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Density and vapor pressure measurements for and gas solubility and oxygen and hydrogen diffusivities in potassium hydroxide solutions
Equilibrium solubilities of niobium and tantalum in molten potassium
Solubility limit of potassium and cesium in liquid lithium
Gas solubility and transport properties in fuel cell electrolytes
Nitrogen solubility in liquid and solid chromium at elevated gas phase pressure
YC-1 [3-(5'-hydroxymethyl-2'furyl)-1-benzyl indazole] is an allosteric activator of soluble guanylyl cyclase (sGC). YC-1 increases the catalytic rate of the enzyme and sensitizes the enzyme toward its gaseous activators nitric oxide or carbon monoxide. In other studies the administration of YC-1 to experimental animals resulted in the inhibition of the platelet-rich thrombosis and a decrease of the mean arterial pressure, which correlated with increased cGMP levels. However, details of YC-1 interaction with sGC and enzyme activation are incomplete. Although evidence in the literature indicates that YC-1 activation of sGC is strictly heme-dependent, this report presents evidence for both heme-dependent and heme-independent activation of sGC by YC-1. The oxidation of the sGC heme by 1H-(1,2,4)oxadiazole(4,3-a)quinoxalin-1-one completely inhibited the response to NO, but only partially attenuated activation by YC-1. We also observed activation by YC-1 of a mutant sGC, which lacks heme. These findings indicate that YC-1 activation of sGC can occur independently of heme, but that activation is substantially increased when the heme moiety is present in the enzyme.
Thermal configurational data on neat liquids are used to obtain the work of formation of hard spherical cavities of atomic size in six molecular solvents: n-hexane, n-dodecane, n-undecyl alcohol, chloroform, carbon tetrachloride, and water. These results are used to test a recent suggestion that the differences between nonaqueous solvents and liquid water in solvation of inert gases are not principally due to the hydrogen-bonded structure of liquid water but rather to the comparatively small size of the water molecule. The frequencies of occurrence of cavities in liquid water can be meaningfully distinguished from those in the organic solvents. Liquid water has a larger fractional free volume, but that free volume is distributed in smaller packets. With respect to cavity work, water is compared to a solvent of the same molecular density and composed of hard spheres of the same size as the water molecule. That comparison indicates that the hard-sphere liquid finds more ways to configure its free volume in order to accommodate an atomic solute of substantial size and thus, would be more favorable solvent for inert gases. The scaled particle model of inert gas solubility in liquid water predicts cavity works 20% below the numerical data for TIP4P water at 300 K and 1.0 g/cm3 for cavity radii near 2.0 angstroms. It is argued that the sign of this difference is just the sign that ought to be expected and that the magnitude of this difference measures structural differences between water and the directly comparable hard-sphere liquid. In conjunction with previous data, these results indicate that atomic sized cavities should be considered submacroscopic.
A test program to characterize the solution of helium in nitrogen tetroxide/mixed oxides of nitrogen (NTO)/(MON) and monomethylhydrazine (MMH) at anticipated flight-representative pressures/temperatures was completed. Updated relations for helium solubility in MMH and NTO were generated and documented.
A thorough understanding of the non-ideal behavior of the chemical components utilized in solvent extraction contributes to the success of any large-scale spent nuclear fuel treatment. To address this, our current work uses vapor pressure osmometry to characterize the non-ideal behavior of the solvent extraction agent di-(2-ethylhexyl) phosphoric acid (HDEHP), a common extractant in proposed separation schemes. Solubility parameters were fit to data on HDEHP at four temperatures using models based on Scatchard Hildebrand regular solution theory with Flory Huggins entropic corrections. The results are comparable but not identical to the activity coefficients from prior slope analysis in the literature. (authors)
Abstract The development of high performance lubricants has been driven by increasingly growing industrial demands and environmental concerns. Herein, we demonstrate oil‐soluble polymer brush‐grafted inorganic nanoparticles (hairy NPs) as highly effective lubricant additives for friction and wear reduction. A series of oil‐miscible poly(lauryl methacrylate) brush‐grafted silica and titania NPs were synthesized by surface‐initiated atom transfer radical polymerization. These hairy NPs showed exceptional stability in poly(alphaolefin) (PAO) base oil; no change in transparency was observed after being kept at −20, 22, and 100 °C for ≥55 days. High‐contact stress ball‐on‐flat reciprocating sliding tribological tests at 100 °C showed that addition of 1 wt % of hairy NPs into PAO led to significant reductions in coefficient of friction (up to ≈40 %) and wear volume (up to ≈90 %). The excellent lubricating properties of hairy NPs were further elucidated by the characterization of the tribofilm formed on the flat. These hairy NPs represent a new type of lubricating oil additives with high efficiency in friction and wear reduction.
Abstract This Review addresses the use of X‐ray and neutron scattering as well as X‐ray absorption to describe how inorganic nanostructured materials assemble, evolve, and function in solution. We first provide an overview of techniques and instrumentation (both large user facilities and benchtop). We review recent studies of soluble inorganic nanostructure assembly, covering the disciplines of materials synthesis, processes in nature, nuclear materials, and the widely applicable fundamental processes of hydrophobic interactions and ion pairing. Reviewed studies cover size regimes and length scales ranging from sub‐Ångström (coordination chemistry and ion pairing) to several nanometers (molecular clusters, i.e. polyoxometalates, polyoxocations, and metal‐organic polyhedra), to the mesoscale (supramolecular assembly processes). Reviewed studies predominantly exploit 1) SAXS/WAXS/SANS (small‐ and wide‐angle X‐ray or neutron scattering), 2) PDF (pair‐distribution function analysis of X‐ray total scattering), and 3) XANES and EXAFS (X‐ray absorption near‐edge structure and extended X‐ray absorption fine structure, respectively). While the scattering techniques provide structural information, X‐ray absorption yields the oxidation state in addition to the local coordination. Our goal for this Review is to provide information and inspiration for the inorganic/materials science communities that may benefit from elucidating the role of solution speciation in natural and synthetic processes.
Developments of high performance lubricants are driven by increasingly growing industrial demands and environmental concerns. We demonstrate oil-soluble polymer brush-grafted inorganic nanoparticles (hairy NPs) as highly effective lubricant additives for friction and wear reduction. A series of oil-miscible poly(lauryl methacrylate) brush-grafted silica and titania NPs were synthesized by surface-initiated atom transfer radical polymerization. Moreover, these hairy NPs showed exceptional stability in poly(alphaolefin) (PAO) base oil; no change in transparency was observed after being kept at -20, 22, and 100°C for ≥55 days. High-contact stress ball-on-flat reciprocating sliding tribological tests at 100°C showed that addition of 1 wt% of hairy NPs into PAO led to significant reductions in coefficient of friction (up to ≈40%) and wear volume (up to ≈90%). The excellent lubricating properties of hairy NPs were further elucidated by the characterization of the tribofilm formed on the flat. These hairy NPs represent a new type of lubricating oil additives with high efficiency in friction and wear reduction.
Herein, a route to produce highly electrically conductive doped hydroxymethyl functionalized poly(3,4-ethylenedioxythiophene) (PEDOT) films, termed PEDOT(OH) with metal-like charge transport properties using a fully solution processable precursor polymer is reported. Further, this is achieved via an ester-functionalized PEDOT derivative [PEDOT(EHE)] that is soluble in a range of solvents with excellent film-forming ability. PEDOT(EHE) demonstrates moderate electrical conductivities of 20–60 S cm -1 and hopping-like (i.e., thermally activated) transport when doped with ferric tosylate (FeTos 3 ). Upon basic hydrolysis of PEDOT(EHE) films, the electrically insulative side chains are cleaved and washed from the polymer film, leaving a densified film of PEDOT(OH). These films, when optimally doped, reach electrical conductivities of ≈1200 S cm -1 and demonstrate metal-like (i.e., thermally deactivated and band-like) transport properties and high stability at comparable doping levels.
This Review addresses the use of X-ray and neutron scattering as well as X-ray absorption to describe how inorganic nanostructured materials assemble, evolve, and function in solution. We first provide an overview of techniques and instrumentation (both large user facilities and benchtop). We review recent studies of soluble inorganic nanostructure assembly, covering the disciplines of materials synthesis, processes in nature, nuclear materials, and the widely applicable fundamental processes of hydrophobic interactions and ion pairing. Reviewed studies cover size regimes and length scales ranging from sub-Ångström (coordination chemistry and ion pairing) to several nanometers (molecular clusters, i.e. polyoxometalates, polyoxocations, and metal-organic polyhedra), to the mesoscale (supramolecular assembly processes). Reviewed studies predominantly exploit 1) SAXS/WAXS/SANS (small- and wide-angle X-ray or neutron scattering), 2) PDF (pair-distribution function analysis of X-ray total scattering), and 3) XANES and EXAFS (X-ray absorption near-edge structure and extended X-ray absorption fine structure, respectively). While the scattering techniques provide structural information, X-ray absorption yields the oxidation state in addition to the local coordination. Our goal for this Review is to provide information and inspiration for the inorganic/materials science communities that may benefit from elucidating the role of solution speciation in natural and synthetic processes.
Abstract Creating structure–property correlations at different distance scales is one of the important challenges to the rational design of molecular gelators. Here, a series of dihydroxylated derivatives of long‐chain fatty acids, derived from three naturally occurring molecules—oleic, erucic and ricinoleic acids—are investigated as gelators of a wide variety of liquids. Conclusions about what constitutes a more (or less!) efficient gelator are based upon analyses of a variety of thermal, structural, molecular modeling, and rheological results. Correlations between the manner of molecular packing in the neat solid or gel states of the gelators and Hansen solubility data from the liquids leads to the conclusion that diol stereochemistry, the number of carbon atoms separating the two hydroxyl groups, and the length of the alkanoic chains are the most important structural parameters controlling efficiency of gel formation for these gelators. Some of the diol gelators are as efficient or even more efficient than the well‐known, excellent gelator, ( R )‐12‐hydroxystearic acid; others are much worse. The ability to form extensive intermolecular H‐bonding networks along the alkyl chains appears to play a key role in promoting fiber growth and, thus, gelation. In toto, the results demonstrate how the efficiency of gelation can be modulated by very small structural changes and also suggest how other structural modifications may be exploited to create efficient gelators.
Underspecified composition ranges often lead to alloys with unpredictable mechanical performance. To better understand the changes in microstructure and mechanical performance associated with variations of key elements, three versions of P92 are formulated within, or close to, the specified allowable for N, B, and C ranges. Chromium and Si are also varied to influence N solubility. Different service conditions (i.e., temperature and stress) are explored. It is observed that >80% decrease in creep life occurs at 625 °C and 155 MPa for the highest B and N containing alloy. Multiscale characterization reveals key changes due to the trace element variation. The high B and N containing alloy forms deleterious BN precipitates with morphology that promotes crack nucleation and damage accumulation, but this alloy additionally forms higher fractions of beneficial MX precipitates. The alloy with the lowest B and N concentrations but greater C content shows the best creep performance—a consequence of the refined M 23 C 6 carbide precipitate population and the absence of large-scale inclusions or BN precipitates. Calculations of creep activation energy reveal that the high B and N containing alloy is more prone to damage accumulation which causes an early onset of accelerating creep and greater minimum creep rate.
Radiative deactivation of lowest excited triplet and singlet states for series of free bases and Zn{sup 2+}-complexes of water-soluble 5,10,15,20-tetrakis-(4-sulfonatophenyl)porphyrin (H{sub 2}T4SPP); 5,10,15,20-tetrakis-(4-N-alkylpyridyl) porphyrin (H{sub 2}T4AlkPyP); and 5,10,15,20-tetrakis-(3-N-alkylpyridyl)porphyrin (H{sub 2}T3AlkPyP) was studied in solutions at 77 and 293 K. The fluorescence and phosphorescence quantum yields were found to have small but detectable differences for derivatives of the same porphyrin ligand with different counterions for the ionized aryl substituents. It was shown that these differences were due to spin–orbit coupling effects and variation of the electron donor/acceptor properties of the peripheral substituents that changed the electronic energy levels in the porphyrin–counterion system.
Water-soluble nanobiocomposite CdSe quantum dots were obtained using the stabilizing potential of natural biologically active polysaccharides galactomannan and κ-carrageenan. A complex of physicochemical methods was used to investigate the biphasic amorphous-crystalline structure of the obtained nanocomposites, the size range (4.8—6.9 nm) of the formed CdSe particles was determined, and, additionally, it was shown that aqueous solutions of the nanocomposites in question were characterized by the presence of photoluminescence in two spectral regions, namely, 410—450 and 510—580 nm.