全文获取类型
收费全文 | 324篇 |
免费 | 2篇 |
专业分类
化学 | 234篇 |
晶体学 | 10篇 |
力学 | 2篇 |
数学 | 11篇 |
物理学 | 69篇 |
出版年
2023年 | 2篇 |
2022年 | 4篇 |
2021年 | 2篇 |
2019年 | 6篇 |
2016年 | 2篇 |
2015年 | 5篇 |
2014年 | 3篇 |
2013年 | 13篇 |
2012年 | 12篇 |
2011年 | 21篇 |
2010年 | 10篇 |
2009年 | 5篇 |
2008年 | 19篇 |
2007年 | 26篇 |
2006年 | 20篇 |
2005年 | 20篇 |
2004年 | 20篇 |
2003年 | 9篇 |
2002年 | 11篇 |
2001年 | 10篇 |
2000年 | 13篇 |
1999年 | 2篇 |
1997年 | 5篇 |
1996年 | 6篇 |
1995年 | 5篇 |
1994年 | 2篇 |
1993年 | 5篇 |
1992年 | 1篇 |
1991年 | 2篇 |
1990年 | 4篇 |
1989年 | 1篇 |
1988年 | 2篇 |
1987年 | 5篇 |
1986年 | 2篇 |
1985年 | 1篇 |
1984年 | 3篇 |
1983年 | 3篇 |
1982年 | 4篇 |
1981年 | 5篇 |
1980年 | 2篇 |
1979年 | 8篇 |
1978年 | 2篇 |
1977年 | 5篇 |
1976年 | 2篇 |
1975年 | 4篇 |
1974年 | 2篇 |
1973年 | 3篇 |
1972年 | 1篇 |
1968年 | 1篇 |
1966年 | 1篇 |
排序方式: 共有326条查询结果,搜索用时 15 毫秒
11.
The rate constants for the gas-phase reactions of isopropyl- and tert-butylperoxy radicals with nitric oxide (NO) have been studied at 298 +/- 2 K and a total pressure of 3-4 Torr (He buffer) using a laser flash photolysis technique coupled with a time-resolved negative-ionization mass spectrometry. The alkyl peroxy radicals were generated by the reaction of alkyl radicals with excess O(2), where alkyl radicals were prepared by laser photolysis of several precursor molecules. The rate constants were determined to be k(i-C(3)H(7)O(2) + NO) = (8.0 +/- 1.5) x 10(-12) and k(t-C(4)H(9)O(2) + NO) = (8.6 +/- 1.4) x 10(-12) cm(3) molecule(-1) s(-1). The results in combination with our previous studies are discussed in terms of the systematic reactivity of alkyl peroxy radicals toward NO. 相似文献
12.
The reaction of conjugated dienes such as 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2,5-dimethyl-2,4-hexadiene, 1,3-cyclopentadiene, and 1,3-cyclohexadiene, with thallium(III)acetate in acetic acid at 10–65° for 0.5–15 hr affords an isomeric mixture of the corresponding diacetoxyalkenes (1,2- and 1,4-addition products) in 10–92% yields. The 1,2-addition products are predominantly formed in all cases examined except the case of 1,3-cyclopentadiene. The reaction is assumed to proceed through acetoxythallation and dethallation steps, the latter step being accompanied and/or followed by an attack of acetoxyl group. An initial attack of thallium moiety is proposed to occur mainly at C-1 and C-2 carbons in the cases of linear terminal dienes and cyclic dienes, respectively. 相似文献
13.
14.
This study shows the ESR spectra of oxoiron(IV) porphyrin pi-cation radicals of 1-8 in dichloromethane-methanol (5:1) mixture. We reported in a previous paper that oxoiron(IV) porphyrin pi-cation radicals of 1-4 are in an a(1u) radical state while those of 5-8 are in an a(2u) radical. The ESR spectra (g( perpendicular)(eff) approximately 3.1 and g( parallel)(eff) approximately 2.0) for the a(1u) radical complexes, 1-4, appear quite different from those reported previously for the oxoiron(IV) porphyrin pi-cation radical of 5 (g(y) = 4.5, g(x) = 3.6, and g(z) = 1.99). The unique ESR spectra of the a(1u) radical complexes rather resemble those of compound I from Micrococcus lysodeikticus catalase (CAT) and ascorbate peroxidase (ASP). This is the first examples to mimic the ESR spectra of compound I in the enzymes. From spectral analysis based on a spin Hamiltonian containing an exchange interaction, the ESR spectra of 1-4 can be explained as a moderate ferromagnetic state (J/D approximately 0.3) between ferryl S = 1 and the porphyrin pi-cation radical S' = (1)/(2). The magnitudes of zero-field splitting (D) for ferryl iron and isotropic J value, estimated from the temperature-dependence of the half-saturation power of the ESR signals, are approximately 28 and approximately +8 cm(-1), respectively. A change in the electronegativity of the beta-pyrrole substituent hardly changes the ESR spectral feature while that of the meso-substituent slightly does owing to the change in the E/D value. On the basis of the present ESR results, we propose the a(1u) radical state for compound I of CAT and ASP. 相似文献
15.
Akihiko Ishii Masashi Saitoh Tetsuhiko Kawai Masami Murata Juzo Nakayama 《Phosphorus, sulfur, and silicon and the related elements》2013,188(8-9):2025-2026
The reaction of isolable dithiirane 1-oxides with (Ph 3 P) 2 Pt( m 2 -C 2 H 4 ) provided the title complexes in high yields. 31 P NMR spectroscopy of the phosphine ligands of the complexes and x-ray crystallographic analysis of a complex were reported. 相似文献
16.
Kazuyuki Kubo Hiroshi Nakazawa Hiroyasu Inagaki Tomoyuki Miyake Tsutomu Mizuta Katsuhiko Miyoshi 《Phosphorus, sulfur, and silicon and the related elements》2013,188(8-9):2159-2160
Treatment of [Cp*(CO) 2 M{P(NHPh)(OMe) 2 }]PF 6 (M = Fe and Ru) with NaNH 2 gives metallaiminophosphoranes, Cp*(CO) 2 M{P(NPh)(OMe) 2 }. The x-ray structures and reactivity of the complexes are reported. 相似文献
17.
Yasuo Tokit Yoshio Inoue Riichir Chûj Yasuhiro Miyoshi 《Magnetic resonance in chemistry : MRC》1975,7(10):485-487
Carbon-13 NMR spectra have been obtained for all-trans-N-retinylidene-n-butylamine as an analogue of the Schiff's base linkage compound in visual pigment. The chemical shift changes on going from all-trans-retinal1 to all-trans-N-retinylidene-n-butylamine are observed. These changes indicate the collapse of the bond alternation in conjugated polyene carbons, whereas N-protonation in all-trans-N-retinylidene-n-butylamine does not affect the bond alternation. 相似文献
18.
Cho T Yoshida M Kohagura J Hirata M Numakura T Higaki H Hojo H Ichimura M Ishii K Islam KM Itakura A Katanuma I Nakashima Y Saito T Tatematsu Y Yoshikawa M Kojima Y Tokioka S Yokoyama N Tomii Y Imai T Pastukhov VP Miyoshi S;GAMMA Group 《Physical review letters》2005,94(8):085002
Vortexlike turbulent structures in hot-ion mode plasmas with several keV are observed in the case with a radially produced weak shear of electric fields E(r). However, a strong E(r) shear formation due to a high ion-confining potential phi(c) production clears up these vortices together with plasma-confinement improvement and disappearance of both drift-wave and turbulencelike Fourier spectral signals. These findings are based on three-time progress in phi(c) in comparison to phi(c) attained 1992-2002. The significant advance of phi(c) is well extended in line with proposed potential-formation physics scalings. 相似文献
19.
T. Watanabe P. Bydžovský K. Dobashi S. Endo Y. Fujii O. Hashimoto T. Ishikawa K. Itoh H. Kanda M. Katoh T. Kinoshita O. Konno K. Maeda A. Matsumura F. Miyahara H. Miyase T. Miyoshi K. Mizunuma Y. Miura S.N. Nakamura H. Nomura Y. Okayasu T. Osaka M. Oyamada A. Sasaki T. Satoh H. Shimizu M. Sotona T. Takahashi T. Tamae H. Tamura T. Terasawa H. Tsubota K. Tsukada M. Ukai M. Wakamatsu H. Yamauchi H. Yamazaki 《Physics letters. [Part B]》2007
20.
The 7-endo Friedel-Crafts cyclization of arylpropyl vinyloxiranes was found to proceed regio- and stereoselectively to afford polyfunctional seven-membered carbocycles in excellent yields. 相似文献