Variability in functional brain networks predicts expertise during action observation.

Observing an action performed by another individual activates, in the observer, similar circuits as those involved in the actual execution of that action. This activation is modulated by prior experience; indeed, sustained training in a particular motor domain leads to structural and functional changes in critical brain areas. Here, we capitalized on a novel graph-theory approach to electroencephalographic data (Fraiman et al.

Palladium-Catalyzed Enantioselective Redox-Relay Heck Arylation of 1,1-Disubstituted Homoallylic Alcohols.

An enantioselective redox-relay oxidative Heck arylation of 1,1-disubstituted alkenes to construct β-stereocenters was developed using a new pyridyl-oxazoline ligand. Various 1,2-diaryl carbonyl compounds were readily obtained in moderate yield and good to excellent enantioselectivity. Additionally, analysis of the reaction outcomes using multidimensional correlations revealed that enantioselectivity is tied to specific electronic features of the 1,1-disubstituted alkenol and the extent of polarizability of the ligand.

Perceptual learning effect on decision and confidence thresholds.

Practice can enhance of perceptual sensitivity, a well-known phenomenon called perceptual learning. However, the effect of practice on subjective perception has received little attention. We approach this problem from a visual psychophysics and computational modeling perspective.

How language flows when movements don't: An automated analysis of spontaneous discourse in Parkinson's disease.

To assess the impact of Parkinson's disease (PD) on spontaneous discourse, we conducted computerized analyses of brief monologues produced by 51 patients and 50 controls. We explored differences in semantic fields (via latent semantic analysis), grammatical choices (using part-of-speech tagging), and word-level repetitions (with graph embedding tools). Although overall output was quantitatively similar between groups, patients relied less heavily on action-related concepts and used more subordinate structures.

Mechanism and Selectivity in the Pd-Catalyzed Difunctionalization of Isoprene.

The three-component coupling of isoprene, an alkenyl triflate, and styrenylboronic acid catalyzed by a palladium pyrox complex affords access to skipped dienes from simple chemical feedstocks. Unfortunately, the transformation proceeds with only moderate selectivity and yields. The reaction mechanism and factors responsible for the resulting regioselectivity were elucidated using M06/SDD/6-311++G(d,p) + SMD calculations.

Neural markers of social and monetary rewards in children with Attention-Deficit/Hyperactivity Disorder and Autism Spectrum Disorder.

Recent theories of decision making propose a shared value-related brain mechanism for encoding monetary and social rewards. We tested this model in children with Attention-Deficit/Hyperactivity Disorder (ADHD), children with Autism Spectrum Disorder (ASD) and control children. We monitored participants' brain dynamics using high density-electroencephalography while they played a monetary and social reward tasks.

Exploring the anatomical encoding of voice with a mathematical model of the vocal system.

The faculty of language depends on the interplay between the production and perception of speech sounds. A relevant open question is whether the dimensions that organize voice perception in the brain are acoustical or depend on properties of the vocal system that produced it. One of the main empirical difficulties in answering this question is to generate sounds that vary along a continuum according to the anatomical properties the vocal apparatus that produced them.

Child-mother attachments in the face of grandparent HIV.

Child-mother attachment, as observed in the Strange Situation (SSP), was assessed in 61 families affected by HIV and 18 neighborhood comparison families not affected by HIV, but of similar ethnicity and socioeconomic status. Children were aged one to three years at the assessment. Secure attachment was significantly less likely among children in the HIV-affected group than among comparison group children (36% versus 67%).

The Development of Multidimensional Analysis Tools for Asymmetric Catalysis and Beyond.

In most modern organic chemistry reports, including many of ours, reaction optimization schemes are typically presented to showcase how reaction conditions have been tailored to augment the reaction's yield and selectivity. In asymmetric catalysis, this often involves evaluation of catalyst, solvent, reagent, and, sometimes, substrate features. Such an article will then detail the process's scope, which mainly focuses on its successes and briefly outlines the "limitations".

Parameterization of phosphine ligands reveals mechanistic pathways and predicts reaction outcomes.

The mechanistic foundation behind the identity of a phosphine ligand that best promotes a desired reaction outcome is often non-intuitive, and thus has been addressed in numerous experimental and theoretical studies. In this work, multivariate correlations of reaction outcomes using 38 different phosphine ligands were combined with classic potentiometric analyses to study a Suzuki reaction, for which the site selectivity of oxidative addition is highly dependent on the nature of the phosphine. These studies shed light on the generality of hypotheses regarding the structural influence of different classes of phosphine ligands on the reaction mechanism(s), and deliver a methodology that should prove useful in future studies of phosphine ligands.

Iridium(iii)-bis(imidazolinyl)phenyl catalysts for enantioselective C-H functionalization with ethyl diazoacetate.

The intermolecular enantioselective C-H functionalization with acceptor-only metallocarbenes is reported using a new family of Ir(iii)-bis(imidazolinyl)phenyl catalysts, developed based on the interplay of experimental and computational insights. The reaction is tolerant of a variety of diazoacetate precursors and is found to be heavily influenced by the steric and electronic properties of the substrate. Phthalan and dihydrofuran derivatives are functionalized in good yields and excellent enantioselectivities.

Intra- and inter-individual differences in human sperm DNA methylation.

There is growing evidence that sperm DNA methylation is important in maintaining proper sperm health and function. Previous studies have associated sperm DNA methylation levels with sperm quality and function, however, little is known regarding the intra- and inter-individual variability in sperm methylation levels. This study characterizes this variation.

Ghrelin Inhibits Post-Operative Adhesions via Blockage of the TGF-β Signaling Pathway.

Post-operative adhesions are a critical problem in pelvic and abdominal surgery despite a multitude of studies dedicated to finding modalities to prevent their occurrence. Ghrelin administration promotes an anti-fibrotic response in a surgical mouse model of adhesion-induction, but the mechanisms mediating this effect have not been established. In the current study, the molecular mechanisms that underlie the anti-adhesion effect of ghrelin were investigated.

Assessing evidentiary value in fire debris analysis by chemometric and likelihood ratio approaches.

Results are presented from support vector machine (SVM), linear and quadratic discriminant analysis (LDA and QDA) and k-nearest neighbors (kNN) methods of binary classification of fire debris samples as positive or negative for ignitable liquid residue. Training samples were prepared by computationally mixing data from ignitable liquid and substrate pyrolysis databases. Validation was performed on an unseen set of computationally mixed (in silico) data and on fire debris from large-scale research burns.

Palladium-Catalyzed 1,3-Difunctionalization Using Terminal Alkenes with Alkenyl Nonaflates and Aryl Boronic Acids.

A Pd-catalyzed 1,3-difunctionalization of terminal alkenes using 1,1-disubstituted alkenyl nonaflates and arylboronic acid coupling partners is reported. This transformation affords allylic arene products that are difficult to selectively access using traditional Heck cross-coupling methodologies. The evaluation of seldom employed 1,1-disubstituted alkenyl nonaflate coupling partners led to the elucidation of subtle mechanistic features of π-allyl stabilized Pd-intermediates.

Substrate channelling as an approach to cascade reactions.

Millions of years of evolution have produced biological systems capable of efficient one-pot multi-step catalysis. The underlying mechanisms that facilitate these reaction processes are increasingly providing inspiration in synthetic chemistry. Substrate channelling, where intermediates between enzymatic steps are not in equilibrium with the bulk solution, enables increased efficiencies and yields in reaction and diffusion processes.

Enantiodivergent Fluorination of Allylic Alcohols: Data Set Design Reveals Structural Interplay between Achiral Directing Group and Chiral Anion.

Enantioselectivity values represent relative rate measurements that are sensitive to the structural features of the substrates and catalysts interacting to produce them. Therefore, well-designed enantioselectivity data sets are information rich and can provide key insights regarding specific molecular interactions. However, if the mechanism for enantioselection varies throughout a data set, these values cannot be easily compared.

Confidence through consensus: a neural mechanism for uncertainty monitoring.

Models that integrate sensory evidence to a threshold can explain task accuracy, response times and confidence, yet it is still unclear how confidence is encoded in the brain. Classic models assume that confidence is encoded in some form of balance between the evidence integrated in favor and against the selected option. However, recent experiments that measure the sensory evidence's influence on choice and confidence contradict these classic models.

Brain Network Organization and Social Executive Performance in Frontotemporal Dementia.

Objectives: Behavioral variant frontotemporal dementia (bvFTD) is characterized by early atrophy in the frontotemporoinsular regions. These regions overlap with networks that are engaged in social cognition-executive functions, two hallmarks deficits of bvFTD. We examine (i) whether Network Centrality (a graph theory metric that measures how important a node is in a brain network) in the frontotemporoinsular network is disrupted in bvFTD, and (ii) the level of involvement of this network in social-executive performance.

The First Rule of Plant Transposable Element Silencing: Location, Location, Location.

Transposable elements (TEs) are mobile units of DNA that comprise large portions of plant genomes. Besides creating mutations via transposition and contributing to genome size, TEs play key roles in chromosome architecture and gene regulation. TE activity is repressed by overlapping mechanisms of chromatin condensation, epigenetic transcriptional silencing, and targeting by small interfering RNAs.

Ghrelin ameliorates adhesions in a postsurgical mouse model.

Background: Peritoneal adhesion formation is a well-recognized consequence of abdominal and pelvic surgery, causing infertility, chronic pelvic pain, and intestinal obstruction. We hypothesized that ghrelin, a 28-amino acid peptide predominantly found in the stomach, plays an important role in preventing postoperative surgical adhesions. The purpose of this study was to develop a new surgical peritoneal adhesion model to define the role that ghrelin plays in wound healing and adhesion formation.

Recurrent varicocele.

Varicocele recurrence is one of the most common complications associated with varicocele repair. A systematic review was performed to evaluate varicocele recurrence rates, anatomic causes of recurrence, and methods of management of recurrent varicoceles. The PubMed database was evaluated using keywords "recurrent" and "varicocele" as well as MESH criteria "recurrent" and "varicocele.

Nudging Cooperation in a Crowd Experiment.

We examine the hypothesis that driven by a competition heuristic, people don't even reflect or consider whether a cooperation strategy may be better. As a paradigmatic example of this behavior we propose the zero-sum game fallacy, according to which people believe that resources are fixed even when they are not. We demonstrate that people only cooperate if the competitive heuristic is explicitly overridden in an experiment in which participants play two rounds of a game in which competition is suboptimal.