Mid- and Far-Infrared Marker Bands of the Metal Coordination Sites of the Histidine Side Chains in the Protein Cu,Zn-Superoxide Dismutase

International audienceVibrational spectroscopy gives important information on the properties of ligand and metal–ligand bonds in metalloenzymes. Infrared spectroscopy is appealing for the study of metal active sites that are not amenable to Raman spectroscopy. We present a combined experimental and theoretical approach to analyze the mid- and far-IR spectra of Cu,Zn-superoxide dismutase (Cu,Zn-SOD) as a probe of the histidine ligands. This metalloenzyme provides a unique model to identify specific IR signatures of metal–histidine coordination and to study their alterations as a function of the metal (copper/zinc), the copper valence state (+I/+II), the histidine coordination mode (Nτ and Nπ) and the histidine protonation state. DFT calculations combined with normal mode descriptions from potential energy distribution calculations were performed on two slightly different cluster models. Differences in the constraints at the side chain of one histidine Cu ligand sensibly modify the geometric parameters and vibrational properties. Electrochemically induced FTIR difference spectroscopy provided mid- and far-IR fingerprint spectra of the Cu protein in aqueous media that are sensitive to the redox state of the Cu centre at the active site. Comparisons of the DFT predictions with the experimental IR modes of the histidine ligands at the Cu,Zn-SOD active site showed that useful mid-IR markers of histidine Nτ and Nπ coordination were predicted with good accuracy. The DFT analysis further demonstrated a link between the ν(C4–C5) mode frequency of His46 and the specific properties of the His46–Cu bond in Cu,Zn-SOD. A combined theoretical and experimental approach on samples in H2O and 2H2O or 15N-labelled samples identified the contributions from the histidine side chain modes in the 669–629 cm–1 region

Texture in ITO films deposited at oblique incidence by ion beam sputtering

Texture of crystalline In2O3:Sn (ITO) thin films prepared by combining ion beam sputtering (IBS) at room temperature and oblique angle deposition (OAD) has been studied depending on the vapor incidence on Si substrates (alpha, ranging from 50 degrees to 85 degrees) and the ions used to sputter the target (argon or xenon accelerated at 1.2 keV). Films obtained using Xe ions show an unusual evolution depending on the deposition angle alpha, with the development of a dual biaxial (1 1 1) off-axis texture for alpha 70 degrees that leads to a biaxial (0 0 1) texture at highest deposition angles. These behaviors are well described by mechanisms involving a maximization of the direct capture of the adatoms on {1 1 1} planes, which can however be hindered when mobilities are exalted such as in the case of Ar deposition. The tuning of adatoms mobilities through the IBS process mixed with the control of the deposition angle offered by the OAD geometry appears as an efficient route to achieve an upgraded texture engineering in nanostructured ITO thin films

Application of advanced (S)TEM methods for the study of nanostructured porous functional surfaces: A few working examples

Nanostructured films offer the ability of modifying surface properties, even more, when they can generate layers with controlled porosity. The lower implicit integrity of these (multi)layers when compared to their compact counterparts, hinders the attainment of electron-transparent sections of submicron thicknesses (lamellae), which becomes one of the main reason for the scarcity of studies thorough (scanning-)transmission electron microscopy ((S)TEM). Aware of this opportunity, this report provides an overview of the possibilities offered by the application of a variety of (S)TEM techniques for the study of nanostructured and porous photonic surfaces. A few working examples are presented to illustrate the type of information that can be obtained in the case of mesoporous films prepared either by at oblique angles physical processes as well as nitride nanowire arrays prepared by epitaxy methods. It will be demonstrated that this approach enables the realization of several pioneering works, which are essential to complete the characterization of such porosity-controlled coatings. Topics as diverse as the preparation of electron-transparent specimens and the advanced characterization of their structures, morphologies, interfaces and compositions are addressed thanks to the implementation of new breakthroughs in (S)TEM, which allow to obtain high-resolution imaging, spectroscopies, or tomography, at both microscopic and nanoscopic levels. Finally, establishing (S)TEM as a reference tool for the advanced structural, chemical and morphological characterization of porous nanostructured skins, will open new horizons, providing better and new insights and thus allowing the optimization of the fabrication and design of such architectures

The pivotal role of effort beliefs in mediating implicit theories of intelligence and achievement goals & academic motivations

Empirical studies into meaning systems surrounding implicit theories of intelligence typically entail two stringent assumptions: that different implicit theories and different effort beliefs represent opposite poles on a single scale, and that implicit theories directly impact the constructs as achievement goals and academic motivations. Through an empirical study based on a large sample of university students, we aim to demonstrate that relaxing these stringent assumptions, and thereby using the meaning system framework to its full potential, will provide strong benefits: effort beliefs are crucial mediators of relationships between implicit theories and achievement goals and academic motivations, and the different poles of implicit theories and effort beliefs do expose different relationships with goal setting behaviour and academic motivations. A structural equation model, cross-validated by demonstrating gender-invariance of path coefficients, demonstrates that incremental and entity theory views have less predictive power than positive and negative effort beliefs in explaining achievement goals and motivations

Cognitive engagement in the problem-based learning classroom

The objective of the present study was to examine to what extent autonomy in problem-based learning (PBL) results in cognitive engagement with the topic at hand. To that end, a short self-report instrument was devised and validated. Moreover, it was examined how cognitive engagement develops as a function of the learning process and the extent to which cognitive engagement determines subsequent levels of cognitive engagement during a one-day PBL event. Data were analyzed by means of confirmatory factor analysis, repeated measures ANOVA, and path analysis. The results showed that the new measure of situational cognitive engagement is valid and reliable. Furthermore, the results revealed that students’ cognitive engagement significantly increased as a function of the learning event. Implications of these findings for PBL are discussed