全文获取类型
收费全文 | 4622篇 |
免费 | 712篇 |
国内免费 | 394篇 |
专业分类
化学 | 1984篇 |
晶体学 | 59篇 |
力学 | 1485篇 |
综合类 | 56篇 |
数学 | 350篇 |
物理学 | 1794篇 |
出版年
2024年 | 15篇 |
2023年 | 63篇 |
2022年 | 105篇 |
2021年 | 141篇 |
2020年 | 161篇 |
2019年 | 147篇 |
2018年 | 116篇 |
2017年 | 233篇 |
2016年 | 244篇 |
2015年 | 198篇 |
2014年 | 254篇 |
2013年 | 349篇 |
2012年 | 254篇 |
2011年 | 311篇 |
2010年 | 228篇 |
2009年 | 257篇 |
2008年 | 287篇 |
2007年 | 260篇 |
2006年 | 246篇 |
2005年 | 242篇 |
2004年 | 206篇 |
2003年 | 206篇 |
2002年 | 163篇 |
2001年 | 157篇 |
2000年 | 134篇 |
1999年 | 130篇 |
1998年 | 96篇 |
1997年 | 89篇 |
1996年 | 79篇 |
1995年 | 59篇 |
1994年 | 50篇 |
1993年 | 41篇 |
1992年 | 31篇 |
1991年 | 27篇 |
1990年 | 32篇 |
1989年 | 27篇 |
1988年 | 21篇 |
1987年 | 19篇 |
1986年 | 10篇 |
1985年 | 11篇 |
1984年 | 7篇 |
1982年 | 5篇 |
1981年 | 7篇 |
1980年 | 1篇 |
1979年 | 5篇 |
1978年 | 1篇 |
1977年 | 2篇 |
1957年 | 1篇 |
排序方式: 共有5728条查询结果,搜索用时 62 毫秒
51.
Three new aromatic diester–dicarboxylic acids containing furan rings, namely, benzofuro[2,3-b]benzofuran-2,9-dicarboxyl-bis-phenyl ester-4,4′-dicarboxylic acid, benzofuro[2,3-b]benzofuran-2,9-dicarboxyl-bis-phenyl ester-3,3′-dicarboxylic acid and benzofuro[2,3-b]benzofuran-2,9-dicarboxyl-bis-naphthyl ester-2,2′-dicarboxylic acid were synthesized by the reaction of benzofuro[2,3-b]benzofuran-2,9-dicarbonyl chloride with 4-hydroxybenzoic acid, 3-hydroxybenzoic acid and 3-hydroxy-naphthalene-2-carboxylic acid, respectively. Diester–dicarboxylic acids were characterized by FT-IR and NMR spectroscopy and elemental analyses. Then, these monomers were converted to aromatic copoly(ester–amide)s by their reaction with various aromatic diamines via the direct polycondensation. These polymers were characterized by viscosity measurements, solubility tests, FT-IR, Ultraviolet and 1H-NMR spectroscopy and thermogravimetry. The polymers with inherent viscosities in the range of 0.16–0.37 dl/g in dimethyl sulfoxide at 30 °C were obtained in high yield. Most of them dissolved readily at room temperature in polar solvents. The synthesized copoly(ester–amide)s possessed glass-transition temperatures from 210–255 °C. The copoly(ester–amide)s exhibited excellent thermal stabilities and had 10% weight loss at temperature above 295 °C under nitrogen atmosphere. 相似文献
52.
The strain energies and through-space distances between the two bridgehead E atoms of a selection of 1,3-dimethyl-1,3-ditetrelbicyclo[1.1.1]pentanes
(tetrel E = Si, Ge or Sn) were examined by quantum chemical calculations at MP2 and B3LYP levels. The aim is to identify which
bridges lead to short through-space E,E distances, and simultaneously, to as low strain as possible. A short E,E distance
should improve through-space interaction, and a low strain should promote the thermal stability and possibly also facilitate
their synthesis. The bridges examined included CH2, CMe2, CtBu2, C(CH2)n (n = 2–4), O, NMe, S, PMe, SiMe2, GeMe2, and SnMe2. The calculations indicate that the phospha bridge is a good compromise providing reasonably low strain as well as E,E through-space
distances which are only longer than normal E–E single bonds by factors of 1.06–1.10.
This paper is dedicated to Professor Mitsuo Kira in recognition of his stimulating Si chemistry and his 2005 Wacker Award. 相似文献
53.
Cl···O intramolecular contacts are analysed here. Hence the Cambridge Structural Database (CSD) search was performed to find
five-membered Cl–C=C–C=O pseudo-rings closed through Cl···O intramolecular contacts. Such rings were analysed and it was found
that some of Cl···O distances are smaller than the corresponding sum of van der Waals radii. Additionally ab initio MP2/6-311++G(d,p)
calculations and AIM analyses were carried out here on 3-chloropropenal and its fluoro derivatives to deepen the nature of
intramolecular Cl···O interactions, some of findings may indicate that they are attractive and stabilizing ones.
This paper is dedicated to Prof. T. M. Krygowski on the occasion of his 70th birthday 相似文献
54.
Ileana A. Zucchi 《European Polymer Journal》2006,42(4):815-822
Films that can be reversibly switched from opaque to transparent states by varying temperature (TRLS films), have potential applications in thermal sensors, optical devices, recording media, etc. A dispersion of organic crystals in a thermoset may be used for these purposes provided that at temperatures higher than the melting point there is a matching of refractive indices of both phases. A model system consisting on a dispersion of diphenyl (DP) crystals in an epoxy matrix based on diglycidyl ether of bisphenol A and m-xylylenediamine, was analyzed as a possible TRLS film encapsulated between transparent covers to avoid sublimation of DP. To obtain a uniform dispersion of DP-rich domains in the epoxy matrix by polymerization-induced phase separation, it was necessary to add 5 wt% of polystyrene (PS) to the initial formulation. Phase separation induced by polymerization at 80 °C led to a dispersion of PS/DP domains in the epoxy matrix due to the low compatibility of PS with the epoxy and its high compatibility with DP. Crystallization and melting processes were confined to the interior of dispersed domains leading to an excellent reproducibility of the optical properties of TRLS films in the course of successive heating-cooling cycles. 相似文献
55.
Nicolas Le Calvez 《中国化学会会志》2002,49(4):585-592
The aim of this study was to develop an analytical method to determine the organochlorine concentrations in sediments. Combination of Microwave assisted Solvent Extraction (MASE) and capillary gas chromatography with specific detection (electron capture detector) was a viable approach for the determination of pesticides in solid matrixes. In this study, MASE development was focused on the selection of a suitable extraction solvent for all the target analytes. MASE procedure was validated by comparison with conventional methods such as Soxhlet and sonication extraction. The proposed method was then applied to determine the organochlorine insecticides concentrations in samples from Authie Bay (France). Environmental water samples were analysed and five target analytes were detected in concentrations from 0.03 to 0.56 ng/g of dry sediment. These investigations showed the accumulation and the persistency of these products in sediments in spite of the fact they were banned a few decades ago. 相似文献
56.
57.
Jocelyn Jalbert Roland Gilbert Pierre Tétreault Brigitte Morin Denise Lessard-Déziel 《Cellulose (London, England)》2007,14(4):295-309
In this study, headspace gas chromatography/mass spectrometry has been used to assess the volatile by-products generated by
the ageing of oil-impregnated paper insulation of power transformers. Sealed-glass ampoules were used to age under oxidative
conditions 0.5-g specimens of insulating paper in 9 mL of inhibited mineral oil in a temperature range of 60–120 °C and moisture
of 0.5, 1 and 2% (w/w). A linear relationship between one of the oil-soluble degradation by-products, i.e. methanol, and the
number of ruptured 1,4-β-glycosidic bonds of cellulose, regardless of the type of paper (ordinary Kraft or thermally-upgraded
(TU) Kraft paper), was established for the first time in this field. Ageing at 130 °C of model compounds of the Kraft paper
constituents (α-cellulose, hemicellulose and lignin) and two cellulosic breakdown by-products (D-(+)-glucose and 1,6-anhydro-β-d-glucopyranose) confirmed that the α-cellulose degradation was mostly responsible for the presence of this molecule in the
system. Furthermore, additional 130 °C-tests with six different papers and pressboard samples under a tight control of initial
moisture indicated that at least one molecule of methanol is formed for each rupture of 1,4-β-glucosidic bond of the molecular
chains. Stability tests showed that the ageing indicator is stable under the oxygen and temperature conditions of open-breathing
transformers. The presence of methanol was detected in 94% of oil samples collected from over than 900 in-service pieces of
equipment, confirming the potential for this application. Lastly, the tests have shown that oil-oxidation by-products and
TU-nitrogenous agents modify the methanol partitioning coefficients in the paper/oil/air system, which makes their study essential
over a range of field conditions encountered by power transformers. Results are presented and discussed in comparison with
2-furfuraldehyde, which is the current reference in the domain. 相似文献
58.
Michelini Mdel C Russo N Alikhani ME Silvi B 《Journal of computational chemistry》2004,25(13):1647-1655
The Density functional theory has been applied to characterize the structural features of Mo(1,2)-NH(3),-C(2)H(4), and -C(2)H(2) compounds. Coordination modes, geometrical structures, and binding energies have been calculated for several spin multiplets. It has been shown that in contrast to the conserved spin cases (Mo(1,2)-NH(3)), the interaction between Mo (or Mo(2)) and C(2)H(4) (or C(2)H(2)) are the low-spin (Mo-C(2)H(4) and -C(2)H(2)) and high-spin (Mo(2)-C(2)H(4) and -C(2)H(2)) complexes. In the ground state of Mo(1,2)-C(2)H(4) and -C(2)H(2), the metal-center always reacts with the C-C center. The spontaneous formation of the global minima is found to be possible due to the crossing between the potential energy surfaces (ground and excited states with respect to the metallic center). The bonding characterization has been performed using the topological analysis of the Electron Localization Function. It has been shown that the most stable electronic structure for a pi-acceptor ligand correlates with a maximum charge transfer from the metal center to the C-C bond of the unsaturated hydrocarbons, resulting in the formation of two new basins located on the carbon atoms (away from hydrogen atoms) and the reduction of the number of attractors of the C-C basin. The interaction between Mo(1,2) and C(2)H(4) (or C(2)H(2)) should be considered as a chemical reaction, which causes the multiplicity change. Contrarily, there is no charge transfer between Mo(1,2) and NH(3), and the partners are bound by an electrostatic interaction. 相似文献
59.
Polychlorinated biphenyls (PCBs) and chlorobenzenes (CBzs) are two classes of dioxin precursors formed in municipal solid waste incinerators (MSWIs); they produce negative health effects similar to those of dioxins. Reducing the analytical time required for determining the concentrations of these compounds in MSWIs is important for quickly evaluating their importance and assessing associated health risks. In the present study, water is used as a safe and environmentally friendly solvent in microwave-assisted extraction (MAE) for PCB and CBz analyses. MAE is compared with traditional Soxhlet extraction (SE) to determine the extraction efficiencies. The evaluation of extraction efficiencies shows that MAE has a high extraction efficiency compared with that of SE when water content is lower than 60%. Furthermore, the extraction time and organic solvent consumption are reduced with MAE compared with SE. 相似文献
60.
Takayasu Yamauchi Hiroyuki Sazanami Yuuichi Sasaki Kimio Higashiyama 《Tetrahedron》2005,61(7):1731-1736
1,3-Oxazolidines were easily obtained by condensation of N-substituted (R)-phenylglycinol with aldehydes. Addition of organolithium reagents to 1,3-oxazolidines by complexation with the bulky Lewis acid aluminum tris(2,6-diphenylphenoxide) (ATPH) readily produced the corresponding chiral amines with good yield and high diastereoselectivity. The configuration of the new stereogenic center was shown to be opposite to that of adducts obtained for the same 1,3-oxazolidines using Grignard reagents. The best diastereoselectivity was achieved using N-isopropyl-1,3-oxazolidines. The mechanism of addition was deduced by determining the stereochemistry of the iminium-aluminum complex by NOE experiments. 相似文献