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111.
Molina I. Yu. Plyasova L. M. Nizovski A. I. Gavrilov A. N. Kustova G. N. Rudina N. A. 《Crystallography Reports》2006,51(1):S130-S138
The structure of oxotungstate films (as-deposited and subjected to heat treatment at temperatures of up to 600°C) prepared through electrodeposition on platinum and gold polycrystalline substrates is investigated using different physicochemical methods. It is shown that the oxotungstate films consist of X-ray amorphous hydrated mixtures of isopoly compounds, predominantly in the form of paratungstates with [H2W12O42]10− anions. The structural transformation with an increase in the temperature in air is accompanied by the loss of water, the transformation of paratungstate anions into more oxidized forms, their destruction, and the crystallization of nonstoichiometric hydroxylated oxide phases.
相似文献112.
Jorge J. Betancor Claudio Jerez Sandra M. Molina Lourdes Rodríguez-Mesa 《Monatshefte für Mathematik》2008,153(2):89-103
In this paper we study the Hankel transformation and convolution on certain spaces
of entire functions and its dual
that is a space of hyperfunctions and contains the (even)-Schwartz space S
e
′. We prove that the Hankel transform is an automorphism of
. Also the Hankel convolutors of
are investigated.
Authors’ addresses: Jorge J. Betancor, Claudio Jerez and Lourdes Rodríguez-Mesa, Departamento de Análisis Matemático, Universidad
de la Laguna, Campus de Anchieta, Avda. Astrofísico Francisco Sánchez, s/n, 38271 La Laguna (Sta. Cruz de Tenerife), Espa?a;
Sandra M. Molina, Departamento de Matemáticas, Facultad de Ciencias Exactas y Naturales, Universidad Nacional de Mar del Plata,
Funes 3350 (7600), Mar del Plata, Argentina 相似文献
113.
O. V. Cherstiouk A. N. Gavrilov L. M. Plyasova I. Yu. Molina G. A. Tsirlina E. R. Savinova 《Journal of Solid State Electrochemistry》2008,12(5):497-509
Structural defects play major role in catalysis and electrocatalysis. Nanocrystalline (or nanostructured) materials composed
of nanometer-sized crystallites joined via grain boundaries have been recognized for their specific structure and properties,
differentiating them from single crystals, coarsely grained materials or nanometer-sized supported single-grained particles
(Gleiter, Nanostruct Mater 1:1–19, 1992). In this paper, we use Pt electrodes, prepared by electrodeposition on glassy carbon and gold supports, as model nanocrystalline
materials to explore the influence of grain boundaries and other structural defects on electrocatalysis of CO and methanol
oxidation. We build on the recently established correlations between the nanostructure (lattice parameter, grain size, and
microstrains) of electrodeposited Pt and the deposition potential (Plyasova et al., Electrochim. Acta 51:4447–4488, 2006) and use the latter to obtain materials with variable density of grain boundary regions. The activity of electrodeposited
Pt in the oxidation of methanol and adsorbed CO exceeds greatly that for Pt(111), polycrystalline Pt, or single-grained Pt
particles. It is proposed that active sites in nanostructured Pt are located at the emergence of grain boundaries at the surface.
For methanol electrooxidation, the electrodes with optimal nanostructure exhibit relatively high rates of the “direct” oxidation
pathway and of the oxidation of strongly adsorbed poisoning intermediate (COads), but not-too-high methanol dehydrogenation rate constant. These electrodes exhibit an initial current increase during potentiostatic
methanol oxidation explained by the COads oxidation rate constant exceeding the methanol decomposition rate constant.
相似文献
E. R. SavinovaEmail: |
114.
An experimental study of the dependence of the OH uptake coefficient gamma OH over a relative humidity of 0-48% was carried out at 100 Torr and room temperature, using a differential bead-filled flow tube coupled to a high-pressure chemical ionization mass spectrometer. Various organic (paraffin wax, pyrene, glutaric acid, and soot) and inorganic (NaCl, KCl, MgCl2, CaCl2, Na2SO4, and sea salt) surfaces served as proxies for tropospheric aerosols. A virtual cylindrical flow tube approximation and a surface coating dilution technique were successfully employed in the study, which included measurements of high radical uptake with an initial probability of near unity. For inorganic salts, the effect of water vapor, enhancement or inhibition of gamma OH, was found to be dependent on the blocking of anions and changes in surface pH. Although OH uptake by NaCl, the major component of sea-salt aerosols, is weakly dependent on water vapor, it is enhanced by a factor of approximately 2 for MgCl2 and determines the net relative humidity dependence of the radical uptake on sea salt, which is enhanced by a factor of approximately 4. For the organic surfaces studied, the enhancement effect of a factor 4 was also observed only for a hydrophilic organic surface, namely, glutaric acid. Results of the uptake studies suggest that the effect of relative humidity is important and should be accounted for in atmospheric modeling of tropospheric aerosol chemistry. 相似文献
115.
Adrián de Miguel-Jiménez Bastian Ebeling Julieta I. Paez Claudia Fink-Straube Samuel Pearson Aránzazu del Campo 《Macromolecular bioscience》2023,23(2):2200419
Hydrogel precursors that crosslink within minutes are essential for the development of cell encapsulation matrices and their implementation in automated systems. Such timescales allow sufficient mixing of cells and hydrogel precursors under low shear forces and the achievement of homogeneous networks and cell distributions in the 3D cell culture. The previous work showed that the thiol-tetrazole methylsulfone (TzMS) reaction crosslinks star-poly(ethylene glycol) (PEG) hydrogels within minutes at around physiological pH and can be accelerated or slowed down with small pH changes. The resulting hydrogels are cytocompatible and stable in cell culture conditions. Here, the gelation kinetics and mechanical properties of PEG-based hydrogels formed by thiol-TzMS crosslinking as a function of buffer, crosslinker structure and degree of TzMS functionality are reported. Crosslinkers of different architecture, length and chemical nature (PEG versus peptide) are tested, and degree of TzMS functionality is modified by inclusion of RGD cell-adhesive ligand, all at concentration ranges typically used in cell culture. These studies corroborate that thiol/PEG-4TzMS hydrogels show gelation times and stiffnesses that are suitable for 3D cell encapsulation and tunable through changes in hydrogel composition. The results of this study guide formulation of encapsulating hydrogels for manual and automated 3D cell culture. 相似文献
116.
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
117.
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
$$ r \, = \{ K_{1} k_{2} /(1 \, + \, K_{1} {\text{H}}_{ 2} )\} [{\text{Rh}}][{\text{H}}_{ 2} ]^{2} $$
$$ r \, = \, K_{1} k_{2} [{\text{Rh}}][{\text{H}}_{ 2} ]^{2} $$
118.
Cover Picture: Radiation Damage and Racemic Protein Crystallography Reveal the Unique Structure of the GASA/Snakin Protein Superfamily (Angew. Chem. Int. Ed. 28/2016) 下载免费PDF全文
119.
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
120.
Ivanov AV Trakhtenberg S Bertram AK Gershenzon YM Molina MJ 《The journal of physical chemistry. A》2007,111(9):1632-1637
The diffusion of OH, HO2, and O3 in He, and of OH in air, has been investigated using a coated-wall flow tube reactor coupled to a chemical ionization mass spectrometry. The diffusion coefficients were determined from measurements of the loss of the reactive species to the flow tube wall as a function of pressure. On the basis of the experimental results, D(OH-He) = 662 +/- 33 Torr cm2 s-1, D(OH-air) = 165 +/- 20 Torr cm2 s-1, D(HO2-He) = 430 +/- 30 Torr cm2 s-1, and D(O3-He) = 410 +/- 25 Torr cm2 s-1 at 296 K. We show that the measured values for OH and HO2 are in better agreement with measured values of their polar analogues (H2O and H2O2) compared with measured values of their nonpolar analogues (O and O2). The measured value for OH in air is 25% smaller than that for O (the nonpolar analogue). The difference between the measured value for HO2 and O2 (the nonpolar analogue) in air is expected to be even larger. Also we show that calculations of the diffusion coefficients based on Lennard-Jones potentials are in excellent agreement with the measurements. This gives further confidence that these calculations can be used to estimate accurate diffusion coefficients for conditions where laboratory data currently do not exist. 相似文献