全文获取类型
收费全文 | 490篇 |
免费 | 10篇 |
国内免费 | 2篇 |
专业分类
化学 | 370篇 |
晶体学 | 2篇 |
力学 | 15篇 |
数学 | 45篇 |
物理学 | 70篇 |
出版年
2023年 | 3篇 |
2022年 | 9篇 |
2021年 | 8篇 |
2020年 | 3篇 |
2019年 | 7篇 |
2018年 | 5篇 |
2017年 | 3篇 |
2016年 | 7篇 |
2015年 | 9篇 |
2014年 | 9篇 |
2013年 | 36篇 |
2012年 | 36篇 |
2011年 | 52篇 |
2010年 | 25篇 |
2009年 | 19篇 |
2008年 | 33篇 |
2007年 | 27篇 |
2006年 | 27篇 |
2005年 | 27篇 |
2004年 | 30篇 |
2003年 | 26篇 |
2002年 | 22篇 |
2001年 | 4篇 |
2000年 | 6篇 |
1999年 | 11篇 |
1998年 | 3篇 |
1997年 | 4篇 |
1996年 | 7篇 |
1995年 | 5篇 |
1994年 | 6篇 |
1993年 | 3篇 |
1992年 | 5篇 |
1991年 | 3篇 |
1990年 | 2篇 |
1989年 | 1篇 |
1988年 | 2篇 |
1987年 | 1篇 |
1986年 | 1篇 |
1985年 | 3篇 |
1984年 | 2篇 |
1983年 | 2篇 |
1982年 | 3篇 |
1980年 | 1篇 |
1978年 | 2篇 |
1975年 | 1篇 |
1939年 | 1篇 |
排序方式: 共有502条查询结果,搜索用时 0 毫秒
51.
Alarcón SH Palleschi G Compagnone D Pascale M Visconti A Barna-Vetró I 《Talanta》2006,69(4):1031-1037
Competitive electrochemical enzyme-linked immunosorbent assays based on disposable screen-printed electrodes have been developed for quantitative determination of ochratoxin A (OTA). The assays were carried out using monoclonal antibodies in the direct and indirect format. OTA working range, I50 and detection limits were 0.05-2.5 and 0.1-7.5 μg L−1, 0.35 (±0.04) μg L−1 and 0.9 (±0.1) μg L−1, 60 and 100 μg L−1 in the direct and indirect assay format, respectively. The immunosensor in the direct format was selected for the determination of OTA in wheat. Samples were extracted with aqueous acetonitrile and the extract analyzed directly by the assay without clean-up. The I50 in real samples was 0.2 μg L−1 corresponding to 1.6 μg/kg in the wheat sample with a detection limit of 0.4 μg/kg (calculated as blank signal −3σ). Within- and between-assay variability were less than 5 and 10%, respectively. A good correlation (r = 0.9992) was found by comparative analysis of naturally contaminated wheat samples using this assay and an HPLC/immunoaffinity clean-up method based on the AOAC Official Method 2000.03 for the determination of OTA in barley. 相似文献
52.
A study of the microbiological reduction of different α-halogenoketones (4-chloro-3-octanone, 4-chloro-5-nonanone, 5-bromo-4-nonanone and 5-chloro-4-nonanone) with several strains of microorganism showed great difficulty in reducing ketone functions located in the middle of carbon chains. However, by choosing the appropriate microorganism, several enantiomerically pure diastereoisomers of the corresponding halohydrins have been obtained and were transformed into chiral epoxides. 相似文献
53.
The synthesis of a series of novel indazole-5,6-diamine derivatives is described. This indazole ring system was incorporated in an octahydropyrrolo[3,4-b]phenazine scaffold and was diversely and regioselectively substituted on the nitrogen atoms at the 5- and 10-positions. Thus, the nitrogen atom at the 5-position was found to be more reactive toward electrophiles than the one at the 10-position. This difference of reactivity could be attributed to the electronic effect of the pyrazole moiety. Moreover, an unexpected tetrahydropyran protecting group migration was observed from the N-1 atom to the C-11 position of the octahydropyrrolo[3,4-b]phenazine scaffold. 相似文献
54.
The synthesis of a generation 5 (G5) poly(amidoamine) (PAMAM) dendrimer platform having cyclooctyne ligands that were subsequently be used for a copper-free Huisgen 1,3-dipolar cycloaddition (click reaction) with azido modified methotrexate is described. The G5 PAMAM dendrimer was first partially (70%) acetylated and then coupled with 20 cyclooctyne ligands through amide bonds. The remaining primary amine groups on the dendrimer surface were neutralized by acetylation. The platform was then ‘clicked’ with different numbers (5, 10, and 17) of γ-azido functionalized methotrexate. The copper-free click reactions were stoichiometric with excellent yields. 相似文献
55.
56.
Fourmigué M Reinheimer EW Assaf A Jeannin O Saad A Auban-Senzier P Alemany P Rodríguez-Fortea A Canadell E 《Inorganic chemistry》2011,50(9):4171-4181
An efficient synthetic procedure for the preparation of unsymmetrically substituted tetrathiafulvalene (TTF) donors has been used to obtain the trimethylene-tetrathiafulvalene (tTTF) donor with high purity. Good quality crystals of the two (tTTF)(2)X (X = Br, I) salts have been obtained by electrocrystallization. The two salts are isomorphous and contain tTTF layers which are built from (tTTF)(2) dimeric units. Both systems are low-dimensional antiferromagnets with the highest Ne?el temperatures for TTF based radical cation salts: ≈ 35 K (Br salt) and ≈43 K (I salt). The resistivity is found to substantially decrease with pressure although both salts still have activated conductivity at 25 kbar. First-principles Density Functional Theory (DFT) calculations have been used to investigate the relative strength of the three different types of magnetic interactions in the tTTF layers as well as the potential magnetic ground states. These calculations successfully predict the nature of the ground state and suggest a possible correlation between structural details and Ne?el temperatures for the bromine and iodine salts. Remarkably, the calculated antiferromagnetic ground state can be predicted from the nesting properties of the Fermi surface for the hypothetical Pauli paramagnetic metallic state. 相似文献
57.
Lamoureux N Mercier X Pauwels JF Desgroux P 《The journal of physical chemistry. A》2011,115(21):5346-5353
NCO is a short-lived species involved in NO(x) formation. It has never been quantitatively measured in flame conditions. In the present study, laser-induced fluorescence (LIF) and cavity ring-down spectroscopy (CRDS) were combined to measure NCO radical concentrations in premixed low-pressure flames (p = 5.3 kPa). NCO LIF excitation spectrum and absorption spectrum (using CRDS) measured in a stoichiometric CH(4)/O(2)/N(2)O/N(2) flame were found in good agreement with a simulated spectrum using PGOPHER program that was used to calculate the high-temperature absorption cross section of NCO in the A(2)Σ(+)-X(2)Π transition around 440.479 nm. The relative NCO-LIF profiles were measured in stoichiometric CH(4)/O(2)/N(2)O/N(2) flames where the ratio N(2)O/O(2) was progressively decreased from 0.50 to 0.01 and in rich CH(4)/O(2)/N(2) premixed flames. Then, the LIF profiles were converted into NCO mole fraction profiles from the absorption measurements using CRDS in a N(2)O-doped flame. 相似文献
58.
The kinetics of the noncatalyzed reaction between α, ω -dicarboxypoly-amide-11 and α, ω -dihydroxypolyoxyalkylenes is investigated by using the reactions of 11-dodecylamidoundecanoic acid with 1-dodecanol, 2-tridecanol, α-dodecyl-ω-hydroxypolyoxyethylene or α-dodecyl-ω;-hydroxypolyoxypropylene as models. Kinetic data fit a 3rd overall order (2 in acid and 1 in alcohol). Rate constants and activation parameters are determined and compared. 相似文献
59.
Daniel Plusquellec Catherine Brenner-Hénaff Pascale Léon-Ruaud Stéphane Duquenoy Martine Lefeuvre Henri Wróblewski 《Journal of carbohydrate chemistry》2013,32(5):737-751
Abstract Treatment of free glycosylamines with 3-acyl-5-methyl-1,3,4-thiadiazole-2 (3H)-thiones 6 or with acids and 5-methyl-2-thioxo-1,3,4-thiadiazole-3(2H)-carbothioic acid S-(5-methyl-1,3,4-thiadiazol-2-yl) ester 7 in hydroorganic media afforded N-acylglycosylamines in high yields and without any competitive deglycosylation. This reaction found applications in the synthesis of N-glycopeptide building blocks and of glycosidic non ionic surfactants. Results concerning surface activities of two N-acylglycosylamines are reported. The new non ionic N-octanoyl-β-D-glucosylamine surfactant exhibited efficacy and selectivity in the extraction of membrane proteins, enhanced the activity of a membrane succinate dehydrogenase and proved thus useful for membrane studies. 相似文献
60.
Dr. Akos Banyasz Dr. Thomas Gustavsson Dr. Delphine Onidas Dr. Pascale Changenet‐Barret Dr. Dimitra Markovitsi Dr. Roberto Improta 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(11):3762-3774
The singlet excited states of adenine oligomers, model systems widely used for the understanding of the interaction of ultraviolet radiation with DNA, are investigated by fluorescence spectroscopy and time‐dependent (TD) DFT calculations. Fluorescence decays, fluorescence anisotropy decays, and time‐resolved fluorescence spectra are recorded from the femtosecond to the nanosecond timescales for single strand (dA)20 in aqueous solution. These experimental observations and, in particular, the comparison of the fluorescence behavior upon UVC and UVA excitation allow the identification of various types of electronic transitions with different energy and polarization. Calculations performed for up to five stacked 9‐methyladenines, taking into account the solvent, show that different excited states are responsible for the absorption in the UVC and UVA spectral domains. Independently of the number of bases, bright excitons may evolve toward two types of excited dimers having π–π* or charge‐transfer character, each one distinguished by its own geometry and spectroscopic signature. According to the picture arising from the joint experimental and theoretical investigation, UVC‐induced fluorescence contains contribution from 1) exciton states with a different degree of localization, decaying within a few ps, 2) “neutral” excited dimers decaying on the sub‐nanosecond timescale, being the dominant species, and 3) charge‐transfer states decaying on the nanosecond timescale. The majority of the photons emitted upon UVA excitation are related to charge‐transfer states. 相似文献