全文获取类型
收费全文 | 6042篇 |
免费 | 1000篇 |
国内免费 | 1081篇 |
专业分类
化学 | 6678篇 |
晶体学 | 135篇 |
力学 | 67篇 |
综合类 | 48篇 |
数学 | 7篇 |
物理学 | 485篇 |
无线电 | 703篇 |
出版年
2024年 | 7篇 |
2023年 | 77篇 |
2022年 | 116篇 |
2021年 | 202篇 |
2020年 | 338篇 |
2019年 | 226篇 |
2018年 | 203篇 |
2017年 | 206篇 |
2016年 | 359篇 |
2015年 | 353篇 |
2014年 | 391篇 |
2013年 | 606篇 |
2012年 | 562篇 |
2011年 | 386篇 |
2010年 | 314篇 |
2009年 | 310篇 |
2008年 | 351篇 |
2007年 | 359篇 |
2006年 | 355篇 |
2005年 | 377篇 |
2004年 | 345篇 |
2003年 | 301篇 |
2002年 | 179篇 |
2001年 | 154篇 |
2000年 | 149篇 |
1999年 | 111篇 |
1998年 | 94篇 |
1997年 | 116篇 |
1996年 | 99篇 |
1995年 | 88篇 |
1994年 | 77篇 |
1993年 | 46篇 |
1992年 | 80篇 |
1991年 | 43篇 |
1990年 | 40篇 |
1989年 | 31篇 |
1988年 | 13篇 |
1987年 | 10篇 |
1986年 | 10篇 |
1985年 | 9篇 |
1984年 | 3篇 |
1983年 | 4篇 |
1982年 | 3篇 |
1981年 | 3篇 |
1980年 | 3篇 |
1979年 | 2篇 |
1977年 | 4篇 |
1974年 | 1篇 |
1973年 | 4篇 |
1972年 | 2篇 |
排序方式: 共有8123条查询结果,搜索用时 250 毫秒
91.
The catalytic mechanism of molybdenum containing CO dehydrogenase has been studied using hybrid DFT methods with quite large chemical models. The recent high-resolution X-ray structure, showing the surprising presence of copper linked to molybdenum, was used as a starting point. A pathway was initially found with a low barrier for C-O bond formation and CO2 release. However, this pathway did not include the formation of any S-CO2 species, which had been suggested by experiments with an n-butylisocyanide inhibitor. When these SCO2 structures were studied they were found to lead to deep minima, making CO2 release much more difficult. A large effort was spent, including investigations of other spin states, varying the number of protons and electrons, adding water, etc., until a plausible pathway for S-C bond cleavage was found. In this pathway a water molecule is inserted in between molybdenum and the SCO2 group. Full catalytic cycles, including electron and proton transfers, are constructed both with and without S-C bond formation. When these pathways are extended to two full catalytic cycles it can be understood why the formation of the S-C bond actually makes catalysis faster, even though the individual step of CO2 release becomes much more difficult. These results agree well with experimental findings. 相似文献
92.
93.
本文首次以LB技术将四苯基卟啉铜(CuTPP)分子沉积到高定向热解石墨上,并用STM研究其表面形貌,得到了原子级分辨的CuTPP分子的表面形貌图,结果表明,CuTPP分子具有近似圆状平面结构,分子直径为1.0nm,与理论结果十分吻合,结合STM原理,讨论了有机大分子STM成像的条件。 相似文献
94.
Square planar mixed ligand complexes of the type [CuLL′] where L = 5-chlorosalicylaldehyde and L′ = acetoacetanilide, have
been synthesized on treatment with ammonia. Amine exchange of the above Schiff base complexes has been carried out on treatment
with different amines. The reaction with ethanol amine is quite interesting compared to other amines. It reacts with 5-chlorosalicylaldehyde
to form a Schiff base, while the β-diketone part is removed in the complex formation. All the complexes were characterized
by elemental analysis, spectral studies, magnetic measurement, TLC, and conductane. 相似文献
95.
Masaru Mitsuda 《Tetrahedron letters》2006,47(46):8073-8077
Kinetic resolution of N-benzoylated vic-amino alcohols was achieved by benzoylation in the presence of copper triflate and (R,R)-Ph-BOX as catalysts. The observed enantioselectivity was moderate to high. The method was applied to a kinetic resolution of racemic prolinol and piperidinemethanol derivatives as well as an asymmetric desymmetrization of 2-amino-1,3-diol derivatives. 相似文献
96.
97.
Joaquim Branco Catarina de Jesus Dias Antnio Pereira Gonalves Teresa Almeida Gasche Antnio Pires de Matos 《Thermochimica Acta》2004,420(1-2):169-173
In our laboratories we have been studying the synthesis and reactivity of binary actinide and lanthanide intermetallic compounds. In this work, the air-oxidation of ThCu2 and AnNi2 (An = Th, U) was followed by thermogravimetry (TG) and the products were characterized by X-ray powder diffraction (XRD). The heterobimetallic oxides obtained are described by the formulas 2MO·ThO2 (M = Cu, Ni) and 2NiO·UO3. The thermogravimetric analysis under hydrogen of these heterobimetallic oxides show one mass loss for 2MO·ThO2 and two mass losses for 2NiO·UO3 over a wide range of temperature (293–1273 K). The characterization by XRD shows that the reduction products are 2M·ThO2 (M = Cu, Ni) and 2Ni·UO2, with all the actinides in the 4+ oxidation state. The actinide heterobimetallic oxides were described as copper or nickel supported catalysts. 相似文献
98.
Liliana N. Trevani Jenene C. Roberts Peter R. Tremaine 《Journal of solution chemistry》2001,30(7):585-622
The spectra of copper(II)–ammonia solutions in 2 mol-kg–1 NH4NO3(aq) were recorded as a function of pH with a new UV–visible flow cell, capable of operating at conditions up to 325°C and 300 bars. Equilibrium constants for the formation of copper(II)–ammonia complexes Cu(NH3)n
2+, 1 n 4, from 30 to 150°C were determined by evolving factor analysis and nonlinear least-squares regression. Measurements at higher temperatures were limited by thermal decomposition of NH4NO3(aq). The formation constants of Cu(NH3)n
2+ decrease with temperature, consistent with extrapolations of literature data from measurements below 100°C. Measurements above 150°C were carried out in 0.5 mol-kg–1 CF3SO3H (aq), at the very high ammonia concentrations required to avoid the precipitation of CuO(s). The spectra are consistent with Cu(NH3)4
2+ as the predominant species, based on extrapolations of peak maxima and molar absorptivities from lower temperatures. Shifts in the spectra of Cu2+ and the Cu(NH3)n
2+ species to higher wavelength and increases in molar absorbance with increasing temperature are discussed in terms of the structure of the complexes. 相似文献
99.
Kłonkowski Andrzej M. Widernik Teresa Grobelna Beata Jóźwiak Wojciech K. Proga Henryk Szubiakiewicz Ewa 《Journal of Sol-Gel Science and Technology》2001,20(2):161-180
The sol-gel process is a useful method for preparing two series of organically and co-ordinately modified xerogels of the types [CuN
n
]·N
5–n
·5xSiO4/2 (n < 4) and [Cu(N–N)n]·(N–N)2–n
·2x SiO4/2(n 2), where N = NH2(CH2)3 SiO3/2, N–N = NH2(CH2)2NH·(CH2)3SiO3/2 and x = [SiO4/2]/[N] or [SiO4/2]/[N–N]. The amino groups in the materials are coordinately active and participate partly in the coordination sphere of Cu(II) ions. The composition of the coordination sphere can be varied with the SiO4/2 content and also as a result of the thermal decomposition of the organic residues at higher temperatures.Because the xerogel materials are considered to be catalyst precursors, this study is focused on their coordination and thermal properties. The prepared xerogels, such as silica, aminated silicates with N and N–N, as well as those entities complexed with Cu(II), were characterised by FT-IR spectroscopy. During gelation and thermal decomposition the materials were analysed by electron paramagnetic resonance (EPR) spectroscopy. The xerogels were additionally studied by UV-Vis absorption spectroscopy. The gaseous products of the thermal decomposition of these materials in an Ar atmosphere were investigated by the use of FT-IR spectroscopy coupled with TG and DTG thermal analysis. These data were complemented by temperature-programmed decomposition (TPDec) in a 2% O2 + 98% Ar stream coupled with quadrupole mass spectroscopy. 相似文献
100.
Fernando Mendizabal Dana Reyes Claudio Olea‐Azar 《International journal of quantum chemistry》2006,106(4):906-912
Hydrogen bonding and metallophilic attractions are studied in the model systems: [(AuNH3Cl)2], [(AuNH(CH3)2Cl)2], [{Au2(μ‐SH)(PH2O)(PH2OH)}2], [(CuNH3Cl)2], and [{Cu(NH3)Cl}4] at the Hartree–Fock (HF) and second‐order Møller–Plesset (MP2) levels. The two interactions are found to be comparable and prevailing in the final structure. It is determined that the aurophilic contact has a same magnitude that the hydrogen bonding, and is stronger than the cuprophilic interaction. The presence of hydrogen bond directs the growth of the crystal. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2006 相似文献