全文获取类型
收费全文 | 2832篇 |
免费 | 101篇 |
国内免费 | 9篇 |
专业分类
化学 | 2264篇 |
晶体学 | 18篇 |
力学 | 18篇 |
数学 | 328篇 |
物理学 | 314篇 |
出版年
2024年 | 2篇 |
2023年 | 16篇 |
2022年 | 25篇 |
2021年 | 59篇 |
2020年 | 42篇 |
2019年 | 61篇 |
2018年 | 44篇 |
2017年 | 30篇 |
2016年 | 97篇 |
2015年 | 89篇 |
2014年 | 80篇 |
2013年 | 192篇 |
2012年 | 201篇 |
2011年 | 242篇 |
2010年 | 148篇 |
2009年 | 141篇 |
2008年 | 219篇 |
2007年 | 205篇 |
2006年 | 179篇 |
2005年 | 180篇 |
2004年 | 121篇 |
2003年 | 86篇 |
2002年 | 102篇 |
2001年 | 40篇 |
2000年 | 25篇 |
1999年 | 28篇 |
1998年 | 24篇 |
1997年 | 23篇 |
1996年 | 42篇 |
1995年 | 19篇 |
1994年 | 10篇 |
1993年 | 17篇 |
1992年 | 16篇 |
1991年 | 11篇 |
1990年 | 17篇 |
1989年 | 8篇 |
1988年 | 7篇 |
1987年 | 10篇 |
1986年 | 8篇 |
1985年 | 7篇 |
1984年 | 16篇 |
1983年 | 6篇 |
1982年 | 11篇 |
1981年 | 8篇 |
1980年 | 9篇 |
1978年 | 6篇 |
1972年 | 2篇 |
1970年 | 3篇 |
1967年 | 1篇 |
1956年 | 1篇 |
排序方式: 共有2942条查询结果,搜索用时 31 毫秒
11.
Marcos F. de Campos Marília Emura Fernando J.G. Landgraf 《Journal of magnetism and magnetic materials》2006
Electrical steels, when submitted to operation, present continuous decrease of their magnetic properties, depending on the carbon content. This effect is attributed to the increase of the size of carbides, a process also known as coarsening or Ostwald Ripening. Loss separation can offer a better understanding of this phenomenon. Experimental results show that all effect of aging is inside the hysteresis loss component, with the excess losses unaffected. The carbon content in electrical steels should be less than 25 ppm to avoid magnetic aging. 相似文献
12.
We describe all isometric immersions f:S
n
s
S
s
n
+2/S
s
n
n–s4, whenever the set of totally geodesic points does not disconnect S
s
n
, where S
n
s
denotes the complete n-dimensional indefinite Riemannian space form of constant positive curvature 1 and signature s. 相似文献
13.
Joan Albaigés Josep M. Bayona Pilar Fernandez Joan Grimalt Antoni Rosell Rafel Simó 《Mikrochimica acta》1991,104(1-6):13-27
An analytical procedure is described for a comprehensive determination of the composition of hydrocarbons in the atmosphere, based on: (a) aerosol filtration and subsequent adsorption of the vapor phase onto active charcoal and polyurethane foam; (b) GPC and HPLC fractionation of the extracts, and (c) analysis of the fractions by GC-MS under EI and NICI modes. Special emphasis is placed onn-alkanes, PAHs and their oxygenated derivatives.The characterization of samples collected in a coastal urban area (Barcelona city), and far away over the Western Mediterranean, at sea level and at 1100 m of altitude, revealed significant changes in the aerosol composition, mainly attributed to initial vapor-particle partitioning processes, influenced by ambient temperature variations, and to others taking place during long-range atmospheric transport, related with the different compound photoreactivities and with an unexplained source-decoupling phenomenon. 相似文献
14.
Pilar Alonso Isabel de Frutos Teresa Gutiérrez Antonio Doadrio López 《Transition Metal Chemistry》1987,12(2):133-136
Summary The synthesis and the dinuclear or mononuclear nature of several molybdenum(VI) and molybdenum(V) oxocomplexes derived from 1,3-diphenyl-1,3-propanedione (HLL) are described. These complexes were identified by i.r. and electronic spectra, magnetic susceptibility and analytical data, and are assigned the following formulae: [MoO2(LL)2], [Mo2O5(LL)2], [Mo2O4(LL)2], [MoOCl(LL)2], [MoCl2(LL)] and [MoO(OH)(LL)2)]. The low magnetic moments of the dinuclear complexes are due, in part, to intramolecular interactions. The i.r. data show that the dionate is bound by two oxygen atoms forming a chelate six-membered ring. 相似文献
15.
Nilo Zanatta Darlene C. Flores Claudia C. Madruga Alex F.C. Flores Helio G. Bonacorso Marcos A.P. Martins 《Tetrahedron letters》2006,47(4):573-576
This work reports a two-step synthetic strategy to obtain a series of 6-methylenesubstituted-4-trichloromethyl-2-methylsulfanylpyrimidines from the cyclization of 5-bromo-4-methoxy-1,1,1-trichloro-pent-3-en-2-ones with 2-methyl-2-pseudothiourea sulfate, followed by nucleophilic substitution of 6-bromomethyl-4-trichloromethyl-2-methylsulfanylpyrimidine with a series of nucleophiles. Alternative strategies to obtain 6-halomethyl-4-trichloro[fluoro]methyl-2-methylsulfanyl pyrimidines have been addressed. 相似文献
16.
Eugenio?Garcia-Pa?eda Pilar?Guardado Alfredo?MaestreEmail author 《Journal of solution chemistry》2004,33(10):1277-1293
Partial molar volumes at infinite dilution, V02, of alkali–metal halides (LiCl, NaCl KCl RbCl CsCl, NaBr, KBr, KI), tetra-n-alkylammonium bromides, R4NBr (R=Me, Et, n-Pr, n-Bu, n-Pen), NaBPh4, and Ph4PCl have been determined in binary solvent mixtures of water with 2-methyl-2-butanol covering the water-rich region and the alcohol-rich region at 298.15 K. V02 for alkali–metal halides show relatively little dependence on the solvent composition. However, in the case of hydrophobic electrolytes the observed effects are more pronounced. A good linear dependence between V02(R4NBr) and the molecular weight of the tetra-n-alkylammonium cation is found. Limiting single-ion volumes have been obtained using the assumption that V0(Ph4P+)–V0(BPh–4)=2.0 cm3-mol–1. The trends in the single-ion volumes are discussed in both solvent regions. 相似文献
17.
The present work is an attempt to assess racemization in stepwise solid-phase peptide synthesis at elevated temperatures (SPPS-ET), a high-speed approach in which peptide elongation occurs at 55-75 °C. This attempt was based on the notion that a high propensity for this side reaction would hamper employment of this alternative approach and would dampen interest in its further development. Simple peptide models were synthesized using customized protocols for classical SPPS or SPPS-ET. Systematic analyses of the resulting crude peptides by reversed-phase HPLC, ion-exchange HPLC, capillary electrophoresis and electrospray ionization mass spectrometry revealed low diastereomeric byproduct contents. These results indicate that, from the standpoint of racemization, classical SPPS and SPPS-ET protocols were equivalent. Therefore, further studies employing SPPS-ET protocols are justified. 相似文献
18.
Barriga S Fuertes P Marcos CF Rakitin OA Torroba T 《The Journal of organic chemistry》2002,67(18):6439-6448
We report the synthesis of some new polysulfur-nitrogen heterocycles by cycloaddition reactions to readily available tricyclic condensed 1,2-dithiole-3-thiones. Thus, treatment of bis[1,2]dithiolopyrrole ketothione 1 with diacyl acetylenes gave the bis-aducts 2a-d. On the other hand, cycloaddition of bis[1,2]dithiolo[1,4]thiazine ketothione 3 with 1 equiv of acyl or diacyl acetylenes gave [1,3]dithiolylidenyl[1,2]dithiolo[1,4]thiazines 4a-f in fair to high yields. Catalysis by scandium triflate was used in the reactions that implied the less reactive dipolarophiles. Treatment of 3 with 2 equiv of DBA gave the bis-aduct 5a, and reaction of 4c with DMAD gave the mixed bis-adduct 5b. Cyclic voltammetry of selected examples showed irreversible processes that were influenced by the electrochemical activity of peripheral groups bonded to the heterocyclic system. 相似文献
19.
Barberá J Puig L Romero P Serrano JL Sierra T 《Journal of the American Chemical Society》2005,127(1):458-464
The work described here concerns a challenge of general interest in supramolecular chemistry: the achievement of chiral helical organizations with controlled structures. This work provides a strategy to obtain supramolecular polymers in which a chiral helical conformation has been induced by a noncovalent association, that is, through hydrogen bonding. Polycatenar 2,4,6-triarylamino-1,3,5-triazines, which organize into columnar mesophases and are susceptible to H-bonding interactions, were chosen as a starting point to build up the chiral supramolecular structure. The stacking of these mesogens has been forced to wind in a helical way by means of H-bond association with (R)-3-methyladipic acid, within the mesophase. The optically active columnar organization has been studied in depth by optical microscopy, differential scanning calorimetry (DSC), X-ray diffraction, and circular dichroism. Formation of stable complexes between the triazine units and (R)-3-methyladipic acid has also been investigated by means of NMR diffusion-ordered spectroscopy (DOSY) experiments in chloroform. 相似文献
20.
The hydride transfer process between the isoalloxazine moiety of flavins and the nicotinamide moiety of NAD(P)H has been explored by using density functional theory based reactivity index in the 1-methylnicotinamide-lumiflavine model system. Based on crystallographic data available, we have found that the group softness index helps to locate and orientate reactive regions in these interacting molecules while the electrophilicity index successfully describes the reactivity pattern of this system. 相似文献