Developmental differences in the control of action selection by social information

Our everyday actions are often performed in the context of a social interaction. We previously showed that, in adults, selecting an action on the basis of either social or symbolic cues was associated with activations in the fronto-parietal cognitive control network, whereas the presence and use of social versus symbolic cues was in addition associated with activations in the temporal and medial prefrontal cortex (MPFC) social brain network. Here we investigated developmental changes in these two networks. Fourteen adults (21–30 years of age) and 14 adolescents (11–16 years) followed instructions to move objects in a set of shelves. Interpretation of the instructions was conditional on the point of view of a visible “director” or the meaning of a symbolic cue (Director Present vs. Director Absent) and the number of potential referent objects in the shelves (3-object vs. 1-object). 3-object trials elicited increased fronto-parietal and temporal activations, with greater left lateral prefrontal cortex and parietal activations in adults than adolescents. Social versus symbolic information led to activations in superior dorsal MPFC, precuneus, and along the superior/middle temporal sulci. Both dorsal MPFC and left temporal clusters exhibited a Director × Object interaction, with greater activation when participants needed to consider the directors' viewpoints. This effect differed with age in dorsal MPFC. Adolescents showed greater activation whenever social information was present, whereas adults showed greater activation only when the directors' viewpoints were relevant to task performance. This study thus shows developmental differences in domain-general and domain-specific PFC activations associated with action selection in a social interaction context

Puberty and risky decision-making in male adolescents

Pubertal development is a potential trigger for increases in risk-taking behaviours during adolescence. Here, we sought to investigate the relationship between puberty and neural activation during risky decision-making in males using functional magnetic resonance imaging (fMRI). Forty-seven males aged 12.5-14.5 years completed an fMRI risk-taking task (BART) and reported their tendencies for risky decision-making using a self-report questionnaire. Puberty was assessed through self-reported pubertal status and salivary testosterone levels. Testosterone concentration, but not physical pubertal status, was positively correlated with self-reported risk-taking behaviour, while neither was correlated with BART performance. Across the whole sample, participants had greater activation of the bilateral nucleus accumbens and right caudate on trials when they made a successful risky decision compared to trials when they made a safe choice or when their risky decision was unsuccessful. There was a negative correlation between pubertal stage and brain activation during unsuccessful risky decision-making trials compared within unsuccessful control trials. Males at a lower stage of pubertal development showed increased activation in the left insula, right cingulate cortex, dorsomedial prefrontal cortex (dmPFC), right putamen and right orbitofrontal cortex (OFC) relative to more pubertally mature males during trials when they chose to take a risk and the balloon popped compared to when they watched the computer make an unsuccessful risky decision. Less pubertally mature males also showed greater activation in brain regions including the dmPFC, right temporal and frontal cortices, right OFC, right hippocampus and occipital cortex in unsuccessful risky trials compared to successful risky trials. These results suggest a puberty-related shift in neural activation within key brain regions when processing outcomes of risky decisions, which may reduce their sensitivity to negative feedback, and in turn contribute to increases in adolescent risk-taking behaviours

Identity of electrons and ionization equilibrium

It is perhaps appropriate that, in a year marking the 90th anniversary of Meghnad Saha seminal paper (1920), new developments should call fresh attention to the problem of ionization equilibrium in gases. Ionization equilibrium is considered in the simplest "physical" model for an electronic subsystem of matter in a rarefied state, consisting of one localized electronic state in each nucleus and delocalized electronic states considered as free ones. It is shown that, despite the qualitative agreement, there is a significant quantitative difference from the results of applying the Saha formula to the degree of ionization. This is caused by the fact that the Saha formula corresponds to the "chemical" model of matter.Comment: 9 pages, 2 figure

Design of robust 2,2′-bipyridine ligand linkers for the stable immobilization of molecular catalysts on silicon(111) surfaces

The attachment of the 2,2′-bipyridine (bpy) moieties to the surface of planar silicon(111) (photo)electrodes was investigated using ab initio simulations performed on a new cluster model for methyl-terminated silicon. Density functional theory (B3LYP) with implicit solvation techniques indicated that adventitious chlorine atoms, when present in the organic linker backbone, led to instability at very negative potentials of the surface-modified electrode. In prior experimental work, chlorine atoms were present as a trace surface impurity due to required surface processing chemistry, and thus could plausibly result in the observed surface instability of the linker. Free energy calculations for the Cl-atom release process with model silyl-linker constructs revealed a modest barrier (14.9 kcal mol⁻¹) that decreased as the electrode potential became more negative. A small library of new bpy-derived structures has additionally been explored computationally to identify strategies that could minimize chlorine-induced linker instability. Structures with fluorine substituents are predicted to be more stable than their chlorine analogues, whereas fully non-halogenated structures are predicted to exhibit the highest stability. The behavior of a hydrogen-evolving molecular catalyst Cp*Rh(bpy) (Cp* = pentamethylcyclopentadienyl) immobilized on a silicon(111) cluster was explored theoretically to evaluate differences between the homogeneous and surface-attached behavior of this species in a tautomerization reaction observed under reductive conditions for catalytic H₂ evolution. The calculated free energy difference between the tautomers is small, hence the results suggest that use of reductively stable linkers can enable robust attachment of catalysts while maintaining chemical behavior on the electrode similar to that exhibited in homogeneous solution

Combined approach of density functional theory and quantum Monte Carlo method to electron correlation in dilute magnetic semiconductors

We present a realistic study for electronic and magnetic properties in dilute magnetic semiconductor (Ga,Mn)As. A multi-orbital Haldane-Anderson model parameterized by density-functional calculations is presented and solved with the Hirsch-Fye quantum Monte Carlo algorithm. Results well reproduce experimental results in the dilute limit. When the chemical potential is located between the top of the valence band and an impurity bound state, a long-range ferromagnetic correlations between the impurities, mediated by antiferromagnetic impurity-host couplings, are drastically developed. We observe an anisotropic character in local density of states at the impurity-bound-state energy, which is consistent with the STM measurements. The presented combined approach thus offers a firm starting point for realistic calculations of the various family of dilute magnetic semiconductors.Comment: 5 pages, 4 figure

Structure of the complex of an Fab fragment of a neutralizing antibody with foot-and-mouth disease virus: Positioning of a highly mobile antigenic loop

Data from cryo-electron microscopy and X-ray crystallography have been combined to study the interactions of foot-and-mouth disease virus serotype C (FMDV-C) with a strongly neutralizing monoclonal antibody (mAb) SD6. The mAb SD6 binds to the long flexible GH-loop of viral protein 1 (VP1) which also binds to an integrin receptor. The structure of the virus-Fab complex was determined to 30 Å resolution using cryo-electron microscopy and image analysis. The known structure of FMDV-C, and of the SD6 Fab co-crystallized with a synthetic peptide corresponding to the GH-loop of VP1, were fitted to the cryo-electron microscope density map. The SD6 Fab is seen to project almost radially from the viral surface in an orientation which is only compatible with monovalent binding of the mAb. Even taking into account the mAb hinge and elbow flexibility, it is not possible to model bivalent binding without severely distorting the Fabs. The bound GH-loop is essentially in what has previously been termed the 'up' position in the best fit Fab orientation. The SD6 Fab interacts almost exclusively with the GH-loop of VP1, making very few other contacts with the viral capsid. The position and orientation of the SD6 Fab bound to FMDV-C is in accord with previous immunogenic data.Peer Reviewe

Magnetoconductivity of quantum wires with elastic and inelastic scattering

We use a Boltzmann equation to determine the magnetoconductivity of quantum wires. The presence of a confining potential in addition to the magnetic field removes the degeneracy of the Landau levels and allows one to associate a group velocity with each single-particle state. The distribution function describing the occupation of these single-particle states satisfies a Boltzmann equation, which may be solved exactly in the case of impurity scattering. In the case where the electrons scatter against both phonons and impurities we solve numerically - and in certain limits analytically - the integral equation for the distribution function, and determine the conductivity as a function of temperature and magnetic field. The magnetoconductivity exhibits a maximum at a temperature, which depends on the relative strength of the impurity and electron-phonon scattering, and shows oscillations when the Fermi energy or the magnetic field is varied.Comment: 21 pages (revtex 3.0), 5 postscript figures available upon request at [email protected] or [email protected]

Regularization of the Coulomb scattering problem

Exact solutions of the Schr\"odinger equation for the Coulomb potential are used in the scope of both stationary and time-dependent scattering theories in order to find the parameters which define regularization of the Rutherford cross-section when the scattering angle tends to zero but the distance r from the center remains fixed. Angular distribution of the particles scattered in the Coulomb field is investigated on the rather large but finite distance r from the center. It is shown that the standard asymptotic representation of the wave functions is not available in the case when small scattering angles are considered. Unitary property of the scattering matrix is analyzed and the "optical" theorem for this case is discussed. The total and transport cross-sections for scattering of the particle by the Coulomb center proved to be finite values and are calculated in the analytical form. It is shown that the considered effects can be essential for the observed characteristics of the transport processes in semiconductors which are defined by the electron and hole scattering in the fields of the charged impurity centers.Comment: 20 pages, 6 figure

Role of Ligand Protonation in Dihydrogen Evolution from a Pentamethylcyclopentadienyl Rhodium Catalyst

Recent work has shown that Cp*Rh(bpy) [Cp* = pentamethylcyclopentadienyl, bpy = 2,2′- bipyridine] undergoes endo protonation at the [Cp*] ligand in the presence of weak acid (Et_3NH^+; pK_a = 18.8 in MeCN). Upon exposure to stronger acid (e.g., DMFH+; pK_a = 6.1), hydrogen is evolved with unity yield. Here, we study the mechanisms by which this catalyst evolves dihydrogen using density functional theory (M06) with polarizable continuum solvation. The calculations show that the complex can be protonated by weak acid first at the metal center with a barrier of 3.2 kcal/mol; this proton then migrates to the ring to form the detected intermediate, a rhodium(I) compound bearing endo η^4-Cp*H. Stronger acid is required to evolve hydrogen, which calculations show happens via a concerted mechanism. The acid approaches and protonates the metal, while the second proton simultaneously migrates from the ring with a barrier of ∼12 kcal/mol. Under strongly acidic conditions, we find that hydrogen evolution can proceed through a traditional metal–hydride species; protonation of the initial hydride to form an H–H bond occurs before migration of the hydride (in the form of a proton) to the [Cp*] ring (i.e., H–H bond formation is faster than hydride–proton tautomerization). This work demonstrates the role of acid strength in accessing different mechanisms of hydrogen evolution. Calculations also predict that modification of the bpy ligand by a variety of functional groups does not affect the preference for [Cp*] protonation, although the driving force for protonation changes. However, we predict that exchange of bpy for a bidentate phosphine ligand will stabilize a rhodium(III) hydride, reversing the preference for bound [Cp*H] found in all computed bpy derivatives and offering an appealing alternative ligand platform for future experimental and computational mechanistic studies of H_2 evolution

Vocabulary intervention for adolescents with language disorder: a systematic review

Background: Language disorder and associated vocabulary difficulties can persist into adolescence, and can impact on long-term life outcomes. Previous reviews have shown that a variety of intervention techniques can successfully enhance students’ vocabulary skills; however, none has investigated vocabulary intervention specifically for adolescents with language disorder. Aims: To carry out a systematic review of the literature on vocabulary interventions for adolescents with language disorder. Methods & Procedures: A systematic search of 14 databases and other sources yielded 1320 studies, of which 13 met inclusion criteria. Inclusion criteria were: intervention effectiveness studies with a focus on enhancing oral receptive and/or expressive vocabulary skills in the study's aims; participants in the age range 11;0–16;11 with receptive and/or expressive language difficulties of any aetiology. Main Contribution: There was a high degree of diversity between studies. Types of intervention included: semantic intervention (four studies); comparison of phonological versus semantic intervention (two); and combined phonological–semantic intervention (seven). The strongest evidence for effectiveness was found with a combined phonological–semantic approach. The evidence suggested a potential for all models of delivery to be helpful (individual, small group and whole class). Conclusions & Implications: Tentative evidence is emerging for the effectiveness of a phonological–semantic approach in enhancing the vocabulary skills of adolescents who have language disorder. Future research needs to refine and develop the methodologies used in this diverse group of studies in order to replicate their findings and to build consensus