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Query: UMLS:C0847097 (acidity)
 15,165 document(s) hit in 31,850,051 MEDLINE articles (0.00 seconds)

Silica-based, reversed-phase liquid chromatographic (RPLC) stationary phases are very widely used to separate basic compounds in acidic eluents due to their high efficiency, good mechanical strength, and the versatile selectivity offered by different functional groups and the chemistry on the silica surface. However, the stability in acid of most silica-based stationary phases is poor, especially at elevated temperatures, due to hydrolysis of the siloxane bonds, which hold silanes on the silica substrate. This hydrolysis is commonly believed to be solely the result of catalysis by protons. However, we show that various metal cations (principally Fe3+/Fe2+, Ni2+, and Cr3+) released from acid corrosion of the stainless steel inlet frit greatly accelerate the hydrolysis of the siloxane bond. Furthermore, these metal cations, and not the high acidity per se, are mainly responsible for column instability. We show that removing the stainless steel inlet frit, or use of a titanium frit, greatly reduces or totally eliminates corrosion of the inlet frit and radically improves retention stability. The effects of various acids and types of organic modifier were also studied. These observations suggest a number of practical approaches that can significantly extend the lifetime of any RPLC stationary phase in acidic media at elevated temperature.
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PMID:Loss of bonded phase in reversed-phase liquid chromatography in acidic eluents and practical ways to improve column stability. 1750 22

Amphoteric, inorganic particles used as pigments and extenders in dried coatings are not completely inert, particularly when exposed to acidity similar to atmospheric pollution, or when in a water-borne paint suspension at alkaline pH. Changes to these materials may harm the integrity of the dried coating and thus its performance during weathering or affect the colloidal stability during storage within liquid paint. The effect on aqueous titanium dioxide pigment suspensions was examined under various pH conditions. A substantial amount of aluminum was dissolved, but little silicon or titanium. Dissolution occurred at both acid and alkali pH leaving a different balance of hydrated alumina phases and overall surface composition. Changes in particle surface were apparent in topography, colloidal properties and by thermogravimetry. Such changes show that other, more complicated, changes may be possible, particularly in an aqueous paint medium where there are many other ingredients in solution or suspension.
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PMID:Hydrated alumina surface treatment on a titanium dioxide pigment: changes at acidic and basic pH. 1761 37

Ambient air particulate matter (PM) originates as either primary particles emitted directly into the atmosphere from a specific source or as secondary particles produced from atmospheric chemical reactions between precursor gases or between these gases and primary particles. PM can derive from both natural and anthropogenic sources, resulting in a complex chemical mix. The "fine" size mode of ambient PM, designated as PM(2.5), is defined as comprising those particles having aerodynamic diameters below 2.5 microm. While the total mass of PM(2.5) has been associated with adverse human health outcomes, the relationship between these and specific chemical components has not been resolved. This article provides a perspective on the current state of the science concerning health effects from a major group of chemical species found within PM(2.5), namely common inorganic constituents. The specific chemical classes discussed herein are secondary inorganic species, namely, sulfate, nitrate, and acidity, and generally crustal-derived species, namely, phosphate, sodium, potassium, calcium, magnesium, silicon, and aluminum. The article discusses evidence for adverse health effects from inorganic PM(2.5) components within the framework of various caveats surrounding both epidemiology and toxicology assessments. The largest database exists for sulfate, but conclusions that attribute sulfate to health outcomes have not been consistent across all epidemiology studies, and there is a lack of coherence with toxicology studies, which show biological responses only at high levels of exposure. Limited epidemiological and toxicological data for nitrate suggests little or no adverse health effects at current levels. Epidemiological studies specifically identifying crustal components of PM(2.5) suggest that they are not likely, by themselves, to produce a significant health risk, and these components do not have unequivocal biological plausibility from toxicological studies for being significant contributors to adverse health outcomes.
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PMID:The health impact of common inorganic components of fine particulate matter (PM2.5) in ambient air: a critical review. 1768 14

Silica and hybrid organic-inorganic films, ca. 100-200 nm thick, can be grown on glassy carbon electrodes through reactions initiated by electrogenerated hydroxide or hydronium ions in water under reductive and oxidative conditions, respectively. A variety of different alkoxysilanes (tetramethoxysilane and organoalkoxysilanes) and supporting electrolytes were used to evaluate whether film formation takes place on glassy carbon electrodes. The results of the study indicate that the acid-base properties of the supporting electrolyte are an important factor in determining whether film formation will take place. For cathodic electrodeposition, thin films can be formed using supporting electrolytes that are close to neutral, such as KCl, KNO3, and NaClO4. For anodic electrodeposition, thin films can be formed using supporting electrolytes that are acidic, such as, KH2PO4, HNO3, H2SO4, etc. The acidity/basicity effects of the electrolytes arise in part from the strong dependence of the hydrolysis and condensation rates of the silicon alkoxide precursors on pH.
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PMID:Electrodeposited silicate films: importance of supporting electrolyte. 1930 51

The generation of ions from silicon substrates in surface-assisted laser desorption ionization (SALDI) has been studied using silicon substrates prepared and etched by a variety of different methods. The different substrates were compared with respect to their ability to generate peptide mass spectra using standard liquid sample deposition. The desorption/ionization processes were studied using gas-phase analyte deposition. Mass spectra were obtained from compounds with gas-phase basicities above 850 kJmol and with molecular weights up to 370 Da. UV, VIS, and IR lasers were used for desorption. Ionization efficiencies were measured as a function of laser fluence and accumulated laser irradiance dose. Solvent vapors were added to the ion source and shown to result in fundamental laser-induced chemical and physical changes to the substrate surfaces. It is demonstrated that both the chemical properties of the substrate surface and the presence of a highly disordered structure with a high concentration of "dangling bonds" or deep gap states are required for efficient ion generation. In particular, amorphous silicon is shown to be an excellent SALDI substrate with ionization efficiencies as high as 1%, while hydrogen-passivated amorphous silicon is SALDI inactive. Based on the results, a novel model for SALDI ion generation is proposed with the following reaction steps: (1) the adsorption of neutral analyte molecules on the SALDI surface with formation of a hydrogen bond to surface Si-OH groups, (2) the electronic excitation of the substrate to form free electron/hole pairs (their relaxation results in trapped positive charges in near-surface deep gap states, causing an increase in the acidity of the Si-OH groups and proton transfer to the analyte molecules), and (3) the thermally activated dissociation of the analyte ions from the surface via a "loose" transition state.
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PMID:On the role of defects and surface chemistry for surface-assisted laser desorption ionization from silicon. 1819 Feb 16

Residual silanol acidity and activity of one immobilized artificial membrane (IAM) column have been measured from the retention of LiNO(3) in the column with a methanol/buffer (1mM in Na(+)) (60:40, v/v) mobile phase buffered to different pH values. Just one type of silanol with pssK(a)=7.61 (near the pH limit recommended by the manufacturer) was found, although these silanols show large activity. The results obtained have been compared with those obtained previously for Resolve C18, Resolve Silica, Symmetry C18, Symmetry Silica, XTerra MS C18, underivatized XTerra, Lichrospher 100 RP-18, Purospher RP-18e, Luna C18 (2) and Chromolith Perfomance RP-18e, showing that the IAM column is similar to Luna C18 and Symmetry C18 in terms of silica quality, as measured by Li(+) retention. A warning about the use of IAM columns for emulation of biological systems at physiological pH 7 is given because the ionized silanols may contribute to the retention of some drugs at this pH.
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PMID:Characterization of the acidity of residual silanol groups in immobilized artificial membranes. 1823 35

Thin PVP films deposited on a silicon oxide surface have been found to form a dewetting pattern when treated with basic solutions (pH > or = 10). We studied the dependence of pattern morphology on the polymer's molecular weight and thickness of the polymer layer, and observed the formation of three distinctive structures. The structure formed by large drops of polymer is characteristic of a polymer with low molecular weight and the thinnest polymer layer, whereas other samples form holes or a weblike pattern upon dewetting. These experiments have demonstrated for the first time the reversibility of the dewetting process in a liquid environment. The polymer layer has revealed reversible behavior toward flat film when exposed to a pH 4 buffer solution. More complex structures can be obtained by consecutive treatments with acidic (pH 4) and basic (pH 10) solutions. We used atomic force microscopy (AFM) to study both the morphology and elastic properties of polymers in media with different acidity, in order to determine the mechanism behind the dewetting process.
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PMID:Reversibility of pH-induced dewetting of poly(vinyl pyridine) thin films on silicon oxide substrate. 1846 86

A method is described for the spectrophotometric determination of 0-4% silicon in ferrophosphorus, following fusion with sodium peroxide in a zirconium crucible. Silicomolybdic acid is formed with sodium molybdate. The acidity is increased to 2N and the solution stood for 10 min to destroy phosphomolybdic and arsenomolybdic acids. The silicomolybdic acid is reduced with ascorbic acid and the absorbance measured at 810 nm. The colour is stable, and a standard deviation of 0.006% was achieved for 0.7% silicon. Results obtained for three samples with alternative procedures are compared.
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PMID:Spectrophotometric determination of silicon in ferrophosphorus. 1896 33

Stable solid adducts of substituted pyridines (Rpy) with HSiCl(3) and HSiCl(2)Me were prepared in high yields under aprotic and anaerobic conditions at room temperature. The octahedral complexes of HSiCl(3) underwent dismutation reactions in polar solvents. In contrast, the HSiCl(2)Me(Rpy)(2) adducts were not susceptible to dismutation under comparable conditions, but they tended to dissociate more easily because of the reduced Lewis acidity of HSiCl(2)Me relative to HSiCl(3). The bonding between silicon and its surrounding ligands is highly ionic, as can be seen from QTAIM and charge distribution analyses. (29)Si CP/MAS spectra in combination with quantum-chemical calculations show that the lowest shielding is along the Cl-Si-Cl axis. The other two components of the shielding tensor are oriented along the N-Si-N and H-Si-Cl/Me axes. It is known that many reactions of (hydrido)chlorosilanes are catalyzed by pyridine bases. Therefore, the results presented here provide a basis for better control of these reactions, especially chlorine substitution and hydrosilylation.
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PMID:Octahedral HSiCl3 and HSiCl2Me adducts with pyridines. 1939 95

The high sensitivity of silole- and silafluorene-containing polymers for detecting organic nitro, nitrate, and nitramine explosives cannot be solely attributed to favorable analyte-polymer hydrophobic interactions and amplified fluorescence quenching due to delocalization along the polymer chain. The Lewis acidity of silicon in conjugated poly(silafluorene-vinylene)s is shown to be important. This was established by examining the (29)Si NMR chemical shifts (Delta) for the model trimer fragment of the polymer CH(3)-silafluorene-(trans-C(2)H(2))-silafluorene-(trans-C(2)H(2))-silafluorene-CH(3). The peripheral and central silicon resonances are up-field from a TMS reference at -9.50 and -18.9 ppm, respectively. Both resonances shift down-field in the presence of donor analytes and the observed shifts (0 to 1 ppm) correlate with the basicity of a variety of added Lewis bases, including TNT. The most basic analyte studied was acetonitrile and an association constant (K(a)) of 0.12 M(-1) was calculated its binding to the peripheral silicon centers using the Scatchard method. Spin-lattice relaxation times (T(1)) of 5.86(3) and 4.83(4) s were measured for the methyl protons of acetonitrile in benzene-d(6) at 20 degrees C in the absence and presence of the silafluorene trimer, respectively. The significant change in T(1) values further supports a binding event between acetonitrile and the silafluorene trimer. These studies as well as significant changes and shifts observed in the characteristic UV-Vis absorption of the silafluorene group support an important role for the Lewis acid character of Si in polymer sensors that incorporate strained silacycles. The nitro groups of high explosives may act as weak Lewis-base donors to silacycles. This provides a donor-acceptor interaction that may be crucial for orienting the explosive analyte in the polymer film to provide an efficient pathway for inner-sphere electron transfer during the electron-transfer quenching process.
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PMID:Lewis acid-base interactions enhance explosives sensing in silacycle polymers. 1950 42


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