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141.
I. G. Voigt-Martin G. M. Stack A. J. Peacock L. Mandelkern 《Journal of Polymer Science.Polymer Physics》1989,27(5):957-965
A detailed quantitative comparison between thin section electron microscopy, utilizing the chlorosulfonation technique, and the Raman low-frequency acoustical mode (LAM) in determining the crystallite size distribution in polyethylenes having narrow distributions is made. Three different polyethylene systems have been analyzed, one of which was specifically prepared for this work. Very good quantitative agreement is obtained between these two analytical methods when account is taken of the chain tilt and the distribution is restrained to be narrow. Systems having broad crystallite size distributions introduce complexities into this comparison. 相似文献
142.
Mathur M Haller G Peacock T Ruppert-Felsot JE Swinney HL 《Physical review letters》2007,98(14):144502
We present a technique that uncovers the Lagrangian building blocks of turbulence, and apply this technique to a quasi-two-dimensional turbulent flow experiment. Our analysis identifies an intricate network of attracting and repelling material lines. This chaotic tangle, the Lagrangian skeleton of turbulence, shows a level of complexity found previously only in theoretical and numerical examples of strange attractors. We quantify the strength (hyperbolicity) of each material line in the skeleton and demonstrate dramatically different mixing properties in different parts of the tangle. 相似文献
143.
Leonard JP Jensen P McCabe T O'Brien JE Peacock RD Kruger PE Gunnlaugsson T 《Journal of the American Chemical Society》2007,129(36):10986-10987
144.
Adamec J Jannasch A Huang J Hohman E Fleet JC Peacock M Ferruzzi MG Martin B Weaver CM 《Journal of separation science》2011,34(1):11-20
Simultaneous and accurate measurement of vitamin D and 25-hydroxyvitamin D in biological samples is a barrier limiting our ability to define "optimal" vitamin D status. Thus, our goal was to optimize conditions and evaluate an LC-MS method for simultaneous detection and quantification of vitamin D(2) , vitamin D(3) , 25-hydroxyvitamin D(2) and 25-hydroxyvitamin D(3) in serum. Extraction and separation of vitamin D forms were achieved using acetone liquid-liquid extraction and by a reversed phase C8 column, respectively. Detection was performed on a triple quadrupole tandem mass spectrometer (QQQ-MS/MS) equipped with atmospheric pressure photo ionization source. The LOQs for all analytes tested were 1 ng/mL for hydroxylated molecules and 2 ng/mL for the parent vitamin Ds. RSD at lower LOQ (2 ng/mL) and in medium (80 ng/mL) and high (200 ng/mL) quality control samples did not exceed 20 and 15% CV, respectively. Accuracy of the method for determination of hydroxylated molecules was also validated using National Institutes of Standards and Technology standard samples and found to be in the range of 90.9-111.2%. In summary, a sensitive and reproducible method is reported for simultaneous quantification of vitamin D(2) , vitamin D(3) , 25-hydroxyvitamin D(2) and 25-hydroxyvitamin D(3) molecules in biological samples. 相似文献
145.
146.
Montgomery CP New EJ Parker D Peacock RD 《Chemical communications (Cambridge, England)》2008,(36):4261-4263
The helicity of the (SSS)-Delta enantiomer of a terbium and europium(iii) complex is inverted on reversible binding to 'drug site II' of serum albumin, signalled by a switch in its circularly polarised emission; no such behaviour occurs with the (RRR)-Lambda complexes, thereby defining a unique chiroptical probe of albumin binding. 相似文献
147.
JM Ibarra-Soza AA Morris P Jayalath H Peacock WE Conrad MB Donald MJ Kurth PA Beal 《Organic & biomolecular chemistry》2012,10(32):6491-6497
Here we describe the synthesis of new 7-substituted 8-aza-7-deazaadenosine ribonucleoside phosphoramidites and their use in generating major groove-modified duplex RNAs. A 7-ethynyl analog leads to further structural diversification of the RNA via post-automated RNA synthesis azide-alkyne cycloaddition reactions. In addition, we report preliminary studies on the effects of eight different purine 7-position modifications on RNA duplex stability and pairing specificity. Finally, the effect on RNAi activity of this type of modification at eight different positions in an siRNA guide strand has been explored. Analogs were identified with large 7-position substituents that maintain adenosine pairing specificity and are well-tolerated at specific positions in an siRNA guide strand. 相似文献
148.
Tuning the reactivity of osmium(II) and ruthenium(II) arene complexes under physiological conditions
Peacock AF Habtemariam A Fernández R Walland V Fabbiani FP Parsons S Aird RE Jodrell DI Sadler PJ 《Journal of the American Chemical Society》2006,128(5):1739-1748
The Os(II) arene ethylenediamine (en) complexes [(eta(6)-biphenyl)Os(en)Cl][Z], Z = BPh(4) (4) and BF(4) (5), are inactive toward A2780 ovarian cancer cells despite 4 being isostructural with an active Ru(II) analogue, 4R. Hydrolysis of 5 occurred 40 times more slowly than 4R. The aqua adduct 5A has a low pK(a) (6.3) compared to that of [(eta(6)-biphenyl)Ru(en)(OH(2))](2+) (7.7) and is therefore largely in the hydroxo form at physiological pH. The rate and extent of reaction of 5 with 9-ethylguanine were also less than those of 4R. We replaced the neutral en ligand by anionic acetylacetonate (acac). The complexes [(eta(6)-arene)Os(acac)Cl], arene = biphenyl (6), benzene (7), and p-cymene (8), adopt piano-stool structures similar to those of the Ru(II) analogues and form weak dimers through intermolecular (arene)C-H...O(acac) H-bonds. Remarkably, these Os(II) acac complexes undergo rapid hydrolysis to produce not only the aqua adduct, [(eta(6)-arene)Os(acac)(OH(2))](+), but also the hydroxo-bridged dimer, [(eta(6)-arene)Os(mu(2)-OH)(3)Os(eta(6)-arene)](+). The pK(a) values for the aqua adducts 6A, 7A, and 8A (7.1, 7.3, and 7.6, respectively) are lower than that for [(eta(6)-p-cymene)Ru(acac)(OH(2))](+) (9.4). Complex 8A rapidly forms adducts with 9-ethylguanine and adenosine, but not with cytidine or thymidine. Despite their reactivity toward nucleobases, complexes 6-8 were inactive toward A549 lung cancer cells. This is attributable to rapid hydrolysis and formation of unreactive hydroxo-bridged dimers which, surprisingly, were the only species present in aqueous solution at biologically relevant concentrations. Hence, the choice of chelating ligand in Os(II) (and Ru(II)) arene complexes can have a dramatic effect on hydrolysis behavior and nucleobase binding and provides a means of tuning the reactivity and the potential for discovery of anticancer complexes. 相似文献
149.
G. Brammertz A. Golubov A. Peacock P. Verhoeve D. J. Goldie R. Venn 《Physica C: Superconductivity and its Applications》2001,350(3-4):227-236
We present an application of the generalised proximity effect theory. The theory has been used to determine the energy gap (Δg) in proximised transition metal/aluminium bilayer structures such as Nb/Al, Ta/Al, V/Al and Mo/Al. These bilayers have different film thicknesses ranging from 5 to 260 nm. For the cases of Nb/Al, Ta/Al and V/Al bilayers, the interface parameters γ and γBN (here we define γ as the ratio of the products of normal state resistivity and coherence length in each film of the bilayer while γBN is the ratio of the boundary resistance between films 1 and 2 to the product of the resistivity and coherence length in the second film), which were used as input parameters to the model, were inferred experimentally from an existing bilayer of each kind and then suitably modified for different film thicknesses. This experimental assessment is therefore based on a comparison of measurements of the critical temperature and the energy gap at 300 mK with the predictions from the model for various values of γ, γBN. The energy gap of the bilayer was experimentally determined by using symmetrical superconducting tunnel junctions (STJs) of the form S–Al–AlOx–Al–S, where each electrode corresponds to a proximised bilayer. However for the case of Mo/Al bilayers the interface parameters were determined theoretically since currently no STJ data for this configuration are available. The results for the Nb/Al, Ta/Al and V/Al bilayers have also then been compared to experimentally determined energy gaps found for a series of STJs with different film thicknesses. The correspondence between experiment and theory is very good. 相似文献