全文获取类型
收费全文 | 1940篇 |
免费 | 54篇 |
国内免费 | 4篇 |
专业分类
化学 | 1598篇 |
晶体学 | 4篇 |
力学 | 13篇 |
数学 | 230篇 |
物理学 | 153篇 |
出版年
2024年 | 2篇 |
2023年 | 13篇 |
2022年 | 69篇 |
2021年 | 104篇 |
2020年 | 66篇 |
2019年 | 56篇 |
2018年 | 44篇 |
2017年 | 37篇 |
2016年 | 80篇 |
2015年 | 83篇 |
2014年 | 73篇 |
2013年 | 154篇 |
2012年 | 136篇 |
2011年 | 136篇 |
2010年 | 106篇 |
2009年 | 86篇 |
2008年 | 113篇 |
2007年 | 107篇 |
2006年 | 104篇 |
2005年 | 91篇 |
2004年 | 88篇 |
2003年 | 55篇 |
2002年 | 53篇 |
2001年 | 25篇 |
2000年 | 20篇 |
1999年 | 11篇 |
1998年 | 8篇 |
1997年 | 15篇 |
1996年 | 7篇 |
1995年 | 5篇 |
1994年 | 9篇 |
1992年 | 3篇 |
1990年 | 2篇 |
1989年 | 3篇 |
1988年 | 3篇 |
1985年 | 3篇 |
1984年 | 1篇 |
1983年 | 3篇 |
1982年 | 1篇 |
1981年 | 1篇 |
1979年 | 5篇 |
1978年 | 2篇 |
1977年 | 2篇 |
1970年 | 1篇 |
1969年 | 1篇 |
1968年 | 1篇 |
1936年 | 2篇 |
1927年 | 2篇 |
1924年 | 2篇 |
1923年 | 1篇 |
排序方式: 共有1998条查询结果,搜索用时 15 毫秒
71.
Peter Q. Tranchida Simona Salivo Flavio A. Franchina Ivana Bonaccorsi Paola Dugo Luigi Mondello 《Analytical and bioanalytical chemistry》2013,405(13):4655-4663
The present investigation is focused on the development of a comprehensive two-dimensional GC (GC?×?GC) method, with dual MS/FID detection, for the qualitative and quantitative analysis of the entire unsaponifiable fraction of vegetable oils. The unsaponifiable fraction forms a minor, highly specific part of a vegetable oil, and can be used as an indicator of genuineness. The column set used consisted of a low-polarity first dimension, and a medium-polarity secondary one, both characterized by a high thermal stability. The use of dual detection enabled the attainment of both mass spectral information and relative % FID data. The complexity of the fingerprint, generated by the unsaponifiable fraction, fully justified the employment of the two-dimensional GC technology. Furthermore, two other GC?×?GC benefits contributed greatly to the attainment of promising results, namely sensitivity enhancement and the formation of group-type patterns. The method herein proposed could potentially open a new opportunity for the more in-depth knowledge of the unsaponifiable fraction of vegetable oils. 相似文献
72.
Daniel Wright Mariagioia Zampagni Elisa Evangelisti Simona Conti Giampiero D'Adamio Andrea Goti Matteo Becatti Claudia Fiorillo Niccolò Taddei Gianfranco Liguri 《Photochemistry and photobiology》2013,89(2):442-452
UV‐induced toxicity is characterized by marked oxidative stress, accompanied by the depletion of key cellular antioxidants, particularly glutathione (GSH). Replenishing cellular GSH may represent a means of counteracting UV‐induced toxicity: however, treatment with free GSH is not therapeutically effective due to its unfavorable pharmacokinetic properties. In this study, we show that S‐acyl‐glutathione (acyl‐SG) derivatives, which consist of an acyl chain (of variable length and saturation) linked via a thioester bond to GSH, increase intracellular levels of reduced GSH in primary skin fibroblasts, adenocarcinoma HeLa and neuroblastoma SH‐SY5Y cells. Consistent with this, acyl‐SG derivatives protect against UV‐induced reactive oxygen species (ROS) production and UV‐B/C‐mediated lipid peroxidation and caspase‐3 activation in the analyzed cell lines, with unsaturated thioesters displaying a significantly greater protective effect. Taken together, our findings suggest that acyl‐SG thioesters may be therapeutically effective in the treatment of UV‐related skin disorders and oxidative stress‐mediated conditions in general. 相似文献
73.
The stereocontrolled condensation of methyl ketones to trans α,β‐aziridine aldehydes creates functionalized aldols, valuable precursors for different amino hydroxylated structures, such as amino alcohols, amino diols, α‐tetrahydrofuryl amides, and α‐furyl amides. 相似文献
74.
Emanuele Aresu Laura CarrocciaStefania Fioravanti Simona GasbarriLucio Pellacani Fabio Sciubba 《Tetrahedron》2013
Chiral racemic α-diimines, tested in aziridination reactions with NsONHCO2Et, for the first time led to the synthesis of (±)-bidiaziridines, stereoselectively derived from the corresponding meso (E-s-trans-E)-α-diimines. Moreover, a minor bidiaziridine isomer, probably a meso form that was lost under classical work-up conditions, can be obtained by adding water to the crude mixtures at the end of amination reactions. The results definitively prove that the imine aziridination by carbamates is a two-step domino process. The structures of the compounds were determined using 2D NMR on purified bidiaziridines. 相似文献
75.
Raiza Fernández Freddy Galarraga Zully Benzo Gonzalo Márquez M. Gabriela Requiz 《International journal of environmental analytical chemistry》2013,93(3):230-240
Biomonitoring of PAH air pollution using lichens was carried out. Sixteen PAHs were studied in 11 locations along the valley of Caracas (Venezuela). The results of this work indicate that 14 of the 16 analysed PAHs were highly accumulated into the lichen thalli of Pyxine coralligera Malme. PAH levels in the samples revealed that the several volatile PAHs (naphthalene, acenaphtylene, acenaphtene, and fluoranthene) have the highest levels in the majority of the studied locations. The fluoranthene/pyrene and phenantrene/antracene ratios suggested that the major sources of PAHs are anthropogenic, mainly associated with gasoline and diesel combustion (pyrolytic) and unburnt oil derivates (petrogenic). The total PAH concentrations obtained in the present study were in the range of 0.24 to 9.08?µg/g, similar to those reported by other works in European and Asian cities. 相似文献
76.
Francesco Soggia Maria Luisa Abelmoschi Simona Dalla Riva Rodolfo De Pellegrini Roberto Frache 《International journal of environmental analytical chemistry》2013,93(4):367-378
Abstract The Project on an Antarctic Environmental Specimen Bank (Banca Campioni Ambientali Antartici—BCAA) began in 1994 in order to collect and classify samples from the Antarctic ecosystem to be used for future studies. The objectives of the project are similar to the general aims of the Environmental Specimen Banks, but they specifically focus on the chemical aspects concerning the research activities of the Italian Project on the “Micropollutants Chemistry” (Sector “Chemical Contamination” of the Italian Antarctic Research Programme—PNRA). During these first years the facilities suitable for storing a significant number of specimens (now over 2,000) at different temperatures (from ?30°C to ?150°C) and a database system, specifically designed for managing and consulting information concerning both the storage of samples and data on their chemical characterisation, have been developed. In addition, a programme for validating the procedures of Antarctic organisms storage by checking the stability of some chemical parameters both in fresh and freeze-dried specimens has been developed. 相似文献
77.
Nicoleta Gabriela Hădărugă Daniel Ioan Hădărugă Heinz-Dieter Isengard 《Journal of inclusion phenomena and macrocyclic chemistry》2013,75(3-4):297-302
Cyclodextrins are some of the most used carriers for bioactive compounds (as host–guest complex) and many factors influence the association–dissociation of this complex, some of them being related to hydrophobicity. In the solid state, cyclodextrins contain two types of water molecules: “surface” water molecules (especially close to the crystal surface) and “strong-bonded” water molecules (especially from the cyclodextrin cavity), but the classification is hard to do, and the concentration of these water molecules are relatively difficult to estimate by simple methods. In the present study we used the volumetric Karl Fischer titration to estimate these types of water molecules in cyclodextrins by means of the rate of water reaction (related to diffusion from cyclodextrin crystals). “Surface” water molecules are titrated with rates between 1.8–2.8 mM/s for α-cyclodextrin, while for β-cyclodextrin these rates are little bit higher (2.9–3.4 mM/s). The rates corresponding to “strong-bonded” water molecules are approximately tens fold lower (0.05–0.3 mM/s for α-cyclodextrin and 0.15–0.33 mM/s for β-cyclodextrin). The approximate ratio between “surface” and “strong-bonded” water molecules could also be estimated by this simple and rapid method. 相似文献
78.
Prof. Tiziana Benincori Dr. Valentina Bonometti Dr. Roberto Cirilli Prof. Patrizia R. Mussini Dr. Andrea Marchesi Prof. Marco Pierini Dr. Tullio Pilati Dr. Simona Rizzo Prof. Francesco Sannicolò 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(1):165-181
A series of tris‐aryl phosphane oxides existing as residual enantiomers or diastereoisomers with substituents on the aryl rings differing in size and electronic properties were synthesized and characterized. Their electronic properties were evaluated on the basis of their electrochemical oxidation and reduction potentials together with those of the corresponding “blade bromides” (i.e., the naphthalene derivatives displaying the same substitution pattern of the tris‐naphthyl phosphane oxide blades, with a bromo substituent where the phosphorus atom is located) determined by CV. The residual stereoisomeric phosphane oxides were isolated in a stereochemically pure state and were found to be highly configurationally stable at room temperature (stereoisomerization barriers of about 27 kcal mol?1). The chiroptical properties of the residual stereoisomers and the assignments of absolute configuration are discussed. The configurational stability of residual tris‐aryl phosphane oxides was found to be scarcely influenced by the electronic properties of the substituents present on the aromatic rings constituting the blades, while steric effects play the most relevant role. Detailed theoretical calculations are in agreement with the experimental results and also contribute to a rational interpretation of the stereodynamics of these systems. 相似文献
79.
Interactions between CdTe quantum dots and DNA revealed by capillary electrophoresis with laser‐induced fluorescence detection
下载免费PDF全文
![点击此处可从《Electrophoresis》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Maja Stanisavljevic Jana Chomoucka Simona Dostalova Sona Krizkova Marketa Vaculovicova Vojtech Adam Rene Kizek 《Electrophoresis》2014,35(18):2587-2592
Quantum dots (QDs) are one of the most promising nanomaterials, due to their size‐dependent characteristics as well as easily controllable size during the synthesis process. They are promising label material and their interaction with biomolecules is of great interest for science. In this study, CdTe QDs were synthesized under optimal conditions for 2 nm size. Characterization and verification of QDs synthesis procedure were done by fluorimetric method and with CE. Afterwards, QDs interaction with chicken genomic DNA and 500 bpDNA fragment was observed employing CE‐LIF and gel electrophoresis. Performed interaction relies on possible matching between size of QDs and major groove of the DNA, which is approximately 2.1 nm. 相似文献
80.
Amanda S. Santana Diego B. Carvalho Nadla S. Cassemiro Luiz H. Viana Gabriela R. Hurtado Marcos S. Amaral Najla M. Kassab Palimécio G. Guerrero Jr. Sandro L. Barbosa Miguel J. Dabdoub Adriano C.M. Baroni 《Tetrahedron letters》2014
A simple synthesis of 3-iodothiophenes was demonstrated using a wide range of (Z)-thioenynes. The key step in the iodocyclofunctionalization was the selective reduction of the triple bond in (Z)-thioenynes by the addition of iodine as an electrophilic agent. The 3-iodothiophenes were obtained in good to excellent yields of 61–92%. The 3-iodothiophenes were used as substrates in Sonogashira cross-coupling reactions to obtain thiophene acetylenes. 相似文献