全文获取类型
收费全文 | 2595篇 |
免费 | 283篇 |
国内免费 | 324篇 |
专业分类
化学 | 2407篇 |
晶体学 | 59篇 |
力学 | 21篇 |
综合类 | 13篇 |
数学 | 5篇 |
物理学 | 697篇 |
出版年
2024年 | 9篇 |
2023年 | 27篇 |
2022年 | 56篇 |
2021年 | 68篇 |
2020年 | 110篇 |
2019年 | 81篇 |
2018年 | 64篇 |
2017年 | 62篇 |
2016年 | 112篇 |
2015年 | 107篇 |
2014年 | 127篇 |
2013年 | 237篇 |
2012年 | 141篇 |
2011年 | 153篇 |
2010年 | 111篇 |
2009年 | 157篇 |
2008年 | 153篇 |
2007年 | 175篇 |
2006年 | 195篇 |
2005年 | 143篇 |
2004年 | 139篇 |
2003年 | 149篇 |
2002年 | 101篇 |
2001年 | 64篇 |
2000年 | 74篇 |
1999年 | 73篇 |
1998年 | 55篇 |
1997年 | 50篇 |
1996年 | 43篇 |
1995年 | 41篇 |
1994年 | 24篇 |
1993年 | 20篇 |
1992年 | 26篇 |
1991年 | 7篇 |
1990年 | 7篇 |
1989年 | 5篇 |
1988年 | 8篇 |
1987年 | 9篇 |
1986年 | 3篇 |
1985年 | 4篇 |
1984年 | 1篇 |
1983年 | 1篇 |
1982年 | 3篇 |
1980年 | 2篇 |
1979年 | 3篇 |
1977年 | 1篇 |
1973年 | 1篇 |
排序方式: 共有3202条查询结果,搜索用时 0 毫秒
51.
A convenient synthetic approach is established to prepare a new class of 1-l-α-amino acid derivatives of phospholene oxides by amination of (±)-1-chloro-2-phospholene-1-oxides with several optically pure l-α-amino acid esters. All compounds obtained as a diastereomeric mixture in good to high yields. The two diastereomers were successfully separated by column chromatography and structurally identified by their spectral analyses. 相似文献
52.
Lorenzo MalavasiPaolo Ghigna Gaetano ChiodelliGiorgio Maggi Giorgio Flor 《Journal of solid state chemistry》2002,166(1):171-176
The synthesis and structural properties of Mg1−xMn2+xO4, for 0≤x≤1 are described. Complete miscibility in the solid state exists for this system. For the material with the correct stoichiometry, i.e. MgMn2O4, the effect of temperature on the cation distribution was investigated= above 600°C the inversion degree (m) starts increasing. The electrical conductivity shows a small dependence on P(O2) which is consistent with the small oxygen non-stoichiometry determined by means of thermogravimetry. The main contribution to the transport properties arises from the inversion equilibrium. Two distinct conductivity regimes, below and above the inversion threshold, can be assumed to explain the electrical conductivity and thermoelectric power results. 相似文献
53.
54.
G. S. Zakharova L. Yu. Buldakova V. L. Volkov L. S. Molochnikov E. G. Kovaleva 《Russian Journal of Electrochemistry》2006,42(1):53-58
Complex vanadium and titanium oxides modified by copper ions are studied by the electrochemical and ESR methods. Oxides Cu x V2?y Ti y O5?δ·nH2O (0<y<1.33) have a layered structure and oxides Cu x Ti1?y V y O5+δ·nH2O (0<y<0.25), an anatase structure. The intercalation of cations Cu2+ into the hydrates leads to oxidation of V4+. According to ESR data, V4+ exists in the oxides in the form of VO2+ and an octahedral surround of oxygen (V4+?O6), respectively. The electroreduction of ions of d-elements and chemisorbed oxygen in the oxides is analyzed. The intercalation of cations Cu2+ alters the content of V4+ and the chemisorption ability of the oxides. Possible reasons for this phenomenon are discussed. 相似文献
55.
In the Claus process hydrogen sulfide reacts to elemental sulfur. Because the Claus reaction is thermodynamically limited, sulfur compounds are still present in Claus tailgas. To avoid air pollution, the tailgas has to be treated.Alfa- and gamma-alumina are being used either as a catalyst or as a support for an active component in the Claus process and some tailgas treatment processes. In order to elucidate the mechanism of the Claus reaction, the adsorption of sulfur dioxide on both of the above aluminas was investigated using Fourier transform infrared spectroscopy.Different adsorbed species displaying a different heat of adsorption were detected. A broad band near 3500 cm–1 is associated with the basic hydroxyl groups. This band is assigned to a hydrogen bond between the surface of alumina and a bisulfite species. As bisulfite species are reactive towards hydrogen sulfide, we assume that bisulfite species are active intermediates on alumina in the Claus reaction. 相似文献
56.
Maria Grazia Bonicelli Gianfranco Ceccaroni Franco Gauzzi Giuseppe Mariano 《Thermochimica Acta》2005,430(1-2):95-99
Differential scanning calorimetry (DSC) and particle size measurements were carried out on disproportionation products of pure SnO to investigate the fusion and solidification behaviour of Sn droplets and their catalytic nucleation on Sn oxides. If disproportionation reaction takes place at T ≥ 798 K, the products are metallic Sn and SnO2; but for 523 < T < 798 K, SnO2 is replaced by an intermediate oxide (IO) SnxO(1+x). On melting, samples with IO show a drop of melting point of metallic tin due to Gibbs–Thomson effect; no lowering of melting point was observed in samples with SnO2. On the other hand, if solidification occurs in the presence of IO, Tin droplets always displayed three distinct exothermic solidification peaks, but if it takes place in the presence of SnO2, only one exothermic peak is observed. Undercooling values and contact angles were determined for each of the heterogeneous nucleation processes. The different behaviour of metallic Tin droplets was related to the different lattice symmetry of SnO2 and IO, which act as nucleation catalysts. 相似文献
57.
Yanlong Kang 《Tetrahedron》2004,60(49):11219-11225
The use of simple calix[4]arenes 1a,b for NO2/N2O4 sensing and conversion is demonstrated, both in solution and in the solid state. Upon reacting with these gases, compounds 1a,b encapsulate reactive NO+ cations within their cavities with the formation of deeply colored (λmax∼570 nm) charge-transfer complexes 2a,b. Further functionalization of the calix[4]arene platform is reported for attachment to solid supports. Polymer-supported calixarene material 3 was prepared, which reversibly traps NO2/N2O4 with the formation of nitrosonium storing polymer 4. Material 4 was effectively used for nitrosation of amides. 相似文献
58.
Nanorods of Various Oxides and Hierarchically Structured Mesoporous Silica by Sol-Gel Electrophoresis 总被引:1,自引:0,他引:1
Steven J. Limmer Timothy L. Hubler Guozhong Cao 《Journal of Sol-Gel Science and Technology》2003,26(1-3):577-581
In this paper, we report the template-based growth of nanorods of oxides and hierarchically structured mesoporous silica, formed by means of a combination of sol-gel processing and electrophoretic deposition. Both single metal oxides (TiO2) and complex oxides (Pb(Zr0.52Ti0.48)O3) have been grown by this method. This method has also been applied to the growth of nanorods of mesoporous silica having an ordered pore structure, where the pores are aligned parallel to the long axis of the nanorod. Uniformly sized nanorods of about 125–200 nm in diameter and 10 m in length were grown over large areas with near unidirectional alignment. Appropriate sol preparation yielded the desired stoichiometric chemical composition and crystal structure of the oxide nanorods, with a heat treatment (500–700°C for 15–30 min) for crystallization, densification and any necessary pyrolysis. 相似文献
59.
Yu. G. Yatluk N. A. Zhuravlev O. V. Koryakova L. K. Neudachina Yu. A. Skorik 《Russian Chemical Bulletin》2005,54(8):1836-1841
A series of new hybrid organo-inorganic sorbents with the 3-aminopropionate chelating group was synthesized. The synthesis
includes the copolycondensation (sol—gel method) of tetraethoxysilane, 3-aminopropyltriethoxysilane, and several modifiers
(MeSi(OEt)3, EtSi(OEt)3, Ti(OEt)4, AlONO3, ZrOCl2) followed by carboxyethylation with acrylic acid. The obtained chelating sorbents were characterized by elemental analysis,
FT-IR and 1H NMR spectroscopy, and thermogravimetry. The N-carboxylated sorbents have a higher sorption capacity with respect to metal ions (0.5–0.9 mmol g−1, pH 6.3, NH4OAc, 20 °C) than the starting sorbents with the primary amino group (0.05–0.2 mmol g−1) and manifest high selectivity for copper(II) ion extraction.
__________
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1783–1788, August, 2005. 相似文献
60.