全文获取类型
收费全文 | 460548篇 |
免费 | 5281篇 |
国内免费 | 1608篇 |
专业分类
化学 | 254447篇 |
晶体学 | 6844篇 |
力学 | 19020篇 |
综合类 | 12篇 |
数学 | 52043篇 |
物理学 | 135071篇 |
出版年
2018年 | 2999篇 |
2016年 | 5731篇 |
2015年 | 4579篇 |
2014年 | 6307篇 |
2013年 | 20009篇 |
2012年 | 14469篇 |
2011年 | 18103篇 |
2010年 | 11536篇 |
2009年 | 11390篇 |
2008年 | 16629篇 |
2007年 | 16979篇 |
2006年 | 16333篇 |
2005年 | 14926篇 |
2004年 | 13508篇 |
2003年 | 11972篇 |
2002年 | 11780篇 |
2001年 | 13897篇 |
2000年 | 10670篇 |
1999年 | 8561篇 |
1998年 | 6836篇 |
1997年 | 6719篇 |
1996年 | 6754篇 |
1995年 | 6177篇 |
1994年 | 5940篇 |
1993年 | 5631篇 |
1992年 | 6498篇 |
1991年 | 6211篇 |
1990年 | 5905篇 |
1989年 | 5787篇 |
1988年 | 5990篇 |
1987年 | 5736篇 |
1986年 | 5473篇 |
1985年 | 7714篇 |
1984年 | 7805篇 |
1983年 | 6406篇 |
1982年 | 6869篇 |
1981年 | 6867篇 |
1980年 | 6515篇 |
1979年 | 6784篇 |
1978年 | 6963篇 |
1977年 | 6854篇 |
1976年 | 6738篇 |
1975年 | 6524篇 |
1974年 | 6318篇 |
1973年 | 6507篇 |
1972年 | 3939篇 |
1971年 | 3068篇 |
1968年 | 3389篇 |
1967年 | 3293篇 |
1966年 | 3007篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
951.
The rotational Raman spectra of butadiene and butadiene-d6 are found to consist of discrete lines having small ≈0·4 cm−1) yet almost constant spacings, as would be expected for symmetric or nearly symmetric top molecules. An infra-red absorption band (Type C) of butadiene at 908 cm−1 is observed to have a spacing of about 2·5 cm−1. Both the Raman and infra-red spectra provide evidence for the trans structure of the butadiene molecule. From the rotational constants A″ and
″ the following structural parameters were obtained: C=C---C) = 122·9 ± 0·5° rC---C) = 1·476 ± 0·010 Å dy]somewhat shorter than recently determined from electron-diffraction experiments). 相似文献
952.
The solid-state E/Z-photoisomerization of 1,2-dibenzoylethene 总被引:1,自引:0,他引:1
The E/Z-photoisomerization of trans-1,2-dibenzoylethene (DBE) in the confinement of its crystal lattice proceeds readily, but not as a single crystal to single crystal process which was claimed previously by others. This model for the Z-->E isomerization at the 11-12 double bond of the retinal moiety in the crystal-like confinement of rhodopsin was investigated in view of the fact that the precise geometric features are crucial for a better understanding of the postulated twist mechanism. Atomic force microscopy (AFM) monitored long-range anisotropic molecular movements if trans-DBE was photoisomerized, but cis-DBE was unreactive even at the extreme sensitivity of AFM. The crystal lattices of both isomers cannot accommodate a rotational mechanism but at best the twist mechanism with the large groups not leaving their planes. The unidirectional solid-state photochemistry derives from the crystal packing of cis-DBE which exhibits severe 3D-interlocking. Thus, trans-DBE molecules are not formed in the cis-lattice, because their moving away would be prohibited. Conversely, photochemically formed cis-DBE molecules escape the foreign trans-DBE lattice easily along its glide planes, as is experimentally observed by AFM. These findings are reminiscent of the escape of 11-trans-retinal from the rhodopsin array in the vision cascade. 相似文献
953.
A low density, low temperature plasma formed by two merged beams of electrons and ions at near zero relative velocity is studied by solving a set of time-dependent rate equations. In particular, we investigate the role played by the radiative recombination (RR) and three-body recombination (TBR) on the population of excited states during the initial stage of plasma rearrangement and relaxation. It is found in the case of hydrogenic plasmas that low-lying states are filled predominantly by RR, while high Rydberg states are populated mainly by TBR. As the plasma further relaxes, the collisional excitation and de-excitation, and radiative decays become important, filling the median excited states. The dependence of the TBR and RR rates on ionic chargeZ is discussed to extend the result to plasmas of highZ ions. 相似文献
954.
Résumé L'hydrure d'aluminium AlH3- a été obtenu par action de LiAlH4 sur AlCl3 ou ZnCl2 dans l'éther éthylique. La décomposition thermique a été étudiée par thermogravimé trie sous pression réduite (10–2 torr). La capacité calorifique molaire à 298 K, l'enthalpie de décomposition, ainsi que l'enthalpie de formation ont été déterminées avec un microcalorimètre Calvet.
Ce travail a été effectué dans le cadre d'un contrat de recherches passé par le laboratoire de Thermochimie Minérale avec la Direction des Recherches et Moyen d'Essai. Nous remercions bien vivement cet organisme de l'aide qu'il nous a apportée. 相似文献
Aluminium hydride,-AlH3, was prepared by reaction of LiAlH4 on A1C13 or ZnCl2 in diethyl ether. Thermogravimetry was used to investigate its thermal decomposition under low pressure (10–2 torr). The molar heat capacity at 298 K, the heat of decomposition, and the heat of formation, were measured with a Calvet microcalorimeter.
Zusammenfassung Aluminiumhydrid AlH3- wurde durch Einwirkung von LiAlH4 auf AlCl3 oder ZnCl2 in DiÄthylether hergestellt. Die Thermo gravimetrie wurde zur Untersuchung der thermischen Zersetzung bei niedrigem Druck (10–2 torr) herangezogen. Die molare WÄrmekapazitÄt bei 298 K, die Zersetzungsenthalpie sowie die Bildungsenthalpie wurden mit einem Calvet-Mikrokalorimeter bestimmt.
— - l3 LiAlH4 ll3 ZnCl2 . (10–2 ) . 298 , .
Ce travail a été effectué dans le cadre d'un contrat de recherches passé par le laboratoire de Thermochimie Minérale avec la Direction des Recherches et Moyen d'Essai. Nous remercions bien vivement cet organisme de l'aide qu'il nous a apportée. 相似文献
955.
D. Beese R. Steiner H. Scheer A. Angerhofer B. Robert M. Lutz 《Photochemistry and photobiology》1988,47(2):293-304
Abstract— Reaction centers from Rhodobacter sphaeroides have been modified by treatment with sodium borohydride similar to the original procedure [Ditson et al., Biochim. Biophys. Acta 766 , 623 (1984)], and investigated spectroscopically and by gel electrophoresis.
(1) Low temperature (1.2 K) absorption, fluorescence, absorption- and fluorescence-detected ODMR, and microwave-induced singlet-triplet absorption difference spectra (MIA) suggest that the treatment produces a spectroscopically homogeneous preparation with one of the 'additional' bacteriochlorophylls being removed. The modification does not alter the zero field splitting parameters of the primary donor triplet (T P870).
(2) From the circular dichroism and Raman resonance spectra in the1500–1800 cm-1 region, the removed pigment is assigned to BchlM , e.g. the "extra" Bchl on the "inactive" M-branch.
(3) A strong coupling among all pigment molecules is deduced from the circular dichroism spectra, because pronounced band-shifts and/or intensity changes occur in the spectral components assigned to all pigments. This is supported by distinct differences among the MIA spectra of untreated and modified reaction centers, as well as by Raman resonance.
(4) The modification is accompanied by partial proteolytic cleavage of the M-subunit. The preparation is thus spectroscopically homogeneous, but biochemically heterogenous. 相似文献
(1) Low temperature (1.2 K) absorption, fluorescence, absorption- and fluorescence-detected ODMR, and microwave-induced singlet-triplet absorption difference spectra (MIA) suggest that the treatment produces a spectroscopically homogeneous preparation with one of the 'additional' bacteriochlorophylls being removed. The modification does not alter the zero field splitting parameters of the primary donor triplet (
(2) From the circular dichroism and Raman resonance spectra in the1500–1800 cm
(3) A strong coupling among all pigment molecules is deduced from the circular dichroism spectra, because pronounced band-shifts and/or intensity changes occur in the spectral components assigned to all pigments. This is supported by distinct differences among the MIA spectra of untreated and modified reaction centers, as well as by Raman resonance.
(4) The modification is accompanied by partial proteolytic cleavage of the M-subunit. The preparation is thus spectroscopically homogeneous, but biochemically heterogenous. 相似文献
956.
Light-dependent oxygen uptake was observed and studied in thylakoids from early greening barley in comparison to oxygen uptake in chlorophyll solutions and in thylakoids from fully green leaves. Substantial oxygen uptake was observed in chlorophyll solutions supplemented with tryptophan, histidine, ascorbic acid or linoleic acid. This uptake was diminished by adding azide, beta-carotene and alpha-tocopherol, which are specific singlet-oxygen quenchers. Illuminated thylakoids from greening barley also exhibited marked oxygen uptake that, likewise, was strongly quenched by azide. In comparison, azide was found not to affect oxygen uptake that is associated with the methyl viologen-catalyzed Mehler reaction. It is reasoned that in the first two cases the oxygen uptake arises from chlorophyll-photosensitized activation of oxygen to the singlet state and its consumption by exogenous or endogenous substrates. In greening, we propose that disorganized chlorophyll photo-sensitizes the oxygen uptake. 相似文献
957.
Abstract— The fluorescence decay kinetics of the reduced nicotinamides NMNH, NADH and NADPH in aqueous solution were investigated using an Ar ion laser, mode locked in the UV, as source of excitation and single photon counting electronics in the detection system allowing for a time resolution in the picosecond range. Analysis of the experimental fluorescence decay showed that the dinucleotides did not follow a single exponential decay law. Good fitting was accomplished with a sum of two exponentials. The mononucleotide fluorescence decay was a single exponential for at least 95% of its amplitude.
The heterogeneity in lifetimes of the fluorescence of the dinucleotides was interpreted in terms of an exciplex mechanism. 相似文献
The heterogeneity in lifetimes of the fluorescence of the dinucleotides was interpreted in terms of an exciplex mechanism. 相似文献
958.
Subnanosecond transient-dichroism experiments have been performed to investigate the rotational diffusion of dyes in solution. Dyes and solvents were chosen in a way to obtain information on the influence of size, shape and hydrogen-bonding abilities either of the solute or the solvent molecules. One finds slow orientational relaxation of di-anionic xanthene dyes in alcohols, while oblate cationic dyes rotate faster in spite of their comparable size. The rotational diffusion times for alcohol solutions exceed the theoretical values predicted by the Debye-Einstein model except for prolate molecules. For a solute molecule with internal mobility the rotational diffusion exhibits a partial slip behaviour. It is shown that the deviations from the Debye-Einstein model are restricted to alcohols since for other solvents either with or without strong hydrogen-bonding abilities the experimental values agree with the hydrodynamic model including the stick-boundary condition. Experiments on erythrosine B reveal the influence of size and shape of the attached solvent molecules. 相似文献
959.
J. D. Woollins 《Polyhedron》1984,3(12):1365-1367
Deprotonation of heptasulphurmonoimide at −78°C using BuLi followed by reaction with HAuCl4 yields AuCl2(S3N), in moderate yield (21%), characterised by IR/Raman and UV/Vis spectroscopies. 相似文献
960.
The Raman and infrared spectra of (CH3)3SiSi(CH3)3 (I), (CD3)3SiSi(CD3)3, (C6H5)3SiSi(C6H5)3 (II), (CH3)3SiSi(C6H5)3 (III), and (CD3)3SiSi(C6H5)3 are reported. Assignments are based on symmetry G
36
+
(free internal rotation) forI, D3d forII, and C3v forIII. Normal coordinate treatment has been done using some simplifications in the phenyl coordinates. The SiSi stretching force constant inI amounts to 1,65 N/cm. In compoundsII andIII strong vibrational coupling is elucidated byPED calculations. 相似文献