‐oxyl)‐modified electrodes prepared by electrochemical copolymerization of TEMPO precursor containing pyrrole side chain and 2,2′‐bithiophene. The modified electrode exhibits electrocatalytic activity for the oxidation of primary and secondary amines. Cyclic voltammetric studies showed that the peak current of the cyclic voltammogram increased linearly with increasing concentration of amine in the sample solution. 相似文献
4.
Tao Wang Shuai Shi Dr. Mie Højer Vilhelmsen Tuo Zhang Dr. Matthias Rudolph Prof. Dr. A. Stephen K. Hashmi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(37):12512-12516
New and chemoselective gold(I)‐catalyzed transformations of 1‐(arylethynyl)‐7‐oxabicyclo[4.1.0]‐ heptan‐2‐ones were developed. Two completely different products—6,7‐dihydrobenzofuran‐4(5H)‐ones and benzofurans—could be obtained from the same starting material. The selectivity is determined by the ligand of the gold catalyst: triphenylphosphine delivers 6,7‐dihydrobenzofuran‐4(5H)‐ones, and 1,3‐bis(diisopropylphenyl)imidazol‐2‐ylidene leads to benzofurans. Eleven examples of each case are provided. The mechanistic suggestions for the pathways to both product types are supported by isotope labeling experiments. 相似文献
5.
Prof. Dr. A. Stephen K. Hashmi Tobias Lauterbach Dipl.‐Chem. Pascal Nösel Dr. Mie Højer Vilhelmsen Dr. Matthias Rudolph Dr. Frank Rominger 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(3):1058-1065
A series of dinuclear gold σ,π‐propyne acetylide complexes were prepared and tested for their catalytic ability in dual gold catalysis that was based on the reaction of an electrophilic π‐complex of gold with a gold acetylide. The air‐stable and storable catalysts can be isolated as silver‐free catalysts in their activated form. These dual catalysts allow a fast initiation phase for the dual catalytic cycles without the need for additional additives for acetylide formation. Because propyne serves as a throw‐away ligand, no traces of the precatalyst are generated. Based on the fast initiation process, side products are minimized and reaction rates are higher for these catalysts. A series of test reactions were used to demonstrate the general applicability of these catalysts. Lower catalyst loadings, faster reaction rates, and better selectivity, combined with the practicability of these catalysts, make them ideal catalysts for dual gold catalysis. 相似文献
6.
Dr. Julian Heinrich Dr. Karolina Bossak-Ahmad Mie Riisom Dr. Haleh H. Haeri Tasha R. Steel Vinja Hergl Alexander Langhans Corinna Schattschneider Jannis Barrera Dr. Stephen M. F. Jamieson Prof. Matthias Stein Prof. Dariush Hinderberger Prof. Christian G. Hartinger Prof. Wojciech Bal Prof. Nora Kulak 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(72):18093-18102
Redox-active Cu(II) complexes are able to form reactive oxygen species (ROS) in the presence of oxygen and reducing agents. Recently, Faller et al. reported that ROS generation by Cu(II) ATCUN complexes is not as high as assumed for decades. High complex stability results in silencing of the Cu(II)/Cu(I) redox cycle and therefore leads to low ROS generation. In this work, we demonstrate that an exchange of the α-amino acid Gly with the β-amino acid β-Ala at position 2 (Gly2→β-Ala2) of the ATCUN motif reinstates ROS production (•OH and H2O2). Potentiometry, cyclic voltammetry, EPR spectroscopy and DFT simulations were utilized to explain the increased ROS generation of these β-Ala2-containing ATCUN complexes. We also observed enhanced oxidative cleavage activity towards plasmid DNA for β-Ala2 compared to the Gly2 complexes. Modifications with positively charged Lys residues increased the DNA affinity through electrostatic interactions as determined by UV/VIS, fluorescence, and CD spectroscopy, and consequently led to a further increase in nuclease activity. A similar trend was observed regarding the cytotoxic activity of the complexes against several human cancer cell lines where β-Ala2 peptide complexes had lower IC50 values compared to Gly2. The higher cytotoxicity could be attributed to an increased cellular uptake as determined by ICP-MS measurements. 相似文献
7.
8.
9.
G. Mie 《Colloid and polymer science》1907,2(5):129-133
Ohne ZusammenfassungEigenbericht über einen auf der Naturforscherversammlung in Dresden gehaltenen Vortrag. 相似文献
10.