Conformational preferences of natural and C3-modified epothilones in aqueous solution

The conformational properties of the microtubule-stabilizing agent epothilone A ( 1a) and its 3-deoxy and 3-deoxy-2,3-didehydro derivatives 2 and 3 have been investigated in aqueous solution by a combination of NMR spectroscopic methods, Monte Carlo conformational searches, and NAMFIS calculations. The tubulin-bound conformation of epothilone A ( 1a), as previously proposed on the basis of solution NMR data, was found to represent a significant fraction of the ensemble of conformations present for the free ligands in aqueous solution.

On the acidity and reactivity of HNO in aqueous solution and biological systems

The gas phase and aqueous thermochemistry and reactivity of nitroxyl (nitrosyl hydride, HNO) were elucidated with multiconfigurational self-consistent field and hybrid density functional theory calculations and continuum solvation methods. The pKa of HNO is predicted to be 7.2 ± 1.0, considerably different from the value of 4.7 reported from pulse radiolysis experiments. The ground-state triplet nature of NO− affects the rates of acid-base chemistry of the HNO/NO− couple. HNO is highly reactive toward dimerization and addition of soft nucleophiles but is predicted to undergo negligible hydration (Keq = 6.9 × 10−5). HNO is predicted to exist as a discrete species in solution and is a viable participant in the chemical biology of nitric oxide and derivatives.

Removal of 8-quinolinecarboxylic acid pesticide from aqueous solution by adsorption on activated montmorillonites

Sodium montmorillonite (Na-M), acidic montmorillonite (H-M), and organo-acidic montmorillonite (Org-H-M) were applied to remove the herbicide 8-quinolinecarboxylic acid (8-QCA). The montmorillonites containing adsorbed 8-QCA were investigated by transmission electron microscopy, FT-IR spectroscopy, X-ray diffraction analysis, X-ray fluorescence thermogravimetric analysis, and physical adsorption of gases. Experiments showed that the amount of adsorbed 8-QCA increased at lower pH, reaching a maximum at pH 2. The adsorption kinetics was found to follow the pseudo-second-order kinetic model. The Langmuir model provided the best correlation of experimental data for adsorption equilibria. The adsorption of 8-QCA decreased in the order Org-H-M > H-M > Na-M. Isotherms were also used to obtain the thermodynamic parameters. The negative values of ΔG indicated the spontaneous nature of the adsorption process.

Production of methanol from CO2 electroreduction at Cu2O and Cu2O/ZnO-based electrodes in aqueous solution

In this study, we examine the performance of Cu2O and Cu2O/ZnO surfaces in a filter-press electrochemical cell for the continuous electroreduction of CO2 into methanol. The electrodes are prepared by airbrushing the metal particles onto a porous carbon paper and then are electrochemically characterized by cyclic voltammetry analyses. Particular emphasis is placed on evaluating and comparing the methanol production and Faradaic efficiencies at different loadings of Cu2O particles (0.5, 1 and 1.8 mg cm−2), Cu2O/ZnO weight ratios (1:0.5, 1:1 and 1:2) and electrolyte flow rates (1, 2 and 3 ml min−1 cm−2). The electrodes including ZnO in their catalytic surface were stable after 5 h, in contrast with Cu2O-deposited carbon papers that present strong deactivation with time. The maximum methanol formation rate and Faradaic efficiency for Cu2O/ZnO (1:1)-based electrodes, at an applied potential of −1.3 V vs. Ag/AgCl, were r = 3.17 × 10−5 mol m−2 s−1 and FE = 17.7 %, respectively. Consequently, the use of Cu2O–ZnO mixtures may be of application for the continuous electrochemical formation of methanol, although further research is still required in order to develop highly active, selective and stable catalysts the electroreduction of CO2 to methanol.

Algerian natural montmorillonites for arsenic(III) removal in aqueous solution

The adsorption of As(III) from aqueous solutions using naturally occurring and modified Algerian montmorillonites has been investigated as a function of contact time, pH, and temperature. Kinetic studies reveal that uptake of As(III) ions is rapid within the first 3 h, and it slows down thereafter. Equilibrium studies show that As(III) shows the highest affinity toward acidic montmorillonite even at very low concentration of arsenic. The kinetics of As(III) adsorption on all montmorillonites used is well described by a pseudo-second-order chemical reaction model, which indicates that the adsorption process of these species is likely to be chemisorption. Adsorption isotherms of As(III) fitted the Langmuir and Freundlich isotherm models well. The adsorption of As(III) is pH-dependent obtaining an optimal adsorption at pH 5. From the thermodynamic parameters, it is concluded that the process is exothermic, spontaneous, and favorable. The results suggest that M1, M2, and acidic-M2 could be used as low-cost and effective filtering materials for removal of arsenic from water.

Enhanced removal of 8-quinolinecarboxylic acid in an activated carbon cloth by electroadsorption in aqueous solution

The effect of the electrochemical treatment (potentiostatic treatment in a filter-press electrochemical cell) on the adsorption capacity of an activated carbon cloth (ACC) was analyzed in relation with the removal of 8-quinolinecarboxylic acid pollutant from water. The adsorption capacity of an ACC is quantitatively improved in the presence of an electric field (electroadsorption process) reaching values of 96% in comparison to 55% in absence of applied potential. In addition, the cathodic treatment results in higher removal efficiencies than the anodic treatment. The enhanced adsorption capacity has been proved to be irreversible, since the removed compound remains adsorbed after switching the applied potential. The kinetics of the adsorption processes is also improved by the presence of an applied potential.

Evaluation of fe oxide-coated granular activated carbon for removal and recovery of Cu(II) and Cr(VI) from aqueous solution /

"April 1994."--Cover.

The secondary nucleation threshold and crystal growth of alpha-glucose monohydrate in aqueous solution

Investigation of the secondary nucleation threshold (SNT) of alpha-glucose monohydrate was conducted in aqueous solutions in agitated batch systems for the temperature range 10 to 40 degrees C. The width of the SNT decreased as the induction time increased and was found to be temperature independent when supersaturation was based on the absolute concentration driving force. Nonnucleating seeded batch bulk crystallizations of this sugar were performed isothermally in the same temperature range as the SNT experiments, and within the SNT region to avoid nucleation. The growth kinetics were found to be linearly dependent on the supersaturation of total glucose in the system when the mutarotation reaction is not rate limiting. The growth rate constant increases with increasing temperature and follows an Arrhenius relationship with an activation energy of 50 +/- 2 kJ/mol. alpha-Glucose monohydrate shows significant crystal growth rate dispersion (GRD). For the seeds used, the 95% range of growth rates was within a factor of 6 for seeds with a narrow particle size distribution, and 8 for seeds with a wider distribution that was used at 25 degrees C. The results will be used to model the significance of the mutarotation reaction on the overall crystallization rate of D-glucose in industrial crystallization.

Characterisation and environmental application of an Australian natural zeolite for basic dye removal from aqueous solution

An Australian natural zeolite was collected, characterised and employed for basic dye adsorption in aqueous solution. The natural zeolite is mainly composed of clinoptiloite, quartz and mordenite and has cation-exchange capacity of 120 meq/100 g. The natural zeolite presents higher adsorption capacity for methylene blue than rhodamine B with the maximal adsorption capacity of 2.8 x 10(-5) and 7.9 x 10(-5) Mot/g at 50 degrees C for rhodamine B and methylene blue, respectively. Kinetic studies indicated that the adsorption followed the pseudo second-order kinetics and could be described as two-stage diffusion process. The adsorption isotherm could be fitted by the Langmuir and Freundlich models. Thermodynamic calculations showed that the adsorption is endothermic process with Delta H degrees at 2.0 and 8.7 kJ/mol for rhodamine B and methylene blue. It has also found that the regenerated zeolites by high-temperature calcination and Fenton oxidation showed similar adsorption capacity but lower than the fresh sample. Only 60% capacity could be recovered by the two regeneration techniques. (c) 2006 Elsevier B.V. All rights reserved.

Geopolymeric adsorbents from fly ash for dye removal from aqueous solution

Adsorbents from coal fly ash treated by a solid-state fusion method using NaOH were prepared. It was found that amorphous aluminosilicate, geopolymers would be formed. These fly ash-derived inorganic polymers were assessed as potential adsorbents for removal of some basic dyes, methylene blue and crystal violet, from aqueous solution. It was found that the adsorption capacity of the synthesised adsorbents depends on the preparation conditions such as NaOH:fly-ash ratio and fusion temperature with the optimal conditions being at 121 weight ratio of Na:fly-ash at 250-350 degrees C. The synthesised materials exhibit much higher adsorption capacity than fly ash itself and natural zeolite. The adsorption isotherm can be fitted by Langmuir and Freundlich models while the two-site Langmuir model producing the best results. It was also found that the fly ash derived geopolymeric adsorbents show higher adsorption capacity for crystal violet than methylene blue and the adsorption temperature influences the adsorption capacity. Kinetic studies show that the adsorption process follows the pseudo second-order kinetics. (c) 2006 Elsevier Inc. All rights reserved.

Molecular dynamics characterization of n-octyl-beta-D-glucopyranoside micelle structure in aqueous solution

n-Octyl-beta-D-glueopyranoside (OG) is a non-ionic glycolipid, which is used widely in biotechnical and biochemical applications. All-atom molecular dynamics simulations from two different initial coordinates and velocities in explicit solvent have been performed to characterize the structural behaviour of an OG aggregate at equilibrium conditions. Geometric packing properties determined from the simulations and small angle neutron scattering experiment state that OG micelles are more likely to exist in a non-spherical shape, even at the concentration range near to the critical micelle concentration (0.025 M). Despite few large deviations in the principal moment of inertia ratios, the average micelle shape calculated from both simulations is a prolate ellipsoid. The deviations at these time scales are presumably the temporary shape change of a micelle. However, the size of the micelle and the accessible surface areas were constant during the simulations with the micelle surface being rough and partially elongated. Radial distribution functions computed for the hydroxyl oxygen atoms of an OG show sharper peaks at a minimum van der Waals contact distance than the acetal oxygen, ring oxygen, and anomeric carbon atoms. This result indicates that these atoms are pointed outwards at the hydrophilic/hydrophobic interface, form hydrogen bonds with the water molecules, and thus hydrate the micelle surface effectively. (c) 2005 Elsevier Inc. All rights reserved.

Stable suspension of layered double hydroxide nanoparticles in aqueous solution

Seriously aggregated LDH agglomerates can be dispersed by a hydrothermal treatment into homogeneous stable suspensions that contain LDH particles in the range of 50−300 nm.

Flexibility of short-strand RNA in aqueous solution as revealed by molecular dynamics simulation:are A′-RNA and A-RNA distinct conformational structures?

We use molecular dynamics simulations to compare the conformational structure and dynamics of a 21-base pair RNA sequence initially constructed according to the canonical A-RNA and A'-RNA forms in the presence of counterions and explicit water. Our study aims to add a dynamical perspective to the solid-state structural information that has been derived from X-ray data for these two characteristic forms of RNA. Analysis of the three main structural descriptors commonly used to differentiate between the two forms of RNA namely major groove width, inclination and the number of base pairs in a helical twist over a 30 ns simulation period reveals a flexible structure in aqueous solution with fluctuations in the values of these structural parameters encompassing the range between the two crystal forms and more. This provides evidence to suggest that the identification of distinct A-RNA and A'-RNA structures, while relevant in the crystalline form, may not be generally relevant in the context of RNA in the aqueous phase. The apparent structural flexibility observed in our simulations is likely to bear ramifications for the interactions of RNA with biological molecules (e.g. proteins) and non-biological molecules (e.g. non-viral gene delivery vectors). © CSIRO 2009.