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51.
In this paper, the conversion of azoxystrobin in a strongly fluorescent degradation product by UV irradiation with quantitative purposes and its fluorimetric determination are reported for the first time. A multicommuted flow injection-solid phase spectroscopy (FI-SPS) system combined with photochemically-induced fluorescence (PIF) is developed for the determination of azoxystrobin in grapes, must and wine. Grape samples were homogenized and extracted with methanol and further cleaned-up by solid-phase extraction on C18 silica gel. Wine samples were solid-phase extracted on C18 sorbent using dichloromethane as eluent. Recoveries of azoxystrobin from spiked grapes (0.5-2.0 mg Kg−1), must (0.5-2.0 μg mL−1) and wine (0.5-2.0 μg mL−1) were 84.0-87.6%, 95.5-105.9% and 88.5-111.2%, respectively. The quantification limit for grapes was 0.021 mg Kg−1, being within European Union regulations, and 18 μg L−1 and 8 μg L−1 for must and wine, respectively. 相似文献
52.
Merlin Rosales Karely Molina Regina Vallejo Edgar Ocando-Mavárez 《Transition Metal Chemistry》2016,41(4):467-473
The complex Rh(acac)(CO)[P(tBu)(CH2CH=CH2)2] (1) proved to be an efficient precatalyst for the regioselective hydrogenation of quinoline (Q) to 1,2,3,4-tetrahydroquinoline (THQ) under mild reaction conditions (125 °C and 4 atm H2). A kinetic study of this reaction led to the rate law: which becomes at hydrogen pressures below 4 atm. The active catalytic species is the cationic complex {Rh(Q)2(CO)[P(tBu)(CH2CH=CH2)2]}+ (2). The mechanism involves the partial hydrogenation of one coordinated Q of (2) to yield a complex containing a 1,2-dihydroquinoline (DHQ) ligand, {Rh(DHQ)(Q)(CO)[P(tBu)(CH2CH=CH2)2]}+ (3), followed by hydrogenation of the DHQ ligand to give THQ and a coordinatively unsaturated species {Rh(Q)(CO)[P(tBu)(CH2CH=CH2)2]}+ (4); this reaction is considered to be the rate-determining step. Coordination of a new Q molecule to (4) regenerates the active species (2) and restarts the catalytic cycle.
相似文献
$$ r \, = \{ K_{1} k_{2} /(1 \, + \, K_{1} {\text{H}}_{ 2} )\} [{\text{Rh}}][{\text{H}}_{ 2} ]^{2} $$
$$ r \, = \, K_{1} k_{2} [{\text{Rh}}][{\text{H}}_{ 2} ]^{2} $$
53.
Radiation Damage and Racemic Protein Crystallography Reveal the Unique Structure of the GASA/Snakin Protein Superfamily 下载免费PDF全文
Ho Yeung Dr. Christopher J. Squire Yuliana Yosaatmadja Dr. Santosh Panjikar Gemma López Prof. Dr. Antonio Molina Prof. Dr. Edward N. Baker Dr. Paul W. R. Harris Prof. Dr. Margaret A. Brimble 《Angewandte Chemie (International ed. in English)》2016,55(28):7930-7933
Proteins from the GASA/snakin superfamily are common in plant proteomes and have diverse functions, including hormonal crosstalk, development, and defense. One 63‐residue member of this family, snakin‐1, an antimicrobial protein from potatoes, has previously been chemically synthesized in a fully active form. Herein the 1.5 Å structure of snakin‐1, determined by a novel combination of racemic protein crystallization and radiation‐damage‐induced phasing (RIP), is reported. Racemic crystals of snakin‐1 and quasi‐racemic crystals incorporating an unnatural 4‐iodophenylalanine residue were prepared from chemically synthesized d ‐ and l ‐proteins. Breakage of the C?I bonds in the quasi‐racemic crystals facilitated structure determination by RIP. The crystal structure reveals a unique protein fold with six disulfide crosslinks, presenting a distinct electrostatic surface that may target the protein to microbial cell surfaces. 相似文献
54.
Caballero A Lloveras V Curiel D Tárraga A Espinosa A García R Vidal-Gancedo J Rovira C Wurst K Molina P Veciana J 《Inorganic chemistry》2007,46(3):825-838
The synthesis, optical and electrochemical properties, and X-ray characterization of two thiazole derivatives capped by ferrocenyl groups (5 and 7) and their model compounds with one ferrocenyl, either at 2 or 5 position of the mono- or bis-thiazolyl rings (3, 9, 11, and 14), are presented. Bisferrocenyl thiazole 5 forms the mixed-valence species 5*+ by partial oxidation which, interestingly, shows an intramolecular electron-transfer phenomenon. Moreover, the reported heteroaromatic compounds show selective ion-sensing properties. Thus, ferrocenylthiazoles linked across the 5 position of the heteroaromatic ring are selective chemosensors for Hg2+ and Pb2+ metal ions; 5-ferrocenylthiazole 3 operates through two channels, optical and redox, for Hg2+ and only optical for Pb2+, whereas 1,1'-bis(thiazolyl)ferrocene 14 is only an optical sensor for both metal ions. Moreover, complex 3 behaves as an electrochemically induced switchable chemosensor because of the low metal-ion affinity of the oxidized 3*+ species. On the other hand, ferrocenylthiazole 9, in which the heterocyclic ring and the ferrocene group are linked across the 2 position, is a selective redox sensor for Hg2+ metal ions, and it responds optically, as does bis(thiazolyl)ferrocene 11, to a narrow range of cations (Zn2+, Cd2+, Hg2+, Ni2+, and Pb2+). Finally, bis(ferrocenyl)thiazole 5 is a dual optical and redox sensor for Zn2+, Cd2+, Hg2+, Ni2+, and Pb2+, whereas bis(ferrocenyl) compound 7, bearing a bis(thiazole) unit as a bridge, is only a chromogenic sensor for Zn2+, Cd2+, Hg2+, Ni2+, and Pb2+. The experimental data and conclusions about both the electronic and ion-sensing properties are supported by DFT calculations which show, in addition, an unprecedented intramolecular electron-transfer reorganization after the first one-electron oxidation of compound 5. 相似文献
55.
56.
Colombo L González G Marshall G Molina FV Soba A Suarez C Turjanski P 《Bioelectrochemistry (Amsterdam, Netherlands)》2007,71(2):223-232
The electrochemical treatment of cancer (EChT) consists in the passage of a direct electric current through two or more electrodes inserted locally in the tumor tissue. The extreme pH changes induced have been proposed as the main tumor destruction mechanism. Here, we study ion transport during EChT through a combined modeling methodology: in vivo modeling with BALB/c mice bearing a subcutaneous tumor, in vitro modeling with agar and collagen gels, and in silico modeling using the one-dimensional Nernst-Planck and Poisson equations for ion transport in a four-ion electrolyte. This combined modeling approach reveals that, under EChT modeling, an initial condition with almost neutral pH evolves between electrodes into extreme cathodic alkaline and anodic acidic fronts moving towards each other, leaving the possible existence of a biological pH region between them; towards the periphery, the pH decays to its neutral values. pH front tracking unveils a time scaling close to t(1/2), signature of a diffusion-controlled process. These results could have significant implications in EChT optimal operative conditions and dose planning, in particular, in the way in which the evolving EChT pH region covers the active cancer cells spherical casket. 相似文献
57.
F. J. Molina A. O. Vila C. Llcer M. J. Martos J. E. Figueruelo 《Journal of separation science》1991,14(9):590-592
Internal calibration in modified hydrodynamic chromatography has been realized by the approach of Prieve and Hoysan, i.e. the use of polystyrene monodisperse latexes to evaluate the equivalent capillary radius, R. The value obtained has been used to estimate the average sizes of a variety of liposome samples from egg yolk lecithin. 相似文献
58.
59.
Kassandra Cendejas Hope E. Parker Dennis Molina Rajib Choudhury 《Journal of inclusion phenomena and macrocyclic chemistry》2017,89(1-2):199-205
In this study, we have examined supramolecular self-assembly process of a hydrophobic guest with a water-soluble host known by the trivial name octa acid (OA). Two octa acids form a capsular assembly only in presence of a nonpolar guest(s). Size and shape of the guest control the stoichiometry of the capsular complex. Here, all atom molecular dynamics simulation has been utilized to investigate complex formation mechanisms of a nonpolar guest (nonylbenzene) with two OA cavitands. Nonylbenzene was encapsulated into the nonpolar cavity of OA capsule owing to solvophobic interactions. Upon encapsulation it was twisted and bent due to lack of free space within the capsule. These unusual forms obtained from the simulation study were in accord with experimental findings. The post-complexation attributes of the guest were regulated by the available free space within the OA and favorable non-covalent interactions between the guest and the walls of the OA capsule. In the identical simulation condition two OA cavitands did not form a capsule without a guest, thus indicating requirement of a guest during the self-assembly of OA cavitands. 相似文献
60.
Ricardo Aguilar-Villalva Gustavo A. Molina Beatriz Liliana España-Sánchez Luis Fernando Díaz-Peña Alberto Elizalde-Mata Edgar Valerio Cristy Azanza-Ricardo Miriam Estevez 《Arabian Journal of Chemistry》2021,14(7):103239
In recent years, the food, pharmacy, and cosmetic industries have focused on the search of natural compounds with antimicrobial and antioxidant properties; commonly, these compounds are obtained from Kingdom plantae. The aim of the present work is comparing antibacterial and antioxidant capacity of Annona cherimola Mill leaves, using different extraction methods. The ultrasound assisted extraction technique (UAE) was compared with conventional techniques: Soxhlet and maceration. Water and ethanol were used as solvents for leaves extractions performed with these three methods. The main acetogenins reported in Annona cherimola Mill and Annona muricata L. species were simulated using the functional hybrid B3LYP and to confirm its presence, analysis of the compound composition was performed using FT-IR, UV–Vis and HPLC. Total phenolics (TP) and flavonoids (TF) were determined by spectroscopy techniques and novel Differential Pulse Voltammetry (DPV) electrochemical technique. Total Antioxidant Capacity (TAC) of the extracts was measured, using the DPPH, FRAP and CUPRAC techniques. The highest antioxidant content was found in the Soxhlet water extracts; even so, the UAE technique presented an attractive alternative due to considerable reduction in extraction time, which was greater than 99%, and possible selectivity in compounds extraction. Finally, antibacterial activity of the extracts was evaluated, obtaining the best results against gram-positive bacteria using UAE water extract. In this way, the UAE technique presents an excellent extraction option due to the considerable reduction in time and energy, as well as the increase in antibacterial activity. 相似文献