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241.
Hui Jiang Fong-Fu Hsu Marsha S. Farmer Linda R. Peterson Jean E. Schaffer Daniel S. Ory Xuntian Jiang 《Analytical and bioanalytical chemistry》2013,405(23):7357-7365
Ceramide is a key metabolite in both anabolic and catabolic pathways of sphingolipids. The very long fatty acyl chain ceramides N-(docosanoyl)-sphing-4-enine (Cer(22:0)) and N-(tetracosanoyl)-sphing-4-enine (Cer(24:0)) are associated with multiple biological functions. Elevated levels of these sphingolipids in tissues and in the circulation have been associated with insulin resistance and diabetes. To facilitate quantification of these very long chain ceramides in clinical samples from human subjects, we have developed a sensitive, accurate, and high-throughput assay for determination of Cer(22:0) and Cer(24:0) in human plasma. Cer(22:0) and Cer(24:0) and their deuterated internal standards were extracted by protein precipitation and chromatographically separated by HPLC. The analytes and their internal standards were ionized using positive-ion electrospray mass spectrometry, then detected by multiple-reaction monitoring with a tandem mass spectrometer. Total liquid chromatography–tandem mass spectrometry (LC-MS/MS) runtime was 5 min. The assay exhibited a linear dynamic range of 0.02–4 and 0.08–16 μg/ml for Cer(22:0) and Cer(24:0), respectively, in human plasma with corresponding absolute recoveries from plasma at 109 and 114 %, respectively. The lower limit of quantifications were 0.02 and 0.08 μg/ml for Cer(22:0) and Cer(24:0), respectively. Acceptable precision and accuracy were obtained for concentrations over the calibration curve ranges. With the semi-automated format and short LC runtime for the assay, a throughput of ~200 samples/day can easily be achieved. Figure
LC-MS/MS chromatograms for Cer(22:0) and Cer(24:0) in LLOQ, in which the analyte and internal standard are shown in blue and red, respectively 相似文献
242.
Thione-substituted derivatives of maltol are of interest in several applications of metal-based drugs. In order to investigate the effect of the oxygenation on such thione chelates, Ru complexes of 3-hydroxy-2-methyl-4-thiopyrone (thiomaltol or Htma) and 3-hydroxy-2-methyl-4H-thiopyran-4-thione (dithiomaltol or Httma), [Ru(bpy)2(tma)](+), 1, and [Ru(bpy) 2(ttma)] (+), 2, were synthesized as diamagnetic PF6(-) salts. Peroxidation of 2 unexpectedly generated products of C-H activation at its pendant methyl group; an air-stable aldehyde [Ru(bpy)2(ttma-aldehyde)](+), 4, was the major product. In addition, an intermediate oxidation product [Ru(bpy) 2(ttma-alcohol)](PF6), 3, was characterized. Both 3 and 4 are also formed by reaction of 2 with outersphere oxidants (e.g., Na2IrCl6) and by bulk electrolysis under anaerobic conditions. Similar oxidations of the analogous [Ru(bpy)2(ettma)](+), 2' , complex (3-hydroxy-2-ethyl-4H-thiopyran-4-thione; ethyl dithiomaltol or Hettma) formed the corresponding ketone, [Ru(bpy)2(ettma-ketone)](PF6), 4', by oxidation at the same position adjacent to the conjugated ring. The structures of the aldehyde 4 and starting materials 1 and 2 have been confirmed by X-ray crystallography, and all complexes have been characterized by UV-vis, (1)H NMR, and IR spectroscopies. Initial mechanistic investigations are discussed. 相似文献
243.
Martí A Antolín E Stanley CR Farmer CD López N Díaz P Cánovas E Linares PG Luque A 《Physical review letters》2006,97(24):247701
We present intermediate-band solar cells manufactured using quantum dot technology that show for the first time the production of photocurrent when two sub-band-gap energy photons are absorbed simultaneously. One photon produces an optical transition from the intermediate-band to the conduction band while the second pumps an electron from the valence band to the intermediate-band. The detection of this two-photon absorption process is essential to verify the principles of operation of the intermediate-band solar cell. The phenomenon is the cornerstone physical principle that ultimately allows the production of photocurrent in a solar cell by below band gap photon absorption, without degradation of its output voltage. 相似文献
244.
H. Hernández J. H. Lamb J. R. Cushnir S. Naylor P. B. Farmer 《Rapid communications in mass spectrometry : RCM》1996,10(4):399-404
Selected ion recording (SIR) and multiple-reaction monitoring (MRM) are used extensively in conjunction with GC/MS. A comparison of MRM and low and high resolution SIR is presented which contrasts the susceptibility of the techniques to artefactual responses. An assay developed for the quantitation of the tert -butyldimethylsilyl ( t -BDMS) derivative of thymine glycol was chosen as the test experiment. The effect of the elution of two unrelated compounds of lower relative molecular mass than the ion to be monitored was then observed. The greatest effect was observed with low resolution SIR, where both positive and negative artefactual responses were observed in the monitored channels. In high resolution SIR, artefacts were observed in the lock-mass channel only, while in MRM no artefacts were detected. Discussion of the results includes the possible role of the column stationary phase in producing the observed artefacts, together with suggestions for reducing artefacts in GC/MS. 相似文献
245.
Soo‐Young Park Leonard V. Interrante B. L. Farmer 《Macromolecular rapid communications》2003,24(13):793-798
The packing of poly(di‐n‐alkylsilylenemethylene) (PDASMs) chains was studied by using X‐ray, electron diffraction, and molecular modeling methods. X‐ray and electron diffraction measurements revealed unit cells in which the PDASMs were efficiently packed. The PDASM with the longer alkyl side chains, such as poly(di‐n‐propylsilylenemethylene) (PDPrSM), showed packing with the alkyl side chains interlocked with each other like cross‐shaped gears in the two‐dimensional monoclinic unit cell. The PDASM with the shorter ethyl substituent, poly(di‐n‐ethylsilylenemethylene) (PDESM), showed a lack of ability to interlock its side chains due to the short length of the alkyl groups. In these studies, we found that the length of the alkyl side chains could change the packing arrangement of PDASMs from monoclinic to orthorhombic to hexagonal with only short‐range order as the alkyl side chain length decreases at room temperature.