全文获取类型
收费全文 | 857篇 |
免费 | 35篇 |
专业分类
化学 | 643篇 |
晶体学 | 6篇 |
力学 | 18篇 |
数学 | 22篇 |
物理学 | 203篇 |
出版年
2021年 | 8篇 |
2019年 | 10篇 |
2018年 | 7篇 |
2016年 | 24篇 |
2015年 | 26篇 |
2014年 | 16篇 |
2013年 | 41篇 |
2012年 | 41篇 |
2011年 | 59篇 |
2010年 | 26篇 |
2009年 | 30篇 |
2008年 | 56篇 |
2007年 | 31篇 |
2006年 | 38篇 |
2005年 | 38篇 |
2004年 | 34篇 |
2003年 | 40篇 |
2002年 | 30篇 |
2001年 | 22篇 |
2000年 | 17篇 |
1999年 | 12篇 |
1998年 | 4篇 |
1997年 | 13篇 |
1996年 | 9篇 |
1995年 | 12篇 |
1994年 | 15篇 |
1993年 | 11篇 |
1992年 | 14篇 |
1991年 | 7篇 |
1990年 | 11篇 |
1989年 | 5篇 |
1988年 | 8篇 |
1987年 | 10篇 |
1986年 | 4篇 |
1985年 | 13篇 |
1984年 | 9篇 |
1983年 | 14篇 |
1982年 | 7篇 |
1981年 | 9篇 |
1980年 | 12篇 |
1979年 | 13篇 |
1978年 | 12篇 |
1977年 | 7篇 |
1976年 | 13篇 |
1975年 | 5篇 |
1974年 | 6篇 |
1973年 | 7篇 |
1970年 | 4篇 |
1968年 | 5篇 |
1964年 | 4篇 |
排序方式: 共有892条查询结果,搜索用时 15 毫秒
1.
Yutaka Matsuo Ya Wang Hiroshi Ueno Takafumi Nakagawa Hiroshi Okada 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(26):8854-8859
(N‐Phenylfluorenylidene)acridane (Ph‐FA) compounds with electron‐withdrawing and ‐donating substituents (H, MeO, Ph, NO2, Br, F) at the para position of the phenyl group were successfully synthesized by Barton–Kellogg reactions of N‐aryl thioacridones and diazofluorene. By using the substituent on the nitrogen atom to alter the electronic properties, both the folded and twisted conformers of p‐NO2‐C6H4‐FA could be crystallographically characterized, which enabled the charge transfer from the electron‐donating acridane moiety to the electron‐accepting fluorenylidene moiety to be understood. Ground‐state mechanochromism, thermochromism, vapochromism, and proton‐induced chromism were demonstrated between the folded and twisted conformations of the conformers. Protonation and chemical oxidation of Ph‐FA gave two stable acridinium compounds, namely, the fluorenylacridinium and acridinium radical cations. The present study will contribute to the development of functional dyes and organic semiconductors. 相似文献
2.
Meccanica - The static deformation of symmetric bow limbs has been widely studied in the last century. However, asymmetries in shape and length which correspond to a more realistic situation, have... 相似文献
3.
Dr. Koichi Mitsudo Ren Matsuo Toki Yonezawa Haruka Inoue Dr. Hiroki Mandai Prof. Dr. Seiji Suga 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(20):7877-7881
The first electrochemical dehydrogenative C−S bond formation leading to thienoacene derivatives is described. Several thienoacene derivatives were synthesized by dehydrogenative C−H/S−H coupling. The addition of nBu4NBr, which catalytically promoted the reaction as a halogen mediator, was essential. 相似文献
4.
5.
Emiko Igarashi Kenta Sakamoto Tomoyuki Yoshimura Jun-ichi Matsuo 《Tetrahedron letters》2019,60(1):13-15
Various 3-phenylcyclobutanones reacted with aliphatic and aromatic nitriles in the presence of Me3SiOTf to afford dihydropyridones by formal [4+2] cycloaddition. 相似文献
6.
Dr. Neil J. Stewart Hitomi Nakano Shuto Sugai Mitsushi Tomohiro Yuki Kase Yoshiki Uchio Dr. Toru Yamaguchi Yujirou Matsuo Dr. Tatsuya Naganuma Dr. Norihiko Takeda Dr. Ikuya Nishimura Dr. Hiroshi Hirata Dr. Takuya Hashimoto Dr. Shingo Matsumoto 《Chemphyschem》2021,22(10):915-923
Hyperpolarized [1-13C]fumarate is a promising magnetic resonance imaging (MRI) biomarker for cellular necrosis, which plays an important role in various disease and cancerous pathological processes. To demonstrate the feasibility of MRI of [1-13C]fumarate metabolism using parahydrogen-induced polarization (PHIP), a low-cost alternative to dissolution dynamic nuclear polarization (dDNP), a cost-effective and high-yield synthetic pathway of hydrogenation precursor [1-13C]acetylenedicarboxylate (ADC) was developed. The trans-selectivity of the hydrogenation reaction of ADC using a ruthenium-based catalyst was elucidated employing density functional theory (DFT) simulations. A simple PHIP set-up was used to generate hyperpolarized [1-13C]fumarate at sufficient 13C polarization for ex vivo detection of hyperpolarized 13C malate metabolized from fumarate in murine liver tissue homogenates, and in vivo 13C MR spectroscopy and imaging in a murine model of acetaminophen-induced hepatitis. 相似文献
7.
8.
Dr. Motoki Toganoh Hideaki Matsuo Ayumi Sato Prof. Hiroyuki Furuta 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(24):8316-8322
Ruthenocene‐type hybrid complexes with N‐fused porphyrinato ligands, [Ru(NFp)Cp] (NFp=N‐fused porphyrin, Cp=cyclopentadienyl), have been prepared and characterized by NMR and UV/Vis/NIR spectroscopy, cyclovoltammetry, and X‐ray crystallography. [Ru(NFp)Cp] is a common low‐spin ruthenium(II) complex and shows strong aromaticity. The Ru–Cp distance (1.833 Å) in [Ru(NFp)Cp] is comparable to that in [RuCp2] (1.840 Å). DFT calculations on [Ru(NFp)Cp] showed the unequivocal contribution of the RuCp moiety as well as the NFp moiety to both the HOMO and LUMO, constructing a three‐dimensional d–π conjugated system. The HOMO–LUMO gaps of [Ru(NFp)Cp] are insensitive to the substituents on the NFp ligand, which is illustrated spectroscopically as well as theoretically. This is in sharp contrast to the ligand precursor, the N‐fused porphyrin, in which the HOMO–LUMO gap is affected by substituents in a similar manner to standard porphyrins and related macrocycles. 相似文献
9.
Takashi Yoshimoto Prof. Dr. Hisako Hashimoto Dr. Nozomi Takagi Prof. Dr. Shigeyoshi Sakaki Naoki Hayakawa Dr. Tsukasa Matsuo Prof. Dr. Hiromi Tobita 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(15):3795-3798
A tungsten silylyne complex having a W≡Si triple bond reacted with two molecules of aldehydes at room temperature to give W−Si−O−C four-membered metallacycles by [2+2] cycloaddition and subsequent formyl hydrogen transfer from one aldehyde molecule to another. Upon heating to 70 °C, the four-membered metallacycles underwent metathesis-like fragmentation cleanly to afford carbyne complexes and “silanoic esters,” in a manner similar to that of metallacyclobutadiene, an intermediate of alkyne metathesis reactions, and dimerization of the latter products gave 1,3-cyclodisiloxanes. The “silanoic ester” was also trapped by pivalaldehyde to give a [2+2] cycloaddition product in high yield. 相似文献
10.
Organic synthesis using biocatalysts has been developed over many years and is still a prominent area of research. In this context, various hybrid biocatalysts composed of a synthetic metal complex catalyst and a protein scaffold (i.e. “artificial metalloenzymes”) have been constructed. One of the most recent research areas in biocatalysts-mediated synthesis is CC bond/cleavage, the most important type of reaction in organic chemistry. Some of the artificial enzymes were applied to in-cell reactions as well as in vitro systems. The effects of the structural fluctuation in biomacromolecules on their functions have also been realized. This review article includes recent research examples of artificial metalloenzymes used to CC bond formation/cleavage. As a perspective, we also focus on how we apply protein dynamics factor for the creation of new generation artificial metalloenzymes. 相似文献