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81.
Planetary-scale cloud patterns seen in ultraviolet images of Venus are produced by atmospheric waves traveling slowly with respect to the cloud-top winds. The cloud features often combine to produce a dark horizontal “Y” shape that encircles the planet. Linear wave theory and detailed observations of the waves show that the “Y” is a combination of two components-a midlatitude wave traveling somewhat slower than the winds and an equatorial wave moving slightly faster. However, nonlinear effects must be invoked in order to couple the two modes in such a way as to reproduce the observations. 相似文献
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Identification of transformation products from β‐blocking agents formed in wetland microcosms using LC‐Q‐ToF 下载免费PDF全文
Alfred Svan Mikael Hedeland Torbjörn Arvidsson Justin T. Jasper David L. Sedlak Curt E. Pettersson 《Journal of mass spectrometry : JMS》2016,51(3):207-218
Identification of degradation products from trace organic compounds, which may retain the biological activity of the parent compound, is an important step in understanding the long‐term effects of these compounds on the environment. Constructed wetlands have been successfully utilized to remove contaminants from wastewater effluent, including pharmacologically active compounds. However, relatively little is known about the transformation products formed during wetland treatment. In this study, three different wetland microcosm treatments were used to determine the biotransformation products of the β‐adrenoreceptor antagonists atenolol, metoprolol and propranolol. LC/ESI‐Q‐ToF run in the MSE and MS/MS modes was used to identify and characterize the degradation products through the accurate masses of precursor and product ions. The results were compared with those of a reference standard when available. Several compounds not previously described as biotransformation products produced in wetlands were identified, including propranolol‐O‐sulfate, 1‐naphthol and the human metabolite N‐deaminated metoprolol. Transformation pathways were significantly affected by microcosm conditions and differed between compounds, despite the compounds' structural similarities. Altogether, a diverse range of transformation products in wetland microcosms were identified and elucidated using high resolving MS. This work shows that transformation products are not always easily predicted, nor formed via the same pathways even for structurally similar compounds. Copyright © 2016 John Wiley & Sons, Ltd. 相似文献
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Stoyanov AV Rohlfing CL Connolly S Roberts ML Nauser CL Little RR 《Journal of chromatography. A》2011,1218(51):9244-9249
An application of ion exchange chromatography for C-peptide analysis is described here. At the stage of C-peptide isolation, a strong cation exchanger (SP HP or MonoS) was used to purify the analyte from ballast proteins and peptides. The conditions of ion-exchange chromatographic separations were optimized using theoretical modeling of the net surface electric charge of the peptide as a function of pH. The purified and concentrated sample was further subjected to LC-MS/MS. In order to improve the reliability of analysis, two fragment ions were monitored simultaneously both for native C-peptide and internal standard, isotopically labeled C-peptides analogues (fragments with m/z of 927.7 and 147.2). Using ion-exchange chromatography, it became possible to process larger sample volumes, important for testing patients with very low C peptide levels, compared to currently used solid phase extraction methods. 相似文献
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The structures and reactivities of nitrile imines are subjects of continuing debate. Several nitrile imines were generated photochemically or thermally and investigated by IR spectroscopy in Ar matrices at cryogenic temperatures (Ph-CNN-H 6, Ph-CNN-CH(3)17, Ph-CNN-SiMe(3)23, Ph-CNN-Ph 29, Ph(3)C-CNN-CPh(3)34, and the boryl-CNN-boryl derivative 39). The effect of substituents on the structures and IR absorptions of nitrile imines was investigated computationally at the B3LYP/6-31G* level. IR spectra were analyzed in terms of calculated anharmonic vibrational spectra and were generally in very good agreement with the calculated spectra. Infrared spectra were found to reflect the structures of nitrile imines accurately. Nitrile imines with IR absorptions above 2200 cm(-1) have essentially propargylic structures, possessing a CN triple bond (typically PhCNNSiMe(3)23, PhCNNPh 29, and boryl-CNN-boryl 39). Nitrile imines with IR absorptions below ca. 2200 cm(-1) are more likely to be allenic (e.g., HCNNH 1, PhCNNH 6, HCNNPh 43, PhCNNCH(3)17, and Ph(3)C-CNN-CPh(3)34). All nitrile imines isomerize to the corresponding carbodiimides both thermally and photochemically. Monosubstituted carbodiimides isomerize thermally to the corresponding cyanamides (e.g., Ph-N═C═N-H 5 → Ph-NH-CN 8), which are therefore the thermal end products for nitrile imines of the types RCNNH and HCNNR. This tautomerization is reversible under flash vacuum thermolysis conditions. 相似文献
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Peter L. Lee Deming Shu Mohan Ramanathan Curt Preissner Jun Wang Mark A. Beno Robert B. Von Dreele Lynn Ribaud Charles Kurtz Sytle M. Antao Xuesong Jiao Brian H. Toby 《Journal of synchrotron radiation》2008,15(5):427-432
A dedicated high‐resolution high‐throughput X‐ray powder diffraction beamline has been constructed at the Advanced Photon Source (APS). In order to achieve the goals of both high resolution and high throughput in a powder instrument, a multi‐analyzer detector system is required. The design and performance of the 12‐analyzer detector system installed on the powder diffractometer at the 11‐BM beamline of APS are presented. 相似文献
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Sergey Shleev Viktor Andoralov Magnus Falk Curt T. Reimann Tautgirdas Ruzgas Martin Srnec Ulf Ryde Lubomír Rulíšek 《Electroanalysis》2012,24(7):1524-1540
The catalytic cycle of multicopper oxidases (MCOs) involves intramolecular electron transfer (IET) from the Cu‐T1 copper ion, which is the primary site of the one‐electron oxidations of the substrate, to the trinuclear copper cluster (TNC), which is the site of the four‐electron reduction of dioxygen to water. In this study we report a detailed characterization of the kinetic and electrochemical properties of bilirubin oxidase (BOx) – a member of the MCO family. The experimental results strongly indicate that under certain conditions, e.g. in alkaline solutions, the IET can be the rate‐limiting step in the BOx catalytic cycle. The data also suggest that one of the catalytically relevant intermediates (most likely characterized by an intermediate oxidation state of the TNC) formed during the catalytic cycle of BOx has a redox potential close to 0.4 V, indicating an uphill IET process from the T1 copper site (0.7 V) to the Cu‐T23. These suggestions are supported by calculations of the IET rate, based on the experimentally observed Gibbs free energy change and theoretical estimates of reorganization energy obtained by combined quantum and molecular mechanical (QM/MM) calculations. 相似文献
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