A Theoretical mechanistic investigation of asymmetric aziridination by N-Aryl-O-acylhydroxylamines

This paper reports a theoretical investigation of the most probable mechanism for the asymmetric aziridination of olefins by N‐aryl‐O‐acylhydroxylamines. The transition states of two possible mechanisms (Scheme 2) were studied. The transition state for pathway 2 (oxaziridine as intermediate) has a lower energy of activation than the energy of the transition state for pathway 1. The anionic transition state of pathway 2 is more stable than the neutral transition state

Chemoselective polymerizations from mixtures of epoxide, lactone, anhydride, and carbon dioxide

Controlling polymer composition starting from mixtures of monomers is an important, but rarely achieved, target. Here a single switchable catalyst for both ring-opening polymeri-zation (ROP) of lactones and ring-opening copolymerization (ROCOP) of epoxides, anhydrides and CO2 is investigated, using both experimental and theoretical methods. Different combinations of four model monomers: -caprolactone, cyclohexene oxide, phthalic anhydride and carbon dioxide are investigated using a single dizinc catalyst. The catalyst switches between the distinct polymerization cycles and shows high monomer selectivity resulting in block sequence control and predictable compositions (esters and car-bonates) in the polymer chain. The understanding gained of the orthogonal reactivity of monomers, specifically con-trolled by the nature of the metal-chain end group, opens the way to engineer polymer block sequences

Blunted neural response to anticipation, effort and consummation of reward and aversion in adolescents with depression symptomatology

Neural reward function has been proposed as a possible biomarker for depression. However how the neural response to reward and aversion might differ in young adolescents with current symptoms of depression is as yet unclear. 33 adolescents were recruited. 17 scoring low on the Mood and Feelings Questionnaire (MFQ) (Low Risk: LR) and 16 scoring high on the MFQ (High Risk: HR). Our fMRI task measured; anticipation (pleasant/unpleasant cue), effort (achieve a pleasant taste or avoid an unpleasant taste) and consummation (pleasant/unpleasant tastes) in Regions of Interest; ventral medial prefrontal cortex (vmPFC), pregenual cingulate cortex (pgACC), the insula and ventral striatum. We also examined whole brain group differences. In the ROI analysis we found reduced activity in the HR group in the pgACC during anticipation and reduced pgACC and vmPFC during effort and consummation. In the whole brain analysis we also found reduced activity in the HR group in the prefrontal cortex and the precuneus during anticipation. We found reduced activity in the hippocampus during the effort phase and in the anterior cingulate/frontal pole during consummation in the HR group. Increased anhedonia measures correlated with decreased pgACC activity during consummation in the HR group only. Our results are the first to show that adolescents with depression symptoms have blunted neural responses during the anticipation, effort and consummation of rewarding and aversive stimuli. This study suggests that interventions in young people at risk of depression, that can reverse blunted responses, might be beneficial as preventative strategies

Blue Obelisk - Interoperability in chemical informatics

The Blue Obelisk Movement (http://www.blueobelisk.org/) is the name used by a diverse Internet group promoting reusable chemistry via open source software development, consistent and complimentary chemoinformatics research, open data, and open standards. We outline recent examples of cooperation in the Blue Obelisk group:  a shared dictionary of algorithms and implementations in chemoinformatics algorithms drawing from our various software projects; a shared repository of chemoinformatics data including elemental properties, atomic radii, isotopes, atom typing rules, and so forth; and Web services for the platform-independent use of chemoinformatics programs

Expanding TCAD Simulations from Grid to Cloud

Abstract-In this work, the distribution, execution and performance of TCAD simulations on grid and cloud systems are investigated. A module for distributed computing which can uniformly interface both grid and cloud computing systems has been implemented within GTS Framework. Automated allocation of resources for user jobs on a combined platform has been achieved. Traditional grid-computing systems are compared with cloud-based systems. Strategies for cost-effective allocation of cloud-resources are presented. The performance of a typical TCAD application run on a grid, in the cloud, and a hybrid system combining both are assessed

(±)-Polysiphenol and other Analogues via Symmetrical Intermolecular Dimerizations: a Synthetic, Spectroscopic, Structural and Computational Study

We report an improved total synthesis of 4,5-dibromo-9,10-dihydrophenanthrene-2,3,6,7-tetraol, (±)-polysiphenol, via intermolecular McMurray dimerization of 5-bromovanillin and subsequent intramolecular oxidative coupling as the key steps. The synthetic route is applicable to 4,5-dichloro- and 4,5-difluoro-halologues (as well as a 4,5-dialkyl-analogue). Distinctive AA′BB′ multiplets in their 1H NMR spectra for the dimethylene bridges of the dibromo and dichloro compounds reveal them to be room-temperature stable atropisomers, while for the difluoro compound they present as a singlet. X-ray crystal structure determinations of their tetramethylated synthetic precursors show atropisomeric twist angles of 48°, 46°, and 32°, respectively, with the former representing the largest yet observed in any 4,5-disubstituted-9,10-dihydrophenanthrene. DFT computational studies reveal an unprecedented two-stage atropisomeric interconversion process involving time-independent asynchronous rotations of the dimethylene bridge and the biaryl axis for halologues containing chlorine or bromine, but a more synchronous rotation for the difluoro analogue

Research Data Management 'Green Shoots' Pilot Programme, Final Reports

This document contains the final reports of six Research Data Management Green Shoots projects run at Imperial College in 2014

Spin states of zigzag-edged Mobius graphene nanoribbons from first principles

Mobius graphene nanoribbons have only one edge topologically. How the magnetic structures, previously associated with the two edges of zigzag-edged flat nanoribbons or cyclic nanorings, would change for their Mobius counterparts is an intriguing question. Using spin-polarized density functional theory, we shed light on this question. We examine spin states of zigzag-edged Mobius graphene nanoribbons (ZMGNRs) with different widths and lengths. We find a triplet ground state for a Mobius cyclacene, while the corresponding two-edged cyclacene has an open-shell singlet ground state. For wider ZMGNRs, the total magnetization of the ground state is found to increase with the ribbon length. For example, a quintet ground state is found for a ZMGNR. Local magnetic moments on the edge carbon atoms form domains of majority and minor spins along the edge. Spins at the domain boundaries are found to be frustrated. Our findings show that the Mobius topology (i.e., only one edge) causes ZMGNRs to favor one spin over the other, leading to a ground state with non-zero total magnetization.Comment: 17 pages, 4 figure