全文获取类型
收费全文 | 166篇 |
免费 | 9篇 |
专业分类
化学 | 155篇 |
力学 | 4篇 |
数学 | 1篇 |
物理学 | 15篇 |
出版年
2022年 | 5篇 |
2021年 | 8篇 |
2020年 | 6篇 |
2019年 | 8篇 |
2018年 | 6篇 |
2017年 | 3篇 |
2016年 | 5篇 |
2015年 | 6篇 |
2014年 | 3篇 |
2013年 | 4篇 |
2012年 | 13篇 |
2011年 | 18篇 |
2010年 | 21篇 |
2009年 | 15篇 |
2008年 | 13篇 |
2007年 | 13篇 |
2006年 | 9篇 |
2005年 | 6篇 |
2004年 | 3篇 |
2003年 | 1篇 |
2001年 | 1篇 |
1998年 | 1篇 |
1996年 | 1篇 |
1993年 | 1篇 |
1992年 | 1篇 |
1990年 | 1篇 |
1984年 | 1篇 |
1983年 | 1篇 |
1940年 | 1篇 |
排序方式: 共有175条查询结果,搜索用时 0 毫秒
1.
Rafael Fogel Rafaela Rodrigues Garcia Rebeca da Silva Oliveira Denise Neves Menchero Palacio Luciana da Silva Madeira Nei Pereira Jr. 《Applied biochemistry and biotechnology》2005,122(1-3):741-752
The dilute-acid hydrolysis of sugarcane bagasse was optimized using a statistical experimental design resulting in hydrolysates
containing 57.25 g/L of xylose, which were fermented with a high inoculum concentration (10 g/L of the yeast Candida guilliermondii IM/UFRJ 50088). The addition of urea reduced the time of conversion (t
C) to 75 h (without nitrogen source addition t
C>127 h), and, consequently, improving the rates of xylitol bioproduction. Fermentator experiments, using the optimized conditions,
resulted in enhanced conversion rates, reducing t
C to 30 h. The stability of the yeast in the hydrolysate was also verified in a 480-h cultivation. 相似文献
2.
3.
Rebeca Infante Dr. Javier Nieto Prof. Dr. Celia Andrés 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(14):4375-4379
A highly efficient enantioselective addition of Me2Zn to α‐ketoesters, assisted by a chiral perhydro‐1,3‐benzoxazine ligand, is described. This novel catalytic system offers homogeneous elevated enantioselectivities in the preparation of α‐hydroxyesters that bear a quaternary stereocenter, with a minor dependence on electronic and steric effects when aromatic, heteroaromatic, or aliphatic α‐ketoesters are employed. The catalyst can be recovered and reused without loss of activity. 相似文献
4.
Rebeca López-Serna Barbara Kasprzyk-Hordern Mira Petrović Damià Barceló 《Analytical and bioanalytical chemistry》2013,405(18):5859-5873
This paper describes the development and application of a multi-residue chiral liquid chromatography coupled with tandem mass spectrometry method for simultaneous enantiomeric profiling of 18 chiral pharmaceuticals and their active metabolites (belonging to several therapeutic classes including analgesics, psychiatric drugs, antibiotics, cardiovascular drugs and β-agonists) in surface water and wastewater. To the authors’ knowledge, this is the first time an enantiomeric method including such a high number of pharmaceuticals and their metabolites has been reported. Some of the pharmaceuticals have never been studied before in environmental matrices. Among them are timolol, betaxolol, carazolol and clenbuterol. A monitoring programme of the Guadalquivir River basin (South Spain), including 24 sampling sites and five wastewater treatment plants along the basin, revealed that enantiomeric composition of studied pharmaceuticals is dependent on compound and sampling site. Several compounds such as ibuprofen, atenolol, sotalol and metoprolol were frequently found as racemic mixtures. On the other hand, fluoxetine, propranolol and albuterol were found to be enriched with one enantiomer. Such an outcome might be of significant environmental relevance as two enantiomers of the same chiral compound might reveal different ecotoxicity. For example, propranolol was enriched with S(?)-enantiomer, which is known to be more toxic to Pimephales promelas than R(+)-propranolol. Fluoxetine was found to be enriched with S(+)-enantiomer, which is more toxic to P. promelas than R(?)-fluoxetine. 相似文献
5.
pH‐controlled reaction divergence of decarboxylation versus fragmentation in reactions of dihydroxyfumarate with glyoxylate and formaldehyde: parallels to biological pathways 下载免费PDF全文
Christopher J. Butch Jing Wang Jiande Gu Rebeca Vindas Jacob Crowe Pamela Pollet Leslie Gelbaum Jerzy Leszczynski Ramanarayanan Krishnamurthy Charles L. Liotta 《Journal of Physical Organic Chemistry》2016,29(7):352-360
The reactions of dihydroxyfumarate with glyoxylate and formaldehyde exhibit a unique pH‐controlled mechanistic divergence leading to different product suites by two distinct pathways. The divergent reactions proceed via a central intermediate (2,3‐dihydroxy‐oxalosuccinate, 3 , in the reaction with glyoxylate and 2‐hydroxy‐2‐hydroxymethyl‐3‐oxosuccinate, 14 , in the reaction with formaldehyde). At pH 7–8, products ( 7 , 8 , and 15 ) exclusively from a decarboxylation of the intermediate are observed, while at pH 13–14, products ( 9 , 10 , and 16 ) solely derived from a hydroxide‐promoted fragmentation of the intermediate are formed. The decarboxylative and fragmentation pathways are mutually exclusive and do not appear to coexist under the range of pH (7–14) conditions investigated. Herein, we employ a combination of quantitative 13C NMR measurements and density functional theory calculations to provide a rationale for this pH‐driven reaction divergence. These rationalizations also hold true for the reactions of dihydroxyfumarate produced in situ by the catalytic cyanide‐mediated dimerization of glyoxylate. In addition, the non‐enzymatic decarboxylation and fragmentation transformations of these central intermediates ( 3 and 14 ) appear to have intriguing parallels to the enzymatic reactions of oxalosuccinate and formation of glyceric acid derivatives in extant metabolism – the high and low pH mimicking the precise control exerted by the enzymes over reaction pathways. Copyright © 2016 John Wiley & Sons, Ltd. 相似文献
6.
A. Marcilla A. Gómez-Siurana S. Menargues 《Journal of Thermal Analysis and Calorimetry》2007,87(2):519-527
A study of the catalytic degradation of EVA
copolymers under air atmosphere has been carried out using thermogravimety
(TG). Three commercial EVA copolymers and five zeolites and related materials
catalysts have been selected. The degradation process in air atmosphere involves
four main decomposition steps (as observed in TG), being more complex than
the corresponding process in inert atmosphere. The presence of MCM-41, HY
and H-β does not seem to noticeably affect to the overall degradation
temperature, despite the temperature of maximum reaction rate for the second
decomposition step being slightly displaced towards lower temperatures. Contrarily,
the presence of HZSM-5 and HUSY zeolites seems to displace the main stage
of the oxidative degradation process towards higher temperatures. Moreover,
the relative importance of the second and third decomposition step is different
depending on the amount and the nature of the zeolite mixed with the EVA sample.
The results obtained show that the presence of the catalyst also enhances
the formation of the carbonous residue. 相似文献
7.
8.
Dongre C Dekker R Hoekstra HJ Pollnau M Martinez-Vazquez R Osellame R Cerullo G Ramponi R van Weeghel R Besselink GA van den Vlekkert HH 《Optics letters》2008,33(21):2503-2505
Using femtosecond laser writing, optical waveguides were monolithically integrated into a commercial microfluidic lab-on-a-chip device, with the waveguides intersecting a microfluidic channel. Continuous-wave laser excitation through these optical waveguides confines the excitation window to a width of 12 microm, enabling high-resolution monitoring of the passage of different types of fluorescent analytes when migrating and being separated in the microfluidic channel by microchip capillary electrophoresis. Furthermore, we demonstrate on-chip-integrated waveguide excitation and detection of a biologically relevant species, fluorescently labeled DNA molecules, during microchip capillary electrophoresis. Well-controlled plug formation as required for on-chip integrated capillary electrophoresis separation of DNA molecules, and the combination of waveguide excitation and a low limit of detection, will enable monitoring of extremely small quantities with high spatial resolution. 相似文献
9.
Rebeca D. Gonçalves Sérgio Azevedo Fernando Moraes M. Machado 《International journal of quantum chemistry》2010,110(9):1778-1783
We have investigated, using first‐principles calculations, the role of a substitutional carbon atom on the geometric stability of boron nitride monolayers, nanotubes, and nanocones. It is shown that the formation of energy depends on the number of atoms for the monolayers and on the diameter for the tubes. It is also found, for the carbon‐doped boron nitride nanotubes, that the value for the strain energy approaches the one obtained for nondoped tubes with increasing diameter. For the structural stability, we have verified that the doping, which introduces an excess of nitrogen or boron, makes each structure more favorable in its reverse atmosphere, i.e., excess of nitrogen is more stable in a boron‐rich growth environment, whereas excess of boron is preferred in a nitrogen‐rich condition. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010 相似文献
10.
Diogo P. Rivelli Carlos A. H. Filho Rebeca L. Almeida Cristina D. Ropke Tânia C. H. Sawada Silvia B. M. Barros 《Photochemistry and photobiology》2010,86(5):1005-1007
Chlorogenic acid is a natural potent antioxidant. It can be used in cosmetics formulations, but for this purpose its photochemical stability should be determined to ensure that the compound will not be degraded after UV radiation exposure. To evaluate this possibility, the concentration of a chlorogenic acid solution was determined by HPLC before and after UVA and UVB irradiation. The results indicate that chlorogenic acid is not degraded under UVA or UVB irradiation. 相似文献