全文获取类型
收费全文 | 1018篇 |
免费 | 60篇 |
国内免费 | 28篇 |
专业分类
化学 | 248篇 |
晶体学 | 2篇 |
力学 | 62篇 |
综合类 | 1篇 |
数学 | 408篇 |
物理学 | 385篇 |
出版年
2023年 | 2篇 |
2022年 | 11篇 |
2021年 | 13篇 |
2020年 | 27篇 |
2019年 | 34篇 |
2018年 | 16篇 |
2017年 | 25篇 |
2016年 | 18篇 |
2015年 | 17篇 |
2014年 | 34篇 |
2013年 | 91篇 |
2012年 | 28篇 |
2011年 | 40篇 |
2010年 | 30篇 |
2009年 | 68篇 |
2008年 | 67篇 |
2007年 | 69篇 |
2006年 | 58篇 |
2005年 | 46篇 |
2004年 | 42篇 |
2003年 | 49篇 |
2002年 | 62篇 |
2001年 | 39篇 |
2000年 | 38篇 |
1999年 | 26篇 |
1998年 | 36篇 |
1997年 | 29篇 |
1996年 | 8篇 |
1995年 | 21篇 |
1994年 | 7篇 |
1993年 | 6篇 |
1992年 | 7篇 |
1991年 | 7篇 |
1990年 | 2篇 |
1989年 | 2篇 |
1988年 | 1篇 |
1987年 | 4篇 |
1986年 | 1篇 |
1985年 | 4篇 |
1984年 | 6篇 |
1982年 | 1篇 |
1981年 | 1篇 |
1980年 | 2篇 |
1979年 | 1篇 |
1977年 | 3篇 |
1976年 | 2篇 |
1972年 | 1篇 |
1971年 | 1篇 |
1970年 | 1篇 |
1969年 | 1篇 |
排序方式: 共有1106条查询结果,搜索用时 31 毫秒
31.
The microbiological transformation of 7-oxo-ent-kaur-16-ene by the fungus Gibberella fujikuroi gave fujenoic acid as the main compound, whilst the incubation of 18-hydroxy-7-oxo-ent-kaur-16-ene and 3α,18-dihydroxy-7-oxo-ent-kaur-16-ene afforded the corresponding 6β-hydroxy-derivatives. These facts indicate that the formation of fujenoic acid in this biotransformation should occur via a 7-oxo-6β-hydroxy derivative. In the three biotransformations, an 11β-hydroxylation was also produced, in low yield, indicating that a 7-oxo-group also directs hydroxylation at C-11. 相似文献
32.
《Tetrahedron》2004,60(36):7921-7932
The microbiological transformation of 13α,17-dihydroxy-stemodane (2) by the fungus Mucor plumbeus afforded 13α,17,19-trihydroxy-stemodane (3), 3β,13α,17-trihydroxy-stemodane (5), 3-oxo-13α,17-dihydroxy-stemodane (7), 7α,13α,17,19-tetrahydroxy-stemodane (8), 3β,11α,13α,17-tetrahydroxy-stemodane (10), 3β,7α,13α,17-tetrahydroxy-stemodane (12), 3β,8β,13α,17-tetrahydroxy-stemodane (14), 2α,13α,17-trihydroxy-stemodane (16), 2α,13α,17,19-tetrahydroxy-stemodane (17), 2α,3β,13α,17-tetrahydroxy-stemodane (20) and 3β,11β,13α,17-tetrahydroxy-stemodane (22), whilst the incubation of 13α,14-dihydroxy-stemodane (25) gave 3β,13α,14-trihydroxy-stemodane (28), 2α,13α,14-trihydroxy-stemodane (29) and 13α,14,19-trihydroxy-stemodane (30). Preference for hydroxylations of ring A at C-2(α), C-3(β) and C-19 were observed in both incubations. An interesting rearrangement of 13α,14α-dihydroxy-stemodanes to 14-oxo derivatives with an unusual carbon framework has been observed under acetylation conditions. We have named this skeleton prestemodane, which, as a hydrocarbon ion, had been postulated as a biogenetic precursor of stemodane. 相似文献
33.
Three‐center nuclear attraction integrals over exponential‐type functions are required for ab initio molecular structure calculations and density functional theory (DFT). These integrals occur in many millions of terms, even for small molecules, and they require rapid and accurate numerical evaluation. The use of a basis set of B functions to represent atomic orbitals, combined with the Fourier transform method, led to the development of analytic expressions for these molecular integrals. Unfortunately, the numerical evaluation of the analytic expressions obtained turned out to be extremely difficult due to the presence of two‐dimensional integral representations, involving spherical Bessel integral functions. % The present work concerns the development of an extremely accurate and rapid algorithm for the numerical evaluation of these spherical Bessel integrals. This algorithm, which is based on the nonlinear D transformation and the W algorithm of Sidi, can be computed recursively, allowing the control of the degree of accuracy. Numerical analysis tests were performed to further improve the efficiency of our algorithm. The numerical results section demonstrates the efficiency of this new algorithm for the numerical evaluation of three‐center nuclear attraction integrals. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 相似文献
34.
Asish K Bhattacharya Mahesh PalDharam C Jain Bhawani S JoshiRaja Roy Urszula RychlewskaRam P Sharma 《Tetrahedron》2003,59(16):2871-2876
Absolute stereochemistry of dihydroarteannuin B 5 obtained by the reduction of arteannuin B 3 with Ni2B, NaBH4 or CdCl2-Mg-MeOH-H2O has been established by 2D NMR and single crystal X-ray diffraction studies. Some experiments aimed at the synthesis of dihydrodeoxyarteannuin B [C-4, 5 double bond isomer of 11] are also discussed. 相似文献
35.
S. V. Klement’eva N. F. Cherepennikova V. V. Semenov A. I. Kirillov M. A. Lopatin O. V. Kuznetsova Yu. A. Kurskii A. A. Zaitsev L. G. Klapshina V. E. Duglas G. A. Domrachev 《Russian Chemical Bulletin》2007,56(11):2214-2224
A method for the synthesis of polyphosphosiloxane by the thermal condensation of an equimolar mixture of trimethyl phosphate
and (3-aminopropyl)triethoxysilane at 200 °C was developed. The reaction affords ethanol and polyphosphosiloxane-{Si(OEt)[(CH2)3NR1R2]-O-P(O)(OMe)-O}n-(R1 = H, Me; R2 = Me), whose composition and structure were confirmed by 1H, 13C, and 31P NMR spectroscopy, IR spectroscopy, and elemental analysis. The scheme of polymerization involving the intermediate formation
of methyl-and dimethylphosphoric acids and their condensation with ethoxysilanes was proposed. The calcination of the obtained
polyphosphosiloxane in vacuo at 350 °C results in the elimination of the amino groups and alkoxide substituents, and a spatially cross-linked polymer
is formed as an amorphous powder. Its further thermolysis at 600 and 1000 °C gives crystalline phosphosilicates Si5O(PO4)6 or SiP2O7. Their amorphous and crystalline samples were characterized by IR spectroscopy, X-ray diffraction analysis, and solid-state
13C and 31P spectroscopy.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2138–2148, November, 2007. 相似文献
36.
In this article we will apply the first- and second-order supersymmetric quantum mechanics to obtain new exactly-solvable real potentials departing from the inverted oscillator potential. This system has some special properties; in particular, only very specific second-order transformations produce non-singular real potentials. It will be shown that these transformations turn out to be the so-called complex ones. Moreover, we will study the factorization method applied to the inverted oscillator and the algebraic structure of the new Hamiltonians. 相似文献
37.
Recently a classification of contactly-nonequivalent three-dimensional linearly degenerate equations of the second order was presented by E.V. Ferapontov and J. Moss. The equations are Lax-integrable. In our paper we prove that all these equations are connected with each other by appropriate Bäcklund transformations. 相似文献
38.
Jose M.R. Mendez Perez 《Applicable analysis》2013,92(1-4):81-97
By using Hilbert space techniques, the finite Tchebycheff transformations of the first and the second kind are defined on appropriate spaces of generalized functions. The inversion theorems are established and some operation transform formulas are obtained. These results are applied in solving certain distributional differential equations. 相似文献
39.
40.
Daisuke Saito Dr. Tomasz Galica Prof. Dr. Eiji Nishibori Dr. Masaki Yoshida Dr. Atsushi Kobayashi Prof. Dr. Masako Kato 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(32):e202200703
The vapochromic single-crystal-to-single-crystal (SCSC) transformation of a highly luminescent PtII complex bearing an N-heterocyclic carbene [Pt(CN)2(tBu-impy)] (tBu-impyH+=1-tert-butyl-3-(2-pyridyl)-1H-imidazolium) is reported. The trihydrate form of the complex, which exhibits blue 3MMLCT emission owing to weak Pt⋅⋅⋅Pt interactions, changed its luminescence color from blue to yellowish-green upon the desorption of water molecules while keeping the high emission quantum yield of more than 0.45. Variable-temperature and continuous in-situ tracking of single-crystal X-ray diffraction measurements revealed that the SCSC transformation proceeds reversibly by the release and reabsorption of water molecules, thereby changing the stacked structure slightly. As a result, the dynamics of vapor-induced SCSC transformation were elucidated: that the anhydrous form returned to the original trihydrate form in a two-step process under a water vapor atmosphere. In addition, the PtII complex exhibited a similar SCSC response accompanied by a luminescence color change in the presence of methanol vapor, while being inactive toward ethanol vapor. 相似文献