全文获取类型
收费全文 | 1147篇 |
免费 | 40篇 |
国内免费 | 6篇 |
专业分类
化学 | 779篇 |
力学 | 28篇 |
数学 | 149篇 |
物理学 | 237篇 |
出版年
2024年 | 4篇 |
2023年 | 9篇 |
2022年 | 29篇 |
2021年 | 43篇 |
2020年 | 29篇 |
2019年 | 45篇 |
2018年 | 28篇 |
2017年 | 32篇 |
2016年 | 48篇 |
2015年 | 42篇 |
2014年 | 37篇 |
2013年 | 64篇 |
2012年 | 65篇 |
2011年 | 97篇 |
2010年 | 54篇 |
2009年 | 69篇 |
2008年 | 70篇 |
2007年 | 77篇 |
2006年 | 73篇 |
2005年 | 55篇 |
2004年 | 36篇 |
2003年 | 28篇 |
2002年 | 30篇 |
2001年 | 8篇 |
2000年 | 8篇 |
1999年 | 8篇 |
1998年 | 8篇 |
1997年 | 9篇 |
1996年 | 7篇 |
1995年 | 8篇 |
1994年 | 6篇 |
1993年 | 7篇 |
1992年 | 6篇 |
1991年 | 3篇 |
1990年 | 7篇 |
1989年 | 6篇 |
1988年 | 4篇 |
1987年 | 3篇 |
1986年 | 2篇 |
1985年 | 4篇 |
1984年 | 3篇 |
1983年 | 2篇 |
1982年 | 3篇 |
1981年 | 3篇 |
1980年 | 2篇 |
1977年 | 3篇 |
1975年 | 2篇 |
1973年 | 1篇 |
1964年 | 1篇 |
1916年 | 3篇 |
排序方式: 共有1193条查询结果,搜索用时 359 毫秒
211.
Salvatore Sotgia Ciriaco Carru Bastianina Scanu Elisabetta Pisanu Manuela Sanna Gerard Aime Pinna Leonardo Gaspa Luca Deiana Angelo Zinellu 《Analytical and bioanalytical chemistry》2009,395(8):2577-2582
A rapid and simple short-end injection capillary zone electrophoresis method was developed for the quantification of plasma
uric acid. The separation was performed in an uncoated fused-silica capillary (50 μm ID, 60 cm total length, 10.2 cm effective
length) by using as a background electrolyte a 75 mmol/L glycylglycine solution titrated with NaOH 5 mol/L to pH 9.0, a voltage
of 28 kV, a cartridge temperature of 15 °C, and direct UV detection at 292 nm. Under optimized conditions, uric acid was determinate
in little more than 1 min (1.076 minutes). In order to verify the accuracy of the analysis, urate levels were measured in
543 apparently healthy volunteers by the new assay and our previous method, and the obtained data were compared by Passing–Bablock
regression, Bland–Altman test, and a new regression-based approach, which showed a good agreement between two methods. 相似文献
212.
In Europe, the auctions organized by “power exchanges” one day ahead of delivery are multi-unit, double-sided, uniformly priced combinatorial auctions. Generators, retailers, large consumers and traders participate at the demand as well as at the supply side, depending or whether they are short or long in electric energy. Because generators face nonconvex costs, in particular startup costs and minimum run levels, the exchanges allow “block orders” that are all-or-nothing orders of a given amount of electric energy in multiple consecutive hours, while the standard order consists of an amount for a single hour that can be curtailed. All exchanges restrict the size (MWh/h), the type (span in terms of hours) or the number (per participant per day) of blocks that can be introduced. This paper discusses the rationale of block order restrictions. Based on simulations with representative scenarios, it is argued that the restrictions could be relaxed, which some exchanges have already started doing. 相似文献
213.
Leonardo Di G. Sigalotti Antonio Mejias Leonardo Trujillo 《Chaos, solitons, and fractals》2009,42(5):3177-3178
In a previous note, we have provided a formal derivation of the transverse Doppler shift of special relativity from the generalization of El Naschie’s complex time. Here, we show that the relativistic energy–momentum equation, and hence the Klein–Gordon equation, are also natural consequences of the complex time generalization. 相似文献
214.
Videla M Jacinto JS Baggio R Garland MT Singh P Kaim W Slep LD Olabe JA 《Inorganic chemistry》2006,45(21):8608-8617
215.
Santos LS Dalmázio I Eberlin MN Claeys M Augusti R 《Rapid communications in mass spectrometry : RCM》2006,20(14):2104-2108
Recently, it has been proposed (M. Claeys et al., Science 2004; 303: 1173) that the atmospheric OH-radical-mediated photooxidation of isoprene is a source of two major secondary organic aerosol (SOA) components, that is, 2-methylthreitol and 2-methylerythritol. These diastereoisomeric tetrols, which were characterized for the first time in the fine size fraction (<2.5 microm aerodynamic diameter) of aerosols collected in the Amazon rain forest during the wet season, were proposed to enhance the capability of the aerosols to act as cloud-condensation nuclei. In the present study, we performed the oxidation of isoprene in aqueous solution under conditions that attempted to mimic atmospheric OH-radical-induced photooxidization, and monitored and characterized on-line the reaction products via electrospray ionization mass (and tandem mass) spectrometry in the negative ion mode. The results show that the reaction of isoprene with photo- or chemically generated hydroxyl radicals indeed yields 2-methyltetrols. Other polyols were also detected, and they may therefore be considered as plausible SOA components eventually formed in normal or more extreme OH-radical-mediated photooxidation of biogenic isoprene. 相似文献
216.
Belpassi L Tarantelli F Sgamellotti A Quiney HM 《The Journal of chemical physics》2006,124(12):124104
A density fitting approach for the Coulomb matrix representation within the four-component formulation of relativistic density-functional theory is presented. Our implementation, which uses G-spinor basis sets, shares all the advantages of those found in nonrelativistic quantum chemistry. We show that very accurate Coulomb energies may be obtained using a modest number of scalar auxiliary basis functions for molecules containing heavy atoms. The efficiency of this new implementation is demonstrated in a detailed study of the spectroscopic properties of the gold dimer, and its scaling behavior has been tested by calculations of some closed-shell gold clusters (Au2, Au3+, Au4, Au5+). The algorithm is found to scale as O(N3), just as it does in the nonrelativistic case, and represents a dramatic improvement in efficiency over the conventional approach in the calculation of the Coulomb matrix, with computation times that are reduced to less than 3% for Au2 and up to 1% in the case of Au5+. 相似文献
217.
Bramanti E Toncelli D Morelli E Lampugnani L Zamboni R Miller KE Zemetra J D'Ulivo A 《Journal of chromatography. A》2006,1133(1-2):195-203
Liquid chromatography (LC) coupled on line with UV/visible diode array detector (DAD) and cold vapour generation atomic fluorescence spectrometry (CVGAFS) has been developed for the speciation, determination and characterization of phytochelatins (PCs). The method is based on a bidimensional approach, e.g. on the analysis of synthetic PC solutions (apo-PCs and Cd(2+)-complexed PCs) (i) by size exclusion chromatography coupled to UV diode array detector (SEC-DAD); (ii) by the derivatization of PC -SH groups in SEC fractions by p-hydroxymercurybenzoate (PHMB) and the indirect detection of PC-PHMB complexes by reversed phase liquid chromatography coupled to atomic fluorescence detector (RPLC-CVGAFS). MALDI-TOF/MS (matrix assisted laser desorption ionization time of flight mass spectrometry) analysis of underivatized synthetic PC samples was performed in order have a qualitative information of their composition. Quantitative analysis of synthetic PC solutions has been performed on the basis of peak area of PC-PHMB complexes of the mercury specific chromatogram and calibration curve of standard solution of glutathione (GSH) complexed to PHMB (GS-PHMB). The limit of quantitation (LOQ) in terms of GS-PHMB complex was 90 nM (CV 5%) with an injection volume of 35 microL, corresponding to 3.2 pmol (0.97 ng) of GSH. The method has been applied to analysis of extracts of cell cultures from Phaeodactylum tricornutum grown in Cd-containing nutrient solutions, analysed by SEC-DAD-CVGAFS and RPLC-DAD-CVGAFS. 相似文献
218.
219.
Qualtieri A Urso E Le Pera M Scornaienchi M Quattrone A Di Donna L Napoli A Sindona G 《Journal of the American Society for Mass Spectrometry》2006,17(2):117-123
The glycoprotein P0, the major structural protein of the peripheral nerve myelin, plays a critical role in holding myelin lamellae together via interaction of both extracellular and cytoplasmic domains. Mutations in the human P0 gene give rise to severe and progressive forms of dominantly inherited peripheral neuropathies like CMT1B. Here we report on the characterization of a bovine P0-derived protein of nearly 26 kD that corresponds to the P0 protein truncated in its cytoplasmic domain. Matrix assisted laser desorption ionization (MALDI)-time-of-flight/time-of-flight (TOF/TOF) mass spectrometry (MS) analysis on its tryptic digest has provided a peptide mapping, the main difference of which from the normal P0 analog was represented by the absence of the cluster of peaks at m/z 1513.7501, 1530.7701, and 1546.7651. The latter corresponds to the P0 fragment QTPVLYAMLDHSR and to its pyroglutamic and methionine-oxidized derivatives. The species at 1530.7701 covering the sequence 186-198 of P0 is not an artifact and might have a functional role in the myelin architecture. 相似文献
220.
Noronha LA Judson TJ Dias JF Santos LS Eberlin MN Mota CJ 《The Journal of organic chemistry》2006,71(7):2625-2629
The intrinsic acidity of dimethylhalonium ions has been determined, both by theoretical methods and by gas-phase reactions of the isolated ions with pyridine bases. The calculated geometry of the dimethylhalonium ions shows a bent structure with the C-X-C angle decreasing in the order Cl > Br > I. Thermochemical calculations for the reaction of the dimethylhalonium ions with pyridine, 2,6-dimethylpyridine, and 2,6-di-tert-butylpyridine indicate that proton transfer, with the formation of the dimethylhalonium ylide is endothermic, whereas methyl transfer, with formation of methylhalide, is exothermic. The endothermicities for proton transfer are, nevertheless, dependent on the steric hindrance of the base. The bulkier the bases, the less endothermic the proton-transfer reaction is. Experimental gas-phase reactions support the calculations, showing that methyl transfer is the major reaction of dimethylchloronium and dimethyliodonium with pyridine, whereas proton transfer, as well as single electron transfer, is observed for the bulkier bases. The calculations also indicate that acidity increases in the order chloronium > bromonium > iodonium. NBO calculations predict that hyperconjugation with the sigma carbon-halogen orbital plays a role in stabilizing the halonium ylide species in the gas phase. 相似文献