全文获取类型
收费全文 | 65篇 |
免费 | 5篇 |
国内免费 | 1篇 |
专业分类
化学 | 58篇 |
数学 | 3篇 |
物理学 | 10篇 |
出版年
2023年 | 1篇 |
2022年 | 1篇 |
2021年 | 1篇 |
2020年 | 4篇 |
2019年 | 1篇 |
2018年 | 3篇 |
2017年 | 1篇 |
2016年 | 4篇 |
2015年 | 1篇 |
2014年 | 4篇 |
2013年 | 1篇 |
2012年 | 7篇 |
2011年 | 6篇 |
2010年 | 3篇 |
2009年 | 3篇 |
2008年 | 8篇 |
2007年 | 1篇 |
2006年 | 2篇 |
2005年 | 1篇 |
2004年 | 4篇 |
2003年 | 4篇 |
2002年 | 1篇 |
2001年 | 2篇 |
1990年 | 1篇 |
1988年 | 1篇 |
1987年 | 2篇 |
1978年 | 2篇 |
1966年 | 1篇 |
排序方式: 共有71条查询结果,搜索用时 15 毫秒
61.
Yamakawa N Sumimoto M Matsumoto T Yuto K Yoshikawa Y Goto M Yamaguchi Y Kurosaki H 《Chemical & pharmaceutical bulletin》2008,56(1):64-69
(1)H-NMR spectra of square-planar complexes with the formula [Pt(L(1))(L(2))]X(2) where L(1) is 2,2'-bipyridine (bpy) or 1,10-phenanthroline (phen) and L(2) is N-(1-naphthyl)methyl-1,2-ethanediamine (Npen) or N-(9-anthryl)methyl-1,2-ethanediamine (Aten) indicate that the N-naphthylmethyl and N-anthrylmethyl groups are forced to adopt a pseudo axial disposition due to intramolecular repulsion of hydrogen atoms of the aromatic diimines. The aromatic-aromatic interactions in the N-arylmethyl-1,2-ethanediamine complexes and aromatic diimines caused them to undergo intramolecular stacking. (1)H-NMR spectra of these complexes showed a significant concentration and temperature dependence. The monomer-dimer equilibrium was estimated, based on the concentration dependency. Restricted single bond rotation was estimated from temperature dependency data. The rotation of the anthracene ring of the [Pt(bpy)(Aten)](2+) complex showed an activation energy of ca. 38 kJ mol(-1), which is in good agreement with a mechanism involving successive rotations about single bonds with restriction by intramolecular aromatic-aromatic ring interactions. 相似文献
62.
Electrochemical Detection of Tryptophan Metabolites via Kynurenine Pathway by Using Nanocarbon Films
We studied nanocarbon film electrodes with the aim of detecting tryptophan metabolites via the kynurenine pathway. The nanocarbon films were formed by using unbalanced magnetron sputtering, and they exhibited superior electrode properties including a wide potential window and a low background current as a result of the sp3-containing structure and ultraflat surface. These properties allowed us to detect certain tryptophan metabolites such as kynurenic acid (KYNA), which has a relatively high oxidation potential. We also investigated the effect of the sp2/sp3 ratio of the nanocarbon film as regards the electrode activity in relation to target molecules. We found that the sp2/sp3 ratio played important roles in both widening the potential window and obtaining superior electrode performance for the metabolites. The nanocarbon film with a high sp3 content was beneficial as regards the electrode performance with respect to the detection limit and sensitivity. Compared with conventional carbon-based electrodes, the nanocarbon film electrode with a high sp3 content exhibited higher electrode activity against KYNA while maintaining a low background current. Computational experiments revealed that the theoretical oxidation potential (Eox) value for some targets coincided with that obtained in electrochemical experiments using our nanocarbon film electrode. 相似文献
63.
Shintaro Mitsunaga Tohru Ohbayashi Shimpei Sugiyama Takahito Saitou Makoto Tadokoro Tsuyoshi Satoh 《Tetrahedron: Asymmetry》2009,20(14):1697-1708
The synthesis of pipecolic acid and homopipecolic acid derivatives was developed from ω-(2-aminophenyl)-1-chloroalkyl p-tolyl sulfoxides by treatment with i-PrMgCl. An intramolecular nucleophilic substitution reaction of a magnesium carbenoid with an N-magnesio arylamine is the key step of this reaction. Proline and pipecolic acid derivatives were also synthesized from ω-(arylamino)-1-chloroalkyl p-tolyl sulfoxides by the same chemistry. Starting from enantiomerically pure (1S,RS)-1-chloro-3-[2-(N-methylamino)phenyl]propyl p-tolyl sulfoxide, enantiomerically pure (R)-pipecolic acid derivative was obtained. The intramolecular nucleophilic substitution reaction of the magnesium carbenoid with N-magnesio arylamine was proven to take place with inversion of the carbenoid carbon. The stereochemistry of these reactions is also discussed. 相似文献
64.
Theoretical study of keto–enol tautomerism by quantum mechanical calculations (the QM/MC/FEP method)
Thanayuth Kaweetirawatt Toru Yamaguchi Tsutomu Higashiyama Michinori Sumimoto Kenji Hori 《Journal of Physical Organic Chemistry》2012,25(12):1097-1104
In this study, the tautomeric equilibrium between the keto and enol forms has been studied for five typical ketones and aldehydes: i‐butanal, acetaldehyde, acetone, acetylacetone, and dimedone. The level of theory used in the gas‐phase calculation was Becke, three‐parameter, Lee–Yang–Parr/6‐311G(d,p)//Becke, three‐parameter, Lee–Yang–Parr/6‐31G(d). The free energies of solvation were included in the calculation by using the free‐energy perturbation method based on Monte Carlo simulation, that is, the quantum mechanical/Monte Carlo/free‐energy perturbation method. Three different models, incorporating no‐water, one‐water, and two‐waters, were adopted. The results showed that in the gas phase the addition of water molecules to the reaction mechanism caused the activation barriers (ΔG?gas) to decrease by half relative to the water‐free mechanism, but there was no effect on the relative difference in free energy, ΔGgas. The solvation effects (ΔGsol), based on quantum mechanical/Monte Carlo/free‐energy perturbation calculations, were added to those of the gas‐phase results of the one‐water and two‐waters models. The two‐waters model produced values that were very consistent with the experimental data for all of the tautomers. The differences in the relative Gibbs free energy (ΔGrxn) were less than 1.0 kcal mol–1. In summary, the inclusion of solvent molecules in gas‐phase calculations plays a very important role in producing results consistent with experimental data. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
65.
Scale‐up synthesis of hyperbranched poly(amidoamine)‐grafted ultrafine silica was successfully achieved by using dendrimer synthesis methodology in solvent‐free dry‐system. The poly(amidoamine) was allowed to grow from silica surface by repeating two steps: (1) Michael addition of methyl acrylate (MA) to amino group on the surface and (2) amidation of terminal ester group with ethylenediamine (EDA). MA was sprayed onto silica having amino group and the silica agitated at 300 rpm at 50 °C. After the reaction, unreacted MA was removed under vacuum. Then EDA was sprayed and the reaction was conducted at 50 °C with agitation. After the reaction, unreacted EDA was also removed under vacuum at 50 °C and MA was sprayed again. The percentage of poly(amidoamine) grafting onto the surface was determined to be 141% with repeated reaction cycles of eight‐times. However, the value was considerably smaller than that of the theoretical value. This indicates that the propagation of poly(amidoamine) dendron from silica surface was not achieved theoretically and hyperbranched poly(amidoamine) was grafted onto the surface because of steric hindrance of grafted polymer. In addition, the effect of initial amino group content on the growth of poly(amidoamine) from the surface was investigated. It was concluded that the method is suitable for the scale‐up synthesis of hyperbranched poly(amidoamine)‐grafted silica. Copyright © 2002 John Wiley & Sons, Ltd. 相似文献
66.
Reaction of 1-chlorovinyl p-tolyl sulfoxides, which were synthesized from chloromethyl p-tolyl sulfoxide and ketones or aldehydes, with lithium enolate of N,N-dimethylacetamide gave the adducts in good to quantitative yields. The adducts were converted to several kinds of amides in high overall yields. Treatment of the adducts with trifluoroacetic anhydride in the presence of NaI resulted in the formation of γ-tolylsulfanylated γ-lactones in high yields. The scope and limitations of this method and the mechanism of the reactions are also discussed. These procedures offer a new and effective method for the synthesis of amides and γ-lactones having substituents on the β-carbon from N,N-dimethylacetamide with carbon elongation. 相似文献
67.
68.
69.
Jukiya Sakamoto Yuhei Umeda Kenta Rakumitsu Prof. Dr. Michinori Sumimoto Prof. Dr. Hayato Ishikawa 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(32):13516-13524
A collective synthesis of glycosylated monoterpenoid indole alkaloids is reported. A highly diastereoselective Pictet–Spengler reaction with α-cyanotryptamine and secologanin tetraacetate as substrates, followed by a reductive decyanation reaction, was developed for the synthesis of (−)-strictosidine, which is an important intermediate in biosynthesis. This two-step chemical method was established as an alternative to the biosynthetically employed strictosidine synthase. Furthermore, after carrying out chemical and computational studies, a transition state for induction of diastereoselectivity in our newly discovered Pictet–Spengler reaction is proposed. Having achieved the first enantioselective total synthesis of (−)-strictosidine in just 10 steps, subsequent bioinspired transformations resulted in the concise total syntheses of (−)-strictosamide, (−)-neonaucleoside A, (−)-cymoside, and (−)-3α-dihydrocadambine. 相似文献
70.
Collective Synthesis and Biological Evaluation of Tryptophan‐Based Dimeric Diketopiperazine Alkaloids 下载免费PDF全文
Shinji Tadano Yukihiro Sugimachi Prof. Dr. Michinori Sumimoto Prof. Dr. Sachiko Tsukamoto Prof. Dr. Hayato Ishikawa 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(4):1277-1291
A concise two one‐pot synthesis of WIN 64821, eurocristatine, 15,15′‐bis‐epi‐eurocristatine, ditryptophenaline, ditryptoleucine A, WIN 64745, cristatumin C, asperdimin, naseseazine A, and naseseazine B is detailed, based on a unique bioinspired dimerization reaction of tryptophan derivatives in aqueous acidic solution and a one‐pot procedure for the construction of diketopiperazine rings. Total yields of these alkaloid syntheses were from 10 up to 27 %. In addition, 1′‐(2‐phenylethylene)‐ditryptophenaline was synthesized by using three one‐pot operations. The studies detailed herein provided synthesized natural products for inhibitory activities of ubiquitin‐specific protease 7 (USP7) and foam cell formation in macrophages. The newly listed biological evaluation for tryptophan‐based dimeric diketopiperazine alkaloids discovered 15,15′‐bis‐epi‐eurocristatine, 1′‐(2‐phenylethylene)‐ditryptophenaline, and WIN 64745 as new drug candidates. 相似文献