Liquid densities, heat capacities, refractive index and excess quantities for {protic ionic liquids plus water} binary system

Densities, rho, of aqueous solutions of the room temperature protic ionic liquid (PIL), pyrrolidinium nitrate are determined at the atmospheric pressure over the temperature range from (283.15 to 323.15) K and within the whole composition range. The molar isobaric heat capacities, C(p), and refractive index, n(D), of {PIL + water} binary system are measured at 298.15 K. The excess molar volumes V(E), excess molar isobaric heat capacities C(p)(E), and deviation from ideality of refractive index Delta(phi)n, of pyrrolidinium nitrate aqueous solutions were deduced from the experimental results as well as apparent molar volumes V(phi), partial molar volumes (V) over bar (m,i), and thermal expansion coefficients alpha(p). The V(E) values were found to be positive over the entire composition range at all temperatures studied therein, whereas deviations from ideality were negative for refractive index Delta(phi)n. The volumetric properties of binary mixtures containing water and four other protic ionic liquids, such as pyrrolidinium hydrogen sulfate, pyrrolidinium formiate, collidinium formate, and diisopropyl-ethylammonium formate were also determined at 298.15 K. Results have been then discussed in terms of molecular interactions and molecular structures in these binary mixtures. (C) 2009 Elsevier Ltd. All rights reserved.

Ethanol-induced water stress and fungal growth

Fungal growth inhibition by ethanol was compared with that caused by five other agents of water stress (at 25, 40 and 42.5°C), using Aspergillus oryzae. Ethanol, KCl, glycerol, glucose, sorbitol, and polyethylene glycol 400 were incorporated into media at concentrations corresponding to water activity (a(w)) values in the range 1 to 0.75. Generally, as temperature increased there was a decrease in the a(w) value at which optimum growth occurred. The a(w) limit for growth on KCl, glycerol, glucose, sorbitol, or polyethylene glycol 400 media was about 0.85, regardless of temperature. However, the a(w) limit for growth on ethanol media varied between 0.97 and 0.99 a(w) and was temperature-dependent. Water stress accounted for up to 31, 18 and 6% of growth inhibition by ethanol at 25, 40, and 42.5°C, respectively. For media containing ethanol, the decrease in growth rate per unit of a(w) reduction was greater as temperature increased. However, ethanol-induced water stress remained constant regardless of temperature, suggesting that other inhibitory effects of ethanol are closely temperature- dependent. Water stress may account for considerably more than 30% of growth inhibition by ethanol in cells that remain metabolically active at higher ethanol concentrations.

Ethanol-induced water stress in yeast

This review considers the effect of ethanol-induced water stress on yeast metabolism and integrity. Ethanol causes water stress by lowering water activity (a(w)) and thereby interferes with hydrogen bonding within and between hydrated cell components, ultimately disrupting enzyme and membrane strut and function. The impact of ethanol on the energetic status of water is considered in relation to cell metabolism. Even moderate ethanol concentrations (5 to 10%, w/v) cause a sufficient reduction of a(w) to have metabolic consequences. When exposed to ethanol, cells synthesize compatible solutes such as glycerol and trehalose that protect against water stress and hydrogen-bond disruption. Ethanol affects the control of gene expression by the mechanism that is normally associated with (so-called) osmotic control. Furthermore, ethanol-induced water stress has ecological implications.

Polarisabilities of alkylimidazolium ionic liquids

The molar polarisability and molar volume for 71 ionic liquids were extracted from 157 measurements of their refractive index and density, which were then further deconstructed into atomic contributions by means of a Designed Regression analysis. Using this approach, the density and refractive index for any chosen ionic liquid with alkyl-substituted imidazolium cations can be predicted in good agreement with experimental data.

Conditioned ethanol preference in rats

The question of whether ethanol has intrinsically rewarding properties, or whether, as a discriminative stimulus, it can become a conditioned reinforcer as a function of context association was examined. Paired rats consumed more of an ethanol solution than isolated rats over a 15 day 'conditioning' phase and their ingestion rate was increased significantly over the 15 day period. Furthermore, animals exposed to the solution with a conspecific companion during this conditioning phase subsequently showed a marked preference for ethanol over water throughout a 10 day test phase (when all animals were alone) compared to those with prior experience of the solution in isolation. Both groups consumed significantly more ethanol than the controls (with no prior ethanol experience at all) during this test phase. The results suggest that the total context of initial exposure to ethanol mediate its subsequent reinforcing properties, with the prior pleasurable context of being with a conspecific companion generalizing to the ethanol stimulus for the paired group.

Development of ELISAs for detecting domoic acid, okadaic acid, and saxitoxin and their applicability for the detection of marine toxins in samples collected in Belgium

Okadaic acid, a diarrhetic shellfish poison, domoic acid, an amnesic shellfish poison, and saxitoxin, a paralytic shellfish poison, are three of the best-known marine biotoxins. The mouse bioassay is the method most widely used to detect many of these toxins in shellfish samples, but animal welfare concerns have prompted researchers to seek alternative methods of detection. In this study, three direct competitive enzyme-linked immunosorbent assays (ELISAs), each based on antibodies raised in rabbits against a conjugate of the analyte of interest, were developed for marine biotoxin detection in mussel, oyster, and scallop. One assay was for okadaic acid, one for saxitoxin, and one for domoic acid usually detected and quantified by high-performance liquid chromatography-ultraviolet light (HPLC-UV). All three compounds and a number of related toxins were extracted quickly and simply from the shellfish matrices with a 9 : 1 mixture of ethanol and water before analysis. The detection capabilities (CC values) of the developed ELISAs were 150 mu g kg-1 for okadaic acid, 50 mu g kg-1 for domoic acid, and 5 mu g kg-1 or less for saxitoxin. The assays proved satisfactory when used over a 4-month period for the analysis of 110 real samples collected in Belgium.

Effects of Undaria pinnatifida, Himanthalia elongata and Porphyra umbilicalis extracts on in vitro α-glucosidase activity and glucose diffusion

Background: Seaweeds are good sources of dietary fibre, which can influence glucose uptake and glycemic control.Objective: To investigate and compare the in vitro inhibitory activity of different extracts from Undaria pinnatifida (Wakame), Himanthalia elongata (Sea spaghetti) and Porphyra umbilicalis (Nori) on α-glucosidase activity and glucose diffusion.Methods: The in vitro effects chloroform-, ethanol- and water-soluble extracts of the three algae were assayed on α- glucosidase activity and glucose diffusion through membrane. Principal Components Analysis (PCA) was applied to identify patterns in the data and to discriminate which extract will show the most proper effect.Results: Only water extracts of Sea spaghetti possessed significant in vitro inhibitory effects on α-glucosidase activity (26.2% less mmol/L glucose production than control, p < 0.05) at 75 min. PCA distinguished Sea spaghetti effects, supporting that soluble fibre and polyphenols were involved. After 6 h, Ethanol-Sea spaghetti and water-Wakame extracts exerted the highest inhibitory effects on glucose diffusion (65.0% and 60.2% vs control, respectively). This extracts displayed the lowest slopes for glucose diffusion-time lineal adjustments (68.2% and 62.8% vs control, respectively).Conclusions: The seaweed hypoglycemic effects appear multi-faceted and not necessarily concatenated. According to present results, ethanol and water extracts of Sea spaghetti, and water extracts of Wakame could be useful for the development of functional foods with specific hypoglycemic properties.

Tunable thermomorphism and applications of ionic liquid analogues of Girard's reagents

A series of ionic liquids based on Girard's reagents was synthesised. Their tunable thermomorphic behaviour with water was demonstrated, and slight modifications in the cationic structure led to drastic changes in their water miscibility. Their phase behaviour, involving monophasic–biphasic transitions, drove a number of practical applications, including scavenging water-soluble dyes and the extraction of metals from water.

On the solubilization of water with ethanol in hydrophobic hexafluorophosphate ionic liquids

The solubility of water in the hydrophobic 1-alkyl-3-methylimidazolium hexafluorophosphate (alkyl = butyl, hexyl, and octyl) ionic liquids, can be significantly increased in the presence of ethanol as a co-solute. 1-Hexyl-3-methylimidazolium hexafluorophosphate and 1-octyl-3-methylimidazolium hexafluorophosphate are completely miscible with ethanol, and immiscible with water, whereas 1-butyl-3-methylimidazolium hexafluorophosphate is totally miscible with aqueous ethanol only between 0.5-0.9 mole fraction ethanol at 25degreesC. At higher and lower mole fraction of ethanol, the aqueous and IL components are only partially miscible and a biphasic system is obtained upon mixing equal volumes of the IL and aqueous ethanol. The observation of a large range of total miscibility between water and the IL in the three-component system has important implications for purifications and separations from IL.

The Role of Water and Adsorbed Hydroxyls on Ethanol Electrochemistry on Pd: New Mechanism, Active Centers and Energetics for Direct Ethanol Fuel Cell Running in Alkaline Medium

First principles calculations with molecular dynamics are
utilized to simulate a simplified electrical double layer formed in the
active electric potential region during the electrocatalytic oxidation of
ethanol on Pd electrodes running in an alkaline electrolyte. Our
simulations provide an atomic level insight into how ethanol oxidation
occurs in fuel cells: New mechanisms in the presence of the simplified
electrical double layer are found to be different from the traditional
ones; through concerted-like dehydrogenation paths, both acetaldehyde
and acetate are produced in such a way as to avoid a variety of
intermediates, which is consistent with the experimental data obtained
from in situ FTIR spectroscopy. Our work shows that adsorbed OH on
the Pd electrode rather than Pd atoms is the active center for the
reactions; the dissociation of the C−H bond is facilitated by the
adsorption of an OH− anion on the surface, resulting in the formation
of water. Our calculations demonstrate that water dissociation rather than H desorption is the main channel through which
electrical current is generated on the Pd electrode. The effects of the inner Helmholtz layer and the outer Helmholtz layer are
decoupled, with only the inner Helmholtz layer being found to have a significant impact on the mechanistics of the reaction. Our
results provide atomic level insight into the significance of the simplified electrical double layer in electrocatalysis, which may be
of general importance.

A simple method to determine the water activity of ethanol-containing samples

The water activity (a(w)) of microbial substrates, biological samples, and foods and drinks is usually determined by direct measurement of the equilibrium relative humidity above a sample. However, these materials can contain ethanol, which disrupts the operation of humidity sensors. Previously, an indirect and problematic technique based on freezing-point depression measurements was needed to calculate the a(w) when ethanol was present. We now describe a rapid and accurate method to determine the a(w) of ethanol-containing samples at ambient temperatures. Disruption of sensor measurements was minimized by using a newly developed, alcohol-resistant humidity sensor fitted with an alcohol filter. Linear equations were derived from a(w) measurements of standard ethanol-water mixtures, and from Norrish's equation, to correct sensor measurements. To our knowledge, this is the first time that electronic sensors have been used to determine the a(w) of ethanol- containing samples.

Solvation of 1-butyl-3-methylimidazolium hexafluorophosphate in aqueous ethanol - a green solution for dissolving 'hydrophobic' ionic liquids

The relatively hydrophobic ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate has been found to be totally miscible with aqueous ethanol between 0.5 and 0.9 mol fraction ethanol, whereas the ionic liquid is only partially miscible with either pure water or absolute ethanol; the ability to dissolve 1-butyl-3-methylimidazolium hexafluorophosphate in a 'green' aqueous solvent system has important implications for cleaning, purification, and separations using ionic liquids.

THE DETECTION OF HOT ETHANOL IN G34.3+0.15

Hot molecular cores in star-forming regions are known to have gas-phase chemical compositions determined by the evaporation of material from the icy mantles of interstellar grains, followed by subsequent reactions in the gas phase. Current models suggest that the evaporated material is rich in hydrogenated species, such as water, methane and methanol. In this paper, we report the detection of 14 rotational transitions of ethanol in the submillimetre spectrum of the molecular cloud associated with the ultra-compact H II region G34.3+0.15. We derive a rotation temperature of 125 K and a beam-averaged column density of 2.0x10(15) cm(-2), corresponding to a fractional abundance on the order of 4x10(-9). This large abundance, which is a lower limit due to the likelihood of beam dilution, cannot be made by purely gas-phase processes, and we conclude that the ethanol must be formed efficiently in the grain surface chemistry. Since it has been argued previously that methanol is formed via surface chemistry, it appears that alcohol formation may be a natural by-product of surface reactions.

HETEROGENEOUS REDOX CATALYSIS - A NOVEL ROUTE FOR REMOVING BROMATE IONS FROM WATER

The oxidation of water to oxygen by bromate ions is mediated by the heterogeneous redox catalyst ruthenium-Adams, a high surface area and very stable form of ruthenium(IV) oxide. The initial kinetics of catalysis are investigated as a function of [BrO3-], [Ru-Adams], temperature and [anion], where ''anion'' = ClO4- Cl- or Br-. An electrochemical model of heterogeneous redox catalysis, in which the two participating redox couples are both electrochemically irreversible, is used to interpret most of the kinetic data. The observed inhibition of the initial rate of the redox reaction by Cl- and, especially, Br- ions is tentatively attributed to competitive adsorption. In the presence of organic species, such as methanol, ethanol and propan-1-ol, which are more easily oxidised than water by bromate ions, the rate of BrO3- ion reduction is significantly faster, i.e. ca 24-34 times.