全文获取类型
收费全文 | 307篇 |
免费 | 7篇 |
国内免费 | 2篇 |
专业分类
化学 | 147篇 |
晶体学 | 2篇 |
力学 | 15篇 |
数学 | 83篇 |
物理学 | 69篇 |
出版年
2022年 | 3篇 |
2021年 | 2篇 |
2020年 | 3篇 |
2018年 | 3篇 |
2017年 | 2篇 |
2016年 | 6篇 |
2015年 | 6篇 |
2014年 | 10篇 |
2013年 | 27篇 |
2012年 | 17篇 |
2011年 | 23篇 |
2010年 | 8篇 |
2009年 | 9篇 |
2008年 | 12篇 |
2007年 | 15篇 |
2006年 | 14篇 |
2005年 | 26篇 |
2004年 | 14篇 |
2003年 | 9篇 |
2002年 | 10篇 |
2001年 | 4篇 |
2000年 | 5篇 |
1999年 | 5篇 |
1998年 | 7篇 |
1997年 | 5篇 |
1996年 | 5篇 |
1994年 | 3篇 |
1993年 | 2篇 |
1990年 | 2篇 |
1989年 | 5篇 |
1988年 | 4篇 |
1985年 | 4篇 |
1982年 | 2篇 |
1979年 | 2篇 |
1978年 | 2篇 |
1977年 | 2篇 |
1976年 | 3篇 |
1975年 | 2篇 |
1974年 | 2篇 |
1973年 | 2篇 |
1937年 | 2篇 |
1922年 | 1篇 |
1918年 | 2篇 |
1917年 | 1篇 |
1913年 | 1篇 |
1912年 | 1篇 |
1908年 | 1篇 |
1905年 | 1篇 |
1904年 | 1篇 |
1903年 | 2篇 |
排序方式: 共有316条查询结果,搜索用时 15 毫秒
11.
Pierre Hamel Nicolas Zajac Yves Girard Joseph G. Atkinson 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-4)
Abstract Desulfenylation of indol-3-yl sulfides liberates the most reactive position of the ring for further transformations. The usual procedure, utilizing Raney Nickel (P. G. Gassman, et. al., J. Am. Chem. SOC. 1974,96, 5495) offers a limited scope due to incompatibility of a number of functional groups towards the reducing agent. Based on our recent mechanistic studies of the acid-catalysed rearrangement of indol-3-yl sulfides to indol-2-yl sulfides (P. Hamel, et. al., Chem. Commun. 1989, 63; J. Org. Chem. 1992, 57, 2694), we have developed a novel, non-reductive desulfenylation method which permits easy access to 3-unsubstituted indoles bearing a wide array of substituents. Thus, 3-indolyl sulfides, readily obtained from appropriate phenylhydrazines (via Fischer indolization) or anilines (Gassman method, vide infra) are smoothly desulfenylated in good yields in trifluoroacetic acid in the presence of an appropriate nucleophilic trapping agent. Thiols proved to be very effective trapping agents and thiosalicylic acid (TSA) is a thiol of choice, being non-volatile and easily separable from reaction products. 相似文献
12.
Giovanni P. Crespi Andreas H. Hamel Carola Schrage 《Journal of Mathematical Analysis and Applications》2015
Extremal problems are studied involving an objective function with values in (order) complete lattices of sets generated by so-called set relations. Contrary to the popular paradigm in vector optimization, the solution concept for such problems, introduced by F. Heyde and A. Löhne, comprises the attainment of the infimum as well as a minimality property. The main result is a Minty type variational inequality for set optimization problems which provides a sufficient optimality condition under lower semicontinuity assumptions and a necessary condition under appropriate generalized convexity assumptions. The variational inequality is based on a new Dini directional derivative for set-valued functions which is defined in terms of a “lattice difference quotient.” A residual operation in a lattice of sets replaces the inverse addition in linear spaces. Relationships to families of scalar problems are pointed out and used for proofs. The appearance of improper scalarizations poses a major difficulty which is dealt with by extending known scalar results such as Diewert's theorem to improper functions. 相似文献
13.
Charly Mayeux Peeter Burk Jean-Francois Gal Ivari Kaljurand Ilmar Koppel Ivo Leito Lauri Sikk 《Journal of the American Society for Mass Spectrometry》2014,25(11):1962-1973
According to high level calculations, the upper part of the previously published FT-ICR lithium cation basicity (LiCB at 373 K) scale appeared to be biased by a systematic downward shift. The purpose of this work was to determine the source of this systematic difference. New experimental LiCB values at 373 K have been measured for 31 ligands by proton-transfer equilibrium techniques, ranging from tetrahydrofuran (137.2 kJ mol?1) to 1,2-dimethoxyethane (202.7 kJ mol?1). The relative basicities (ΔLiCB) were included in a single self-consistent ladder anchored to the absolute LiCB value of pyridine (146.7 kJ mol?1). This new LiCB scale exhibits a good agreement with theoretical values obtained at G2(MP2) level. By means of kinetic modeling, it was also shown that equilibrium measurements can be performed in spite of the formation of Li+ bound dimers. The key feature for achieving accurate equilibrium measurements is the ion trapping time. The potential causes of discrepancies between the new data and previous experimental measurements were analyzed. It was concluded that the disagreement essentially finds its origin in the estimation of temperature and the calibration of Cook’s kinetic method. Graphical Abstract
? 相似文献
14.
N‐(2‐Ethylhexyl)carbazole: A New Fluorophore Highly Suitable as a Monomolecular Liquid Scintillator 下载免费PDF全文
Eva Montbarbon Dr. Fabien Sguerra Dr. Guillaume H. V. Bertrand Élodie Magnier Dr. Romain Coulon Dr. Robert B. Pansu Dr. Matthieu Hamel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(34):12074-12080
The synthesis, photophysical properties, and applications in scintillation counting of N‐(2‐ethylhexyl)carbazole (EHCz) are reported. This molecule displays all of the required characteristics for an efficient liquid scintillator (emission wavelength, scintillation yield), and can be used without any extra fluorophores. Thus, its scintillation properties are discussed, as well as its fast neutron/gamma discrimination. For the latter application, the material is compared with the traditional liquid scintillator BC‐501 A, and other liquid fluorescent molecules classically used as scintillation solvents, such as xylene, pseudocumene (PC), linear alkylbenzenes (LAB), diisopropylnaphthalene (DIN), 1‐methylnaphthalene (1‐MeNapht), and 4‐isopropylbiphenyl (iPrBiph). For the first time, an excimeric form of a molecule has been advantageously used in scintillation counting. A moderate discrimination between fast neutrons and gamma rays was observed in bulk EHCz, with an apparent neutron/gamma discrimination potential half of that of BC‐501 A. 相似文献
15.
In this work we present the development of a new solar cell prototype in order to improve photovoltaic efficiency. In this
model we show that the material can have three successive incident ray absorptions instead of two currently, by varying the
incidence angle, the aperture between the summit of two neighbouring pyramids and their height. This study concerns in particular
the photovoltaic parameters such as the spectral response. This model was checked for angles varying between 54 and 60° and
for pyramid heights between 5 and 10 μm. For these values of incidence angle, the apertures between the summits of two neighbouring
pyramids varied respectively from 14.54 to 11.54 μm for a pyramid height of 10 μm. 相似文献
16.
In basic medium, dimethyl 3,3'-dithiopropionate generates methyl acrylate, which serves in situ as a source of propionate moiety. This property was applied to the alkylation of indoles and other nitrogen heterocycles leading to a series of 3-(heteroaryl-substituted) propionates. A mechanistic rationale for the generation of acrylate is presented along with supportive experimental data. 相似文献
17.
The 52S ground state of Cd+ ions has been oriented by Schearer's technique. The hyperfine structure constant for this level has been determined as ¦A¦ = 14700 ± 700 MHz for the odd isotopes 111 and 113. 相似文献
18.
We compute the 2-rank of the wild kernel WK2(F) of a number field by constructing a 2-class group ad hoc. The main result generalizes in the more intricate case the canonical isomorphism established for odd primes under the assumption in a previous article (cf. (Acta. Arith. 67 (1994) 335; Math. Z. 238 (2001) 335)). It involves a criterium of triviality for the 2-part of the wild kernel of Galois number fields and, in the particular case of quadratic fields, it leads to a logarithmic interpretation of the diophantine conditions obtained by other authors. 相似文献
19.
Ismaili L Truong TT André C Thomassin M Mozer JL Robert JF Xicluna A Refouvelet B Millet J Nicod L Guillaume YC 《Journal of AOAC International》2003,86(2):222-228
The mechanism of the binding of D,L dansyl amino acids to teicoplanin was investigated. Na+ was used as an indicator of the interactions between the solutes and teicoplanin. The number (n) of sodium ions, Na+, excluded from the solute-teicoplanin interface when analyte transfer occurred was determined. A thermodynamic study and enthalpy-entropy compensation were performed to further explore the interaction mechanism. From these results, it was shown that teicoplanin was balanced between 2 conformational states characterized by distinct enantioselective properties. This approach indicates that liquid chromatography (LC) is a useful tool to extract physicochemical and molecular information from retention data. Thus, LC can be used as a complementary technique with the conventional techniques of molecular interaction analysis. 相似文献
20.
A. J. Blotcky W. C. Duckworth A. Ebrahim F. K. Hamel E. P. Rack R. B. Sharma 《Journal of Radioanalytical and Nuclear Chemistry》1989,134(1):151-160
Vanadium in serum was investigated by pre-irradiation chemistry neutron activation analysis employing anion exchange chromatography and post-irradiation neutron activation employing solvent extraction techniques. From a comparison of these techniques it is concluded that vanadium is present in human serum in the sub-ppb range. 相似文献