全文获取类型
收费全文 | 530篇 |
免费 | 24篇 |
国内免费 | 2篇 |
专业分类
化学 | 405篇 |
晶体学 | 2篇 |
力学 | 20篇 |
数学 | 88篇 |
物理学 | 41篇 |
出版年
2022年 | 10篇 |
2021年 | 12篇 |
2020年 | 12篇 |
2019年 | 14篇 |
2018年 | 5篇 |
2017年 | 5篇 |
2016年 | 23篇 |
2015年 | 24篇 |
2014年 | 29篇 |
2013年 | 24篇 |
2012年 | 25篇 |
2011年 | 35篇 |
2010年 | 21篇 |
2009年 | 18篇 |
2008年 | 26篇 |
2007年 | 32篇 |
2006年 | 19篇 |
2005年 | 27篇 |
2004年 | 28篇 |
2003年 | 21篇 |
2002年 | 20篇 |
2001年 | 11篇 |
2000年 | 7篇 |
1999年 | 10篇 |
1998年 | 7篇 |
1997年 | 4篇 |
1996年 | 6篇 |
1995年 | 4篇 |
1994年 | 6篇 |
1993年 | 7篇 |
1992年 | 8篇 |
1989年 | 8篇 |
1988年 | 2篇 |
1987年 | 4篇 |
1984年 | 5篇 |
1983年 | 3篇 |
1982年 | 2篇 |
1981年 | 7篇 |
1979年 | 3篇 |
1976年 | 4篇 |
1971年 | 1篇 |
1970年 | 2篇 |
1969年 | 1篇 |
1967年 | 1篇 |
1966年 | 1篇 |
1964年 | 1篇 |
1963年 | 1篇 |
1956年 | 1篇 |
1933年 | 3篇 |
1905年 | 1篇 |
排序方式: 共有556条查询结果,搜索用时 15 毫秒
11.
Abstract— Cells of the unicellular green alga Scenedesmus obliquus grown under high (20 W m-2 ) or low (5 W m-2 ) irradiancies of white light show all characteristics of sun or shade plants, respectively. When transferred to alternate light conditions, the cells adapt within 6 h. When cells grown under high irradiance of white light are transferred to red (683 nm) or blue (424 nm) light, they show characteristics similar to cells adapted to low or high irradiancies of white light, respectively. This adaptation to different wavelengths takes about 12 h. The underlying changes in the photosynthetic apparatus are discussed. 相似文献
12.
Several novel substituted bis(2‐pyridylimino)isoindolato (BPI) cobalt(II) and iron(II) complexes [M(BPI)(OAc)(H2O)] (M = Co: 1 ‐ 6, Fe: 7) have been synthesized by reaction of bis(2‐pyridylimino)isoindole derivatives with the corresponding metal(II) acetates. Reaction of 1‐6 with 1.5 ‐ 2 molar equivalents of t‐BuOOH gave the corresponding alkylperoxocobalt(III) complexes [Co(BPI)(OAc)(OOtBu)] (10 ‐ 15). Using an aqueous solution of t‐BuOOH (70 %), cyclohexene was selectively catalytically oxidized to the dialkylperoxide cyclohex‐2‐ene‐1‐t‐butylperoxide. 相似文献
13.
Capon RJ Skene C Liu EH Lacey E Gill JH Heiland K Friedel T 《Natural product research》2004,18(4):305-309
Bioassay directed fractionation of a Raspailia (Raspailia) sp. (Order Poecilosclerida; Family Raspailiidae) collected during scientific trawling operations off the Northern Rottnest Shelf yielded as nematocidal agents the known metabolites, phorboxazoles A (1) and B (2). Further examination revealed the new natural product but known synthetic compound, esmodil (3). The structure for 3 was confirmed by spectroscopic analysis and total synthesis. 相似文献
14.
We report the results of a study of the self-assembly of four minimalist peptide strands with a native beta-barrel structure. Using a soft-well potential to mimic cellular crowding, molecular dynamics simulations were performed in confining spheres of varying radii. By utilizing a previously introduced scaling factor lambda for the non-native hydrophobic interactions (0相似文献
15.
New Ternary Clathrate Compounds in the Systems Barium–Indium/Zinc/Cadmium–Germanium: Zintl Compounds with Phase Width? By systematic investigations in the systems barium–indium/zinc/cadmium–germanium we found a couple of new electrovalent ternary compounds with A8X46 clathrate (I) type structures. They crystallize cubically in space-group Pm3n. For Ba8In16Ge30 (a = 1 075.8 pm), Ba8Zn8Ge38 (a = 1 082.0 pm) and Ba8Cd8Ge38 (a = 1 096.0 pm) the structures were verified by X-ray single crystal diffraction data. According to valence and bounding distances the new clathrates should be Zintl compounds. Measurements of the temperature dependence of the electrical resistivity proved, that they are indeed semiconductors. A part of the 2B/3B metal atoms can be substituted by germanium. Charge balance will be retained by creation of vacancies in the A8X46 type structures. By phase analysis the limits of the composition range were determined as Ba8In4Ge9[]3Ge30 (a = 1 084.9 pm), Ba8Zn4Ge10[]2Ge30 (a = 1 073.6 pm) and Ba8Cd4Ge10[]2Ge30 (a = 1 082.0 pm). 相似文献
16.
17.
The stability of the molecular host-guest inclusion complexes of beta-cyclodextrin with benzoate and four different hydroxybenzoates is investigated. For the measurement of the binding constants an experimental method is devised that is based on affinity capillary electrophoresis (ACE) with indirect UV absorbance detection. We derive an explicit equation for effective mobilities in ACE experiments without violation of rigorous mass balance. This equation is employed in the nonlinear least-squares analyses of the experimental data yielding binding constants of 48+/-2 M(-1) for benzoate, 299+/-38 M(-1) for 2-hydroxybenzoate, 37+/-1 M(-1) for 3-hydroxybenzoate, 228+/-9 M(-1) for 4-hydroxybenzoate, and 895+/-110 M(-1) in the case of 2,4-dihydroxybenzoate. 相似文献
18.
Pagel K Seeger K Seiwert B Villa A Mark AE Berger S Koksch B 《Organic & biomolecular chemistry》2005,3(7):1189-1194
We report here an advanced approach for the characterization of the folding pattern of a de novo designed antiparallel coiled coil peptide by high-resolution methods. Incorporation of two fluorescence labels at the C- and N-terminus of the peptide chain as well as modification of two hydrophobic core positions by Phe/[15N,13C]Leu enable the study of the folding characteristics and of distinct amino acid side chain interactions by fluorescence resonance energy transfer (FRET) and NMR spectroscopy. Results of both experiments reveal the antiparallel alignment of the helices and thus prove the design concept. This finding is also supported by molecular dynamics simulations. Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS) in combination with NMR experiments was used for verification of the oligomerization equilibria of the coiled coil peptide. 相似文献
19.
Solid solutions in the system zinc sulfide/zinc phosphide (Zn(2+)(x)S(2-2xP(2x)) were investigated using the cyclic cluster model within the semiempirical MSINDO method. Results of cyclic cluster calculations for binding energies of the perfect ZnS and Zn(3)P(2) are presented and compared with the experimental data. The miscibility of ZnS and Zn(3)P(2) over the whole composition range of 0 < x < 1 was investigated by calculating the Gibbs free energy of mixing Delta(M)G for different values of x. A miscibility gap was found at both ends of the composition range and compared with experimental data. 相似文献
20.
Heinrich Lang Bettina Lühmann Roy Buschbeck 《Journal of organometallic chemistry》2004,689(22):3598-3603
A straightforward method for the preparation of metallo carbosiloxanes of type Si(OCH2CH2CH2SiMe2[OCH2PPh2M(CO)n])4 (n = 3, M = Ni, 7a; n = 4, M = Fe, 7b; n = 5: M = Mo, 7c; M = W, 7d), Si(OCH2CH2CH2SiMe[OCH2PPh2Ni(CO)3]2)4 (8) and Me2Si(OCH2CH2CH2SiMe[OCH2PPh2Ni(CO)3]2)2 (11) is described. The reaction of Si(OCH2CH2CH2SiMeXCl)4 (1: X = Me, 2: X = Cl) or Me2Si(OCH2CH2CH2SiMeCl2)2 (9) with HOCH2PPh2 (3) produces Si(OCH2CH2CH2SiMe2(OCH2PPh2))4 (4), Si(OCH2CH2CH2SiMe(OCH2PPh2)2)4 (5) or Me2Si(OCH2CH2CH2SiMe(OCH2PPh2)2)2 (10) in presence of DABCO. Treatment of the latter molecules with Ni(CO)4 (6a), Fe2(CO)9 (6b), M(CO)5(Thf) (6c: M = Mo; 6d: M = W), respectively, gives the title compounds 7a-7d, 8 and 11 in which the PPh2 groups are datively bound to a 16-valence-electron metal carbonyl fragment.The formation of analytical pure and uniform branched and dendritic metallo carbosiloxanes is based on elemental analysis, and IR, 1H, 13C{1H}, 29Si{1H} and 31P{1H} NMR spectroscopic studies. In addition, ESI-TOF mass spectrometric studies were carried out. 相似文献