全文获取类型
收费全文 | 17966篇 |
免费 | 679篇 |
国内免费 | 198篇 |
专业分类
化学 | 12847篇 |
晶体学 | 133篇 |
力学 | 663篇 |
综合类 | 1篇 |
数学 | 2494篇 |
物理学 | 2705篇 |
出版年
2023年 | 138篇 |
2022年 | 398篇 |
2021年 | 553篇 |
2020年 | 578篇 |
2019年 | 629篇 |
2018年 | 534篇 |
2017年 | 523篇 |
2016年 | 870篇 |
2015年 | 637篇 |
2014年 | 775篇 |
2013年 | 1439篇 |
2012年 | 1243篇 |
2011年 | 1205篇 |
2010年 | 810篇 |
2009年 | 757篇 |
2008年 | 936篇 |
2007年 | 924篇 |
2006年 | 703篇 |
2005年 | 723篇 |
2004年 | 561篇 |
2003年 | 474篇 |
2002年 | 445篇 |
2001年 | 201篇 |
2000年 | 166篇 |
1999年 | 123篇 |
1998年 | 121篇 |
1997年 | 132篇 |
1996年 | 135篇 |
1995年 | 103篇 |
1994年 | 98篇 |
1993年 | 111篇 |
1992年 | 94篇 |
1991年 | 89篇 |
1990年 | 83篇 |
1989年 | 73篇 |
1988年 | 58篇 |
1987年 | 69篇 |
1986年 | 74篇 |
1985年 | 117篇 |
1984年 | 115篇 |
1983年 | 82篇 |
1982年 | 84篇 |
1981年 | 79篇 |
1980年 | 82篇 |
1979年 | 71篇 |
1978年 | 77篇 |
1977年 | 45篇 |
1976年 | 45篇 |
1975年 | 52篇 |
1974年 | 56篇 |
排序方式: 共有10000条查询结果,搜索用时 9 毫秒
961.
Gibasiewicz K Szrajner A Ihalainen JA Germano M Dekker JP van Grondelle R 《The journal of physical chemistry. B》2005,109(44):21180-21186
Almost all photosystem I (PSI) complexes from oxygenic photosynthetic organisms contain chlorophylls that absorb at longer wavelength than that of the primary electron donor P700. We demonstrate here that the low-energy pool of chlorophylls in the PSI-LHCI complex from the green alga Chlamydomonas reinhardtii, containing five to six pigments, is significantly blue-shifted (A(max) at 700 nm at 4 K) compared to that in the PSI core preparations from several species of cyanobacteria and in PSI-LHCI particles from higher plants. This makes them almost isoenergetic with the primary donor. However, they keep the other characteristic features of "red" chlorophylls: clear spectral separation from the bulk chlorophylls, big Stokes shift revealing pronounced electron-phonon coupling, and large homogeneous and inhomogeneous broadening of approximately 170 and approximately 310 cm(-1), respectively. 相似文献
962.
Xu J Mojet BL van Ommen JG Lefferts L 《The journal of physical chemistry. B》2005,109(39):18361-18368
The adsorption of oxygen and d2-propane (CH3CD2CH3) on a series of alkaline-earth-exchanged Y zeolite at room temperature was studied with in situ infrared spectroscopy. Surprisingly at room temperature, oxygen adsorption led to the formation of supercage M2+(O2) species. Further, at low propane coverage, propane was found to adsorb linearly on Mg2+ cations, but a ring-adsorption structure was observed for propane adsorbing on Ca2+, Sr2+, and Ba2+ cations. It is demonstrated that O2 and propane can simultaneously attach to one active center (M2+) to form a M2+(O2)(C3H8) species, which is proposed to be the precursor in thermal propane selective oxidation. Selectivity to acetone in the propane oxidation reaction decreases with increasing temperature and cation size due to the formation of 2-propanol and carboxylate ions. An extended reaction scheme for the selective oxidation of propane over alkaline earth exchanged Y zeolites is proposed. 相似文献
963.
The Ti-mediated reaction of Grignard reagents with nitriles was investigated with sub-stoichiometric amounts of titanium isopropoxide. Cyanoesters were converted to spirocyclopropanelactams in good yields using as low as 0.05 eq of Ti(O(i)Pr)4. Under similar conditions, cyanocarbonates led to spirocyclopropane oxazolidinones and/or aminocyclopropylcarbinols. A very short synthesis of the naturally occurring aminocyclopropanecarboxylic acid illustrates the usefulness of this methodology. 相似文献
964.
Gu R Depraetere S Kotek J Budka J Wagner-Wysiecka E Biernat JF Dehaen W 《Organic & biomolecular chemistry》2005,3(16):2921-2923
The first example of substitution reaction in the free alpha-position of N-confused calix[4]pyrroles is reported: azo-coupling with various arenediazonium salts. The obtained azocompounds were used for studies of their anion-binding properties by UV-Vis spectroscopy. 相似文献
965.
Quantum chemical calculations using gradient-corrected (B3LYP) density functional theory have been carried out to investigate the mechanism of the oxidative cleavage of alkenes by ruthenium tetraoxide. The initial reaction of the tetraoxide with the olefin occurs via a [3+2] cycloaddition as in the case of osmium tetraoxide. The results clearly show that the bond cleavage does not take place at the primary adduct, but much later in the reaction path. After the formation of the ruthenium(VI)dioxo-2,5-dioxolane, the reaction proceeds with the addition of a second olefin to yield ruthenium(IV)-bis(2,5-dioxolane), which in turn becomes oxidized first to rutheniumoxo(VI)-bis(2,5-dioxolane) 6(Ru) and then to ruthenium(VIII)-dioxo-bis(2,5-dioxolane) 7(Ru). Only in complexes containing the metal center in the formal oxidation state +VIII are low activation barriers for C-C bond cleavage and exothermic formation of carbonyl compounds as products calculated. The lowest activation barrier, DeltaH(++) = 2.5 kcal/mol, is calculated for the C-C bond breaking reaction of 7(Ru) which is predicted as the pivotal intermediate of the oxidation reaction. The calculations of the oxidation reaction with OsO(4) show that those reactions where the oxidation state of the metal increases have larger activation barriers for M = Ru than for M = Os, while reactions which reduce the oxidation state have a lower activation barrier for ruthenium compounds. Also, reactions which increase the oxidation state of the metal are in the case of M = Os more exothermic than for M = Ru. In this work, all important points of the potential energy surface (PES) are reported, and the complete catalytic cycle for the oxidative cleavage of olefins by ruthenium tetraoxide is presented. 相似文献
966.
New equations are derived and implemented for efficient and accurate computation of solvation energy derivatives for the conductor-like polarizable continuum model (C-PCM) and the isotropic integral equation formalism polarizable continuum model (IEF-PCM). Two new molecular surface tessellation procedures GEPOL-RT and GEPOL-AS that generate near continuous potential energy surfaces are proposed for PCM geometry optimization. The combined use of these new techniques leads to efficient and convergent geometry optimizations with the PCMs. 相似文献
967.
Mogemark M Gårdmo F Tengel T Kihlberg J Elofsson M 《Organic & biomolecular chemistry》2004,2(12):1770-1776
The spectroscopic properties for seven different commercial resins used in solid-phase synthesis were investigated with (19)F NMR spectroscopy. A fluorine-labeled dipeptide was synthesized on each resin, and the resolution of the (19)F resonances in CDCl(3), DMSO-d(6), benzene-d(6) and CD(3)OD were measured with a conventional NMR spectrometer, i.e. without using magic angle spinning. In general, resins containing poly(ethylene glycol) chains (ArgoGel, TentaGel and PEGA) were found to be favorable for the (19)F NMR spectral quality. Three serine containing tri-, penta-, and heptapeptides were then prepared on an ArgoGel resin functionalized with a fluorine-labeled linker. The resin bound peptides were glycosylated utilizing a thiogalactoside glycosyl donor carrying fluorine-labeled protective groups. Monitoring of the glycosylations with gel-phase (19)F NMR spectroscopy allowed each glycopeptide to be formed in similar 80% yield, using a minimal amount of glycosyl donor (3 x 2 equivalents). In addition, it was found that the glycosylation yields were independent of peptide length. 相似文献
968.
The hindered diffusion and binding of proteins of different sizes (lysozyme, BSA and IgG) in an agarose gel is described using adsorption kinetic and diffusional data together with an experimentally determined pore size distribution in the gel. The validity of the pore model, including variable diffusion coefficients and porosities is tested against experimental confocal microscopy data. No fitting parameters were used in the present model. The importance of knowing the gel structure is demonstrated especially for large proteins such as IgG. Experimental confocal microscopy data can be explained by the present model. 相似文献
969.
A mixed ladderane/n-alkyl glycerol diether membrane lipid in an anaerobic ammonium-oxidizing bacterium 总被引:1,自引:0,他引:1
Sinninghe Damsté JS Rijpstra WI Strous M Jetten MS David OR Geenevasen JA van Maarseveen JH 《Chemical communications (Cambridge, England)》2004,(22):2590-2591
A novel glycerol diether containing ladderane and tetradecyl moieties has been identified in an anaerobic ammonium-oxidizing bacterium by GC/MS and high-field NMR spectroscopy. 相似文献
970.
Superstructures of temporarily stabilized nanocrystalline CaCO3 particles: morphological control via water surface tension variation 总被引:1,自引:0,他引:1
In this paper, the formation of different complex morphologies of nanocrystalline CaCO3 under the control of double hydrophilic block copolymers (DHBCs) carrying phosphate groups is described. The DHBCs consist of a poly(ethylene glycol) (PEG) block and a pendant poly[2-(2-hydroxy ethyl)ethylene] block with different degrees of phosphorylation up to 40%, some of which show surface activity. The polymers furthermore temporarily stabilize CaCO3 nanocrystals, which are formed by slow CO2 evaporation from a supersaturated Ca(HCO3)2 solution (Kitano method). The polymers are active down to concentrations of 10(-4) g/L. In dependence of the nature and concentration of the DHBC, tunable complex shuttlecock flowerlike and other superstructures are formed, which are aggregates of CaCO3 vaterite nanoparticles with an enhanced stability of at least 2 months. It is shown that the aggregation starts around template CO2 gas bubbles at the air/water interface. The size and morphology of the growing aggregates depends on the polymer concentration, phosphorylation degree, and water surface tension. The latter determines when the aggregate sinks to the bottom, interrupting the further growth process. Variation of the water surface tension by addition of the nonionic surfactant Antharox CO880 also allows a variation of the aggregate morphology, thus implying the described method as simple and versatile for the generation of complex CaCO3 morphologies. 相似文献