全文获取类型
收费全文 | 255篇 |
免费 | 12篇 |
专业分类
化学 | 227篇 |
力学 | 5篇 |
数学 | 14篇 |
物理学 | 21篇 |
出版年
2022年 | 3篇 |
2021年 | 5篇 |
2020年 | 2篇 |
2019年 | 13篇 |
2018年 | 3篇 |
2017年 | 4篇 |
2016年 | 9篇 |
2015年 | 12篇 |
2014年 | 7篇 |
2013年 | 14篇 |
2012年 | 19篇 |
2011年 | 23篇 |
2010年 | 19篇 |
2009年 | 11篇 |
2008年 | 25篇 |
2007年 | 25篇 |
2006年 | 19篇 |
2005年 | 8篇 |
2004年 | 14篇 |
2003年 | 12篇 |
2002年 | 6篇 |
2001年 | 5篇 |
1999年 | 3篇 |
1998年 | 2篇 |
1996年 | 2篇 |
1993年 | 1篇 |
1975年 | 1篇 |
排序方式: 共有267条查询结果,搜索用时 15 毫秒
41.
Theocharakis P Glotsos D Kalatzis I Kostopoulos S Georgiadis P Sifaki K Tsakouridou K Malamas M Delibasis G Cavouras D Nikiforidis G 《Magnetic resonance imaging》2009,27(3):417-422
In this study, a pattern recognition system has been developed for the discrimination of multiple sclerosis (MS) from cerebral microangiopathy (CM) lesions based on computer-assisted texture analysis of magnetic resonance images. Twenty-three textural features were calculated from MS and CM regions of interest, delineated by experienced radiologists on fluid attenuated inversion recovery images and obtained from 11 patients diagnosed with clinically definite MS and from 18 patients diagnosed with clinically definite CM. The probabilistic neural network classifier was used to construct the proposed pattern recognition system and the generalization of the system to unseen data was evaluated using an external cross validation process. According to the findings of the present study, statistically significant differences exist in the values of the textural features between CM and MS: MS regions were darker, of higher contrast, less homogeneous and rougher as compared to CM. 相似文献
42.
The synthetic investigation of the CuII/maleamate(−1) ion (HL−)/N,N′,N′′-chelate general reaction system has allowed access to compounds [Cu2(HL)2(bppy)2](ClO4)2·H2O (1·H2O), [Cu(HL)(bppy)(ClO4)] (2) and [Cu(HL)(terpy)(H2O)](ClO4) (4) (bppy = 2,6-bis(pyrazol-1-yl)pyridine, terpy = 2,2′;6′,2′′-terpyridine). In the absence of externally added hydroxides, compound [Cu2(L′)2(bppy)2](ClO4)2 (3) was obtained from MeOH solutions; L′− is the monomethyl maleate(−1) ligand which is formed in situ via the CuII-assisted HL− → L′− transformation. In the case of tptz-containing (tptz = 2,4,6-tris(2-pyridyl)-1,3,5-triazine) reaction systems, the CuII-assisted hydrolysis of tptz to pyridine-2-carboxamide (L1) afforded complex [Cu(L1)2(NO3)2] (5). The crystal structures of 1–5 are stabilized by intermolecular hydrogen bonding and π–π stacking interactions. Characteristic IR bands of the complexes are discussed in terms of the known structures and the coordination modes of the ligands. 相似文献
43.
Miksík I Sedláková P Mikulíková K Eckhardt A Cserhati T Horváth T 《Biomedical chromatography : BMC》2006,20(6-7):458-465
This article gives an overview of uncommon replaceable matrices (gels) for capillary gel electrophoresis. This electrophoretic technique is useful mainly for the separation and analysis of biopolymers-nucleic acids and their fragments, and proteins/peptides. Commonly used gels are not reviewed. Those mentioned and discussed here are gels containing saccharides, newly developed acrylamide-based gels and thermoadjustable viscosity polymers, namely triblock copolymers and grafted polyacrylamide. 相似文献
44.
45.
Danhelova H Hradecky J Prinosilova S Cajka T Riddellova K Vaclavik L Hajslova J 《Analytical and bioanalytical chemistry》2012,403(10):2883-2889
The development and use of a fast method employing a direct analysis in real time (DART) ion source coupled to high-resolution time-of-flight mass spectrometry (TOFMS) for the quantitative analysis of caffeine in various coffee samples has been demonstrated in this study. A simple sample extraction procedure employing hot water was followed by direct, high-throughput (<1 min per run) examination of the extracts spread on a glass rod under optimized conditions of ambient mass spectrometry, without any prior chromatographic separation. For quantification of caffeine using DART-TOFMS, an external calibration was used. Isotopically labeled caffeine was used to compensate for the variations of the ion intensities of caffeine signal. Recoveries of the DART-TOFMS method were 97% for instant coffee at the spiking levels of 20 and 60 mg/g, respectively, while for roasted ground coffee, the obtained values were 106% and 107% at the spiking levels of 10 and 30 mg/g, respectively. The repeatability of the whole analytical procedure (expressed as relative standard deviation, RSD, %) was <5% for all tested spiking levels and matrices. Since the linearity range of the method was relatively narrow (two orders of magnitude), an optimization of sample dilution prior the DART-TOFMS measurement to avoid saturation of the detector was needed. 相似文献
46.
Moravcova E Vaclavik L Lacina O Hrbek V Riddellova K Hajslova J 《Analytical and bioanalytical chemistry》2012,402(9):2871-2883
A sensitive and accurate method utilizing ultra-high performance liquid chromatography (U-HPLC) coupled to high resolution
mass spectrometry based on orbitrap technology (orbitrapMS) for the analysis of nine 3-chloropropane-1,2-diol (3-MCPD) diesters
in vegetable oils was developed. To remove the interfering triacylglycerols that induce strong matrix effects, a clean-up
step on silica gel column was used. The quantitative analysis was performed with the use of deuterium-labeled internal standards.
The lowest calibration levels estimated for the respective analytes ranged from 2 to 5 μg kg−1. Good recovery values (89–120%) and repeatability (RSD 5–9%) was obtained at spiking levels of 2 and 10 mg kg−1. As an alternative, a novel ambient desorption ionization technique, direct analysis in real time (DART), hyphenated with
orbitrapMS, was employed for no separation, high-throughput, semi-quantitative screening of 3-MCPD diesters in samples obtained
by chromatographic fractionation. Additionally, the levels of 3-MCPD diesters measured in real-life vegetable oil samples
(palm oil, sunflower oil, rapeseed oil) using both methods are reported. Relatively good agreement of the data generated by
U-HPLC-orbitrapMS and DART-orbitrapMS were observed. With regard to a low ionization yield achieved for 3-MCPD monoesters,
the methods presented in this paper were not yet applicable for the analysis of these contaminants at the naturally occurring
levels. 相似文献
47.
Medjanik K Chercka D Nagel P Merz M Schuppler S Baumgarten M Müllen K Nepijko SA Elmers HJ Schönhense G Jeschke HO Valenti R 《Journal of the American Chemical Society》2012,134(10):4694-4699
It is demonstrated that the near-edge X-ray absorption fine structure (NEXAFS) provides a powerful local probe of functional groups in novel charge transfer (CT) compounds and their electronic properties. Microcrystals of tetra-/hexamethoxypyrene as donors with the strong acceptor tetracyano-p-quinodimethane (TMP/HMP-TCNQ) were grown by vapor diffusion. The oxygen and nitrogen K-edge spectra are spectroscopic fingerprints of the functional groups in the donor and acceptor moieties, respectively. The orbital selectivity of the NEXAFS pre-edge resonances allows us to precisely elucidate the participation of specific orbitals in the charge transfer process. Upon complex formation, the intensities of several resonances change substantially and a new resonance occurs in the oxygen K-edge spectrum. This gives evidence of a corresponding change of hybridization of specific orbitals in the functional groups of the donor (those derived from the frontier orbitals 2e and 6a(1) of the isolated methoxy group) and acceptor (orbitals b(3g), a(u), b(1g), and b(2u), all located at the cyano group) with π*-orbitals of the ring systems. Along with this intensity effect, the resonance positions associated with the oxygen K-edge (donor) and nitrogen K-edge (acceptor) shift to higher and lower photon energies in the complex, respectively. A calculation based on density functional theory qualitatively explains the experimental results. NEXAFS measurements shine light on the action of the functional groups and elucidate charge transfer on a submolecular level. 相似文献
48.
Lenka Sochorova Mojmir Baron Katerina Dadakova Tomas Kasparovsky Jiri Sochor 《Molecules (Basel, Switzerland)》2021,26(7)
Cadmium (Cd) is a heavy metal that occurs in all areas of the environment, including the food chain. In the body, it causes oxidative stress by producing free radicals that are harmful to the cells. Grape seed extract (GSE) contains a wide range of biologically active components that help to neutralize the adverse effects of free radicals. In this study, the effects of GSE prepared form semi-resistant grapevine cultivar Cerason, which is rich in phenolics, on biochemical markers of brown rats exposed to the effects of cadmium were monitored. GSE increased the plasma antioxidant activity and, in the kidneys and the liver, Cd content was significantly lowered by GSE co-administration. Accordingly, the increase in creatinine content and alanine aminotransferase activity and the decrease of catalase and superoxide dismutase activities caused by cadmium were slowed down by GSE co-administration. The results of this work reveal that grape seed extract offers a protective effect against the intake of heavy metals into the organism. 相似文献
49.
A simple method is suggested for the preparation of 5-alkylsulfinyl-1-aryltetrazoles via oxidation of 5-alkylsulfanyltetrazoles with 34% peracetic acid in high yields under mild conditions. 相似文献