Dynamics of polydisperse hard-spheres under strong confinement

We use molecular simulation to probe the connection between local structure and the unusual re-entrant dynamics observed for polydisperse hard-sphere liquids confined in thin slit pores. The local structure is characterised by calculating 2-D bond-orientational order parameters associated with square and hexatic order for particles in the layer adjacent to the confining walls. When the wall separation is commensurate with the average particle size, the particles primarily exhibit local hexatic order, whereas local square order increases in prevalence for incommensurate geometries. The relaxation time extracted from the ensemble-averaged mean-square displacement increases exponentially with the static correlation length associated with hexatic local order in strongly confined commensurate geometries, in agreement with theoretical predictions for dynamical slowing. Square order, by contrast, is not associated with a growing length scale for either commensurate or incommensurate geometries, indicating that it is strongly geometrically frustrated. Our results suggest that the influence of bond-orientational order on dynamical slowing may be altered by changing the extent of confinement.     

Block designs signed over groups of order 2n3m

We introduce a new piecewise construction technique for generalised Bhaskar Rao designs and the concepts of generalised Bhaskar Rao block design pieces and holey generalised Bhaskar Rao block designs. We prove composition theorems for these designs. Using this construction technique and the theory of group representations, and the representations of $2$-groups over the field with $3$ elements, we show that the established necessary conditions for the existence of generalised Bhaskar Rao designs of block size $3$ are sufficient for all groups of order $2^n{3}^m$.     

Shock tunnel flow visualization using planar laser-induced fluorescence imaging of NO and OH

Temporal sequences of planar laser-induced fluorescence (PLIF) images of several high-speed, transient flowfields created in a reflection-type shock tunnel facility were acquired. In each case, the test gas contained either nitric oxide or the hydroxyl radical, the fluorescent species. The processes of shock reflection from an endwall with a converging nozzle and of underexpanded free jet formation were examined. A comparison was also made between PLIF imaging and shadow photography. The investigation demonstrated some of the capabilities of PLIF imaging diagnostics in complex, transient, hypersonic flowfields, including those with combustion.Nomenclature A spontaneous emission rate - A _las cross sectional area of laser sheet - B laser absorption rate - C _opt constant dependent on optical arrangement, collection efficiency, etc. - D nozzle throat diameter - E _p laser pulse energy - f _J Boltzmann fraction of absorbing state - g spectral convolution of laser and absorption lineshapes - k Boltzmann constant - M _s incident shock Mach number - N noise, root-mean-square signal fluctuation - P static pressure - P ₁ initial pressure of test gas in shock tube - P _a free jet ambient pressure - P _s stagnation pressure - Q electronic quenching rate of excited state - S PLIF signal - t time between shock reflection and image acquisition - T static temperature - T _s stagnation temperature - _a mole fraction of absorbing species     

An Intramolecular Diels-alder Reaction of a Z-Diene. Generation Of The Chiral Isoindolone Nucleus Of Cytochalasin C.1

Aldol/elimination reactions of ß-ketoamides with methyl glyoxylate result in highly selective production of Z-α,ß-unsaturated amides. An intramolecular Diels-Alder reaction of a triply activated dienophile derived from chiral dienylamine 7ZE stereospecifically affords chiral bicyclic lactam 11 at room temperature.     

Combined Chemical Modification and Collision Induced Unfolding Using Native Ion Mobility-Mass Spectrometry Provides Insights into Protein Gas-Phase Structure

Native mass spectrometry is now an important tool in structural biology. Thus, the nature of higher protein structure in the vacuum of the mass spectrometer is an area of significant interest. One of the major goals in the study of gas-phase protein structure is to elucidate the stabilising role of interactions at the level of individual amino acid residues. A strategy combining protein chemical modification together with collision induced unfolding (CIU) was developed and employed to probe the structure of compact protein ions produced by native electrospray ionisation. Tractable chemical modification was used to alter the properties of amino acid residues, and ion mobility-mass spectrometry (IM-MS) utilised to monitor the extent of unfolding as a function of modification. From these data the importance of specific intramolecular interactions for the stability of compact gas-phase protein structure can be inferred. Using this approach, and aided by molecular dynamics simulations, an important stabilising interaction between K6 and H68 in the protein ubiquitin was identified, as was a contact between the N-terminus and E22 in a ubiquitin binding protein UBA2.