Wormlike micelle formation and flow alignment of a pluronic block copolymer in aqueous solution

The self-assembly into wormlike micelles of a poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) triblock copolymer Pluronic P84 in aqueous salt solution (2 M NaCl) has been studied by rheology, small-angle X-ray and neutron scattering (SAXS/SANS), and light scattering. Measurements of the flow curves by controlled stress rheometry indicated phase separation under flow. SAXS on solutions subjected to capillary flow showed alignment of micelles at intermediate shear rates, although loss of alignment was observed for high shear rates. For dilute solutions, SAXS and static light scattering data on unaligned samples could be superposed over three decades in scattering vector, providing unique information on the wormlike micelle structure over several length scales. SANS data provided information on even shorter length scales, in particular, concerning "blob" scattering from the micelle corona. The data could be modeled based on a system of semiflexible self-avoiding cylinders with a circular cross-section, as described by the wormlike chain model with excluded volume interactions. The micelle structure was compared at two temperatures close to the cloud point (47 degrees C). The micellar radius was found not to vary with temperature in this region, although the contour length increased with increasing temperature, whereas the Kuhn length decreased. These variations result in an increase of the low-concentration radius of gyration with increasing temperature. This was consistent with dynamic light scattering results, and, applying theoretical results from the literature, this is in agreement with an increase in endcap energy due to changes in hydration of the poly(ethylene oxide) blocks as the temperature is increased.

Effect of ethanol on the micellization and gelation of Pluronic P123

In certain applications copolymer P123 (E21P67E21) is dissolved in water-ethanol mixtures, initially to form micellar solutions and eventually to gel. For P123 in 10, 20, and 30 wt % aqueous ethanol we used dynamic light scattering from dilute solutions to confirm micellization, oscillatory rheometry, and visual observation of mobility (tube inversion) to determine gel formation in concentrated solutions and small-angle X-ray scattering (SAXS) to determine gel structure. Except for solutions in 30 wt % aqueous ethanol, a clear-turbid transition was encountered on heating dilute and concentrated micellar solutions alike, and as for solutions in water alone (Chaibundit et al. Langmuir 2007, 23, 9229) this could be ascribed to formation of wormlike micelles. Dense clouding, typical of phase separation, was observed at higher temperatures. Regions of isotropic and birefringent gel were defined for concentrated solutions and shown (by SAXS) to have Cubic (fcc and hcp) and hexagonal structures, consistent with packed spherical and elongated micelles, respectively. The cubic gels (0, 10, and 20 wt % ethanol) were clear, while the hex gels were either turbid (0 and 10 wt % ethanol), turbid enclosing a clear region (20 wt % ethanol), or entirely clear (30 wt % ethanol). The SAXS profile was unchanged between turbid and clear regions of the 20 wt % ethanol gel. Temperature scans of dynamic moduli showed (as expected) a clear distinction between high-modulus cubic gels (G'(max) approximate to 20-30 kPa) and lower modulus hex gels (G'(max) < 10 kPa).

Toll-like receptor agonist lipopeptides self-assemble into distinct nanostructures

The self-assembled structure of toll-like receptor agonist lipopeptides containing the CSK4 peptide sequence is examined in aqueous solution. A remarkable dependence of morphology on the number of attached hexadecyl lipid chains is demonstrated, with spherical micelle structures for mono- and di-lipidated structures observed, but flexible wormlike micelles for the homologue containing three lipid chains. The distinct modes of assembly may have an important influence on the bioactivity of this class of lipopeptide.

Capillary flow behavior of worm-like micelles studied by small-angle X-ray scattering and small angle light scattering

A novel capillary flow device has been developed and applied to study the orientation of worm-like micelles, among other systems. Small-angle X-ray scattering (SAXS) data from micelles formed by a Pluronic block copolymer in aqueous salt solution provides evidence for the formation of worm-like micelles, which align under flow. A transition from a rod-like form factor to a less persistent conformation is observed under flow. Flow alignment of worm-like micelles formed by the low molar mass amphiphile system cetyl pyridinium chloride+sodium salicylate is studied for comparative purposes. Here, inhomogenous flow at the micron scale is revealed by streaks in the small-angle light scattering pattern perpendicular to the flow direction. Copyright (c) 2006 John Wiley & Sons, Ltd.

Impact of saturated, polyunsaturated and monounsaturated fatty acid-rich micelles on lipoprotein synthesis and secretion in Caco-2 cells

Meal fatty acids have been shown to modulate the size and composition of triacylglycerol (TAG)-rich lipoproteins influencing the magnitude and duration of the postprandial plasma TAG response. As a result there is considerable interest in the origin of these meal fatty-acid induced differences in particle composition. Caco-2 cells were incubated over 4 days with fatty acid mixtures resembling the composition of saturated (SFA), monounsaturated (MUFA) and polyunsaturated fatty acid (PUFA)-rich meals fed in a previous postprandial study to determine their impact on lipoprotein synthesis and secretion. The MUFA- and PUFA-rich mixtures supported greater intracellular TAG, but not cholesterol accumulation compared with the SFA-rich mixture (P < 0.001). The MUFA-rich mixture promoted significantly greater TAG and cholesterol secretion than the other mixtures and significantly more apolipoprotein B-100 secretion than the PUFA-rich mixture (P < 0.05). Electron microscopy revealed the SFA-rich mixture had led to unfavourable effects on cellular morphology, compared with the unsaturated fatty acid-rich mixtures. Our findings suggest the MUFA-rich mixture, may support the formation of a greater number of TAG-rich lipoproteins, which is consistent with indirect observations from our human study. Our electron micrographs are suggestive that some endocytotic uptake of MUFA-rich taurocholate micelles may promote greater lipoprotein synthesis and secretion in Caco-2 cells.

An empirical study of process-related attributes in segmented software cost-estimation relationships

Parametric software effort estimation models consisting on a single mathematical relationship suffer from poor adjustment and predictive characteristics in cases in which the historical database considered contains data coming from projects of a heterogeneous nature. The segmentation of the input domain according to clusters obtained from the database of historical projects serves as a tool for more realistic models that use several local estimation relationships. Nonetheless, it may be hypothesized that using clustering algorithms without previous consideration of the influence of well-known project attributes misses the opportunity to obtain more realistic segments. In this paper, we describe the results of an empirical study using the ISBSG-8 database and the EM clustering algorithm that studies the influence of the consideration of two process-related attributes as drivers of the clustering process: the use of engineering methodologies and the use of CASE tools. The results provide evidence that such consideration conditions significantly the final model obtained, even though the resulting predictive quality is of a similar magnitude.

Molecular dynamics simulations of threadlike cetyltrimethylammonium chloride micelles: effects of sodium chloride and sodium salicylate salts

We use atomistic molecular dynamics simulations to probe the effects of added sodium chloride (NaCl) and sodium salicylate (NaSal) salts on the spherical-to-threadlike micelle shape transition in aqueous solutions of cetyltrimethylammonium chloride (CTAC) surfactants. Long threadlike micelles are found to be unstable and break into spherical micelles at low concentrations or NaCl, but remain stable for 20 ns above a threshold value of [NaCl] approximate to 3.0 M, which is about 2.5 times larger than the experimental salt concentration at which the transition between spherical and rodlike micelles occurs. The chloride counterions associate weakly oil the surface of the CTAC micelles with the degree of counterion dissociation decreasing slightly with increasing [NaCl] on spherical micelles, but dropping significantly on the threadlike micelles tit high [NaCl]. This effect indicates that the electrolyte ions drive the micellar shape transition by screening the electrostatic repulsions between the micellar headgroups, The aromatic salicylate counterions, on the other hand, penetrate inside the micelle with their hydrophilic groups staying in the surfactant headgroup region and the hydrophobic groups partially embedded into the hydrophobic core of the micelle. The strong association of the salicylate ions with the surfactant headgroups leads to dense packing of the surfactant molecules, which effectively reduces the surface area per surfactant, and increases intramicellar ordering of the surfactant headgroups, favoring the formation of long threadlike micelles. Simulation predictions of the geometric and electrostatic properties of the spherical and threadlike micelles are in good agreement with experiments.

Puroindoline-a, a lipid binding protein from common wheat, spontaneously forms prolate protein micelles in solution

The self-assembly in solution of puroindoline-a (Pin-a), an amphiphilic lipid binding protein from common wheat, was investigated by small angle neutron scattering, dynamic light scattering and size exclusion chromatography. Pin-a was found to form monodisperse prolate ellipsoidal micelles with a major axial radius of 112 +/- 4.5 A ˚ and minor axial radius of 40.4 +/- 0.18 A ˚ . These protein micelles were formed by the spontaneous self-assembly of 38 Pin-a molecules in solution and were stable over a wide pH range (3.5–11) and at elevated temperatures (20–65 degC). Pin-a micelles could be disrupted upon addition of the non-ionic surfactant dodecyl-b-maltoside, suggesting that the protein self-assembly is driven by hydrophobic forces, consisting of intermolecular interactions between Trp residues located within a well-defined Trp-rich domain of Pin-a.

Mozzarella-type curd made from buffalo, cows’ and ultrafiltered cows’ milk. 2. Physicochemical properties, curd yield and quality, casein fractions & micelles size

Buffalo milk contains (40–60 %) more protein, fat and calcium than cows’ milk. These constituents were enhanced by ultrafiltration (UF) of cows’ milk to give a product with similar levels to those found in the buffalo milk. Mozzarella-type curd was made from buffalo, cows’ and UF cows’ milk to compare the overall curd yield and quality. The curd yield on both dry and wet weight basis, curd moisture content and overall curd fat retention were found to be higher in the UF cows’ milk than for either the buffalo or the cows’ milk preparations. The minimum whey fat losses occurred in the UF cows’ curd when compared to the cows’ and the buffalo curd. The whey protein losses were found to be higher in the UF cows’ curd than those for the buffalo and the cows’ curds. The total mineral content of the curd was also higher in the UF cows’ milk than that found in either the buffalo or the cows’ milk. SEM micrographs showed that casein micelles sizes were different in the two different types of milk. Casein micelles were also observed to be deformed in the UF cows’ milk samples. UF cows’ milk contained higher amounts of both the αs1- and αs2-casein moieties than either the buffalo or the cows’ milk. Buffalo milk was found to contain a higher concentration of β-casein than either the UF cows’ or untreated cows’ milk samples. Gel strength was found to be higher in the resultant buffalo curd than for curds made from either native cows’ milk or those made from UF cows’ milk. The mineral distribution was also different in the three different types of bovine milk, measured by energy-dispersive X-ray (EDX) analysis. Differences in the curd quality observed between the buffalo and the cows’ milk appear to result from the differences in casein composition and overall micelle structure, rather than casein concentration alone.

Self-assembly of a peptide amphiphile: transition from nanotape fibrils to micelles

A thermal transition is observed in the peptide amphiphile C16-KTTKS (TFA salt) from nanotapes at 20 degrees C to micelles at higher temperature (the transition temperature depending on concentration). The formation of extended nanotapes by the acetate salt of this peptide amphiphile, which incorporates a pentapeptide from type I procollagen, has been studied previously [V. Castelletto et al., Chem. Commun., 2010, 46, 9185]. Here, proton NMR and SAXS provide evidence for the TFA salt spherical micelles at high temperature. The phase behavior, with a Krafft temperature separating insoluble aggregates (extended nanotapes) at low temperature from the high temperature micellar phase resembles that for conventional surfactants, however this has not previously been reported for peptide amphiphiles.

Geomorphological Map of Ribbed Moraines on the Dubawnt Lake Palaeo-Ice Stream Bed: A Signature of Ice Stream Shut-down?

The beds of active ice streams in Greenland and Antarctica are largely inaccessible, hindering a full understanding of the processes that initiate, sustain and inhibit fast ice flow in ice sheets. Detailed mapping of the glacial geomorphology of palaeo-ice stream tracks is, therefore, a valuable tool for exploring the basal processes that control their behaviour. In this paper we present a map that shows detailed glacial geomorphology from a part of the Dubawnt Lake Palaeo-Ice Stream bed on the north-western Canadian Shield (Northwest Territories), which operated at the end of the last glacial cycle. The map (centred on 63 degrees 55 '' 42'N, 102 degrees 29 '' 11'W, approximate scale 1:90,000) was compiled from digital Landsat Enhanced Thematic Mapper Plus satellite imagery and digital and hard-copy stereo-aerial photographs. The ice stream bed is dominated by parallel mega-scale glacial lineations (MGSL), whose lengths exceed several kilometres but the map also reveals that they have, in places, been superimposed with transverse ridges known as ribbed moraines. The ribbed moraines lie on top of the MSGL and appear to have segmented the individual lineaments. This indicates that formation of the ribbed moraines post-date the formation of the MSGL. The presence of ribbed moraine in the onset zone of another palaeo-ice stream has been linked to oscillations between cold and warm-based ice and/or a patchwork of cold-based areas which led to acceleration and deceleration of ice velocity. Our hypothesis is that the ribbed moraines on the Dubawnt Lake Ice Stream bed are a manifestation of the process that led to ice stream shut-down and may be associated with the process of basal freeze-on. The precise formation of ribbed moraines, however, remains open to debate and field observation of their structure will provide valuable data for formal testing of models of their formation.

A further study of the recovery and purification of surfactin from fermentation broth by membrane filtration

Surfactin is a bacterial lipopeptide produced by Bacillus subtilis and is a powerful surfactant, having also antiviral, antibacterial and antitumor properties. The recovery and purification of surfactin from complex fermentation broths is a major obstacle to its commercialization; therefore, a two-step membrane filtration process was developed using a lab scale tangential flow filtration (TFF) unit with 10 kDa MWCO regenerated cellulose (RC) and polyethersulfone (PES)membranes at three different transmembrane pressure (TMP) of 1.5 bar, 2.0 bar and 2.5 bar. Two modes of filtrations were studied, with and without cleaning of membranes prior to UF-2. In a first step of ultrafiltration (UF-1), surfactin was retained effectively by membranes at above its critical micelle concentration (CMC); subsequently in UF-2, the retentate micelles were disrupted by addition of 50% (v/v) methanol solution to allow recovery of surfactin in the permeate. Main protein contaminants were effectively retained by the membrane in UF-2. Flux of permeates, rejection coefficient (R) of surfactin and proteinwere measured during the filtrations. Overall the three different TMPs applied have no significant effect in the filtrations and PES is the more suitable membrane to selectively separate surfactin from fermentation broth, achieving high recovery and level of purity. In addition this two-step UF process is scalable for larger volume of samples without affecting the original functionality of surfactin, although membranes permeability can be affected due to exposure to methanolic solution used in UF-2.

The influence of age and gender on food choice: a focus group exploration

With 25% of the UK population predicted to be obese by 2010, the costs to individuals and society are set to rise. Due to the extra economic and social pressures obesity causes, there is an increasing need to understand what motivates and prevents consumers from eating a healthy diet so as to be able to tailor policy interventions to specific groups in society. In so doing, it is important to explore potential variations in attitudes, motivation and behaviour as a function of age and gender. Both demographic factors are easily distinguished within society and a future intervention study which targets either, or both, of these would likely be both feasible and cost-effective for policy makers. As part of a preliminary study, six focus groups (total n = 43) were conducted at the University of Reading in November 2006, with groups segmented on the basis of age and gender. In order to gather more sensitive information, participants were also asked to fill out a short anonymous questionnaire before each focus group began, relating to healthy eating, alcohol consumption and body dissatisfaction. Making use of thematic content analysis, results suggested that most participants were aware of the type of foods that contribute to a healthy diet and the importance of achieving a healthy balance within a diet. However, they believed that healthy eating messages were often conflicting, and were uncertain about where to find information on the topic. Participants believed that the family has an important role in educating children about eating habits. Despite these similarities, there were a number of key differences among the groups in terms of their reasons for making food choices. Older participants (60+ years old) were more likely to make food choices based on health considerations. Participants between the ages of 18–30 were less concerned with this link, and instead focused on issues of food preparation and knowledge, prices and time. Younger female participants said they had more energy when they ate healthier diets; however, very often their food choices related to concern with their appearance. Older female participants also expressed this concern within the questionnaire, rather than in the group discussions. Overall, these results suggest that consumer motivations for healthy eating are diverse and that this must be considered by government, retailers and food producers.

Buddenbrockia is a Cnidarian worm

A major evolutionary divide occurs in the animal kingdom between the so-called radially symmetric animals, which includes the cnidarians, and the bilaterally symmetric animals, which includes all worm phyla. Buddenbrockia plumatellae is an active, muscular, parasitic worm that belongs to the phylum Myxozoa, a group of morphologically simplified microscopic endoparasites that has proved difficult to place phylogenetically. Phylogenetic analyses of multiple protein-coding genes demonstrate that Buddenbrockia is a cnidarian. This active muscular worm increases the known diversity in cnidarian body plans and demonstrates that a muscular, wormlike form can evolve in the absence of overt bilateral symmetry.