全文获取类型
收费全文 | 257篇 |
免费 | 12篇 |
专业分类
化学 | 228篇 |
力学 | 5篇 |
数学 | 15篇 |
物理学 | 21篇 |
出版年
2022年 | 5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 | 24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 | 11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269条查询结果,搜索用时 15 毫秒
71.
Chromatographic behavior of synthetic block (co)oligomer samples (EO)n(PO)m(EO)n and (PO)n(EO)m(PO)n with different distribution of propylene oxide (PO) and ethylene oxide (EO) monomer units was investigated on three types of stationary phases on zirconium dioxide support: Zr-PS (polystyrene), Zr-carbon, and Zr-carbon C18. The effects of the distribution and sequence of the oxyethylene and oxypropylene monomer units on the chromatographic retention depend on the type of the stationary phase, but are strongly affected by the organic modifier (methanol or ACN) in aqueous-organic mobile phase. Special attention was focused on the influence of the mobile-phase composition on the separation according to the EO and PO distribution. Zirconia-based columns are stable at elevated temperatures and can be used in high-temperature LC (HTLC); hence, we investigated the temperature effects on the chromatographic behavior up to 90 degrees C. The applications of solvent and temperature gradients were compared on the zirconia stationary phases in the RP mode. 相似文献
72.
Petrusevska K Kuznetsov MA Gedicke K Meshko V Staroverov SM Seidel-Morgenstern A 《Journal of separation science》2006,29(10):1447-1457
The separation of the enantiomers of several a-amino acids was studied on a new chiral stationary phase (CSP) which is based on the macrocyclic glycopeptide antibiotic eremomycin attached to silica particles. Retention and separation factors were determined under analytical conditions at ambient temperature for different mobile phase compositions. In order to evaluate the potential with respect to preparative separations the adsorption isotherms of D- and L-methionine were determined for one mobile phase composition applying the elution by characteristic point method. The isotherms were validated by comparing experimentally determined elution profiles with predictions based on the equilibrium dispersive model. Finally, the performance of the eremomycin CSP was compared with a commercially available CSP based on the macrocyclic antibiotic teicoplanin. After determining the isotherms of D- and L-methionine also for the teicoplanin phase, the equilibrium dispersive model was used for both CSP to identify optimal operating conditions. For the separation and conditions considered the new eremomycin CSP revealed a better performance compared to the teicoplanin CSP. 相似文献
73.
Cahlíková L Opletal L Kurfürst M Macáková K Kulhánková A Hostálková A 《Natural product communications》2010,5(11):1751-1754
The roots and aerial parts of Chelidonium majus L. were extracted with EtOH and fractionated using CHCl3 and EtOH. Repeated column chromatography, preparative TLC and crystallization led to the isolation of five isoquinoline alkaloids, stylopine (3), chelidonine (4), homochelidonine (5), protopine (6), and allocryptopine (7), along with two isolation artifacts 6-ethoxydihydrosanguinarine (1) and 6-ethoxydihydrochelerythrine (2). All isolated compounds were tested for human blood acetylcholinesterase (HuAChE) and human plasma butyrylcholinesterase (HuBuChE) inhibitory activity. The isolation artifacts exhibited the highest activity against HuAChE and HuBuChE with IC50 values of 0.83 +/- 0.04 microM and 4.20 +/- 0.19 microM for 6-ethoxydihydrochelerythrine and 3.25 +/- 0.24 microM and 4.51 +/- 0.31 microM for 6-ethoxydihydrosanguinarine. The most active of the naturally-occurring alkaloids was chelidonine, which inhibited both HuAChE and HuBuChE in a dose-dependent manner with IC50 values of 26.8 +/- 1.2 microM and 31.9 +/- 1.4 microM, respectively. 相似文献
74.
Ballell L van Scherpenzeel M Buchalova K Liskamp RM Pieters RJ 《Organic & biomolecular chemistry》2006,4(23):4387-4394
A chemical probe was developed for the detection of the emerging cancer marker galectin-3. The probe contains a benzophenone moiety which covalently attaches itself to the protein upon binding and irradiation. Introduction of a fluorescent label via'click' chemistry allows the labelled proteins to be visualized in a gel. With the probe, selective visualization of galectin-3 in protein mixtures was shown and remarkably even in cell lysates. 相似文献
75.
76.
Low-pressure gas chromatography-mass spectrometry (LP-GC-MS) using a quadrupole MS instrument was further optimized and evaluated for the fast analysis of multiple pesticide residues in food crops. Performance of two different LP-GC-MS column configurations was compared in various experiments, including ruggedness tests with repeated injections of pesticides in matrix extracts. The tested column configurations employed the same 3 m x 0.15 mm i.d. restriction capillary at the inlet end, but different analytical columns attached to the vacuum: (A) a 10 m x 0.53 mm i.d., 1 microm film thickness RTX-5 Sil MS column; and (B) a 10 m x 0.25 mm i.d., 0.25 microm film thickness DB-5MS column. Under the optimized conditions (compromise between speed and sensitivity), the narrower analytical column with a thinner film provided slightly (<1.1-fold) faster analysis of <5.5 min separation times and somewhat greater separation efficiency. However, lower detection limits for most of the tested pesticides in real extracts were achieved using the mega-bore configuration, which also provided significantly greater ruggedness of the analysis (long-term repeatability of analyte peak intensities, shapes, and retention times). Additionally, the effect of the increasing injection volume (1-5 microl) on analyte signal-to-noise ratios was evaluated. For the majority of the tested analyte-matrix combinations, the increase in sensitivity caused by a larger injection did not translate in the same gain in analyte detectability. Considering the costs and benefits, the injection volume of 2-3 microl was optimal for detectability of the majority of 57 selected pesticides in apple, carrot, lettuce, and wheat extracts. 相似文献
77.
Chromatographic methods have been developed for the separation of the three novel biocompatible iron chelators pyridoxal isonicotinoyl hydrazone (PIH), salicylaldehyde isonicotinoyl hydrazone (SIH), and pyridoxal 2-chlorobenzoyl hydrazone (o-108) from their synthetic precursors and iron chelates. The chromatographic analyses were achieved using analytical columns packed with 5 microm Nucleosil 120-5 C18. For the evaluation of all chelators in the presence of the synthetic precursors, EDTA was added to the mobile phase at a concentration of 2 mM. The best separation of PIH and its synthetic precursors was achieved using a mixture of phosphate buffer (0.01 M NaH2PO4, 5 mM 1-heptanesulfonic acid sodium salt; pH 3.0) and methanol (55:45, v/v). For separation of SIH and its synthetic precursors, the mobile phase was composed of 0.01 M phosphate buffer (pH 6.0) and methanol (60:40, v/v). o-108 was analyzed employing a mixture of 0.01 M phosphate buffer (pH 7.0), methanol, and acetonitrile (60:20:20, v/v/v). These mobile phases were slightly modified to separate each chelator from its iron chelate. Furthermore, a RP-TLC method has also been developed for fast separation of all compounds. The chromatographic methods described herein could be applied in the evaluation of purity and stability of these drug candidates. 相似文献
78.
Desilylation of a series of hydrolytically stable hydroxyquinone t-butyldimethylsilyl ethers was achieved in high yields by the use of potassium fluoride in the presence of catalytic amounts of aqueous 48% hydrobromic acid (HBr), or basic aluminium oxide (Al2O3), and tetra-n-butylammonium fluoride (Bu4NF) as cleaving agents. Copyright © 1998 John Wiley & Sons, Ltd. 相似文献
79.
Spyridon Dimitrakis Efthymios-Spyridon Gavriil Athanasios Pousias Nikolaos Lougiakis Panagiotis Marakos Nicole Pouli Katerina Gioti Roxane Tenta 《Molecules (Basel, Switzerland)》2022,27(1)
A number of pyrrolo[2,3-c]pyridines, pyrrolo[3,2-d]pyrimidines and pyrazolo[4,3-d]pyrimidines were designed and synthesized as antiproliferative agents. The target compounds possessed selected substituents in analogous positions on the central scaffold that allowed the extraction of interesting SARs. The cytotoxic activity of the new derivatives was evaluated against prostatic (PC-3) and colon (HCT116) cell lines, and the most potent analogues showed IC50 values in the nM to low µM range, while they were found to be non-toxic against normal human fibroblasts (WI-38). Flow cytometric analysis of DNA content revealed that the most promising derivative 14b caused a statistically significant accumulation of PC-3 cells at G2/M phase and induced apoptosis in PC-3 cells. 相似文献
80.
Katerina N. Lazarou Iordanis Chadjistamatis Aris Terzis Spyros P. Perlepes Catherine P. Raptopoulou 《Polyhedron》2010
The use of succinamic acid (H2sucm)/N,N′-chelate (2,2′-bipyridine, bpy; 4,4′-dimethyl-2,2′-bipyridine, dmbpy; 1,10-phenanthroline, phen) ‘ligand blends’ in CuX2·yH2O (X = NO3, y = 3; X = Cl, y = 0) chemistry has yielded the new complexes [Cu2(Hsucm)3(bpy)2](NO3)·0.5MeOH (1·0.5MeOH), [Cu2(Hsucm)(OH)Cl(bpy)2](OH)·3.6H2O (5·3.6H2O) and [Cu2(Hsucm)2Cl2(phen)2] (6). The succinamate(−1) ion behaves as a carboxylate ligand and exists in two different coordination modes in the structures of the above complexes, i.e., the common syn, syn μ2-κO:κO′ in 1, 5 and 6, and the μ2-κ2O:κO′ in 1. The primary amide group of Hsucm− remains uncoordinated and participates in intermolecular hydrogen bonding interactions leading to 1D, 2D and 3D networks. Characteristic IR bands of the complexes are discussed in terms of the known structures and the coordination modes of the Hsucm− ligands. 相似文献