Cutinase activity in supercritical and organic media: water activity, solvation and acid–base effects

We performed a comparative study on the activity of Fusarium solani pisi cutinase immobilized on zeolites NaA and NaY, in n-hexane, acetonitrile, supercritical ethane (sc-ethane) and sc-CO2, at two different water activity (aW) values set by salt hydrate pairs in situ and at acid–base conditions fixed with solid-state buffers of aqueous pKa between 4.3 and 10.6. The reaction studied was the transesterification of vinyl butyrate by (R,S)-2-phenyl-1-propanol. The transesterification activity of cutinase was highest and similar in sc-ethane and in n-hexane,about one order of magnitude lower in acetonitrile and even lower in sc-CO2. Activity coefficients (γ) generated for the two substrates indicated that they were better solvated in acetonitrile and thus less available for binding at the active site than in the other three solvents. γ data also suggested higher reaction rates in sc-ethane than in n-hexane, as observed, and provided evidence for a direct negative effect of sc-CO2 on enzyme activity. Manipulation of the acid–base conditions of the media did not afford any improvement of the initial rates of transesterification relative to the blanks (no added acid–base buffer, only salt hydrate pair), except in the case of cutinase immobilized on zeolite NaA in sc-ethane at aW = 0.7. The poor performance of the blank in this case and the great improvement observed in the presence of a basic buffer suggest a deleterious acidic effect in the medium which, an experiment without additives confirmed, was not due to the known acidic character of the salt hydrate pair used to set aW = 0.7. In acetonitrile, increasing aW was accompanied by a decrease in initial rates of transesterification, unlike in the other solvents. There was considerable hydrolysis in acetonitrile, where initial rates of hydrolysis increased about 20-fold from aW = 0.2 to 0.7. Hydrolysis was less pronounced in sc-ethane and in n-hexane, and only at aW = 0.7, and in sc-CO2 butyric acid was detected only at very long reaction times, in agreement with a generally low catalytic activity. Cutinase enantio-selectivity towards the alcohol substrate was low and unaffected by any manipulation of medium conditions.This work has been supported by Fundação para a Ciência e Tecnologia (FCT, Portugal) through the contracts PRAXIS/PBIO/14314/1998 and POCTI/35429/QUI/2000 and the grant PRAXIS XXI/BD/21615/99 (S. Garcia), and by FEDER.We thank Ricardo Baptista for help in the production of cutinase

Thin films composed of Ag nanoclusters dispersed in TiO2: Influence of composition and thermal annealing on the microstructure and physical responses

Noble metal powders containing gold and silver have been used for many centuries, providing different colours in the windows of the medieval cathedrals and in ancient Roman glasses. Nowadays, the interest in nanocomposite materials containing noble nanoparticles embedded in dielectric matrices is related with their potential use for a wide range of advanced technological applications. They have been proposed for environmental and biological sensing, tailoring colour of functional coatings, or for surface enhanced Raman spectroscopy. Most of these applications rely on the so-called localised surface plasmon resonance absorption, which is governed by the type of the noble metal nanoparticles, their distribution, size and shape and as well as of the dielectric characteristics of the host matrix. The aim of this work is to study the influence of the composition and thermal annealing on the morphological and structural changes of thin films composed of Ag metal clusters embedded in a dielectric TiO2 matrix. Since changes in size, shape and distribution of the clusters are fundamental parameters for tailoring the properties of plasmonic materials, a set of films with different Ag concentrations was prepared. The optical properties and the thermal behaviour of the films were correlated with the structural and morphological changes promoted by annealing. The films were deposited by DC magnetron sputtering and in order to promote the clustering of the Ag nanoparticles the as-deposited samples were subjected to an in-air annealing protocol. It was demonstrated that the clustering of metallic Ag affects the optical response spectrum and the thermal behaviour of the films.This research was sponsored by FEDER funds through the COMPETE program (Programa Operacional Factores de Competitividade) and by FCT (Fundação para a Ciência e a Tecnologia), under the projects PEST-C/FIS/UI607/2013 and PEst-C/EME/UI0285/2013. The authors also acknowledge the financial support by the project Nano4color – Design and develop a new generation of color PVD coatings for decorative applications (FP7 EC R4SME Project No. 315286). J. Borges also acknowledges the support by the European social fund within the framework of realising the project “Support of inter-sectoral mobility and quality enhancement of research teams at Czech Technical University in Prague”, CZ.1.07/2.3.00/30.0034. C. Lopes acknowledges FCT for the PhD grant SFRH/BD/103373/2014. F.M. Couto acknowledges CAPES – Foundation, Ministry of Education of Brazil, Brasília – DF 70040-20, Brazil, funding by stage sandwich doctorate, through PDSE – Doctoral Program Sandwich

Phase transitions in the spinless Falicov-Kimball model with correlated hopping

The canonical Monte-Carlo is used to study the phase transitions from the low-temperature ordered phase to the high-temperature disordered phase in the two-dimensional Falicov-Kimball model with correlated hopping. As the low-temperature ordered phase we consider the chessboard phase, the axial striped phase and the segregated phase. It is shown that all three phases persist also at finite temperatures (up to the critical temperature $\tau_c$) and that the phase transition at the critical point is of the first order for the chessboard and axial striped phase and of the second order for the segregated phase. In addition, it is found that the critical temperature is reduced with the increasing amplitude of correlated hopping $t'$ in the chessboard phase and it is strongly enhanced by $t'$ in the axial striped and segregated phase.Comment: 17 pages, 6 figure

Impact of lifting of two types of barrels on postural control, trunk muscle recruitment, and kinematic measures in manual workers

The aim of this study was to evaluate the impact of 2 types of beer barrels on postural control, trunk activation, and kinematic measures in adult workers. Twelve (12) males randomly performed 4 tasks on a force platform for 20 s: (1) hold an empty recyclable barrel, (2) hold a full recyclable barrel (30 L), (3) hold an empty steel barrel, and (4) hold a full steel barrel (30 L). Trunk muscular activation, force platform and kinematic measures at the trunk, hip, and knee joints were computed. The full steel barrel produced greater postural oscillation than other conditions. Higher trunk activity was also reported during the full steel barrel task. Significant kinematic changes only in the trunk were observed between the empty steel barrel and the full recyclable barrel tasks. In conclusion, the full steel barrel produced a negative impact on postural control, increasing trunk activity and changing trunk flexion angle in adult workers

Arapaima gigas stocks have declined drastically in the lower Tocantins River in the Amazon Microregion

Abstract Arapaima gigas, an emblematic species of the Amazon region and a longstanding primary fishing resource, currently holds a “Data Deficient” status on the International Union for Conservation of Nature Red List, and is listed as an endangered species in Brazil. The Tocantins River is the most extensively modified large tributary of the Amazon Basin, and thus can affect the dynamics of ichthyofaunal populations. Over a period of 1 year, representatives of the fishing communities and fishermen from 25 fishing communities from four municipalities in the lower Tocantins River region were interviewed, and the obtained information was evaluated based on the literature to survey the population abundance status of A. gigas in the region and its impact on local communities. Among the fishermen interviewed, only one reported still encountering and fishing A. gigas on Jaracuera Island. The disappearance of A. gigas in the region are viewed as having economically disastrous consequences for the residents. Additionally, other endemic fish species are no longer observed in this locality either. If fishery management officials do not work together with local communities, A. gigas could disappear from the northern region of Brazil, where information on the dynamics of A. gigas fishing is lacking