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51.
Hansen PM Dreyer JK Ferkinghoff-Borg J Oddershede L 《Journal of colloid and interface science》2005,287(2):561-571
We present an experimental method based on video microscopy to perform nanometer scale position detection of a micrometer bead in the direction along the propagation of the detection light. Using the same bead for calibration and detection significantly improves the in depth resolution in comparison to video microscopy methods from literature. This method is used together with an optical trap to measure interaction potentials between a glass surface and colloids made of polystyrene or silica at different electrolyte concentrations. The results are confirmed by an independent method where the optical trap is used in connection with a quadrant photodiode. Also, we present a maximum likelihood analysis method which considerably improves the spatial resolution of interaction potentials by optimizing the underlying potential function to fit all observed position distributions. The measured interaction potentials agree well with DLVO theory for small electrolyte concentrations; however, for larger electrolyte concentrations the potentials differ qualitatively from both DLVO and Lifshitz theory. 相似文献
52.
Alexey Kirilin Serap Sahin Päivi Mäki‐Arvela Johan Wärnå Tapio Salmi Dmitry Yu. Murzin 《国际化学动力学杂志》2010,42(10):629-639
The kinetics of the acylation of (R,S)‐1‐phenylethanol was investigated using lipase as a catalyst. The main parameters were temperature, reaction atmosphere, different acyl donors, and different amounts of acyl donor as well as the presence of some additives in the reaction mixture. The initial reaction rate increased with increasing temperature and with a decreasing amount of an acyl donor. The activated esters, such as isopropenyl‐ and vinyl acetate, exhibited very high acylation rates for R‐1‐phenylethanol, whereas low rates were obtained with ethyl acetate and 2‐methoxyethyl acetate. The addition of water and acetophenone decreased the acylation rate. A kinetic model was developed based on a sequential step mechanism, in which enzyme was reacting in the first step with an acyl donor followed by the reaction of a modified enzyme complex with the reactant, R‐1‐phenylethanol. Comparison with experimental data obtained at different temperatures allowed simplification of this model, leading to a kinetic equation with just one apparent parameter. The influence of the amount of acyl donor, ethyl acetate, could be quantitatively described by taking into account the competitive inhibition of the ethanol produced. The rate constants and apparent activation energy for experiments performed under different temperatures and the amounts of acylation agent were determined. The apparent activation energy was 24.5 kJ/mol. © 2010 Wiley Periodicals, Inc. Int J Chem Kinet 42: 629–639, 2010 相似文献
53.
Esa Toukoniitty Päivi Mäki-Arvela Ahmad Kalantar Neyestanaki Ensio Laine Jyri-Pekka Mikkola Tapio Salmi Dmitry Yu. Murzin 《Reaction Kinetics and Catalysis Letters》2001,73(1):3-11
In the presence of ultrasound both the initial hydrogenation rate of 1-phenyl-1,2- propanedione and the enantiomeric excess of the main product, i.e. (R)-1-hydroxy- 1-phenylpropanone, increased by 75 % and 52 % in toluene, respectively, as compared to the silent hydrogenation. 相似文献
54.
Accelerated beam tracing algorithm 总被引:1,自引:0,他引:1
Determining early specular reflection paths is essential for room acoustics modeling. Beam tracing algorithms have been used to calculate these paths efficiently, thus allowing modeling of acoustics in real-time with a moving listener in simple, or complex but densely occluded, environments with a stationary sound source. In this paper, it is shown that beam tracing algorithms can still be optimized by utilizing the spatial coherence in path validation with a moving listener. Since the precalculations required for the presented technique are relatively fast, the acoustic reflection paths can be calculated even for a moving source in simple cases. Simulations were performed to show how the accelerated algorithm compares with the basic algorithm with varying scene complexity and occlusion. Up to two-orders of magnitude speed-up was achieved. 相似文献
55.
Thomsen AE Jensen H Jorgensen L van de Weert M Ostergaard J 《Colloids and surfaces. B, Biointerfaces》2008,63(2):243-248
Protein adsorption represents a considerable challenge in the development and production of macromolecular drugs. From an analytical point of view the adsorption process is difficult to study in an efficient way using currently available techniques. In this work potential and time dependent adsorption and adsorption kinetics of human insulin at an 1,2-dichloroethane-aqueous interface were studied using a novel electroanalytical approach based on measurements of interfacial capacitance. Two different types of measurements were performed; potential scans and time scans. In the potential scans, the capacitance was measured over a range of applied potential differences across the interface. The interfacial potential difference is linked to the charge at the interface. Adsorption of human insulin was detectable at a bulk phase insulin concentration as low as 0.1 μM as a negative shift in the potential of zero charge (pzc). Adsorption kinetics were further studied using time scans in which the interfacial capacitance was measured at a fixed applied interfacial potential difference. Using this approach it was possible to study how the adsorption kinetics and the shape of the time scan curves were related to the bulk concentration of insulin and the interfacial potential difference. The changes in capacitance could be described phenomenologically by pseudo-first-order kinetics at low concentrations of insulin except at positive interfacial potential differences and high insulin concentrations (≥0.25 μM) where a more complex shape of the time scans curves was observed. 相似文献
56.
P?ivi M?ki-Arvela Serap Sahin Narendra Kumar Jyri-Pekka Mikkola Kari Er?nen Tapio Salmi Dmitry Yu. Murzin 《Reaction Kinetics and Catalysis Letters》2008,94(2):281-288
Liquid phase tert-butylation of m-cresol was carried out using 12-tungstosilicic acid supported on neutral alumina by varying different parameters. The reaction
has also been carried out by using calcined samples under optimized conditions. The present catalyst shows an excellent activity
of 93.2%, conversion of 100% selectivity for the o-isomer, an important industrial product. 相似文献
57.
58.
Shin J Ikonen T Khandkar MD Ala-Nissila T Sung W 《The Journal of chemical physics》2010,133(18):184902
We study the dynamics of flexible, semiflexible, and self-avoiding polymer chains moving under a Kramers metastable potential. Due to thermal noise, the polymers, initially placed in the metastable well, can cross the potential barrier, but these events are extremely rare if the barrier is much larger than thermal energy. To speed up the slow rate processes in computer simulations, we extend the recently proposed path integral hyperdynamics method to the cases of polymers. We consider the cases where the polymers' radii of gyration are comparable to the distance between the well bottom and the barrier top. We find that, for a flexible polymers, the crossing rate (R) monotonically decreases with chain contour length (L), but with the magnitude much larger than the Kramers rate in the globular limit. For a semiflexible polymer, the crossing rate decreases with L but becomes nearly constant for large L. For a fixed L, the crossing rate becomes maximum at an intermediate bending stiffness. For the self-avoiding chain, the rate is a nonmonotonic function of L, first decreasing with L, and then, above a certain length, increasing with L. These findings can be instrumental for efficient separation of biopolymers. 相似文献
59.
60.
The asymmetric synthesis of a series of (7'S,8R,8'R)-7'-hydroxylignano-9,9'-lactones is presented, among them the mammalian lignan (7'S)-hydroxyenterolactone and (7'S)-parabenzlactone, allowing the stereochemistry of natural occurring (-)-parabenzlactone to be re-assigned. A hydroxylactone rearrangement and its possible mechanisms are discussed. Finally a brief survey of the current naming and numbering variants of 7'-hydroxylignano-9,9'-lactones is presented, along with a suggestion for harmonization of the nomenclature. 相似文献