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1.
CM Silva MF Duarte ML Mira MH Florêncio K Versluis AJ Heck 《Rapid communications in mass spectrometry : RCM》1999,13(12):1098-1103
Fast atom bombardment, combined with high-energy collision-induced tandem mass spectrometry, has been used to investigate gas-phase metal-ion interactions with captopril, enalaprilat and lisinopril, all angiotensin-converting enzyme inhibitors.Suggestions for the location of metal-binding sites are presented. For captopril, metal binding occurs most likely at both the sulphur and the nitrogen atom. For enalaprilat and lisinopril, binding preferably occurs at the amine nitrogen. Copyright 1999 John Wiley & Sons, Ltd. 相似文献
2.
Zhang Z Fenter P Cheng L Sturchio NC Bedzyk MJ Predota M Bandura A Kubicki JD Lvov SN Cummings PT Chialvo AA Ridley MK Bénézeth P Anovitz L Palmer DA Machesky ML Wesolowski DJ 《Langmuir : the ACS journal of surfaces and colloids》2004,20(12):4954-4969
A comprehensive picture of the interface between aqueous solutions and the (110) surface of rutile (alpha-TiO2) is being developed by combining molecular-scale and macroscopic approaches, including experimental measurements, quantum calculations, molecular simulations, and Gouy-Chapman-Stern models. In situ X-ray reflectivity and X-ray standing-wave measurements are used to define the atomic arrangement of adsorbed ions, the coordination of interfacial water molecules, and substrate surface termination and structure. Ab initio calculations and molecular dynamics simulations, validated through direct comparison with the X-ray results, are used to predict ion distributions not measured experimentally. Potentiometric titration and ion adsorption results for rutile powders having predominant (110) surface expression provide macroscopic constraints of electrical double layer (EDL) properties (e.g., proton release) which are evaluated by comparison with a three-layer EDL model including surface oxygen proton affinities calculated using ab initio bond lengths and partial charges. These results allow a direct correlation of the three-dimensional, crystallographically controlled arrangements of various species (H2O, Na+, Rb+, Ca2+, Sr2+, Zn2+, Y3+, Nd3+) with macroscopic observables (H+ release, metal uptake, zeta potential) and thermodynamic/electrostatic constraints. All cations are found to be adsorbed as "inner sphere" species bonded directly to surface oxygen atoms, while the specific binding geometries and reaction stoichiometries are dependent on ionic radius. Ternary surface complexes of sorbed cations with electrolyte anions are not observed. Finally, surface oxygen proton affinities computed using the MUSIC model are improved by incorporation of ab initio bond lengths and hydrogen bonding information derived from MD simulations. This multitechnique and multiscale approach demonstrates the compatibility of bond-valence models of surface oxygen proton affinities and Stern-based models of the EDL structure, with the actual molecular interfacial distributions observed experimentally, revealing new insight into EDL properties including specific binding sites and hydration states of sorbed ions, interfacial solvent properties (structure, diffusivity, dielectric constant), surface protonation and hydrolysis, and the effect of solution ionic strength. 相似文献
3.
Zhang Z Fenter P Cheng L Sturchio NC Bedzyk MJ Machesky ML Anovitz LM Wesolowski DJ 《Journal of colloid and interface science》2006,295(1):50-64
The X-ray standing wave technique was used to probe the sensitivity of Zn2+ and Sr2+ ion adsorption to changes in both the adsorbed ion coverage and the background electrolyte species and concentrations at the rutile (alpha-TiO2) (110)-aqueous interface. Measurements were made with various background electrolytes (NaCl, NaTr, RbCl, NaBr) at concentrations as high as 1 m. The results demonstrate that Zn2+ and Sr2+ reside primarily in the condensed layer and that the ion heights above the Ti-O surface plane are insensitive to ionic strength and the choice of background electrolyte (with <0.1 A changes over the full compositional range). The lack of any specific anion coadsorption upon probing with Br-, coupled with the insensitivity of Zn2+ and Sr2+ cation heights to changes in the background electrolyte, implies that anions do not play a significant role in the adsorption of these divalent metal ions to the rutile (110) surface. Absolute ion coverage measurements for Zn2+ and Sr2+ show a maximum Stern-layer coverage of approximately 0.5 monolayer, with no significant variation in height as a function of Stern-layer coverage. These observations are discussed in the context of Gouy-Chapman-Stern models of the electrical double layer developed from macroscopic sorption and pH-titration studies of rutile powder suspensions. Direct comparison between these experimental observations and the MUltiSIte Complexation (MUSIC) model predictions of cation surface coverage as a function of ionic strength revealed good agreement between measured and predicted surface coverages with no adjustable parameters. 相似文献
4.
Catarina IV Ramos Flávio Figueira Marcelo D Polêto Francisco ML Amado Hugo Verli João PC Tomé M Graça PMS Neves 《Journal of mass spectrometry : JMS》2016,51(5):342-349
Electrospray mass spectrometry/mass spectrometry was used to investigate the gas‐phase properties of protonated expanded porphyrins, in order to correlate those with their structure and conformation. We have selected five expanded meso‐pentafluorophenyl porphyrins, respectively, a pair of oxidized/reduced fused pentaphyrins (22 and 24 π electrons), a pair of oxidized/reduced regular hexaphyrins (26 and 28 π electrons) and a regular doubly N‐fused hexaphyrin (28 π electrons). The gas‐phase behavior of the protonated species of oxidized and reduced expanded porphyrins is different. The oxidized species (aromatic Hückel systems) fragment more extensively, mainly by the loss of two HF molecules. The reduced species (Möbius aromatic or Möbius‐like aromatic systems) fragment less than their oxidized counterparts because of their increased flexibility. The protonated regular doubly fused hexaphyrin (non‐aromatic Hückel system) shows the least fragmentation even at higher collision energies. In general, cyclization through losses of HF molecules decreases from the aromatic Hückel systems to Möbius aromatic or Möbius‐like aromatic systems to non‐aromatic Hückel systems and is related to an increase in conformational distortion. Copyright © 2016 John Wiley & Sons, Ltd. 相似文献
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6.
Ridley MK Hackley VA Machesky ML 《Langmuir : the ACS journal of surfaces and colloids》2006,22(26):10972-10982
The chemical and electrostatic interactions at mineral-water interfaces are of fundamental importance in many geochemical, materials science, and technological processes; however, the effects of particle size at the nanoscale on these interactions are poorly known. Therefore, comprehensive experimental and characterization studies were completed, to begin to assess the effects of particle size on the surface reactivity and charging of metal-oxide nanoparticles in aqueous solutions. Commercially available crystalline anatase (TiO2) particles were characterized using neutron and X-ray small-angle scattering, electron microscopy, and laser diffraction techniques. The 4 nm primary nanoparticles were found to exist almost exclusively in a hierarchy of agglomerated structures. Potentiometric and electrophoretic mobility titrations were completed in NaCl media at ionic strengths from (0.005 to 0.3) mol/kg, and 25 degrees C, with these two experimental techniques matched as closely as the different procedures permitted. The pH of zero net proton charge (pHznpc, from potentiometric titration) and isoelectric point pH value (pHiep, from electrophoretic mobility titrations) were both in near perfect agreement (6.85 +/- 0.02). At high ionic strengths the apparent pHznpc value was offset slightly toward lower pH values, which suggests some specific adsorption of the Na+ electrolyte ions. Proton-induced surface charge curves of nanocrystalline anatase were very similar to those of larger rutile crystallites when expressed relative to their respective pHznpc values, indicating that the development of positive and negative surface charge away from the pHznpc for nanocrystalline anatase is similar to that of larger TiO2 crystallites. 相似文献
7.
A Gurtu P K Malhotra I S Mittra P M Sood SC Gupta VK Gupta GL Kaul LK Mangotra Y Prakash NK Rao ML Sharma 《Pramana》1974,3(5):311-322
This is a continuation of our earlier investigation (Gurtuet al 1974Phys. Lett. 50 B 391) on multiparticle production in proton-nucleus collisions based on an exposure of emulsion stack to 200 GeV/c beam at the NAL. It is found that the ratioR em = 〈n s〉/〈n ch〉, where 〈n ch〉 is the charged particle multiplicity in pp-collisions, increases slowly from about 1 at 10 GeV/c to 1·6 at 68 GeV/c and attains a constant value of 1·71 ± 0·04 in the region 200 to 8000 GeV/c. Furthermore,R em = 1·71 implies an effectiveA-dependence ofR A =A 0.18,i.e., a very weak dependence. Predictions ofR em on various models are discussed and compared with the emulsion data. Data seem to favour models of hadron-nucleon collisions in which production of particles takes place through adouble step mechanism,e.g., diffractive excitation, hydrodynamical and energy flux cascade as opposed to models which envisage instantaneous production. 相似文献
8.
Michael L Machesky David J Wesolowski Donald A Palmer Ken Ichiro-Hayashi 《Journal of colloid and interface science》1998,200(2):298
A stirred hydrogen electrode concentration cell was used to conduct potentiometric titrations of rutile suspensions from 25 to 250°C in NaCl and tetramethylammonium chloride media (0.03 to 1.1m). Hydrothermal pretreatment of the rutile improved titration reproducibility, decreased titration hysteresis, and facilitated determination of the point of zero net proton charge (pHznpc). These pHznpc values are 5.4, 5.1, 4.7, 4.4, 4.3 (±0.2 pH units), and 4.2 (±0.3 pH units) at 25, 50, 100, 150, 200, and 250°C, respectively. The difference between these pHznpc values and pKw(the neutral pH of water) is rather constant between 25 and 250°C (−1.45 ± 0.2). This constancy is useful for predictive purposes and, more fundamentally, may reflect similarities between the hydration behavior of surface hydroxyl groups and water. A three-layer, 1pKa surface complexation model with three adjustable parameters (two capacitance values and one counterion binding constant) adequately described all titration data. The most apparent trend in these data for pH values greater than the pHznpc was the increase in proton release (negative surface charge) with increasing temperature. This reflects more efficient screening by Na+relative to Cl−. Replacing Na+with the larger tetramethylammonium cation for some conditions resulted in decreased proton release due to the less efficient screening of negative surface charge by this larger cation. 相似文献
9.
A Soibel SS Banerjee Y Myasoedov ML Rapparort E Zeldov S Ooi T Tamegai 《Pramana》2002,58(5-6):893-898
Using a novel differential magneto-optical imaging technique we investigate the phenomenon of vortex lattice melting in crystals
of Bi2Sr2CaCu2O8 (BSCCO). The images of melting reveal complex patterns in the formation and evolution of the vortex solid-liquid interface
with varying field (H)/temperature (T). We believe that the complex melting patterns are due to a random distribution of material disorder/inhomogeneities across
the sample, which create fluctuations in the local melting temperature or field value. To study the fluctuations in the local
melting temperature/field, we have constructed maps of the melting landscape T
m(H, r), viz., the melting temperature (T
m) at a given location (r) in the sample at a given field (H). A study of these melting landscapes reveals an unexpected feature: the melting landscape is not fixed, but changes rather
dramatically with varying field and temperature along the melting line. It is concluded that the changes in both the scale
and shape of the landscape result from the competing contributions of different types of quenched disorder which have opposite
effects on the local melting transition. 相似文献
10.
Aaron G Filler Garth T Whiteside Mark Bacon Martyn Frederickson Franklyn A Howe Miri D Rabinowitz Alan J Sokoloff Terrence W Deacon Chris Abell Raj Munglani John R Griffiths B Anthony Bell Andrew ML Lever 《BMC neuroscience》2010,11(1):1-26