全文获取类型
收费全文 | 608篇 |
免费 | 26篇 |
国内免费 | 3篇 |
专业分类
化学 | 475篇 |
晶体学 | 6篇 |
力学 | 7篇 |
数学 | 27篇 |
物理学 | 122篇 |
出版年
2023年 | 3篇 |
2021年 | 5篇 |
2020年 | 14篇 |
2019年 | 16篇 |
2018年 | 9篇 |
2017年 | 3篇 |
2016年 | 18篇 |
2015年 | 11篇 |
2014年 | 15篇 |
2013年 | 31篇 |
2012年 | 30篇 |
2011年 | 28篇 |
2010年 | 11篇 |
2009年 | 27篇 |
2008年 | 36篇 |
2007年 | 34篇 |
2006年 | 35篇 |
2005年 | 38篇 |
2004年 | 42篇 |
2003年 | 27篇 |
2002年 | 21篇 |
2001年 | 7篇 |
2000年 | 6篇 |
1999年 | 12篇 |
1998年 | 7篇 |
1997年 | 8篇 |
1996年 | 4篇 |
1995年 | 7篇 |
1994年 | 6篇 |
1993年 | 7篇 |
1992年 | 7篇 |
1991年 | 7篇 |
1990年 | 11篇 |
1989年 | 6篇 |
1988年 | 5篇 |
1987年 | 5篇 |
1986年 | 5篇 |
1985年 | 11篇 |
1984年 | 5篇 |
1983年 | 10篇 |
1982年 | 4篇 |
1981年 | 5篇 |
1980年 | 3篇 |
1979年 | 6篇 |
1978年 | 7篇 |
1976年 | 3篇 |
1974年 | 3篇 |
1970年 | 2篇 |
1969年 | 3篇 |
1968年 | 2篇 |
排序方式: 共有637条查询结果,搜索用时 31 毫秒
1.
Cross‐Coupling of Organolithium with Ethers or Aryl Ammonium Salts by C−O or C−N Bond Cleavage 下载免费PDF全文
Ze‐Kun Yang Dong‐Yu Wang Hiroki Minami Hiroyuki Ogawa Takashi Ozaki Dr. Tatsuo Saito Dr. Kazunori Miyamoto Dr. Chao Wang Prof. Dr. Masanobu Uchiyama 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(44):15693-15699
Various aryl‐, alkenyl‐, and/or alkyllithium species reacted smoothly with aryl and/or benzyl ethers with cleavage of the inert C?O bond to afford cross‐coupled products, catalyzed by commercially available [Ni(cod)2] (cod=1,5‐cyclooctadiene) catalysts with N‐heterocyclic carbene (NHC) ligands. Furthermore, the coupling reaction between the aryllithium compounds and aryl ammonium salts proceeded under mild conditions with C?N bond cleavage in the presence of a [Pd(PPh3)2Cl2] catalyst. These methods enable selective sequential functionalizations of arenes having both C?N and C?O bonds in one pot. 相似文献
2.
Yulu Jiang Dr. Taro Ozaki Mei Harada Tadachika Miyasaka Dr. Hajime Sato Dr. Kazunori Miyamoto Dr. Junichiro Kanazawa Dr. Chengwei Liu Prof. Dr. Jun-ichi Maruyama Dr. Masaatsu Adachi Dr. Atsuo Nakazaki Prof. Dr. Toshio Nishikawa Prof. Dr. Masanobu Uchiyama Dr. Atsushi Minami Prof. Dr. Hideaki Oikawa 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(41):18152-18158
Lolitrems are tremorgenic indole diterpenes that exhibit a unique 5/6 bicyclic system of the indole moiety. Although genetic analysis has indicated that the prenyltransferase LtmE and the cytochrome P450 LtmJ are involved in the construction of this unique structure, the detailed mechanism remains to be elucidated. Herein, we report the reconstitution of the biosynthetic pathway for lolitrems employing a recently established genome-editing technique for the expression host Aspergillus oryzae. Heterologous expression and bioconversion of the various intermediates revealed that LtmJ catalyzes multistep oxidation to furnish the lolitrem core. We also isolated the key reaction intermediate with an epoxyalcohol moiety. This observation allowed us to establish the mechanism of radical-induced cyclization, which was firmly supported by density functional theory calculations and a model experiment with a synthetic analogue. 相似文献
3.
Mitsunori Fukaya Shota Nagamine Dr. Taro Ozaki Yaping Liu Miina Ozeki Taro Matsuyama Dr. Kazunori Miyamoto Prof. Dr. Hirokazu Kawagishi Prof. Dr. Masanobu Uchiyama Prof. Dr. Hideaki Oikawa Dr. Atsushi Minami 《Angewandte Chemie (International ed. in English)》2023,62(44):e202308881
Mushroom terpenoids are biologically and chemically diverse fungal metabolites. Among them, melleolides are representative sesquiterpenoids with a characteristic protoilludane skeleton. In this study, we applied a recently established hot spot knock-in method to elucidate the biosynthetic pathway leading to 1α-hydroxymelleolide. The biosynthesis of the sesquiterpene core involves the cytochrome P450 catalyzing stepwise hydroxylation of the Δ6-protoilludene framework and a stereochemical inversion process at the C5 position catalyzed by short-chain dehydrogenase/reductase family proteins. The highlight of the biosynthesis is that the flavoprotein Mld7 catalyzes an oxidation-triggered double-bond shift accompanying dehydration and acyl-group-assisted substitution with two different nucleophiles at the C6 position to afford the Δ7-protoilludene derivatives, such as melleolide and armillarivin. The complex reaction mechanism was proposed by DFT calculations. Of particular importance is that product distribution is regulated by interaction with the cell membrane. 相似文献
4.
Crystal Structure of the Isopropylzinc Alkoxide of Pyrimidyl Alkanol: Mechanistic Insights for Asymmetric Autocatalysis with Amplification of Enantiomeric Excess 下载免费PDF全文
Dr. Arimasa Matsumoto Takaaki Abe Atsushi Hara Takayuki Tobita Taisuke Sasagawa Prof. Dr. Tsuneomi Kawasaki Prof. Dr. Kenso Soai 《Angewandte Chemie (International ed. in English)》2015,54(50):15218-15221
Asymmetric amplification during self‐replication is a key feature that is used to explain the origin of homochirality. Asymmetric autocatalysis of pyrimidyl alkanol in the asymmetric addition of diisopropylzinc to pyrimidine‐5‐carbaldehyde is a unique example of this phenomenon. Crystallization of zinc alkoxides of this 5‐pyrimidyl alkanol and single‐crystal X‐ray diffraction analysis of the alkoxide crystals reveal the existence of tetramer or higher oligomer structures in this asymmetric autocatalytic system. 相似文献
5.
Daitaro?IshikawaEmail author Daiki?Furukawa Tseng?Tsai?Wei Kummetha?Raghunatha?Reddy Asako?Motomura Yoko?Igarashi Harumi?Sato Sergei?G.?Kazarian Yukihiro?Ozaki 《Analytical and bioanalytical chemistry》2015,407(2):397-403
We aimed to achieve wide area rapid monitoring of the crystallinity change in poly(lactic acid) (PLA) during photodegradation caused by ultraviolet (UV) light by using a newly developed near-infrared (NIR) camera (Compovison). Several kinds of PLA samples with different crystallinities and their blends with poly[(3)-(R)-hydroxybutyrate] were prepared. Their two-dimensional NIR spectra in the 1,000–2,350-nm region were measured by Compovision at a 5-min interval during photolysis. An intensity decrease of the band in the 1,900-1,925-nm region due to the second overtone of the C = O stretching vibration of PLA was observed during photolysis. This suggests that an anhydride carbonyl is produced during photolysis. The NIR image of the crystallinity change monitored by the band at 1,917 nm in the standard normal variate spectra clearly shows the inhomogeneity of crystal evolution. A logarithmic increase was observed for all identified areas in the PLA film; however, the time to reach the maximum crystallinity was slightly different according to the initial crystallinity of the sample. It is likely that the initial crystallinity of the sample influences the degradation speed more than the degradation amount. These imaging results have provided fundamental chemical insights into the photolytic process for PLA, and at the same time they have demonstrated that the two-dimensional spectral data obtained by Compovision are useful for process monitoring of polymers. 相似文献
6.
Prof. Dr. Tsutomu Ishi-i Honoka Tanaka Rihoko Kichise Christopher Davin Takaaki Matsuda Dr. Naoya Aizawa Dr. In Seob Park Prof. Dr. Takuma Yasuda Taisuke Matsumoto 《化学:亚洲杂志》2021,16(15):2136-2145
The regulation of multicolor fluorescence changes in mechanochromic fluorescence (MCF) remains a challenging task. Herein, we report the regulation of MCF using a donor-acceptor structure. Two crystal polymorphs, BTD-pCHO(O) and BTD-pCHO(R) produced by the introduction of formyl groups to an MCF dye, respond to a mechanical stimulus, allowing a three-color fluorescence change. Specifically, the orange-colored fluorescence of the metastable BTD-pCHO(O) polymorph changed to a deep-red color in the amorphous-like state to finally give a red color in the stable BTD-pCHO(R) polymorph. This change occurred by mechanical grinding followed by vapor fuming. The two different crystal packing patterns were selectively regulated by the electronic effect of the introduced functional groups. The two types of selectively formed crystals in BTD(F)-pCHO bearing fluorine atoms, and BTD(OMe)-pCHO bearing methoxy groups, respond to mechanical grinding, allowing for the regulation of multicolor MCL from a three-color change to two different types of two-color changes. 相似文献
7.
Koki Ikemoto Shotaro Harada Seungmin Yang Taisuke Matsuno Hiroyuki Isobe 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2022,134(1):e202114305
A 3-nm molecule comprising a cylindrical core and cross-shaped rims was designed and synthesized by developing a modular synthetic route. By using a cyclic precursor from previous studies as a starting material, multiple carbazole units were installed at the rims of the defective cylinder. The defective cylinder was synthetically doped with two types of nitrogen atoms, that is, pyridinic and pyrrolic nitrogen atoms, which resulted in solvatochromic shifts in fluorescence by charge-transfer interactions. The structure of the large, C552H496N24 molecule was fully disclosed by crystallographic analyses, and the unique helical arrangement of nitrogen-doped cylinders in the crystal was revealed. 相似文献
8.
Takeshi Takeda Shuichi Kuroi Makoto Ozaki Akira Tsubouchi 《Phosphorus, sulfur, and silicon and the related elements》2013,188(5-6):1291-1296
Abstract Trialkylsilyl group-directed regioselective transformations of alkynyl thioacetals to alkynylcyclopropanes and enynes are described. 相似文献
9.
10.
Guangwu Li Taisuke Matsuno Yi Han Hoa Phan Shaofei Wu Qing Jiang Ya Zou Hiroyuki Isobe Jishan Wu 《Angewandte Chemie (International ed. in English)》2020,59(24):9727-9735
Synthesis of fully conjugated cyclophanes containing large‐size polycyclic aromatics is challenging. Now, three benzidine‐linked, hexa‐peri‐hexabenzocoronene (superbenzene)‐based ortho‐, para‐, and meta‐cyclophanes are synthesized through intermolecular Yamamoto coupling reaction of structurally pre‐organized precursors. Subsequent oxidative dehydrogenation gave the corresponding quinoidal benzidine‐linked cyclophanes. Their geometries were confirmed by X‐ray crystallographic analysis and their electronic properties were investigated by electronic absorption, cyclic voltammetry, and DFT calculations. The quinoidal benzidine‐linked cyclophanes show thermally populated paramagnetic activity with a relatively large singlet‐triplet energy gap. Two enantiomers for the ortho‐cyclophanes ( 1‐NH and 1‐N ) were isolated and their chiral figure‐of‐eight macrocyclic structures were identified. The cage‐like cyclophanes 2‐NH and 3‐NH with concave surface can selectively encapsulate fullerene C70. 相似文献