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51.
52.
Localized Crystallization of Enantiomeric Organic Compounds on Chiral Micro‐patterns from Various Organic Solutions 下载免费PDF全文
Dr. Maarten W. van der Meijden Prof. Richard M. Kellogg Prof. David B. Amabilino 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(33):10466-10474
The controlled crystallization of enantiomers of an organic compound (a cyclic phosphoric acid derivative) on templated micro‐patterned functionalised surfaces is demonstrated. Areas where a complementary chiral thiol has been located were effective heterogeneous nucleation centres when a solution of the compound is evaporated slowly. Various organic solvents were employed, which present a challenge with respect to other examples when water is used. The solvent and the crystallization method have an important influence on the crystal growth of these compounds. When chloroform was employed, well‐defined crystals grow away from the surface, whereas crystals grow in the plane from solutions in isopropanol. In both cases, nucleation is confined to the polar patterned regions of the surface, and for isopropanol growth is largely limited within the pattern, which shows the importance of surface chemistry for nucleation and growth. The apparent dependence on the enantiomer used in the latter case could imply stereo‐differentiation as a result of short‐range interactions (the templating monolayer is disordered, even at the nanometre scale). The size of the pattern of chiral monolayer also determines the outcome of the crystallization; 5 μm dots are most effective. Despite the low surface tension of the samples (relative to the high surface tension of water), differential solvation of the polar and hydrophobic layers of the solvents allows crystallization in the polar regions of the monolayer, therefore the polarity of the regions in which heterogeneous nucleation takes place is indeed very important. Despite the complex nature of the crystallization process, these results are an important step towards to the use of patterned surfaces for heterogeneous selective nucleation of enantiomers. 相似文献
53.
Kinetic Modeling of α‐Hydrogen Abstractions from Unsaturated and Saturated Oxygenate Compounds by Carbon‐Centered Radicals 下载免费PDF全文
Paschalis D. Paraskevas Dr. Maarten K. Sabbe Prof. Marie‐Françoise Reyniers Prof. Dr. Nikos Papayannakos Prof. Dr. Guy B. Marin 《Chemphyschem》2014,15(9):1849-1866
Hydrogen abstractions are important elementary reactions in a variety of reacting media at high temperatures in which oxygenates and hydrocarbon radicals are present. Accurate kinetic data are obtained from CBS‐QB3 ab initio (AI) calculations by using conventional transition‐state theory within the high‐pressure limit, including corrections for hindered rotation and tunneling. From the obtained results, a group‐additive (GA) model is developed that allows the Arrhenius parameters and rate coefficients for abstraction of the α‐hydrogen from a wide range of oxygenate compounds to be predicted at temperatures ranging from 300 to 1500 K. From a training set of 60 hydrogen abstractions from oxygenates by carbon‐centered radicals, 15 GA values (ΔGAVos) are obtained for both the forward and reverse reactions. Among them, four ΔGAVos refer to primary contributions, and the remaining 11 ΔGAVos refer to secondary ones. The accuracy of the model is further improved by introducing seven corrections for cross‐resonance stabilization of the transition state from an additional set of 43 reactions. The determined ΔGAVos are validated upon a test set of AI data for 17 reactions. The mean absolute deviation of the pre‐exponential factors (log A) and activation energies (Ea) for the forward reaction at 300 K are 0.238 log(m3 mol?1 s?1) and 1.5 kJ mol?1, respectively, whereas the mean factor of deviation <ρ> between the GA‐predicted and the AI‐calculated rate coefficients is 1.6. In comparison with a compilation of 33 experimental rate coefficients, the <ρ> between the GA‐predicted values and these experimental values is only 2.2. Hence, the constructed GA model can be reliably used in the prediction of the kinetics of α‐hydrogen‐abstraction reactions between a broad range of oxygenates and oxygenate radicals. 相似文献
54.
55.
Water-soluble graft copolymers were synthesized by copolymerization of acrylamide with mono-methoxy-poly(ethylene oxide)-methacrylates (Me-PEO-MA). The Me-PEO-MA macromers were synthesized by a catalytic esterification of methacrylic acid with mono-methoxy-poly(ethylene glycol)s with different molecular weights. The graft copolymers obtained were characterized by 1H-NMR spectroscopy, gel permeation chromatography (GPC) and Ubbelohde viscosimetry. The rheological behaviour of aqueous polymer solutions, which are expected to show hydrophobic association at elevated temperatures, was studied with a cone and plate-rheometer. 相似文献
56.
Wim
Van Uytven Maarten Blommaert Wouter Dekeyser Niels Horsten Martine Baelmans 《等离子体物理论文集》2020,60(5-6):e201900147
In plasma edge transport codes for nuclear fusion devices, fluid-neutral models offer an interesting alternative to the currently used kinetic Monte Carlo simulations, especially for cases of high ion-neutral collisionality. In this paper, we elaborate a separate neutral energy equation in the state-of-the-art SOLPS-ITER code suite, which previously assumed perfect ion-neutral temperature equilibration. Furthermore, we study the coupled plasma-neutral solutions for a range of divertor operating regimes, proving the validity of these fluid-neutral models for high-recycling and detached regimes. 相似文献
57.
Synthesis of oligosaccharides catalyzed by thermostable β-glucosidase fromPyrococcus furiosus 总被引:3,自引:0,他引:3
M. A. Boon J. van der Oost W. M. de Vos A. E. M. Janssen K. van ’t Riet 《Applied biochemistry and biotechnology》1998,73(2-3):269-278
Focusing on CO2 fixation, photoautotrophic cultivation of the red algaPorphyridium cruentum was investigated by means of a batch culture under a 5% CO2-enriched atmosphere. The algal growth kinetics was successfully described with a logistic model, and simulation of a continuous
culture under the optimum growth conditions (30°C, 12 klux and 1.18 g-cells/L) showed that the algal CO2-fixation activity could reach 0.66 g-CO2/(L X d). Under the same growth conditions, eicosapentaenoic acid (20:5 n-3, EPA) and arachidonic acid (20:4 n-6, ARA) yields
were similarly calculated to be 3.6 mg-EPA/(L X d) and 6.5 mg-ARA/(L X d), respectively. 相似文献
58.
J. Mullens A. Vos A. De Backer D. Franco J. Yperman L. C. Van Poucke 《Journal of Thermal Analysis and Calorimetry》1993,40(1):303-311
The 124 superconductor YBa2Cu4O8 was prepared from the oxalate precursor Y2(C2O4)3. ·4BaC2O4·8CuC2O4·xH2O at one atmosphere oxygen pressure. In O2 the precursor decomposes in one step at 300°C and more gradually (300°–600°C) in Ar. The stability of the superconductor is strongly dependent on the gas atmosphere: in O2 and in air there is no significant weight change as long as the temperature does not exceed 800°C, whereas in a 1% O2-99%N2 mixture decomposition starts at about 670°C with the formation of CuO and YBa2Cu3Ox withx<7. The reduction of YBa2Cu4O8 in a 5% H2-95% Ar mixture takes place in at least four major steps with formation of products such as Y2O3, BaO, Cu2O, Cu, BaY2O4 and Ba4Y2O7. 相似文献
59.
Michael G. Pfeffer Tanja Kowacs Dr. Maria Wächtler Dr. Julien Guthmuller Prof. Dr. Benjamin Dietzek Prof. Dr. Johannes G. Vos Prof. Dr. Sven Rau 《Angewandte Chemie (International ed. in English)》2015,54(22):6627-6631
A molecular photocatalyst consisting of a RuII photocenter, a tetrapyridophenazine bridging ligand, and a PtX2 (X=Cl or I) moiety as the catalytic center functions as a stable system for light‐driven hydrogen production. The catalytic activity of this photochemical molecular device (PMD) is significantly enhanced by exchanging the terminal chlorides at the Pt center for iodide ligands. Ultrafast transient absorption spectroscopy shows that the intramolecular photophysics are not affected by this change. Additionally, the general catalytic behavior, that is, instant hydrogen formation, a constant turnover frequency, and stability are maintained. Unlike as observed for the Pd analogue, the presence of excess halide does not affect the hydrogen generation capacity of the PMD. The highly improved catalytic efficiency is explained by an increased electron density at the Pt catalytic center, this is confirmed by DFT studies. 相似文献
60.
A Flexible Photoactive Titanium Metal–Organic Framework Based on a [TiIV3(μ3‐O)(O)2(COO)6] Cluster 下载免费PDF全文
Bart Bueken Dr. Frederik Vermoortele Dr. Danny E. P. Vanpoucke Dr. Helge Reinsch Dr. Chih‐Chin Tsou Dr. Pieterjan Valvekens Dr. Trees De Baerdemaeker Prof. Dr. Rob Ameloot Prof. Dr. Christine E. A. Kirschhock Prof. Dr. Veronique Van Speybroeck Prof. Dr. James M. Mayer Prof. Dr. Dirk De Vos 《Angewandte Chemie (International ed. in English)》2015,54(47):13912-13917
The synthesis of titanium–carboxylate metal–organic frameworks (MOFs) is hampered by the high reactivity of the commonly employed alkoxide precursors. Herein, we present an innovative approach to titanium‐based MOFs by the use of titanocene dichloride to synthesize COK‐69, the first breathing Ti MOF, which is built up from trans‐1,4‐cyclohexanedicarboxylate linkers and an unprecedented [TiIV3(μ3‐O)(O)2(COO)6] cluster. The photoactive properties of COK‐69 were investigated in depth by proton‐coupled electron‐transfer experiments, which revealed that up to one TiIV center per cluster can be photoreduced to TiIII while preserving the structural integrity of the framework. The electronic structure of COK‐69 was determined by molecular modeling, and a band gap of 3.77 eV was found. 相似文献