全文获取类型
收费全文 | 248篇 |
免费 | 3篇 |
专业分类
化学 | 126篇 |
力学 | 3篇 |
数学 | 69篇 |
物理学 | 53篇 |
出版年
2023年 | 2篇 |
2022年 | 8篇 |
2021年 | 12篇 |
2020年 | 13篇 |
2019年 | 5篇 |
2018年 | 6篇 |
2017年 | 4篇 |
2016年 | 12篇 |
2015年 | 7篇 |
2014年 | 9篇 |
2013年 | 22篇 |
2012年 | 23篇 |
2011年 | 23篇 |
2010年 | 6篇 |
2009年 | 5篇 |
2008年 | 8篇 |
2007年 | 11篇 |
2006年 | 13篇 |
2005年 | 10篇 |
2004年 | 9篇 |
2003年 | 10篇 |
2002年 | 7篇 |
2001年 | 1篇 |
2000年 | 2篇 |
1999年 | 1篇 |
1998年 | 3篇 |
1997年 | 3篇 |
1996年 | 1篇 |
1995年 | 2篇 |
1994年 | 1篇 |
1993年 | 1篇 |
1992年 | 1篇 |
1991年 | 1篇 |
1990年 | 1篇 |
1986年 | 1篇 |
1984年 | 1篇 |
1982年 | 2篇 |
1981年 | 2篇 |
1980年 | 1篇 |
1976年 | 1篇 |
排序方式: 共有251条查询结果,搜索用时 31 毫秒
241.
Wiedmer SK D'Orazio G Smått JH Bourdin D Baños-Pérez C Sakeye M Kivilompolo M Kopperi M Ruiz-Jiménez J Fanali S Riekkola ML 《Journal of chromatography. A》2011,1218(30):5020-5029
The need for novel packing materials in both capillary electrochromatography (CEC) and capillary liquid chromatography (CLC) is apparent and the development towards more selective, application-oriented chromatographic phases is under progress world-wide. In this study we have synthesized new polyethyleneimine (PEI) functionalized Mn(2)O(3), SiO(2), SnO(2), and ZrO(2) particles for the fabrication of packed capillary columns for CEC and CLC. The nanocasting approach was successful for the preparation of functionalized metal oxide materials with a controlled porosity and morphology. PEI functionalization was done using ethyleneimine monomers to create particles which are positively charged in aqueous solution below pH 9. This functionalization allowed the possibility to have both hydrophobic (due to its alkyl chain) and ionic interactions (due to positively charged amino groups) with selected compounds. For comparison aminopropyl-functionalized silica was also synthesized and tested. Both slurry pressure and electrokinetic packing procedures used gave similar results, but fast sedimentation of the material caused some problems during the packing. The high stability and wide pH range of PEI-functionalized SiO(2) material, with potential for hydrophobic and electrostatic interactions, proved to be useful for the CEC and CLC separation of some model acidic and neutral compounds. 相似文献
242.
Thiago O. Carvalho Ana E. B. Matias Lilian R. Braga Sheila M. Evangelista Alexandre G. S. Prado 《Journal of Thermal Analysis and Calorimetry》2011,106(2):475-481
Chitosan microspheres were applied to remove the pollutants diclofenac and dipyrone from water. Adsorption studies were adjusted
to Langmuir equation. The maximum number of adsorbed moles gave 5.25 × 10−4 and 4.83 × 10−4 mol of diclofenac and dipyrone, respectively, per gram of chitosan microspheres. The interactions in solid/liquid interface
were calorimetrically followed and gave endothermic values: +22.1 ± 1.3 and +48.7 ± 1.5 kJ mol−1, respectively, for the same sequence. Both Gibbs energy values were negative. Adsorption processes were accompanied by an
increase in entropy. These interactions were studied by FTIR spectroscopy which showed a strengthening of the CN stretching
(dislocated shifts from 1,325 to 1,371 cm−1) related to a weakening of the NH stretch caused by the interaction with drugs. 相似文献
243.
Filipe Ferreira da Silva Carolina Matias Diogo Almeida Gustavo García Oddur Ingólfsson Helga Dögg Flosadóttir Benedikt Ómarsson Sylwia Ptasinska Benjamin Puschnigg Paul Scheier Paulo Limão-Vieira Stephan Denifl 《Journal of the American Society for Mass Spectrometry》2013,24(11):1787-1797
We report gas phase studies on NCO– fragment formation from the nucleobases thymine and uracil and their N-site methylated derivatives upon dissociative electron attachment (DEA) and through electron transfer in potassium collisions. For comparison, the NCO– production in metastable decay of the nucleobases after deprotonation in matrix assisted laser desorption/ionization (MALDI) is also reported. We show that the delayed fragmentation of the dehydrogenated closed-shell anion into NCO– upon DEA proceeds few microseconds after the electron attachment process, indicating a rather slow unimolecular decomposition. Utilizing partially methylated thymine, we demonstrate that the remarkable site selectivity of the initial hydrogen loss as a function of the electron energy is preserved in the prompt as well as the metastable NCO– formation in DEA. Site selectivity in the NCO– yield is also pronounced after deprotonation in MALDI, though distinctly different from that observed in DEA. This is discussed in terms of the different electronic states subjected to metastable decay in these experiments. In potassium collisions with 1- and 3-methylthymine and 1- and 3-methyluracil, the dominant fragment is the NCO– ion and the branching ratios as a function of the collision energy show evidence of extraordinary site-selectivity in the reactions yielding its formation. Graphical abstract
? 相似文献
244.
Johannes Postler Marcelo M. Goulart Carolina Matias Andreas Mauracher Filipe Ferreira da Silva Paul Scheier Paulo Limão-Vieira Stephan Denifl 《Journal of the American Society for Mass Spectrometry》2013,24(5):744-752
In the present study, dissociative electron attachment (DEA) measurements with gas phase HMX, octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine, C4H8N8O8, have been performed by means of a crossed electron-molecular beam experiment. The most intense signals are observed at 46 and 176 u and assigned to NO2 ? and C3H6N5O4 ?, respectively. Anion efficiency curves for 15 negatively charged fragments have been measured in the electron energy region from about 0–20 eV with an energy resolution of ~0.7 eV. Product anions are observed mainly in the low energy region, near 0 eV, arising from surprisingly complex reactions associated with multiple bond cleavages and structural and electronic rearrangement. The remarkable instability of HMX towards electron attachment with virtually zero kinetic energy reflects the highly explosive nature of this compound. Substantially different intensity ratios of resonances for common fragment anions allow distinguishing the nitroamines HMX and royal demolition explosive molecule (RDX) in negative ion mass spectrometry based on free electron capture. 相似文献
245.
Peter Gaal Daniel Schick Marc Herzog André Bojahr Roman Shayduk Jevgeni Goldshteyn Wolfram Leitenberger Ionela Vrejoiu Dmitry Khakhulin Michael Wulff Matias Bargheer 《Journal of synchrotron radiation》2014,21(2):380-385
A new concept for shortening hard X‐ray pulses emitted from a third‐generation synchrotron source down to few picoseconds is presented. The device, called the PicoSwitch, exploits the dynamics of coherent acoustic phonons in a photo‐excited thin film. A characterization of the structure demonstrates switching times of ≤ 5 ps and a peak reflectivity of ~10?3. The device is tested in a real synchrotron‐based pump–probe experiment and reveals features of coherent phonon propagation in a second thin film sample, thus demonstrating the potential to significantly improve the temporal resolution at existing synchrotron facilities. 相似文献
246.
Esther CR Jasin HM Collins LB Swenberg JA Boysen G 《Rapid communications in mass spectrometry : RCM》2008,22(5):701-705
Exhaled breath condensate (EBC) collection is a simple and non-invasive method to sample airway secretions, but analysis is limited by extensive and variable dilution of airway secretions within the condensate. To overcome this limitation, we developed a sensitive and specific liquid chromatography/tandem mass spectrometry (LC/MS/MS) method to simultaneously detect adenyl purines as biomarkers of inflammation and urea as a dilution marker in EBC. Separation prior to mass spectrometry was achieved using a C18 column with methanol and formic acid as the mobile phase, and characteristic precursor to product ion transitions of m/z 268 to 136 (for adenosine), m/z 348 to 136 (for AMP), and m/z 61 to 44 (for urea) were monitored for quantification. To correct for matrix effects, isotopically labeled adenosine, AMP, and urea were used as internal standards. Using these methods, we detected urea and the adenyl purines adenosine and AMP in EBC from seven subjects with cystic fibrosis (CF) and seven healthy controls and found that the AMP/urea ratio was elevated in the CF samples. These results demonstrate that mass spectrometry can be used successfully in EBC analysis to simultaneously detect a biomarker for airway inflammation and control for variable dilution. 相似文献
247.
Jinhee Chun Matias Korman Martin Nöllenburg Takeshi Tokuyama 《Discrete and Computational Geometry》2009,42(3):359-378
Given a fixed origin o in the d-dimensional grid, we give a novel definition of digital rays dig(op) from o to each grid point p. Each digital ray dig(op) approximates the Euclidean line segment \(\overline {op}\) between o and p. The set of all digital rays satisfies a set of axioms analogous to the Euclidean axioms. We measure the approximation quality by the maximum Hausdorff distance between a digital ray and its Euclidean counterpart and establish an asymptotically tight Θ(log?n) bound in the n×n grid. The proof of the bound is based on discrepancy theory and a simple construction algorithm. Without a monotonicity property for digital rays the bound is improved to O(1). Digital rays enable us to define the family of digital star-shaped regions centered at o, which we use to design efficient algorithms for image processing problems. 相似文献
248.
249.
250.
Ana N. Nunes Alexandra Borges Ana A. Matias Maria Rosrio Bronze Joana Oliveira 《Molecules (Basel, Switzerland)》2022,27(2)
Anthocyanins are natural pigments displaying different attractive colors ranging from red, violet, to blue. These pigments present health benefits that increased their use in food, nutraceuticals, and the cosmetic industry. However, anthocyanins are mainly extracted through conventional methods that are time-consuming and involve the use of organic solvents. Moreover, the chemical diversity of the obtained complex extracts make the downstream purification step challenging. Therefore, the growing demand of these high-value pigments has stimulated the interest in designing new, safe, cost-effective, and tunable strategies for their extraction and purification. The current review focuses on the potential application of compressed fluid-based (such as subcritical and supercritical fluid extraction and pressurized liquid extraction) and deep eutectic solvents-based extraction methods for the recovery of anthocyanins. In addition, an updated review of the application of counter-current chromatography for anthocyanins purification is provided as a faster and cost-effective alternative to preparative-scale HPLC. 相似文献