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.

Non-linear photoluminescence from purified aqueous PbS nanocrystals

A simple and effective method for purifying photoluminescent water-soluble surface passivated PbS nanocrystals has been developed. Centrifuging at high speeds removes PbS nanocrystals that exhibit strong red band edge photoluminescence from an original solution containing multiple nanocrystalline species with broad photoluminescence spectra. The ability to purify the PbS nanocrystals allowed two-photon photoluminescence spectroscopy to be performed on water-soluble PbS nanocrystals and be attributed to band edge recombination. (c) 2006 Elsevier B.V. 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.

A worldwide correlation for exponential bed particle size variation in subaerial aqueous flows

The particle size of the bed sediments in or on many natural streams, alluvial fans, laboratory flumes, irrigation canals and mine waste deltas varies exponentially with distance along the stream. A plot of the available worldwide exponential bed particle size diminution coefficient data against stream length is presented which shows that all the data lie within a single narrow band extending over virtually the whole range of stream lengths and bed sediment particle sizes found on Earth. This correlation applies to both natural and artificial flows with both sand and gravel beds, irrespective of either the solids concentration or whether normal or reverse sorting occurs. This strongly suggests that there are common mechanisms underlying the exponential diminution of bed particles in subaerial aqueous flows of all kinds. Thus existing models of sorting and abrasion applicable to some such flows may be applicable to others. A comparison of exponential laboratory abrasion and field diminution coefficients suggests that abrasion is unlikely to be significant in gravel and sand bed streams shorter than about 10 km to 100 km, and about 500 km, respectively. Copyright (C) 1999 John Wiley & Sons, Ltd.

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.

Bile-salt-induced aggregation of poly(N-isopropylacrylamide) and lowering of the lower critical solution temperature in aqueous solutions

The effect of sodium cholate (NaC; concentration 1-16 mM), a biological surfactant, on the aggregation behavior of 1% (w/v, 2.2 × 10(-3) M) poly(N-isopropylacrylamide) (PNIPAM) aqueous solutions was studied as a function of temperature. From turbidity, dynamic light scattering, viscosity, and fluorescence measurements, it was observed that (i) there is NaC-induced nanoscale aggregation of PNIPAM in its sol state and (ii) the lower critical solution temperature corresponding to sol-gel transition shifts to a lower temperature by about 2 °C.

Non-aqueous silicone elastomer gels as a vaginal microbicide delivery system for the HIV-1 entry inhibitor maraviroc

Aqueous semi-solid polymeric gels, such as those based on hydroxyethylcellulose (HEC) and polyacrylic acid (e.g. Carbopol®), have a long history of use in vaginal drug delivery. However, despite their ubiquity, they often provide sub-optimal clinical performance, due to poor mucosal retention and limited solubility for poorly water-soluble actives. These issues are particularly pertinent for vaginal HIV microbicides, since many lead candidates are poorly water-soluble and where a major goal is the development of a coitally independent, once daily gel product. In this study, we report the use of a non-aqueous silicone elastomer gel for vaginal delivery of the HIV-1 entry inhibitor maraviroc. In vitro rheological, syringeability and retention studies demonstrated enhanced performance for silicone gels compared with a conventional aqueous HEC gel, while testing of the gels in the slug model confirmed a lack of mucosal irritancy. Pharmacokinetic studies following single dose vaginal administration of a maraviroc silicone gel in rhesus macaques showed higher and sustained MVC levels in vaginal fluid, vaginal tissue and plasma compared with a HEC gel containing the same maraviroc loading. The results demonstrate that non-aqueous silicone gels have potential as a formulation platform for coitally independent vaginal HIV microbicides.

Mass transfer characteristics of two-aqueous-phase liquid-liquid mixtures

Mass transfer rates were studied using the falling drop method. Cibacron Blue 3 GA dye was the transferring solute from the salt phase to the PEG phase. Measurements were undertaken for several concentrations of the dye and the phase-forming solutes and with a range of different drop sizes, e.g. 2.8, 3.0 and 3.7 mm. The dye was observed to be present in the salt phase as finely dispersed solids but a model confirmed that the mass transfer process could still be described by an equation based upon the Whitman two-film model. The overall mass transfer coefficient increased with increasing concentration of the dye. The apparent mass transfer coefficient ranged from 1 x 10-5 to 2 x 10 -4 m/s. Further experiments suggested that mass transfer was enhanced at high concentration by several mechanisms. The dye was found to change the equilibrium composition of the two phases, leading to transfer of salt between the drop and continuous phases. It also lowered the interfacial tension (i.e. from 1.43 x 10-4 N/m for 0.01% w/w dye concentration to 1.07 x 10-4 N/m for 0.2% w/w dye concentration) between the two phases, which could have caused interfacial instabilities (Marangoni effects). The largest drops were deformable, which resulted in a significant increase in the mass transfer rate. Drop size distribution and Sauter mean drop diameter were studied on-line in a 1 litre agitated vessel using a laser diffraction technique. The effects of phase concentration, dispersed phase hold-up and impeller speed were investigated for the salt-PEG system. An increase in agitation speed in the range 300 rpm to 1000 rpm caused a decrease in mean drop diameter, e.g. from 50 m to 15 m. A characteristic bimodal drop size distribution was established within a very short time. An increase in agitation rate caused a shift of the larger drop size peak to a smaller size.

Ruthenium complexes as potential aqueous romp catalysts

The research described herein relates to studies into the Aqueous Ring-Opening Metathesis Polymerisation (ROMP) of bicyclic monomers using ruthenium complex catalysts. Two monomers were synthesised for the purpose of these studies, namely exo, exo-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid (7-oxanorbornenedicarboxylic acid) and exo, exo-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid (norbornene dicarboxylic acid). A number of ruthenium complexes were synthesised, amongst them a novel complex containing the water soluble phosphine ligand trist(hydroxymethyl)phosphine P(CH2OH)3. Its synthesis and characterisation are described and its physical properties compared and contrasted to analogous compounds of platinum and palladium. Its peculiar properties are ascribed to a trans-placement of the phosphine ligands. Dilatometry was investigated as a technique for the acquisition of kinetic data from aqueous metathesis reactions. For the attempted polymerisation of 7-oxanorbonenedicarboxylic acid the results are explained in terms of a reverse Diels-Alder reaction of the monomer. The reaction between Ru(CO)Cl2(H2O) and 7-oxanorbonenedicarboxylic acid was monitored using UV/Vis spectrometry and kinetic data retrieved. The data are explained in terms of a two stage reaction consisting of consecutive first order processes.The reaction between 7-oxanorbornenedicarboxylic acid and Ru(CO)Cl2(H2O) or Ru(P(CH2OH)3)3Cl2 was found to produce fumaric acid as one of the major products. This reaction is previously unreported in the literature and a mechanism is proposed.