全文获取类型
收费全文 | 517篇 |
免费 | 18篇 |
专业分类
化学 | 286篇 |
晶体学 | 5篇 |
力学 | 33篇 |
数学 | 56篇 |
物理学 | 155篇 |
出版年
2023年 | 3篇 |
2022年 | 7篇 |
2021年 | 19篇 |
2020年 | 5篇 |
2019年 | 10篇 |
2018年 | 14篇 |
2017年 | 8篇 |
2016年 | 17篇 |
2015年 | 12篇 |
2014年 | 12篇 |
2013年 | 44篇 |
2012年 | 29篇 |
2011年 | 40篇 |
2010年 | 21篇 |
2009年 | 30篇 |
2008年 | 20篇 |
2007年 | 25篇 |
2006年 | 20篇 |
2005年 | 24篇 |
2004年 | 18篇 |
2003年 | 19篇 |
2002年 | 13篇 |
2001年 | 6篇 |
2000年 | 7篇 |
1999年 | 2篇 |
1998年 | 3篇 |
1997年 | 4篇 |
1996年 | 8篇 |
1995年 | 3篇 |
1994年 | 5篇 |
1993年 | 5篇 |
1992年 | 4篇 |
1991年 | 4篇 |
1990年 | 4篇 |
1988年 | 2篇 |
1987年 | 4篇 |
1986年 | 9篇 |
1985年 | 3篇 |
1984年 | 3篇 |
1982年 | 9篇 |
1981年 | 5篇 |
1980年 | 2篇 |
1979年 | 4篇 |
1978年 | 3篇 |
1977年 | 5篇 |
1973年 | 4篇 |
1937年 | 2篇 |
1931年 | 2篇 |
1930年 | 2篇 |
1923年 | 1篇 |
排序方式: 共有535条查询结果,搜索用时 15 毫秒
1.
The research presented here concerns the simultaneous grouping of the components of a vocal sound source. McAdams [J. Acoust. Soc. Am. 86, 2148-2159 (1989)] found that when three simultaneous vowels at different pitches were presented with subaudio frequency modulation, subjects judged them as being more prominent than when no vibrato was present. In a normal voice, when the harmonics of a vowel undergo frequency modulation they also undergo an amplitude modulation that traces the spectral envelope. Hypothetically, this spectral tracing could be one of the criteria used by the ear to group components of each vowel, which may help explain the lack of effect of frequency modulation coherence among different vowels in the previous study. In this experiment, two types of vowel synthesis were used in which the component amplitudes of each vowel either remained constant with frequency modulation or traced the spectral envelope. The stimuli for the experiment were chords of three different vowels at pitch intervals of five semitones (ratio 1.33). All the vowels of a given stimulus were produced by the same synthesis method. The subjects' task involved rating the prominence of each vowel in the stimulus. It was assumed that subjects would judge this prominence to be lower when they were not able to distinguish the vowel from the background sound. Also included as stimulus parameters were the different permutations of the three vowels at three pitches and a number of modulation conditions in which vowels were unmodulated, modulated alone, and modulated either coherently with, or independently of, the other vowels. Spectral tracing did not result in increased ratings of vowel prominence compared to stimuli where no spectral tracing was present. It would therefore seem that it has no effect on grouping components of sound sources. Modulated vowels received higher prominence ratings than unmodulated vowels. Vowels modulated alone were judged to be more prominent than vowels modulated with other vowels. There was, however, no significant difference between coherent and independent modulation of the three vowels. Differences among modulation conditions were more marked when the modulation width was 6% than when it was 3%. 相似文献
2.
3.
Claude Didierjean Julien Marin Emmanuel Wenger Jean‐Paul Briand Andr Aubry Gilles Guichard 《Acta Crystallographica. Section C, Structural Chemistry》2004,60(3):o200-o203
X‐ray studies reveal that tert‐butyl (6S)‐6‐isobutyl‐2,4‐dioxopiperidine‐1‐carboxylate occurs in the 4‐enol form, viz. tert‐butyl (6S)‐4‐hydroxy‐6‐isobutyl‐2‐oxo‐1,2,5,6‐tetrahydropyridine‐1‐carboxylate, C14H23NO4, when crystals are grown from a mixture of dichloromethane and pentane, and has an axial orientation of the isobutyl side chain at the 6‐position of the piperidine ring. Reduction of the keto functionality leads predominantly to the corresponding β‐hydroxylated δ‐lactam, tert‐butyl (4R,6S)‐4‐hydroxy‐6‐isobutyl‐2‐oxopiperidine‐1‐carboxylate, C14H25NO4, with a cis configuration of the 4‐hydroxy and 6‐isobutyl groups. The two compounds show similar molecular packing driven by strong O—H⋯O=C hydrogen bonds, leading to infinite chains in the crystal structure. 相似文献
4.
Juray De Wilde Denis Constales Geraldine J. Heynderickx Guy B. Marin 《International Journal of Multiphase Flow》2007
The propagation speeds of linear waves in gas–solid suspensions depend strongly on the solids volume fraction and the wave frequency. The latter is due to gas–solid momentum transfer and allows a simple test on filtered gas–solid momentum transfer models. Such models may predict linear wave propagation speeds different from those obtained with the non-filtered model at wave frequencies higher than the filter frequency, but not at wave frequencies lower than the filter frequency. 相似文献
5.
6.
Poschalko A Lancelot N Marin J Larras V Limal D Elbayed K Raya J Piotto M Briand JP Guichard G Bianco A 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(18):4532-4537
A novel resin called DEUSS (perdeuterated poly(oxyethylene)-based solid support) has been prepared by anionic polymerization of deuterated [D4]ethylene oxide, followed by cross-linking with deuterated epichlorohydrin. DEUSS can be suspended in a wide range of solvents including organic and aqueous solutions, in which it displays a high swelling capacity. As measured by proton HRMAS of the swollen polymer, the signal intensity of the oxyethylene protons is reduced by a factor of 110 relative to the corresponding nondeuterated poly(oxyethylene)poly(oxypropylene) (POEPOP) resin, thus facilitating detailed HRMAS NMR studies of covalently linked molecules. This 1H NMR invisible matrix was used for the solid-phase synthesis of peptides, oligoureas, and a series of amides as well as their characterization by HRMAS NMR spectroscopy. On-bead NMR spectra of high quality and with resolution comparable to that of liquid samples were obtained and readily interpreted. The complete absence of the parasite resin signals will be of great advantage, for example, for the optimization of multistep solid-phase stereoselective reactions, and for the conformational study of resin-bound molecules in a large variety of solvents. 相似文献
7.
The kinetics of peptide release during in vitro digestion of 4 protein sources (casein, cod protein, soy protein, and gluten) were investigated. Samples were sequentially hydrolyzed with pepsin (30 min) and pancreatin (2, 4, or 6 h) in a dialysis cell with continuous removal of digestion products. Nondialyzed digests were fractionated by ion-exchange chromatography and ultrafiltration. Animal proteins were digested at a greater rate than plant proteins. Target amino acids of specific enzymes appeared more rapidly in the dialyzed fractions when compared to other amino acids. Throughout the hydrolysis, nondialyzed digests contained a higher proportion of peptide mixtures with basic-neutral properties. Except for gluten, peptide fractions with molecular weights that exceeded 10 kDa (basic-neutral, BN > 10) were rapidly hydrolyzed during the first 2 h of pancreatin digestion. The kinetics of release and the composition of peptide fractions were different when the protein sources were compared. The analysis of amino acids revealed that threonine and proline proportions were relatively high in BN > 10 and in peptide fractions with molecular weight between 10-1 kDa (BN 10-1), while tyrosine, phenylalanine, lysine, and arginine predominated in the low molecular weight (<1 kDa) fractions. More resistant peptides were generally rich in proline and glutamic acid. The role of in vitro digestion assays in dietary protein quality evaluation is discussed. 相似文献
8.
Matiide Angulo Mercedes Ruiz Montoya Rafael Marin Galvin José Miguel Rodriguez Mellado 《Electroanalysis》1997,9(4):345-349
The electroreductions of the NAD+ model compounds nicotinamide (I), N1-methyl nicotinamide (II), N′-methyl nicotinamide (III) and isonicotinamide (IV) on carbon electrodes have been studied in aqueous media in the pH range 0–12 by linear-sweep cyclic voltammetry (Scheme 1, I-IV). Logarithmic analyses of the reduction peaks were performed by computing the convolution of the current with time as a function of the potential. On the basis of the experimental results it was concluded that the irreversibility of the electron transfers increased when a glassy carbon electrode was used, and this irreversibility being more marked when a plastic formed carbon electrode was employed. The reduction processes occurred with more difficulty on carbon electrodes than on mercury electrodes. Both the reduction and the reoxidation (when occurred) processes changed with respect to those observed on mercury electrodes, being irreversible electron transfers the rate-determining steps in most cases. Thus, for compounds I, II and III at pH < 2 the reductions occurred by the uptake of two electrons and two H+ ions, and the rate determining step was found to be the first one-electron transfer, for I and III, and the irreversible second electron transfer, preceded by the uptake of an H+ ion, for II. At pH>3 the processes consisted of electrodimerization reactions, preceded by the protonation of the heterocyclic nitrogen in cases I and III. The second electron transfer of the electroreduction of IV always appeared irreversible, in contrast with that found for mercury electrodes. 相似文献
9.
Thermoanalytical techniques (TG, DTG, DTA and EGA) can be helpful in studying gel compositions and relating the chemical history and the role of the precipitant to the chemical properties of gels. The objective of our work was to determine the influence of the initial conditions in the reaction mixture on the product characteristics. Zirconia gels were prepared by the gelprecipitation method by the hydrolysis of zirconium tetrachloride dissolved in methanol. The substitution of water by methanol was chosen in order to obtain a reaction medium in which better control of the hydrolysis and condensation reactions of the zirconium precursor were achieved and thus also better control of the final properties of the dried zirconia gel-precipitates could be obtained. The nature of the hydrated zirconia gels obtained during the gelation process is strongly influenced by the conditions of the reaction mixture, e.g. concentration of the zirconium precursor, the mixing rate and particularly by the amount of water added. To distinguish between various types of water in the gel-precipitates, the furnace atmosphere and the partial water pressure were altered appropriately. It was shown that initial zirconium to water molar ratio has a significant effect on the properties of the final products. It was assumed that, according to the preparation conditions, three different types of water are present in the formed zirconia gel-precipitates. Modification of the dehydration processes of zirconia gel-precipitates enables control of the final microstructural and surface properties of the dried gels which are suitable for further catalysts support as well as mixed oxide preparation. 相似文献
10.
Ernesto Carmona Jose M. Marin Manuel L. Poveda Robin D. Rogers Jerry L. Atwood 《Journal of organometallic chemistry》1982,238(4):C63-C66
The reduction of [WCl4(PMe3)3] with dispersed sodium, under dinitrogen, gives cis-[W(N2)2(PMe3)4], while under ethylene trans-[W(C2H4)2(PMe3)4] is obtained. The ethylene complex can also be prepared by displacement of the dinitrogen molecules in cis-[W(N2)2(PMe3)4] by ethylene at room temperature and pressure. Interaction of cis-[M(N2)2(PMe3)4] complexes (M = Mo, W), with PMe3, under helium or argon, yields [M(N2)(PMe3)5]. The molybdenum complex crystallizes in the orthorhombic space group Pnma, with a 22.063(6), b 12.106(4), c 9.745(4) Å. The Mo—P distance trans to the dinitrogen ligand (2.483(7) Å) is slightly longer than the average of the other four Mo—P bonds (2.460(5) Å). 相似文献