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21.
Shaoping Fu David Arráez‐Román Javier A. Menéndez Antonio Segura‐Carretero Alberto Fernández‐Gutiérrez 《Rapid communications in mass spectrometry : RCM》2009,23(1):51-59
In this work, rapid‐resolution liquid chromatography (RRLC) coupled to electrospray ionization time‐of‐flight mass spectrometry (ESI‐TOF‐MS) and ion trap multiple mass spectrometry (IT‐MSn) has been applied to separate and characterize eleven isomers of oleuropein aglycon in fourteen Spanish extra‐virgin olive oils. After the extra‐virgin olive oil sample had been dissolved in hexane and cleaned up by a diol‐bonded phase solid‐phase extraction (SPE) cartridge, the eluting extract was resolved in methanol and analyzed on an Angilent 1200 system with a 4.6 × 150 mm, 1.8 µm Zorbax Eclipse plus C18 column. Mass spectrometry was carried out on a Bruker Daltonics microTOF mass spectrometer and a Bruker Daltonics ion trap mass spectrometer. The characterization of isomers of oleuropein aglycon was based on accurate mass data and the isotope function of characteristic fragment ions in the studied compounds by TOF‐MS, and the fragment ions were further confirmed by IT‐MSn. The fragmentation pathway of oleuropein aglycon was successfully elucidated and all possible transformations among isomers of oleuropein aglycon were suggested. Copyright © 2008 John Wiley & Sons, Ltd. 相似文献
22.
Giovanni Dinelli Antonio Segura Carretero Raffaella Di Silvestro Ilaria Marotti Shaoping Fu Stefano Benedettelli Lisetta Ghiselli Alberto Fernández Gutiérrez 《Journal of chromatography. A》2009,1216(43):7229-7240
An evaluation of the grain functional components of Italian durum wheat cultivars was conducted. The raw material was obtained from the field trial performed in 2006–2007 at the Experimental Farm of the University of Bologna, (Bologna, Italy). The aim of this study was to define the phytochemical profile of ten varieties, comprised of old and modern durum wheat genotypes, including quantitative and qualitative phenolic and flavonoid content (free and bound forms). The results showed that mean values of total phenolic compound and total flavonoid content in old wheat varieties (878.2 ± 19.0 μmol gallic acid equivalent/100 g of grain and 122.6 ± 25.4 μmol catechin equivalent/100 g of grain, respectively) did not differ significantly from those detected in modern genotypes (865.9 ± 128.9 μmol gallic acid equivalent/100 g and 123.5 ± 20.6 μmol catechin equivalent/100 g, respectively). However, the HPLC–ESI-TOF-MS analysis highlighted remarkable differences between modern and old cultivars. The interpretation of the mass spectra allowed the identification of 70 phenolic compounds, including coumarins, phenolic acids, anthocyanins, flavones, isoflavones, proanthocyanidins, stilbenes and lignans. The free extracts of ancient wheat varieties showed the presence of a mean number of phenolic compounds and isomer forms (8.7 ± 2.5 and 7.7 ± 4.7 respectively) significantly higher than in modern genotypes (4.4 ± 2.9 and 2.0 ± 2.4, respectively). A similar trend was observed also for the bound phenolic fraction. Moreover, the phytochemical profiles showed the presence of unique phenolic compounds in both free and bound fractions of some of the investigated wheat genotypes. Results highlighted that investigated old wheat cultivars may offer unique nutraceutical values for their peculiar contents in bioactive phytochemicals, suggesting their uses into a wide range of regular and specialty products naturally enriched with health-promoting compounds. 相似文献
23.
Rocío García‐Villalba Alegría Carrasco‐Pancorbo Gabriela Zurek Marina Behrens Carsten Bäßmann Antonio Segura‐Carretero Alberto Fernández‐Gutiérrez 《Journal of separation science》2010,33(14):2069-2078
The applicability of nanoLC‐ESI‐TOF MS for the analysis of phenolic compounds in olive oil was studied and compared with a HPLC method. After the injection, the compounds were focused on a short capillary trapping column (100 μm id, effective length 20 mm, 5 μm particle size) and then nanoLC analysis was carried out in a fused silica capillary column (75 μm id, effective length 10 μm, 3 μm particle size) packed with C18 stationary phase. The mobile phase was a mixture of water + 0.5% acetic acid and ACN eluting at 300 nL/min in a gradient mode. Phenolic compounds from different families were identified and quantified. The quality parameters of the nanoLC method (linearity, LODs and LOQs, repeatability) were evaluated and compared with those obtained with HPLC. The new methodology presents better sensitivity (reaching LOD values below 1 ppb) with less consumption of mobile phases, but worse repeatability, especially inter‐day repeatability, resulting in more difficulties to get highly accurate quantification. The results described in this article open up the application fields of this technique to cover a larger variety of compounds and its advantages will make it especially useful for the analysis of samples containing low concentration of phenolic compounds, as for instance, in biological samples. 相似文献
24.
25.
The phonon spectrum of the high-pressure simple cubic phase of calcium, in the harmonic approximation, shows imaginary branches that make it mechanically unstable. In this Letter, the phonon spectrum is recalculated by using density-functional theory ab initio methods fully including anharmonic effects up to fourth order at 50 GPa. Considering that the perturbation theory cannot be employed with imaginary harmonic frequencies, a variational procedure based on the Gibbs-Bogoliubov inequality is used to estimate the renormalized phonon frequencies. The results show that strong quantum anharmonic effects make the imaginary phonons become positive even at zero temperature so that the simple cubic phase becomes mechanically stable, as experiments suggest. Moreover, our calculations find a superconducting T(c) in agreement with experiments and predict an anomalous behavior of the specific heat. 相似文献
26.
27.
A segregated method for compressible flow computation. Part II: general divariant compressible flows
Typically, segregated methods have been used for the computation of incompressible flows whereas coupled solvers, for compressible flows. Compared to coupled solvers, segregated methods present the advantage of computational savings in RAM memory and CPU time, although at the cost of an inferior robustness. However, previously published segregated algorithms for general compressible flows are known to present pitfalls, like convergence to wrong solutions, lack of robustness in the presence of strong discontinuities, such as normal and oblique shocks, and complicated boundary condition imposition. Therefore, in this paper a segregated method for non‐isothermal compressible flows is proposed that preserves the thermodynamic coupling and overcomes the criticisms of existing methods. Copyright © 2005 John Wiley & Sons, Ltd. 相似文献
28.
S. Blaya L. Carretero R.F. Madrigal A. Fimia 《Applied physics. B, Lasers and optics》2002,74(3):243-251
We describe a study of the free-radical homopolymerization kinetics for a system based on acrylamide, triethanolamine and
methylene blue by analyzing temporal variations of the diffraction efficiency. The modulation index is related to the component’s
parameters, giving as a result a method that can be used to determine the chain length of the polymer and the kinetic rate
constants. By using this method we have studied the effect of intensity on the kinetic parameters of the photopolymerization
process.
Received: 20 August 2001 / Published online: 7 February 2002 相似文献
29.
A. Murciano S. Blaya L. Carretero M. Ulibarrena A. Fimia 《Applied physics. B, Lasers and optics》2005,81(2-3):167-169
In this paper, we present a photopolymerizable material in a sol-gel matrix suitable for recording a large number of multiplexed diffraction gratings with low total exposure energy. The matrix of this material is an inorganic porous silica glass, a material that does not shrink when radical photopolymerization is initiated. The photosensitive component is based on acrylamide, N,N′-methylenebisacrylamide, triethanolamine and yellow eosine as a photoinitiator. In the reported study, 50 holograms were angularly multiplexed with diffraction efficiencies between 0.1 and 1.9% resulting in a dynamic range of M/# = 3.9. The total exposure was 4.5 mJ/cm2 and the energy used in recording each hologram was 95 μJ/cm2. This indicates a very high sensitivity for this material in the range of 3.3 to 15.5 cm/mJ. Due to this good holographic performance, the material is suitable for holographic data storage applications. 相似文献
30.
Catalytic Enantioselective Synthesis of N,Cα,Cα‐Trisubstituted α‐Amino Acid Derivatives Using 1H‐Imidazol‐4(5H)‐ones as Key Templates
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Julen Etxabe Joseba Izquierdo Dr. Aitor Landa Prof. Mikel Oiarbide Prof. Claudio Palomo 《Angewandte Chemie (International ed. in English)》2015,54(23):6883-6886
1H‐Imidazol‐4(5H)‐ones are introduced as novel nucleophilic α‐amino acid equivalents in asymmetric synthesis. These compounds not only allow highly efficient construction of tetrasubstituted stereogenic centers, but unlike hitherto known templates, provide direct access to N‐substituted (alkyl, allyl, aryl) α‐amino acid derivatives. 相似文献