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61.
Specific ion effects on the electrophoretic mobility of small,highly charged peptides: A modeling study 下载免费PDF全文
Stuart A. Allison Hengfu Wu Tuyen M. Bui Lac Dang Giang H. Huynh Tam Nguyen Linda Soegiarto Bi C. Truong 《Journal of separation science》2014,37(17):2403-2410
In this work, we use coarse‐grained modeling to study the free solution electrophoretic mobility of small highly charged peptides (lysine, arginine, and short oligos thereof (up to nonapeptides)) in NaCl and Na2SO4 aqueous solutions at neutral pH and room temperature. The experimental data are taken from the literature. A bead modeling methodology that treats the electrostatics at the level of the nonlinear Poisson Boltzmann equation developed previously in our laboratory is able to account for the mobility of all peptides in NaCl, but not Na2SO4. The peptide mobilities in Na2SO4 can be accounted for by including sulfate binding in the model and this is proposed as one possible explanation for the discrepancy. Oligo arginine peptides bind more sulfate than oligo lysines and sulfate binding increases with the oligo length. 相似文献
62.
Ferenc Faigl Ervin Kovács Dóra Balogh Tamás Holczbauer Mátyás Czugler Béla Simándi 《Central European Journal of Chemistry》2014,12(1):25-32
The first enzyme-catalyzed kinetic resolution of tert-butyl-3-hydroxy-4-phenylpyrrolidine-1-carboxylate is presented. Enzyme, solvent and temperature optimization resulted in a new resolution method with E = 40 enantioselectivity. The acetate derivative of the (+)-(3S,4R) enantiomer formed while the (?)-(3R,4S) isomer remained intact. Very good enantioselectivities (E > 200) were achieved in the enzyme-catalyzed alcoholysis of the racemic acetate in i-propanol and t-butanol where the (+)-(3S,4R) enantiomer was prepared in pure form (ee > 99.7%). Absolute configuration of the (?)-(3R,4S)-enantiomer was determined by single crystal X-ray diffraction method. 相似文献
63.
Mahitha Udayakumar Bilal El Mrabate Tamás Koós Katalin Szemmelveisz Ferenc Kristály Máté Leskó Ádám Filep Róbert Géber Mateusz Schabikowski Péter Baumli János Lakatos Pál Tóth Zoltán Németh 《Arabian Journal of Chemistry》2021,14(7):103214
Carbon foams have gained significant attention due to their tuneable properties that enable a wide range of applications including catalysis, energy storage and wastewater treatment. Novel synthesis pathways enable novel applications via yielding complex, hierarchical material structure. In this work, activated carbon foams (ACFs) were produced from waste polyurethane elastomer templates using different synthesis pathways, including a novel one-step method. Uniquely, the produced foams exhibited complex structure and contained carbon microspheres. The ACFs were synthesized by impregnating the elastomers in an acidified sucrose solution followed by direct activation using CO2 at 1000 ℃. Different pyrolysis and activation conditions were investigated. The ACFs were characterized by a high specific surface area (SBET) of 2172 m2/g and an enhanced pore volume of 1.08 cm3/g. Computer tomography and morphological studies revealed an inhomogeneous porous structure and the presence of numerous carbon spheres of varying sizes embedded in the porous network of the three-dimensional carbon foam. X-ray diffraction (XRD) and Raman spectroscopy indicated that the obtained carbon foam was amorphous and of turbostratic structure. Moreover, the activation process enhanced the surface of the carbon foam, making it more hydrophilic via altering pore size distribution and introducing oxygen functional groups. In equilibrium, the adsorption of methylene blue on ACF followed the Langmuir isotherm model with a maximum adsorption capacity of 592 mg/g. Based on these results, the produced ACFs have potential applications as adsorbents, catalyst support and electrode material in energy storage systems. 相似文献
64.
Pd/C as a Catalyst for Completely Regioselective CH Functionalization of Thiophenes under Mild Conditions 下载免费PDF全文
Dan‐Tam D. Tang Dr. Karl D. Collins Johannes B. Ernst Prof. Dr. Frank Glorius 《Angewandte Chemie (International ed. in English)》2014,53(7):1809-1813
The completely C3‐selective arylation of thiophenes and benzo[b]thiophenes was achieved by using Pd/C as a heterogeneous catalyst without ligands or additives under mild reaction conditions. The practicability of this transformation is demonstrated by notable functional group tolerance and the insensitivity of the reaction to H2O and air. This method is also applicable to nitrogen‐ and oxygen‐containing heterocycles, yielding the corresponding C2‐arylated products. Three‐phase tests along with Hg‐poisoning and hot‐filtration tests suggest that the catalytically active species is heterogeneous in nature. 相似文献
65.
Dr. Szilárd Varga Péter Angyal Gábor Martin Dr. Orsolya Egyed Dr. Tamás Holczbauer Dr. Tibor Soós 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(32):13649-13653
We report 8-step syntheses of (−)-minovincine and (−)-aspidofractinine using easily available and inexpensive reagents and catalyst. A key element of the strategy was the utilization of a sequence of cascade reactions to rapidly construct the penta- and hexacyclic frameworks. These cascade transformations included organocatalytic Michael-aldol condensation, a multistep anionic Michael-SN2 cascade reaction, and Mannich reaction interrupted Fischer indolization. To streamline the synthetic routes, we also investigated the deliberate use of steric effect to secure various chemo- and regioselective transformations. 相似文献
66.
The goal of the paper is to automatize the construction and parameterization of kinetic reaction mechanisms that can describe a set of experimentally measured concentration versus time curves. Using the framework and theorems of formal reaction kinetics, first, we build a set of possible mechanisms with a given number of measured and unmeasured (real or fictitious) species and reaction steps that fulfill some chemically reasonable requirements. Then we fit all the corresponding mass-action kinetic models and offer the best one to the chemist to help explain the underlying chemical phenomenon or to use it for predictions. We demonstrate the use of the method via two simple examples: on an artificial, simulated set of data and on a small real-life data set. The method can also be used to do a kind of lumping to generate a model that can reproduce the simulation results of a detailed mechanism with less species and thereby can largely accelerate spatially inhomogeneous simulations. 相似文献
67.
Steffen M. Brülls Dr. Valentina Cantatore Zhenping Wang Dr. Pui Lam Tam Dr. Per Malmberg Jessica Stubbe Prof. Dr. Biprajit Sarkar Prof. Dr. Itai Panas Prof. Dr. Jerker Mårtensson Prof. Dr. Siegfried Eigler 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(29):6694-6702
Hybridizing graphene and molecules possess a high potential for developing materials for new applications. However, new methods to characterize such hybrids must be developed. Herein, the wet-chemical non-covalent functionalization of graphene with cationic π-systems is presented and the interaction between graphene and the molecules is characterized in detail. A series of tricationic benzimidazolium salts with various steric demand and counterions was synthesized, characterized and used for the fabrication of graphene hybrids. Subsequently, the doping effects were studied. The molecules are adsorbed onto graphene and studied by Raman spectroscopy, XPS as well as ToF-SIMS. The charged π-systems show a p-doping effect on the underlying graphene. Consequently, the tricationic molecules are reduced through a partial electron transfer process from graphene, a process which is accompanied by the loss of counterions. DFT calculations support this hypothesis and the strong p-doping could be confirmed in fabricated monolayer graphene/hybrid FET devices. The results are the basis to develop sensor applications, which are based on analyte/molecule interactions and effects on doping. 相似文献
68.
69.
Formation of back corona and its effect on the voltage–current characteristics, etc., have been analysed by several authors. It has also been examined how the harmful effect of back corona can be reduced, for example by the application of pulse energisation. However, to find an optimal solution, modelling of the back corona effect is necessary. Different back corona models were created to estimate the time of its development, the change in current–voltage characteristics, the decrease in particle charge and finally, the collection efficiency of the ESP with back corona. In this paper the authors present an improved numerical ESP model that is capable of determining the parameters of back corona in such cases, when pulse energisation is applied for the power supply of the electrostatic precipitator. Based on the modular structure of the model, different modules calculate the distribution of gas velocity, electric field intensity, particle charging and particle movement. All these parameters are important to determine the properties of back corona while it feeds back on these parameters; therefore iteration is necessary to obtain reliable result. The harmful effects of back corona can be characterised with the help of the evaluation of calculated results. 相似文献
70.
Tin-Yau Tam 《Proceedings of the American Mathematical Society》1999,127(1):35-44
For any , let be the following subset of :
We show that if , then is always convex. When , it is an ellipsoid, probably degenerate. The convexity result is best possible in the sense that if we have defined similarly, then there are examples which fail to be convex when and .
The set is also symmetric about the origin for all , and contains the origin when . Equivalent statements of this result are given. The convexity result for is similar to Au-Yeung and Tsing's extension of Westwick's convexity result for .