Selective separation of beta-lactoglobulin from sweet whey using CGAs generated from the cationic surfactant CTAB

The selective separation of whey proteins was studied using colloidal gas aphrons generated from the cationic surfactant cetyl trimethyl ammonium bromide (CTAB). From the titration curves obtained by zeta potential measurements of individual whey proteins, it was expected to selectively adsorb the major whey proteins, i.e., bovine serum albumin, alpha-lactalbumin, and beta-lactoglobulin to the aphrons and elute the remaining proteins (lactoferrin and lactoperoxidase) in the liquid phase. A number of process parameters including pH, ionic strength, and mass ratio of surfactant to protein (M-CTAB/M-TP) were varied in order to evaluate their effect on protein separation. Under optimum conditions (2 mmol/l CTAB, M-CTAB/M-TP = 0.26-0.35, pH 8, and ionic strength = 0.018 mol/l), 80-90% beta-lactoglobulin was removed from the liquid phase as a precipitate, while about 75% lactoferrin and lactoperoxidase, 80% bovine serum albumin, 95% immunoglobulin, and 65% alpha-lactalbumin were recovered in the liquid fraction. Mechanistic studies using zeta potential measurements and fluorescence spectroscopy proved that electrostatic interactions modulate only partially the selectivity of protein separation, as proteins with similar surface charges do not separate to the same extent between the two phases. The selectivity of recovery of beta-lactoglobulin probably occurs in two steps: the first being the selective interaction of the protein with opposite-charged surfactant molecules by means of electrostatic interactions, which leads to denaturation of the protein and subsequent formation and precipitation of the CTAB-beta-lactoglobulin complex. This is followed by the separation of CTAB-beta-lactoglobulin aggregates from the bulk liquid by flotation in the aphron phase. In this way, CGAs act as carriers which facilitate the removal of protein precipitate. (c) 2005 Wiley Periodicals, Inc.

Synthesis of cationic water-soluble copolymers and hydrogels based on [2-(methacryloyloxy)ethyl]trimethylammonium cloride and 2-hydroxyethylacrylate and their complex formation with poly(acrylic acid)

Water-soluble cationic copolymers and hydrogels were synthesized by radical copolymerization of [2-(methacryloyloxy)ethyl]trimetilylammonium chloride (MADQUAT) and 2-hydroxyethylacrylate (HEA). The kinetics of copolymerization has been studied and the reactivity ratios were determined. It was found that MADQUAT exhibits higher reactivity in copolymerization. The complexation between linear MADQUAT-HEA and linear poly(acrylic acid) (PAA) has been studied in aqueous solutions at different pH. It results in the formation of insoluble polyelectrolyte complexes, whose composition and stability to aggregate depends on MADQUAT content in copolymers and pH. The hydrogels were synthesized by three-dimensional radical copolymerization of MADQUAT and HEA in the presence of a crosslinker. The effects of the feed mixture composition on yield and swelling properties of the hydrogels were studied. The interactions of these hydrogels with linear PAA result in formation of gel-polyelectrolyte complexes and contraction of the samples. It was found that the contraction depends on copolymer composition, PAA molecular weight, and solution pH. (c) 2006 Wiley Periodicals, Inc.

Mucoadhesive interactions of amphiphilic cationic copolymers based on [2-(methacryloyloxy)ethyl]trimethylammonium chloride

Three series of water-soluble cationic copolymers have been synthesised by free-radical copolymerisation of [2-(methacryloyloxy)ethyl]-trimethylammonium chloride (MADQUAT) with methyl acrylate (MA), butyl acrylate (BA) and butyl methacrylate (BMA). The interactions between these copolymers and porcine stomach mucin have been studied in aqueous solutions using dynamic light scattering, zeta-potential measurements, turbidimetric titration and transmission electron microscopy (TEM). It was demonstrated that mixing aqueous dispersions of mucin with solutions of the cationic copolymers results in significant changes in size distribution and zeta-potential of its particles. It was found that an increase in the content of hydrophobic groups in copolymers leads to more efficient adsorption of macromolecules on the surface of mucin particles, which evidences the importance of hydrophobic effects in mucoadhesion. The efficiency of mucoadhesive interactions was found to be significantly dependent on pH, which affects the surface charge and aggregation stability of mucin. (C) 2007 Elsevier B.V. All rights reserved.

Rhodium cationic complexes using dithioethers as chiral ligands. Application in styrene hydroformylation

Addition of the dithioethers (−)-DIOSR2 (R=Me, iPr) (2,3-O-isopropylidene-1,4-dimethyl (and diisopropyl) thioether-L-threitol) to a dichloromethane solution of [Rh(COD)2]ClO4 (COD=1,5-cyclooctadiene) yielded the mononuclear complexes [Rh(COD)(DIOSR2)]ClO4. X-ray diffraction methods showed that the [Rh(COD)(DIOSiPr2)]ClO4 complex had an square-planar coordination geometry at the rhodium atom with the iPr groups in anti position. Cyclooctadiene complexes react with carbon monoxide to form dinuclear tetracarbonylated complexes [(CO)2Rh(μ-DIOSR2)2(CO)2](ClO4)2. [Rh(COD)(DIOSR2)]ClO4 are active catalyst precursors in styrene hydroformylation at 30 atm and 65°C which give conversions of up to 99% with a regioselectivity in 2-phenylpropanal as high as 74%. In all cases enantioselectivities are low.

Recovery of gallic acid with colloidal gas aphrons generated from a cationic surfactant

In a previous study we have demonstrated that gallic acid (GA) in its anionic form can be recovered from aqueous solutions using colloidal gas aphrons (CGA) generated from the cationic surfactant cetyltrimethylammonium bromide (CTAB). The aim of the present work is to get a better understanding of the separation mechanism in order to determine the optimum operating conditions to maximise the recovery of GA while preserving its antioxidant properties. Zeta potential measurements were carried out to characterise the surface charge of GA, CTAB and their mixtures at three different pH conditions (both in buffers and in aqueous solutions). GA interacted strongly with CTAB at pH higher than its pKa 3.14 where it is ionised and negatively charged. However, at pH higher than 7 GA becomes oxidised and loses its antioxidant power. GA recovery was mainly affected by pH, ionic strength, surfactant/GA molar ratio, mixing conditions and contact time. Scale-up of the separation using a flotation column resulted in both higher recovery and reproducibility. Preliminary experiments with grape marc extracts confirmed the potential application of this separation for the recovery of polyphenols from complex feedstocks

Interactions of surfactants (edge activators) and skin penetration enhancers with liposomes

Incorporating edge activators (surfactants) into liposomes was shown previously to improve estradiol vesicular skin delivery; this phenomenon was concentration dependent with low or high concentrations being less effective. Replacing surfactants with limonene produced similar behaviour, but oleic acid effects were linear with concentration up to 16% (w/w), beyond which it was incompatible with the phospholipid. This present study thus employed high sensitivity differential scanning calorimetry to probe interactions of additives with ipalmitoylphosphatidylcholine (DPPC) membranes to explain such results. Cholesterol was included as an example of a membrane stabiliser that removed the DPPC pre-transition and produced vesicles with a higher transition temperature (Tm). Surfactants also removed the lipid pre-transition but reduced Tm and co-operativity of the main peak. At higher concentrations, surfactants also formed new species, possibly mixed micelles with a lower Tm. The formation of mixed micelles may explain reduced skin delivery from liposomes containing high concentrations of surfactants. Limonene did not remove the pre-transition but reduced Tm and co-operativity of the main peak, apparently forming new species at high concentrations, again correlating with vesicular delivery of estradiol. Oleic acid obliterated the pre-transition. The Tm and the co-operativity of the main peak were reduced with oleic acid concentrations up to 33.2 mol%, above which there was no further change. At higher concentrations, phase separation was evident, confirming previous skin transport findings.

Interaction between a cationic surfactant-like peptide and lipid vesicles and its relationship to antimicrobial activity

We investigate the properties of an antimicrobial surfactant-like peptide (Ala)6(Arg), A6R, containing a cationic headgroup. The interaction of this peptide with zwitterionic (DPPC) lipid vesicles is investigated using a range of microscopic, X-ray scattering, spectroscopic, and calorimetric methods. The β-sheet structure adopted by A6R is disrupted in the presence of DPPC. A strong effect on the small-angle X-ray scattering profile is observed: the Bragg peaks from the DPPC bilayers in the vesicle walls are eliminated in the presence of A6R and only bilayer form factor peaks are observed. All of these observations point to the interaction of A6R with DPPC bilayers. These studies provide insight into interactions between a model cationic peptide and vesicles, relevant to understanding the action of antimicrobial peptides on lipid membranes. Notably, peptide A6R exhibits antimicrobial activity without membrane lysis.

Efficient masking of corrosion and fission products such as Ni(II) and Pd(II) in the presence of the minor actinide Am(III) using hydrophilic anionic or cationic bis-triazines

Water soluble anionic and cationic bis-triazine ligands are able to suppress (mask) the extraction of corrosion and fission products such as Ni(II) and Pd(II) that are found in PUREX raffinates. Thus it is possible to separate these elements from the minor actinide Am(III). Although some masking agents have previously been developed that retard the extraction of Pd(II), this is the first time a masking agent has been developed for Ni(II).

Separation of natural colorants from the fermented broth of filamentous fungi using colloidal gas aphrons

There is a worldwide interest in the development of processes for producing colorants from natural sources. Microorganisms provide an alternative source of natural colorants produced by cultivation technology and extracted from the fermented broth. The aim of the present work was to study the recovery of red colorants from the fermented broth of Talaromyces amestolkiae using the technique of colloidal gas aphrons (CGA) comprising surfactant-stabilized microbubbles. Preliminary experiments were performed to evaluate the red colorants’ solubility in different organic solvents, octanol/water partitioning, and their stability in surfactant solutions, namely hexadecyl trimethylammonium bromide (CTAB), sodium dodecyl sulfate (SDS), and polyoxyethylenesorbitan monolaurate (Tween 20), which are cationic, anionic and nonionic surfactants, respectively. The first recovery experiments were carried out using CGA generated by these surfactants at different volumetric ratios (VR, 3–18). Subsequently, two different approaches to generate CGA were investigated at VR values of 6 and 12: the first involved the use of CTAB at pH 6.9–10.0, and the second involved the use of Tween 20 using red colorants partially dissolved in ethanol and Tween 20. The characterization results showed that red colorants have a hydrophilic nature. The highest recoveries were obtained with Tween 20 (78%) and CTAB (70%). These results demonstrated that the recovery of the colorants was driven by both electrostatic and hydrophobic interactions. The VR was found to be an important operating parameter and at VR 12 with CTAB (at pH 9) maximum recovery, partitioning coefficient (K = 5.39) and selectivity in relation to protein and sugar (SP = 3.75 and SS = 7.20 respectively) were achieved. Furthermore, with Tween 20, the separation was driven mainly by hydrophobic interactions. Overall CGA show promise for the recovery of red colorants from a fermented broth. Although better results were obtained with CTAB than with Tween 20 the latter may be more suitable for some application due to its lower toxicity.

Effect of surfactants on the functional properties of gelatin-based edible films

The aim of this research was to evaluate the plasticizing effect of natural surfactants lecithin or yucca extract from Yucca schidigera on gelatin-based films Films containing yucca extract showed higher tensile strength values (similar to 90-40 MPa) and moisture contents (similar to 15%) and less elongation (similar to 5%) and water vapor permeability values (similar to 0 22-009 g mm m(-2) h(-1) kPa(-1)) compared to films containing lecithin Soluble films (similar to 20-50%) were obtained when yucca extract was used while lecithin produced low soluble films (<10%) The opacity of the films (similar to 14 5-16 2%) was similar for both surfactants and the film surface morphologies were continuous and homogeneous X-ray diffraction indicated that the addition of surfactants produced amorphous films compared to gelatin-based films and FT-Infrared spectroscopy showed no evidence of association between the surfactants and the gelatin The plasticizing effect was not obtained after surfactants addition and casting technique (C) 2010 Elsevier Ltd All rights reserved

Effect of surfactants on the functional properties of gelatin-polysaccharide-based films

The aim of this study was to evaluate the effects of the addition of surfactants sodium stearoyl lactate (SSL) and sucrose ester (SE) on the functional properties of films produced with polysaccharides mixtures (methylcellulose/glucomannan/pectin in 1/4/1 ratio, respectively) and gelatin. The films were produced by the casting method and characterized for their water vapor permeability (WVP), mechanical (tensile strength and elongation to break point), morphological and optical properties. Films with low WVP were obtained with surfactants. Addition of SE to the films with polysaccharide/gelatin ratio of 90/10 showed improved mechanical properties. Films presented smooth surfaces with micro voids and lumpiness, depending on the surfactant tested. Surfactants increased the opacity of the films by a factor of 1-3%. All film properties were dependent on the surfactant affinity for the biopolymer matrix. SE presented more affinity for biopolymer matrix containing high polysaccharide proportion, and SSL presented more affinity for polymer matrix containing high gelatin proportion. The addition of surfactants decreased the water vapor permeability of the films, increasing their hydrophobic character.

Near-infrared integral field spectroscopy of the Homunculus nebula around eta Carinae using Gemini/CIRPASS

This work presents the first integral field spectroscopy of the Homunculus nebula around eta Carinae in the near-infrared spectral region (J band). We confirmed the presence of a hole on the polar region of each lobe, as indicated by previous near-IR long-slit spectra and mid-IR images. The holes can be described as a cylinder of height (i.e. the thickness of the lobe) and diameter of 6.5 and 6.0 x 10(16) cm, respectively. We also mapped the blue-shifted component of He I lambda 10830 seen towards the NW lobe. Contrary to previous works, we suggested that this blue-shifted component is not related to the Paddle but it is indeed in the equatorial disc. We confirmed the claim of N. Smith and showed that the spatial extent of the Little Homunculus matches remarkably well the radio continuum emission at 3 cm, indicating that the Little Homunculus can be regarded as a small H II region. Therefore, we used the optically thin 1.3 mm radio flux to derive a lower limit for the number of Lyman-continuum photons of the central source in eta Car. In the context of a binary system, and assuming that the ionizing flux comes entirely from the hot companion star, the lower limit for its spectral type and luminosity class ranges from O5.5 III to O7 I. Moreover, we showed that the radio peak at 1.7 arcsec NW from the central star is in the same line-of-sight of the `Sr-filament` but they are obviously spatially separated, while the blue-shifted component of He I lambda 10830 may be related to the radio peak and can be explained by the ultraviolet radiation from the companion star.

THE GEMINI NICI PLANET-FINDING CAMPAIGN: DISCOVERY OF A SUBSTELLAR L DWARF COMPANION TO THE NEARBY YOUNG M DWARF CD-35 2722

We present the discovery of a wide (67 AU) substellar companion to the nearby (21 pc) young solar-metallicity M1 dwarf CD-35 2722, a member of the approximate to 100 Myr AB Doradus association. Two epochs of astrometry from the NICI Planet-Finding Campaign confirm that CD-35 2722 B is physically associated with the primary star. Near-IR spectra indicate a spectral type of L4 +/- 1 with a moderately low surface gravity, making it one of the coolest young companions found to date. The absorption lines and near-IR continuum shape of CD-35 2722 B agree especially well the dusty field L4.5 dwarf 2MASS J22244381-0158521, while the near-IR colors and absolute magnitudes match those of the 5 Myr old L4 planetary-mass companion, 1RXS J160929.1-210524 b. Overall, CD-35 2722 B appears to be an intermediate-age benchmark for L dwarfs, with a less peaked H-band continuum than the youngest objects and near-IR absorption lines comparable to field objects. We fit Ames-Dusty model atmospheres to the near-IR spectra and find T(eff) = 1700-1900 K and log(g) = 4.5 +/- 0.5. The spectra also show that the radial velocities of components A and B agree to within +/- 10 km s(-1), further confirming their physical association. Using the age and bolometric luminosity of CD-35 2722 B, we derive a mass of 31 +/- 8 M(Jup) from the Lyon/Dusty evolutionary models. Altogether, young late-M to mid-L type companions appear to be overluminous for their near-IR spectral type compared with field objects, in contrast to the underluminosity of young late-L and early-T dwarfs.

GEMINI near-infrared spectroscopic observations of young massive stars embedded in molecular clouds

K-band spectra of young stellar candidates in four Southern hemisphere clusters have been obtained with the Gemini Near-Infrared Spectrograph in Gemini South. The clusters are associated with IRAS sources that have colours characteristic of ultracompact H II regions. Spectral types were obtained by comparison of the observed spectra with those of a near-infrared (NIR) library; the results include the spectral classification of nine massive stars and seven objects confirmed as background late-type stars. Two of the studied sources have K-band spectra compatible with those characteristic of very hot stars, as inferred from the presence of C IV, N III and N V emission lines at 2.078, 2.116 and 2.100 mu m, respectively. One of them, I16177_IRS1, has a K-band spectrum similar to that of Cyg OB2 7, an O3If* supergiant star. The nebular K-band spectrum of the associated Ultra-Compact (UC) H II region shows the s-process [Kr III] and [Se IV] high excitation emission lines, previously identified only in planetary nebula. One young stellar object was found in each cluster, associated with either the main IRAS source or a nearby resolved Midecourse Space eXperiment (MSX) component, confirming the results obtained from previous NIR photometric surveys. The distances to the stars were derived from their spectral types and previously determined JHK magnitudes; they agree well with the values obtained from the kinematic method, except in the case of IRAS 15408-5356, for which the spectroscopic distance is about a factor of 2 smaller than the kinematic value.