Vesicle-micelle transition in aqueous mixtures of the cationic dioctadecyldimethylammonium and octadecyltrimethylammonium bromide surfactants

The vesicle-micelle transition in aqueous mixtures of dioctadecyldimethylammonium and octadecyltrimethylammonium bromide (DODAB and C18TAB) cationic surfactants, having respectively double and single chain, was investigated by differential scanning calorimetry (DSC), steady state fluorescence, dynamic light scattering (DLS) and surface tension. The experiments performed at constant up to 1.0 mM total surfactant concentration reveal that these homologue surfactants mix together to form either mixed vesicles and/or micelles, or both of these structures in equilibrium, depending on the relative amount of the surfactants. The main transition melting temperature Tm of the mixed DODAB-C18TAB vesicles is larger than that for the neat DODAB in water owing to the incorporation of C18TAB in the vesicle bilayer, however, little amount of C18TAB having a minor effect on the Tm of DODAB. The surface tension decreases sigmoidally with C18TAB concentration and the inflection point lies around xDODAB ≈ 0.4, indicating the onset of micelle formation owing to saturation of DODAB vesicles by C18TAB molecules and formation of vesicle structures. At low C18TAB concentrations When xDODAB > 0.5 C18TAB molecules are mainly solubilized by the vesicles bilayers, while at high C18TAB concentrations but when xDODAB < 0.25 micelles are dominant. Fluorescence data of the Nile Red probe incorporated in the system at different surfactant molar fractions indicate the formation of micelle and vesicle structures. These structures have apparent hydrodynamic radius RH of about 180 and 500-800 nm, respectively, as obtained by DLS measurements.Fundação para a Ciência e a Tecnologia (FCT

Molecular View of the Interaction between iota-Carrageenan and a Phospholipid Film and Its Role in Enzyme Immobilization

Proteins incorporated into phospholipid Langmuir-Blodgett (LB) films are a good model system for biomembranes and enzyme immobilization studies. The specific fluidity of biomembranes, an important requisite for enzymatic activity, is naturally controlled by varying phospholipid compositions. In a model system, instead, LB film fluidity may be varied by covering the top layer with different substances able to interact simultaneously with the phospholipid and the protein to be immobilized. In this study, we immobilized a carbohydrate rich Neurospora crassa alkaline phosphatase (NCAP) in monolayers of the sodium salt of dihexadecylphosphoric acid (DHP), a synthetic phospholipid that provides very condensed Langmuir films. The binding of NCAP to DHP Langmuir-Blodgett (LB) films was mediated by the anionic polysaccharide iota-carrageenan (iota-car). Combining results from surface isotherms and the quartz crystal microbalance technique, we concluded that the polysaccharide was essential to promote the interaction between DHP and NCAP and also to increase the fluidity of the film. An estimate of DHP:iota-car ratio within the film also revealed that the polysaccharide binds to DHP LB film in an extended conformation. Furthermore, the investigation of the polysaccharide conformation at molecular level, using sum-frequency vibrational spectroscopy (SFG), indicated a preferential conformation of the carrageenan molecules with the sulfate groups oriented toward the phospholipid monolayer, and both the hydroxyl and ether groups interacting preferentially with the protein. These results demonstrate how interfacial electric fields can reorient and induce conformational changes in macromolecules, which may significantly affect intermolecular interactions at interfaces. This detailed knowledge of the interaction mechanism between the enzyme and the LB film is relevant to design strategies for enzyme immobilization when orientation and fluidity properties of the film provided by the matrix are important to improve enzymatic activity.FINEPIMMPFAPESPCNPqCAPE

The finance-growth nexus in the age of financialisation: an empirical reassessment for the European Union countries

This paper draws an empirical reassessment of the finance-growth nexus by performing a panel data econometric analysis for all 28 European Union countries over 27 years from 1990 to 2016. Since the mid-1980s, the financial system has experienced a strong liberalisation and deregulation by preventing its beneficial effects on the real economy. This phenomenon, typically called financialisation, points to a negative view of finance and contradicts the well-entrenched hypothesis on the finance-growth nexus. We estimate both linear and non-linear growth models by incorporating seven proxies of finance (money supply, domestic credit, financial value added, short-term interest rate, long-term interest rate, stock market volume traded and stock market capitalisation) and five control variables (the lagged growth rate of the real per capita gross domestic product, the inflation rate, the general government consumption, the degree of trade openness and the education level of the population). Our results show that finance has impaired economic growth in the EU countries, both in the pre-crisis period and in the crisis and post-crisis periods. The enormous growth of domestic credit and of the financial value added have been restraining the economic growth of the EU countries since 1990 and particularly up until the Great Recession. This implies the need to reduce the prominence of finance, i.e. so-called de-financialisation, in the coming years in order to avoid the potential new ‘secular stagnation’ in the current age of financialisation.info:eu-repo/semantics/publishedVersio

Fabrication of phytic acid sensor based on mixed phytase-lipid Langmuir-Blodgett films

This paper reports the surface activity of phytase at the air-water interface, its interaction with lipid monolayers, and the construction of a new phytic acid biosensor on the basis of the Langmuir-Blodgett (LB) technique. Phytase was inserted in the subphase solution of dipalmitoylphosphatidylglycerol (DPPG) Langmuir monolayers, and its incorporation to the air-water interface was monitored with surface pressure measurements. Phytase was able to incorporate into DPPG monolayers even at high surface pressures, ca. 30 mN/m, under controlled ionic strength, pH, and temperature. Mixed Langmuir monolayers of phytase and DPPG were characterized by surface pressure-area and surface potential-area isotherms, and the presence of the enzyme provided an expansion in the monolayers ( when compared to the pure lipid at the interface). The enzyme incorporation also led to significant changes in the equilibrium surface compressibility (in-plane elasticity), especially in liquid-expanded and liquid-condensed regions. The dynamic surface elasticity for phytase-containing interfaces was investigated using harmonic oscillation and axisymmetric drop shape analysis. The insertion of the enzyme at DPPG monolayers caused an increase in the dynamic surface elasticity at 30 mN m(-1), indicating a strong interaction between the enzyme and lipid molecules at a high-surface packing. Langmuir-Blodgett (LB) films containing 35 layers of mixed phytase-DPPG were characterized by ultraviolet-visible and fluorescence spectroscopy and crystal quartz microbalance nanogravimetry. The ability in detecting phytic acid was studied with voltammetric measurements