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71.
A new analytical methodology for the determination of fully methoxylated flavones (FMFs) in citrus juices is described. Isolation of the FMFs is carried out by percolation of 30 mL of clarified citrus juice (to which tetramethyl-o-kaempferol is previously added as internal standard) through a C18 Sep-Pak cartridge, washing with 3 mL of water followed by 5 mL of water/acetonitrile (3:1), and selective elution of the retained FMFs with 5 mL of water/acetonitrile (9:11). Determination of the isolated FMFs is carried out by reversed-phase high-performance liquid chromatography (HPLC) and UV diode array detection (DAD). Signals at wavelengths 320, 335, and 345 nm (bandwidth 4 nm) are simultaneously acquired, stored, plotted, and integrated. The column used is a microbore (200 x 2.1-mm) Hypersil ODS 5 microns. Elution is in gradient mode, using a ternary mobile phase (water/acetonitrile/tetrahydrofuran). Column temperature is 40 degrees C. Recovery yields are nearly 100% for all the FMFs detected and identified: isosinensetin, hexamethyl-o-gossypetin, sinensetin, tetramethyl-o-isoscutellarein, hexamethyl-o-quercetagetin, nobiletin, tetramethyl-o-scutellarein, heptamethoxyflavone, and tangeretin. Chromatographic separation of the FMFs is extremely dependent upon the minor changes of the mobile phase composition and percentages, gradient rate, and temperature. The UV spectra (230 to 400 nm) of the FMFs obtained under chromatographic conditions are given. The FMFs relative response factors at 320, 335, and 345 nm and their concentrations in hand-squeezed and commercial concentrated orange and mandarin juices are tabulated. The FMF concentration differences found among samples are discussed. 相似文献
72.
Izquierdo S Kogan MJ Parella T Moglioni AG Branchadell V Giralt E Ortuño RM 《The Journal of organic chemistry》2004,69(15):5093-5099
The efficient synthesis of tetrapeptide 5 containing, in alternation, cyclobutane and beta-alanine residues is described. NMR experiments both at low temperature in CDCl(3) and at 298 K in DMSO-d(6) solutions show the contribution of a strong hydrogen bond in the folded major conformation of 5. Temperature coefficients and diffusion times point out a hydrogen bond involving the NH proton from the cyclobutane residue 1 whereas NOEs manifest the high rigidity of the central fragment of the molecule and are compatible with a 14-membered macrocycle. Theoretical calculations predict a most stable folded conformation corresponding to a 14-helix stabilized by a hydrogen bond between NH(10) in the first residue and OC(25) in the third residue. This structure remains unaltered during the molecular dynamics simulation at 298 K in chloroform. All these results provide evidence for a 14-helical folding and reveal the ability of cis-2-aminocyclobutane carboxylic acid residues to promote folded conformations when incorporated into beta-peptides. 相似文献
73.
Roberto Salcedo Ana Martínez L. Enrique Sansores Laura Gasque Isidoro García-Cruz 《Journal of Molecular Structure》2005,732(1-3):113-118
Cyclooctatetraene's (COT) behaviour in some of its Ni and Ru complexes is studied by means of DFT methods (B3LYP and BLYP). The experimentally observed COT fragment conformational changes (tub-shaped or planar) are analysed, together with the different locations of metal–carbon bonds in the complexes. These phenomena are studied using both static and molecular dynamics calculations. The results allow us to predict changes in the COT fragment, which goes from aromatic to totally antiaromatic, depending on its environment. This situation favours the electronic flow through the metal atoms into the organometallic molecules, giving place to different geometries that generate the dynamic fluxional behaviour. 相似文献
74.
Isidoro Izquierdo María T. Plaza Miguel Rodríguez Francisco Franco Alicia Martos 《Tetrahedron》2005,61(49):11697-11704
The readily available 3-O-benzoyl-4-O-benzyl-1,2-O-isopropylidene-β-d-fructopyranose (6) was straightforwardly transformed into 5-azido-3-O-benzoyl-4-O-benzyl-5-deoxy-1,2-O-isopropylidene-β-d-fructopyranose (8), after treatment under modified Garegg's conditions followed by reaction of the resulting 3-O-benzoyl-4-O-benzyl-5-deoxy-5-iodo-1,2-O-isopropylidene-α-l-sorbopyranose (7) with lithium azide in DMF. O-debenzoylation at C(3) in 8, followed by oxidation and reduction caused the inversion of the configuration to afford the corresponding β-d-psicopyranose derivative 11 that was transformed into the related 3,4-di-O-benzyl derivative 12. Cleavage of the acetonide of 12 to give 13 followed by O-tert-butyldiphenylsilylation afforded a resolvable mixture of 14 and 15. Compound 14 was transformed into (2R,3R,4S,5R)- (17) and (2R,3R,4S,5S)-3,4-dibenzyloxy-2′,5′-di-O-tert-butyldiphenylsilyl-2,5-bis(hydroxymethyl)pyrrolidine (18) either by a tandem Staudinger/intramolecular aza-Wittig process and reduction of the resulting intermediate Δ2-pyrroline (16), or only into 18 by a high stereoselective catalytic hydrogenation. When 15 was subjected to the same protocol, (2S,3S,4R,5R)- (21) and (2R,3S,4R,5R)-3,4-dibenzyloxy-2′-O-tert-butyldiphenylsilyl-2,5-bis(hydroxymethyl)pyrrolidine (22) were obtained, respectively. 相似文献
75.
A. Alonso Izquierdo M.A. Gonzalez Leon M. de la Torre Mayado J. Mateos Guilarte 《Physica D: Nonlinear Phenomena》2005,200(3-4):220-241
We discuss the solitary wave solutions of a particular two-component scalar field model in two-dimensional Minkowski space. These solitary waves involve one, two or four lumps of energy. The adiabatic motion of these composite nonlinear non-dispersive waves points to variations in shape. 相似文献
76.
Manuel Herrera Joaquín Izquierdo Idel Montalvo Juan García-Armengol Jos V. Roig 《Mathematical and Computer Modelling》2009,50(5-6):705
Modern data analysis and machine learning are strongly dependent on efficient search techniques. However, in general, further exploration into high-dimensional and multi-modal spaces is needed, and moreover, many real-world problems exhibit inaccurate, noisy, discrete and complex data. Thus, robust methods of optimization are often required to generate results suitable for these data. Some algorithms that imitate certain natural principles, namely the so-called evolutionary algorithms, have been used in different fields with great success. In this paper, we apply a variant of Particle Swarm Optimization (PSO), recently introduced by the authors, to partitional clustering of a real-world data set to distinguish between perioperative practices and associate them with some unknown relevant facts. Our data were obtained from a survey conducted in Spain based on a pool of colorectal surgeons. The PSO derivative we consider here: (i) is adapted to consider mixed discrete-continuous optimization, with statistical clustering criteria arranged to take these types of mixed measures; (ii) is able to find optimum or near-optimum solutions much more efficiently and with considerably less computational effort because of the richer population diversity it introduces; and (iii) is able to select the right parameter values through self-adaptive dynamic parameter control, thus overcoming the cumbersome aspect common to all metaheuristics. 相似文献
77.
The distribution equilibria of the zinc complex with 5,7-dichloro-2-methyl-8-hydroxyquinoline in the water-chloroform system have been studied at 25 degrees . The influence of pH, reagent and metal concentrations, and the presence of sodium perchlorate in the aqueous phase has been determined. From quantitative evaluation of the extraction equilibrium data, it has been deduced that the complex extracted is the simple 1:2 chelate, ZnR(2), although at ligand concentrations higher than 0.3M, the self-adduct complex seems to begin to form. The extraction constant of the ZnR(2) species, refined by means of the program Letagrop-Distribution, has the value log K(ex) = - 6.15 +/- 0.07. 相似文献
78.
79.
A. Alonso Izquierdo J. Mateos Guilarte 《The European Physical Journal C - Particles and Fields》2012,72(10):1-16
In this paper we propose a refinement of the heat-kernel/zeta function treatment of kink quantum fluctuations in scalar field theory, further analyzing the existence and implications of a zero-energy fluctuation mode. Improved understanding of the interplay between zero modes and the kink heat-kernel expansion delivers asymptotic estimations of one-loop kink mass shifts with remarkably higher precision than previously obtained by means of the standard Gilkey–DeWitt heat-kernel expansion. 相似文献
80.
Patrick P. Brisebois Dr. Christian Kuss Dr. Steen B. Schougaard Dr. Ricardo Izquierdo Prof. Mohamed Siaj 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(17):5849-5852
Graphene oxide is regarded as a major precursor for graphene‐based materials. The development of graphene oxide based derivatives with new functionalities requires a thorough understanding of its chemical reactivity, especially for canonical synthetic methods such as the Diels–Alder cycloaddition. The Diels–Alder reaction has been successfully extended with graphene oxide as a source of diene by using maleic anhydride as a dienophile, thereby outlining the presence of the cis diene present in the graphene oxide framework. This reaction provides fundamental information for understanding the exact structure and chemical nature of graphene oxide. On the basis of high‐resolution 13C‐SS NMR spectra, we show evidence for the formation of new sp3 carbon centers covalently bonded to graphene oxide following hydrolysis of the reaction product. DFT calculations are also used to show that the presence of a cis dihydroxyl and C vacancy on the surface of graphene oxide are promoting the reaction with significant negative reaction enthalpies. 相似文献