全文获取类型
收费全文 | 1838篇 |
免费 | 59篇 |
国内免费 | 4篇 |
专业分类
化学 | 1387篇 |
晶体学 | 25篇 |
力学 | 30篇 |
数学 | 74篇 |
物理学 | 385篇 |
出版年
2023年 | 7篇 |
2021年 | 23篇 |
2020年 | 26篇 |
2019年 | 34篇 |
2018年 | 13篇 |
2017年 | 18篇 |
2016年 | 26篇 |
2015年 | 35篇 |
2014年 | 42篇 |
2013年 | 86篇 |
2012年 | 89篇 |
2011年 | 103篇 |
2010年 | 61篇 |
2009年 | 47篇 |
2008年 | 104篇 |
2007年 | 112篇 |
2006年 | 108篇 |
2005年 | 121篇 |
2004年 | 83篇 |
2003年 | 78篇 |
2002年 | 76篇 |
2001年 | 50篇 |
2000年 | 42篇 |
1999年 | 29篇 |
1998年 | 31篇 |
1997年 | 25篇 |
1996年 | 31篇 |
1995年 | 18篇 |
1994年 | 18篇 |
1993年 | 23篇 |
1992年 | 30篇 |
1991年 | 23篇 |
1990年 | 15篇 |
1989年 | 27篇 |
1988年 | 11篇 |
1987年 | 9篇 |
1986年 | 19篇 |
1985年 | 24篇 |
1984年 | 24篇 |
1983年 | 15篇 |
1982年 | 15篇 |
1981年 | 13篇 |
1980年 | 10篇 |
1979年 | 15篇 |
1978年 | 12篇 |
1977年 | 12篇 |
1976年 | 12篇 |
1975年 | 10篇 |
1974年 | 12篇 |
1973年 | 11篇 |
排序方式: 共有1901条查询结果,搜索用时 296 毫秒
101.
Dr. Jun‐ichi Matsuo Prof. Dr. Masahiro Murakami 《Angewandte Chemie (International ed. in English)》2013,52(35):9109-9118
A directed cross‐aldol reaction of silyl enol ethers with carbonyl compounds, such as aldehydes and ketones, promoted by a Lewis acid, a reaction which is now widely known as the Mukaiyama aldol reaction. It was first reported in 1973, and this year marks the 40th anniversary. The directed cross‐aldol reactions mediated by boron enolates and tin(II) enolates also emerged from the Mukaiyama laboratory. These directed cross‐aldol reactions have become invaluable tools for the construction of stereochemically complex molecules from two carbonyl compounds. This Minireview provides a succinct historical overview of their discoveries and the early stages of their development. 相似文献
102.
Masanobu Yamamoto Ryoko Maruyama Yoko Murakami Yuki Sakamoto Rei Yamakawa Tetsu Ando 《Analytical and bioanalytical chemistry》2013,405(23):7405-7414
trans-11,12-Epoxy-(6Z,9Z)-6,9-henicosadiene (posticlure) has been identified from a pheromone gland of the lymantriid species, Orgyia postica. Since the diversity of Lepidoptera suggests that some species utilize the structure-related epoxy compound as a sex pheromone component, epoxydienes and epoxytrienes derived from (6Z,9Z,11E)-6,9,11-trienes and (3Z,6Z,9Z,11E)-3,6,9,11-tetraenes with a C19–C21 chain were systematically synthesized and the chemical data were accumulated in order to contribute to a new pheromone research. Peracid oxidation of each triene and each tetraene produced, respectively, a mixture of three epoxydienes (cis-6,7-epoxy-9,11-diene; cis-9,10-epoxy-6,11-diene; and trans-11,12-epoxy-6,9-diene) and four epoxytrienes (cis-3,4-epoxy-6,9,11-triene; cis-6,7-epoxy-3,9,11-triene; cis-9,10-epoxy-3,6,11-triene; and trans-11,12-epoxy-3,6,9-triene). While the 9,10-epoxy compounds were unstable and, interestingly, converted into 9-ketone derivatives after chromatography over SiO2, each positional isomer was isolated by HPLC equipped with an ODS column, and the chemical structure was determined by NMR analysis. On the GC-MS analysis with a DB-23 column, the positional isomers were also eluted separately and characteristic mass spectra were proposed. By comparing the spectral data of the epoxy compounds with a different carbon chain, diagnostic fragment ions reflecting the chemical structure were determined as follows: m/z 79, 109, 113, and M-114 for the 6,7-epoxydienes; m/z 69, 97, 111, 139, and M-111 for the 9,10-epoxydienes; m/z 57, 79, 109, 136, M-151, and M-111 for the 11,12-epoxydienes; m/z 79, 91, 105, and 119 for the 3,4-epoxytrienes; m/z 79, 124, M-124, M-96, and M-69 for the 6,7-epoxytrienes; m/z 79, 95, 109, 137, and M-108 for the 9,10-epoxytrienes; and m/z 79, 134, M-149, M-109, and M-95 for the 11,12-epoxytrienes. 相似文献
103.
Kenichiro Todoroki Hiroki Hashimoto Kazuyuki Machida Miki Itoyama Tadashi Hayama Hideyuki Yoshida Hitoshi Nohta Manabu Nakashima Masatoshi Yamaguchi 《Journal of separation science》2013,36(2):232-238
In this study, we combined a column‐switching system with a fluorous scavenging derivatization method to develop a fully automated reagent peak‐free LC fluorescence detection protocol for the analysis of highly polar carboxylic acids. In this method, highly polar carboxylic acids were derivatized with fluorescent 1‐pyrenemethylamine in the presence of 1‐ethyl‐3‐(3‐dimethylaminopropyl)carbodiimide and 1‐hydroxy‐1H‐benzotriazole. Residual excess of the unreacted reagent was tagged with 2‐(perfluorooctyl)ethyl isocyanate and then removed selectively using a fluorous column‐switching system placed in front of an analytical reversed‐phase column. The signal of the fluorous‐tagged unreacted reagent was completely absent in the resulting chromatograms; therefore, it did not interfere with the quantification of each acid especially those eluted before 20 min. The detection limits (S/N = 3) for the examined acids were in the range from 4.0 to 22 fmol per injection. We have applied this method to comparative analysis of highly polar carboxylic acids in urine samples obtained from diabetes mellitus type‐II model mice and their control. 相似文献
104.
Takashi Kitayama Maki Nakahira Kae Yamasaki Hiromi Inoue Chika Imada Yuji Yonekura Masataka Awata Hikaru Takaya Yasushi Kawai Kohta Ohnishi Akira Murakami 《Tetrahedron》2013
Zerumbone 1, having powerful latent reactivity and containing two conjugated double bonds and a double conjugated carbonyl group is the major component of the essential oil of wild ginger, Zingiber zerumbet Smith. The conjugation system plays an important role in the expression of biological activity. N-Bromosuccinimide (NBS) reaction of 1 gave high reactive intermediate 2 with an exo-methylene group, which was obtained from 1 quantitatively. Treatment of 2 with nucleophiles gave various zerumbone-pendant derivatives, including C–H, C–O, C–N, and C–C bond formation, maintaining the conjugation system through SN2′-type reaction. Almost all zerumbone-pendant derivatives showed a good value of IC50 against the suppressive effect of NO generation. Among them, amine derivative 5, binding with 2 mol of zerumbone, showed the strongest activity (IC50: 0.24 μM). 相似文献
105.
Satoshi Kaneco Kensuke Hayashi Hideyuki Katsumata Tohru Suzuki 《International journal of environmental analytical chemistry》2013,93(13):1381-1388
A preconcentration method by adsorption of cadmium on a niobium wire was developed for the environmental waters, followed by electrothermal atomic absorption spectrometry with a tungsten tube atomizer. After the preconcentration, the niobium wire was directly inserted into the tungsten tube atomizer. In the preconcentration (adsorption) process of cadmium, the optimal immersing time was 60?s. The effects of large amounts of concomitants on the preconcentration of cadmium were evaluated. When 103–104 fold excess of matrix elements existed in aqueous solution at pH 4 and 9, the cadmium response was profoundly affected by the matrix elements. However, the cadmium absorption signal was not significantly influenced at pH 7. Therefore, pH 7 was selected for the application into the real environmental samples. Under the optimal conditions, the detection limit (3S/N) for cadmium by the niobium wire preconcentration method was 7.0?pg?mL?1 and the relative standard deviation was 6.8%. The method with preconcentration on a niobium wire was applied to the determination of cadmium in water and proved to be sensitive, simple and convenient. Because this preconcentration method can be utilized in the in situ treatment of trace cadmium in environmental water samples, it was unnecessary to carry the water samples to the analytical work place. The technique was shown to be useful for the determination of cadmium in environmental water samples at 0.1–1?µg?L?1 levels. 相似文献
106.
107.
Prof. Dr. Mutsumi Kimura Junya Masuo Yuki Tohata Kazumichi Obuchi Naruhiko Masaki Takurou N. Murakami Nagatoshi Koumura Kojiro Hara Atsushi Fukui Ryohsuke Yamanaka Prof. Dr. Shogo Mori 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(3):1028-1034
A series of panchromatic ruthenium sensitizers ( MJ sensitizers) with attached thiophene and phenyl units bearing alkyl chains was synthesized. A new synthetic route was used to examine all possible positions for the alkyl chains. The absorption spectra showed the sum of a ruthenium complex and peripheral organic chromophore units. The hypochromic effect and blueshift of the metal‐to‐ligand charge‐transfer band observed in the modified ruthenium sensitizers were suppressed by changing the positions of the alkyl chains on the attached thiophene ring. Changing only one alkyl chain also influenced the performance of dye‐sensitized solar cells. Ruthenium sensitizer MJ‐10 with bulky substituent harvests visible and near‐infrared light, and solar cells sensitized by MJ‐10 exhibit an efficiency of 9.1 % under 1 sun irradiation. 相似文献
108.
Synthesis,Crystal Packing,and Ambipolar Carrier Transport Property of Twisted Dibenzo[g,p]chrysenes 下载免费PDF全文
Dr. Yasuyuki Ueda Dr. Hayato Tsuji Dr. Hideyuki Tanaka Prof. Dr. Eiichi Nakamura 《化学:亚洲杂志》2014,9(6):1623-1628
A versatile method for the synthesis of dibenzo[g,p]chrysene (DBC) derivatives based on regio‐ and stereoselective stannyllithiation to diarylacetylenes is described. This method affords a variety of DBCs possessing both electron‐donating and electron‐withdrawing functional groups. These twisted molecules take brickwork packing structures in single crystals. Thus, ambipolar carrier transport properties with mobility values of up to 10?3 cm2 V?1 s?1 in the amorphous state were achieved. Functional groups on DBC frameworks are considered to increase carrier mobility through the enhancement of intermolecular interactions in the brickwork packing structures. 相似文献
109.
Li T Garg U Liu Y Marks R Nayak BK Rao PV Fujiwara M Hashimoto H Kawase K Nakanishi K Okumura S Yosoi M Itoh M Ichikawa M Matsuo R Terazono T Uchida M Kawabata T Akimune H Iwao Y Murakami T Sakaguchi H Terashima S Yasuda Y Zenihiro J Harakeh MN 《Physical review letters》2007,99(16):162503
The strength distributions of the giant monopole resonance (GMR) have been measured in the even-A Sn isotopes (A=112-124) with inelastic scattering of 400-MeV alpha particles in the angular range 0 degrees -8.5 degrees . We find that the experimentally observed GMR energies of the Sn isotopes are lower than the values predicted by theoretical calculations that reproduce the GMR energies in 208Pb and 90Zr very well. From the GMR data, a value of Ktau = -550 +/- 100 MeV is obtained for the asymmetry term in the nuclear incompressibility. 相似文献
110.
Herein reported is a photo-induced production of vicinal diols from alkenes under mild reaction conditions. The present dihydroxylation method using diacetyl (= butane-2,3-dione), oxygen, and water dispenses with toxic reagents and intractable waste generation. 相似文献