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Gianotto AK Hodges BD Harrington Pde B Appelhans AD Olson JE Groenewold GS 《Journal of the American Society for Mass Spectrometry》2003,14(10):1067-1075
Chromium oxyanions, Cr(x)O(y)H(z)(-), were generated in the gas-phase using a quadrupole ion trap secondary ion mass spectrometer (IT-SIMS), where they were reacted with O(2). Only CrO(2)(-) of the Cr(1)O(y)H(z)(-) envelope was observed to react with oxygen, producing primarily CrO(3)(-). The rate constant for the reaction of CrO(2)(-) with O(2) was approximately 38% of the Langevin collision constant at 310 K. CrO(3)(-), CrO(4)(-), and CrO(4)H(-) were unreactive with O(2) in the ion trap. In contrast, Cr(2)O(4)(-) was observed to react with O(2) producing CrO(3)(-) + CrO(3) via oxidative degradation at a rate that was approximately 15% efficient. The presence of background water facilitated the reaction of Cr(2)O(4)(-) + H(2)O to form Cr(2)O(5)H(2)(-); the hydrated product ion Cr(2)O(5)H(2)(-) reacted with O(2) to form Cr(2)O(6)(-) (with concurrent elimination of H(2)O) at a rate that was 6% efficient. Cr(2)O(5)(-) also reacted with O(2) to form Cr(2)O(7)(-) (4% efficient) and Cr(2)O(6)(-) + O (2% efficient); these reactions proceeded in parallel. By comparison, Cr(2)O(6)(-) was unreactive with O(2), and in fact, no further O(2) addition could be observed for any of the Cr(2)O(6)H(z)(-) anions. Generalizing, Cr(x)O(y)H(z)(-) species that have low coordinate, low oxidation state metal centers are susceptible to O(2) oxidation. However, when the metal coordination is >3, or when the formal oxidation state is > or =5, reactivity stops. 相似文献
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LoSecco JM Bionta RM Biewitt G Bratton CB Casper D Chrysicopoulou P Claus R Cortez BG Errede S Foster GW Gajewski W Ganezer KS Goldhaber M Haines TJ Jones TW Kielczewska D Kropp WR Learned JG Lehmann E Park HS Reines F Schultz J Seidel S Shumard E Sinclair D Sobel HW Stone JL Sulak L Svoboda R van der Velde JC Wuest C 《Physical review letters》1985,54(21):2299-2301
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We present a portable spectrometer that uses the frequency-stabilized cavity ring-down spectroscopy technique capable of high-precision measurements of trace water vapor concentration. Measuring one of the strongest rovibrational transitions in the ν1+ν3 water vapor combination band near ˜ν=7181.156 cm-1, we compare spectroscopic and thermodynamic determinations of trace water vapor in N2, and find systematic differences attributable to water vapor background effects and/or uncertainties in line intensities. We also compare the frequency-stabilized ring-down method with other cavity ring-down approaches that are based on unstabilized probe lasers and unstabilized ring-down cavities. We show that for the determination of water vapor concentration, the frequency-stabilized cavity ring-down method has the minimum measurement uncertainty of these techniques. The minimum noise-equivalent absorption coefficient of the spectrometer was 1.2×10-10 cm-1 Hz-1/2, which further corresponds to a minimum detectable water vapor mole fraction equal to 0.7×10-9 for an absorption spectrum of 10 minutes duration. PACS 33.20.-t; 33.70.Jg; 33.70.Fd; 42.62.Fi 相似文献
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DC Muddiman AP Null JC Hannis 《Rapid communications in mass spectrometry : RCM》1999,13(12):1201-1204
Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICRMS) has been used to determine the mass of a double-stranded 500 base-pair (bp) polymerase chain reaction (PCR) product with an average theoretical mass of the blunt-ended (i.e. unadenylated) species of 308 859.35 Da. The PCR product was generated from the linearized bacteriophage Lambda genome which is a double-stranded template. Utilization of ethanol precipitation in tandem with a rapid microdialysis step to purify and desalt the PCR product was crucial to obtain a precise mass measurement. The PCR product (0.8 pmol/μL) was electrosprayed from a solution containing 75% acetonitrile, 25 mM piperidine, and 25 mM imidazole and was infused at a rate of 200 nL/min. The average molecular mass and the corresponding precision were determined using the charge-states ranging from 172 to 235 net negative charges. The experimental mass and corresponding precision (reported as the 95% confidence interval of the mean) was 309 406 +/- 27 Da (87 ppm). The mass accuracy was compromised due to the fact that the PCR generates multiple products when using Taq polymerase due to the non-template directed 3'-adenylation. This results in a mixture of three PCR products with nearly identical mass (i.e. blunt-ended, mono-adenylated and di-adenylated) with unknown relative abundances that were not resolved in the spectrum. Thus, the experimental mass will be a weighted average of the three species which, under our experimental conditions, reflects a nearly equal concentration of the mono- and di-adenylated species. This report demonstrates that precise mass measurements of PCR products up to 309 kDa (500 bp) can be routinely obtained by ESI-FTICR requiring low femtomole amounts. Copyright 1999 John Wiley & Sons, Ltd. 相似文献
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Jonathan Tennyson Peter F. Bernath Linda R. Brown Alain Campargue Michel R. Carleer Attila G. Császár Robert R. Gamache Joseph T. Hodges Alain Jenouvrier Olga V. Naumenko Oleg L. Polyansky Laurence S. Rothman Robert A. Toth Ann Carine Vandaele Nikolai F. Zobov Ludovic Daumont Alexander Z. Fazliev Tibor Furtenbacher Iouli E. Gordon Semen N. Mikhailenko Sergei V. Shirin 《Journal of Quantitative Spectroscopy & Radiative Transfer》2009,110(9-10):573-596
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Sakari Leino Patrick JC May Paavo Alku Lassi A Liikkanen Hannu Tiitinen 《BMC neuroscience》2007,8(1):78