Iridium-Catalyzed Silylation of Five-Membered Heteroarenes: High Sterically Derived Selectivity from a Pyridyl-Imidazoline Ligand.

The steric effects of substituents on five-membered rings are less pronounced than those on six-membered rings because of the difference in bond angles. Thus, the regioselectivities of reactions of five-membered heteroarenes that occur with selectivities dictated by steric effects, such as the borylation of C-H bonds, have been poor in many cases. We report that the silylation of five-membered-ring heteroarenes occurs with high sterically derived regioselectivity when catalyzed by the combination of [Ir(cod)(OMe)]2 (cod=1,5-cyclooctadiene) and a phenanthroline ligand or a new pyridyl-imidazoline ligand that further increases the regioselectivity. The silylation reactions with these catalysts produce high yields of heteroarylsilanes from functionalization at the most sterically accessible C-H bonds of these rings under conditions that the borylation of C-H bonds with previously reported catalysts formed mixtures of products or products that are unstable. The heteroarylsilane products undergo cross-coupling reactions and substitution reactions with ipso selectivity to generate heteroarenes that bear halogen, aryl, and perfluoroalkyl substituents

Aberrant neural signatures of decision-making:Pathological gamblers display cortico-striatal hypersensitivity to extreme gambles

AbstractPathological gambling is an addictive disorder characterized by an irresistible urge to gamble despite severe consequences. One of the hallmarks of pathological gambling is maladaptive and highly risky decision-making, which has been linked to dysregulation of reward-related brain regions such as the ventral striatum. However, previous studies have produced contradictory results regarding the implication of this network, revealing either hypo- or hypersensitivity to monetary gains and losses. One possible explanation is that the gambling brain might be misrepresenting the benefits and costs when weighting the potential outcomes, and not the gains and losses per se. To address this issue, we investigated whether pathological gambling is associated with abnormal brain activity during decisions that weight the utility of possible gains against possible losses. Pathological gamblers and healthy human subjects underwent functional magnetic resonance imaging while they accepted or rejected mixed gain/loss gambles with fifty–fifty chances of winning or losing. Contrary to healthy individuals, gamblers showed a U-shaped response profile reflecting hypersensitivity to the most appetitive and most aversive bets in an executive cortico-striatal network including the dorsolateral prefrontal cortex and caudate nucleus. This network is concerned with the evaluation of action–outcome contingencies, monitoring recent actions and anticipating their consequences. The dysregulation of this specific network, especially for extreme bets with large potentials consequences, offers a novel understanding of the neural basis of pathological gambling in terms of deficient associations between gambling actions and their financial impact

Imaging the Creative Unconscious:Reflexive Neural Responses to Objects in the Visual and Parahippocampal Region Predicts State and Trait Creativity

Abstract What does it take to have a creative mind? Theories of creative cognition assert that the quantity of automatic associations places fundamental constraints on the probability of reaching creative solutions. Due to the difficulties inherent in isolating automated associative responses from cognitive control, the neural basis underlying this faculty remains unknown. Here we acquired fMRI data in an incidental-viewing paradigm in which subjects performed an attention-demanding task whilst viewing task-irrelevant objects. By assigning a standard creativity task on the same objects out of the scanner, as well as a battery of psychometric creativity tests, we could assess whether stimulus-bound neural activity was predictive of state or trait variability in creativity. We found that stimulus-bound responses in superior occipital regions were linearly predictive of trial-by-trial variability in creative performance (state-creativity), and that in more creative individuals (trait-creativity) this response was more strongly expressed in entorhinal cortex. Additionally, the mean response to the onset of objects in parahippocampal gyrus was predictive of trait differences in creativity. This work suggests that, creative individuals are endowed with occipital and medial temporal reflexes that generate a greater fluency in associative representations, making them more accessible for ideation even when no ideation is explicitly called for

Initial results of tests of depth markers as a surface diagnostic for fusion devices

The Accelerator-Based In Situ Materials Surveillance (AIMS) diagnostic was developed to perform in situ ion beam analysis (IBA) on Alcator C-Mod in August 2012 to study divertor surfaces between shots. These results were limited to studying low-Z surface properties, because the Coulomb barrier precludes nuclear reactions between high-Z elements and the ∼1 MeV AIMS deuteron beam. In order to measure the high-Z erosion, a technique using deuteron-induced gamma emission and a low-Z depth marker is being developed. To determine the depth of the marker while eliminating some uncertainty due to beam and detector parameters, the energy dependence of the ratio of two gamma yields produced from the same depth marker will be used to determine the ion beam energy loss in the surface, and thus the thickness of the high-Z surface. This paper presents the results of initial trials of using an implanted depth marker layer with a deuteron beam and the method of ratios. First tests of a lithium depth marker proved unsuccessful due to the production of conflicting gamma peaks, among other issues. However, successful trials with a boron depth marker show that it is possible to measure the depth of the marker layer with the method of gamma yield ratios.United States. Department of Energy. (grant number DE-FG02-94ER54235, cooperative agreement number DEFC02-99ER54512

The native cistrome and sequence motif families of the maize ear

Elucidating the transcriptional regulatory networks that underlie growth and development requires robust ways to define the complete set of transcription factor (TF) binding sites. Although TF-binding sites are known to be generally located within accessible chromatin regions (ACRs), pinpointing these DNA regulatory elements globally remains challenging. Current approaches primarily identify binding sites for a single TF (e.g. ChIP-seq), or globally detect ACRs but lack the resolution to consistently define TF-binding sites (e.g. DNAse-seq, ATAC-seq). To address this challenge, we developed MNase-defined cistrome-Occupancy Analysis (MOA-seq), a high-resolution (< 30 bp), high-throughput, and genome-wide strategy to globally identify putative TF-binding sites within ACRs. We used MOA-seq on developing maize ears as a proof of concept, able to define a cistrome of 145,000 MOA footprints (MFs). While a substantial majority (76%) of the known ATAC-seq ACRs intersected with the MFs, only a minority of MFs overlapped with the ATAC peaks, indicating that the majority of MFs were novel and not detected by ATAC-seq. MFs were associated with promoters and significantly enriched for TF-binding and long-range chromatin interaction sites, including for the well-characterized FASCIATED EAR4, KNOTTED1, and TEOSINTE BRANCHED1. Importantly, the MOA-seq strategy improved the spatial resolution of TF-binding prediction and allowed us to identify 215 motif families collectively distributed over more than 100,000 non-overlapping, putatively-occupied binding sites across the genome. Our study presents a simple, efficient, and high-resolution approach to identify putative TF footprints and binding motifs genome-wide, to ultimately define a native cistrome atlas

An accelerator facility for intermediate energy proton irradiation and testing of nuclear materials

The bulk irradiation of materials with 10-30 MeV protons promises to advance the study of radiation damage for fission and fusion power plants. Intermediate energy proton beams can now be dedicated to materials irradiation within university-scale laboratories. This paper describes the first such facility, with an Ionetix ION-12SC cyclotron producing 12 MeV proton beams. Samples are mm-scale tensile specimens with thicknesses up to 300 um, mounted to a cooled beam target with control over temperature. A specialized tensile tester for radioactive specimens at high temperature (500+ {\deg}C) and/or vacuum represents the conditions in fission and fusion systems, while a digital image correlation system remotely measures strain. Overall, the facility provides university-scale irradiation and testing capability with intermediate energy protons to complement traditional in-core fission reactor and micro-scale ion irradiation. This facility demonstrates that bulk proton irradiation is a scalable and effective approach for nuclear materials research, down-selection, and qualification.Comment: Submitted to NIM B journa

Measurement of the Positive Muon Lifetime and Determination of the Fermi Constant to Part-per-Million Precision

We report a measurement of the positive muon lifetime to a precision of 1.0 parts per million (ppm); it is the most precise particle lifetime ever measured. The experiment used a time-structured, low-energy muon beam and a segmented plastic scintillator array to record more than 2 x 10^{12} decays. Two different stopping target configurations were employed in independent data-taking periods. The combined results give tau_{mu^+}(MuLan) = 2196980.3(2.2) ps, more than 15 times as precise as any previous experiment. The muon lifetime gives the most precise value for the Fermi constant: G_F(MuLan) = 1.1663788 (7) x 10^-5 GeV^-2 (0.6 ppm). It is also used to extract the mu^-p singlet capture rate, which determines the proton's weak induced pseudoscalar coupling g_P.Comment: Accepted for publication in Phys. Rev. Let