全文获取类型
收费全文 | 393篇 |
免费 | 10篇 |
国内免费 | 1篇 |
专业分类
化学 | 328篇 |
数学 | 34篇 |
物理学 | 42篇 |
出版年
2017年 | 5篇 |
2015年 | 7篇 |
2014年 | 14篇 |
2013年 | 10篇 |
2012年 | 11篇 |
2011年 | 15篇 |
2010年 | 10篇 |
2009年 | 6篇 |
2008年 | 24篇 |
2007年 | 21篇 |
2006年 | 21篇 |
2005年 | 18篇 |
2004年 | 7篇 |
2003年 | 10篇 |
2001年 | 4篇 |
2000年 | 4篇 |
1997年 | 6篇 |
1996年 | 3篇 |
1995年 | 6篇 |
1994年 | 5篇 |
1993年 | 8篇 |
1991年 | 8篇 |
1987年 | 5篇 |
1986年 | 3篇 |
1985年 | 5篇 |
1984年 | 4篇 |
1983年 | 3篇 |
1981年 | 10篇 |
1980年 | 9篇 |
1979年 | 5篇 |
1977年 | 5篇 |
1975年 | 4篇 |
1971年 | 6篇 |
1970年 | 4篇 |
1968年 | 12篇 |
1966年 | 4篇 |
1965年 | 16篇 |
1964年 | 6篇 |
1963年 | 4篇 |
1962年 | 5篇 |
1935年 | 3篇 |
1929年 | 2篇 |
1918年 | 4篇 |
1916年 | 2篇 |
1914年 | 2篇 |
1913年 | 5篇 |
1912年 | 3篇 |
1911年 | 3篇 |
1894年 | 2篇 |
1890年 | 2篇 |
排序方式: 共有404条查询结果,搜索用时 46 毫秒
1.
Most developed countries support farming activities through policies that are tailored to meet their specific social, economic and environmental objectives. Economic and environmental efficiency have recently become relevant targets of most of these policies, whose sound implementation can be enhanced by monitoring farm performance from a multidimensional perspective. This paper proposes farm-level technical and environmental efficiency measures that recognize the stochastic conditions in which production takes place. A state-contingent framework is used to model production uncertainty. An implementable representation of the technology is developed using data envelopment analysis. The application focuses on a sample of Catalan arable crop farms. Results suggest that technical efficiency is slightly lower in bad than in good growing conditions. Nitrogen pollution can decrease substantially more under good than bad growing conditions. 相似文献
2.
Anke Kuijk Arnout Imhof Margriet H. W. Verkuijlen Thijs H. Besseling Ernst R. H. van Eck Alfons van Blaaderen 《Particle & Particle Systems Characterization》2014,31(6):706-713
In this paper, the characterization and fluorescent labeling of silica rods are reported. These rods are synthesized following a recently reported method. Material properties of the silica rods measured with NMR, elemental analysis, TGA, and porosimetry are compared with those of well‐established Stöber silica spheres. Additionally, silica rods are made suitable for quantitative real‐space studies by confocal microscopy. Several methods of fluorescent labeling to prepare rods with different fluorescent patterning, ranging from uniform fluorescence levels to gradients from one rod‐end to the other, and even patterns of several colors are presented and discussed. 相似文献
3.
Application of Multi-Parametric Quadratic Programming to Simulation of Deflected Wires in a Wire Saw
Daniel Treyer Sebastian Gaulocher Stefan Niederberger Helge Rafael Alfons Ams 《PAMM》2017,17(1):779-780
In the wire sawing process, a silicon brick is fed into a moving wire web, thus deflecting the wires. By considering static deflections only, the wire displacement and the contact forces between wire and brick may be computed by minimizing the potential energy of the wire, which introduces a constrained quadratic optimization problem. In a time-domain simulation, the continuously changing contour inside the kerf requires the optimization problem to be solved recurringly. This work aims at reducing the optimization-related computational effort by applying multi-parametric quadratic programming. (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
4.
Selective reagent ionisation‐time of flight‐mass spectrometry: a rapid technology for the novel analysis of blends of new psychoactive substances 下载免费PDF全文
Matteo Lanza W. Joe Acton Philipp Sulzer Kostiantyn Breiev Simone Jürschik Alfons Jordan Eugen Hartungen Gernot Hanel Lukas Märk Tilmann D. Märk Chris A. Mayhew 《Journal of mass spectrometry : JMS》2015,50(2):427-431
In this study we demonstrate the potential of selective reagent ionisation‐time of flight‐mass spectrometry for the rapid and selective identification of a popular new psychoactive substance blend called ‘synthacaine’, a mixture that is supposed to imitate the sensory and intoxicating effects of cocaine. Reactions with H3O+ result in protonated parent molecules which can be tentatively assigned to benzocaine and methiopropamine. However, by comparing the product ion branching ratios obtained at two reduced electric field values (90 and 170 Td) for two reagent ions (H3O+ and NO+) to those of the pure chemicals, we show that identification is possible with a much higher level of confidence then when relying solely on the m/z of protonated parent molecules. A rapid and highly selective analytical identification of the constituents of a recreational drug is particularly crucial to medical personnel for the prompt medical treatment of overdoses, toxic effects or allergic reactions. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
5.
Sheng Yang Antonio Gaetano Ricciardulli Dr. Shaohua Liu Dr. Renhao Dong Dr. Martin R. Lohe Alfons Becker Marco A. Squillaci Prof. Paolo Samorì Prof. Klaus Müllen Prof. Xinliang Feng 《Angewandte Chemie (International ed. in English)》2017,56(23):6669-6675
To bridge the gap between laboratory-scale studies and commercial applications, mass production of high quality graphene is essential. A scalable exfoliation strategy towards the production of graphene sheets is presented that has excellent yield (ca. 75 %, 1–3 layers), low defect density (a C/O ratio of 21.2), great solution-processability, and outstanding electronic properties (a hole mobility of 430 cm2 V−1 s−1). By applying alternating currents, dual exfoliation at both graphite electrodes enables a high production rate exceeding 20 g h−1 in laboratory tests. As a cathode material for lithium storage, graphene-wrapped LiFePO4 particles deliver a high capacity of 167 mAh g−1 at 1 C rate after 500 cycles. 相似文献
6.
Chiral Modification of Platinum by Co‐Adsorbed Cinchonidine and Trifluoroacetic Acid: Origin of Enhanced Stereocontrol in the Hydrogenation of Trifluoroacetophenone 下载免费PDF全文
Fabian Meemken Prof. Dr. Alfons Baiker Dr. Sebastian Schenker Prof. Dr. Konrad Hungerbühler 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(5):1298-1309
Cinchonidine (CD) adsorbed onto a platinum metal catalyst leads to rate acceleration and induces strong stereocontrol in the asymmetric hydrogenation of trifluoroacetophenone. Addition of catalytic amounts of trifluoroacetic acid (TFA) significantly enhances the enantiomeric excess from 50 to 92 %. The origin of the enantioselectivity bestowed by co‐adsorbed CD and TFA is investigated by using in situ attenuated total reflection infrared spectroscopy and modulation excitation spectroscopy. Molecular interactions between the chiral modifier (CD), acid additive (TFA) and the trifluoro‐activated substrate at the solid–liquid interface are elucidated under conditions relevant to catalytic hydrogenations, that is, on a technical Pt/Al2O3 catalyst in the presence of H2 and solvent. Monitoring of the unmodified and modified surface during the hydrogenation provides an insight into the phenomenon of rate enhancement and the crucial interactions of CD with the ketone, corresponding product alcohol, and TFA. Comparison of the diastereomeric interactions occurring on the modified surface and in the liquid solution shows a striking difference for the chiral preferences of CD. The spectroscopic data, in combination with calculations of molecular structures and energies, sheds light on the reaction mechanism of the heterogeneous asymmetric hydrogenation of trifluoromethyl ketones and the involvement of TFA in the diastereomeric intermediate surface complex: the quinuclidine N atom of the adsorbed CD forms an N?H?O‐type hydrogen‐bonding interaction not only with the trifluoro‐activated ketone but also with the corresponding alcohol and the acid additive. Strong evidence is provided that it is a monodentate acid/base adduct in which the carboxylate of TFA resides at the quinuclidine N‐atom of CD, which imparts a better stereochemical control. 相似文献
7.
Let a
1,…,a
n
be relatively prime positive integers, and let S be the semigroup consisting of all non-negative integer linear combinations of a
1,…,a
n
. In this paper, we focus our attention on AA-semigroups, that is semigroups being generated by almost arithmetic progressions.
After some general considerations, we give a characterization of the symmetric AA-semigroups. We also present an efficient
method to determine an Apéry set and the Hilbert series of an AA-semigroup.
Dedicated to the memory of Ernst S. Selmer (1920–2006), whose calculations revealed the “Selmer group”. 相似文献
8.
Dongmei Jiang Dr. Atsushi Urakawa Dr. Maxim Yulikov Dr. Tamas Mallat Dr. Gunnar Jeschke Prof. Dr. Alfons Baiker Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(45):12255-12262
{Cu(bpy)(H2O)2(BF4)2(bpy)} (Cu‐MOF; MOF=metal–organic framework; bpy=4,4′‐bipyridine), with a 3D‐interpenetrated structure and saturated Cu coordination sites in the framework, possesses unexpectedly high activity in the ring‐opening reaction of epoxides with MeOH, although the reaction rate drops remarkably with more bulky alcohols. This (apparent) size selection and the single Cu2+ sites in an identical environment of the crystalline matrix resemble zeolites. The real nature of active sites was investigated by attenuated total reflection infrared (ATR‐IR), Raman, EPR, and UV/Vis spectroscopies. Cu‐MOF has highly dynamic structural properties that respond to MeOH; its framework dimensions change from 3D to 2D by restructuring to a symmetric coordination of four bpy units to Cu. This interaction is accompanied by the partial dissolution of Cu‐MOF as multi‐Cu clusters, in which Cu2+ ions are connected with bpy ligands. Although both molecular and surface catalysis contribute to the high rate of alcoholysis, the soluble oligomeric species (Cumbpyn) are far more active. Finally, addition of diethyl ether to the reaction mixture induces the reconstruction of dissolved and solid Cu‐MOF to the original framework structure, thereby allowing excellent recyclability of Cu‐MOF as an apparent heterogeneous catalyst. In contrast, the original Cu‐MOF structure is maintained upon contact with larger alcohols, such as iPrOH and tBuOH, thus leading to poor activity in epoxide ring opening. 相似文献
9.
Eric Messens Alfons Lenaerts Marc Van Montagu André De Bruyn Arnold W.H. Jans Georges Van Binst 《Journal of carbohydrate chemistry》2013,32(4):683-699
The 1H NMR data of agrocinopine in D2O solution as extracted from standard 2D NMR experiments, along with 1D 31P and 13C NMR experiments allow to support the trisaccharide structure originally proposed on basis of comparative 13C NMR measurements. 相似文献
10.
To perform multiple regression, the least squares estimator is commonly used. However, this estimator is not robust to outliers. Therefore, robust methods such as S-estimation have been proposed. These estimators flag any observation with a large residual as an outlier and downweight it in the further procedure. However, a large residual may be caused by an outlier in only one single predictor variable, and downweighting the complete observation results in a loss of information. Therefore, we propose the shooting S-estimator, a regression estimator that is especially designed for situations where a large number of observations suffer from contamination in a small number of predictor variables. The shooting S-estimator combines the ideas of the coordinate descent algorithm with simple S-regression, which makes it robust against componentwise contamination, at the cost of failing the regression equivariance property. 相似文献