Engaging the pyridine-DMAD zwitterion in a novel strategy for the selective synthesis of highly substituted benzene and cyclopentenedione derivatives

[reaction: see text] The pyridine-mediated reaction of dimethyl acetylenedicarboxylate and cyclobutene-1,2-diones affords selective access to either hexasubstituted benzene derivatives or cyclopentenedione derivatives depending on the concentration of pyridine.     

Pyridine-catalyzed addition of diaryl-1,2-diones to dimethyl butynedioate leading to the formation of 1,2-diaroyl dimethyl maleates via an unprecedented rearrangement

[reaction: see text] Pyridine catalyzes the reaction of 1,2-diaryl diones with dimethyl butynedioate to afford diaroyl maleates. This unprecedented rearrangement involves a unique benzoyl migration and proceeds with complete stereoselectivity.     

Real-time evolution of the distribution of nanoparticles in an ultrathin-polymer-film-based waveguide

We report a novel application of an ultrathin-polymer-film-based, resonance-enhanced x-ray waveguide as a real-time nanoprobe for elucidating dilute, yet disordered, gold nanoparticles embedded in the polymer matrix. This nanoprobe promises a sensitivity enhancement of several orders of magnitude, hence revealing in real time the lateral nanoparticle distribution with subnanometer spatial resolution. We observed that the motion of the nanoparticles is strongly anisotropic, with in-plane coalescence taking place more rapidly than out-of-plane diffusion, which can ultimately facilitate the formation of two-dimensional structures.     

D-branes on Calabi–Yau Manifolds and Superpotentials

We show how to compute terms in an expansion of the world-volume superpotential for fairly general D-branes on the quintic Calabi-Yau using linear sigma model techniques, and show in examples that this superpotential captures the geometry and obstruction theory of bundles and sheaves on this Calabi-Yau.Louis Michel Professor     

Wall mediated transport in confined spaces: exact theory for low density

We present a theory for the transport of molecules adsorbed in slit and cylindrical nanopores at low density, considering the axial momentum gain of molecules oscillating between diffuse wall reflections. Good agreement with molecular dynamics simulations is obtained over a wide range of pore sizes, including the regime of single-file diffusion where fluid-fluid interactions are shown to have a negligible effect on the collective transport coefficient. We show that dispersive fluid-wall interactions considerably attenuate transport compared to classical hard sphere theory.     

Interpretation of Light Scattering Spectra of Dispersions – A Hybrid Approach to Account for Interparticle Interactions

The problem of extracting quantitative information on individual particle properties from spectroscopic measurements conducted at concentrations where particle interactions become significant is of great industrial and theoretical importance. For dispersions of charged particles, this can happen at fairly low concentrations. The effect of the fluid (slurry) structure has to be taken into account to interpret the light scattering spectra of such dispersions. In this paper, a hybrid method that addresses the effect of the fluid structure is proposed. The hybrid approach describes the fluid structure by relating the “effective” Percus‐Yevick hard‐sphere parameters to the system parameters using empirical models. The feasibility of this approach is examined through a theoretical study with data generated by Monte Carlo simulations of a monodisperse dispersion of charged spherical particles using realistic interaction potentials under single scattering conditions.     

A sagittally focusing double‐multilayer monochromator for ultrafast X‐ray imaging applications

The development of a sagittally focusing double‐multilayer monochromator is reported, which produces a spatially extended wide‐bandpass X‐ray beam from an intense synchrotron bending‐magnet source at the Advanced Photon Source, for ultrafast X‐ray radiography and tomography applications. This monochromator consists of two W/B₄C multilayers with a 25 Å period coated on Si single‐crystal substrates. The second multilayer is mounted on a sagittally focusing bender, which can dynamically change the bending radius of the multilayer in order to condense and focus the beam to various points along the beamline. With this new apparatus, it becomes possible to adjust the X‐ray beam size to best match the area detector size and the object size to facilitate more efficient data collection using ultrafast X‐ray radiography and tomography.     

Simulation of spray combustion in a lean-direct injection combustor

Large-eddy simulation (LES) of a liquid-fueled lean-direct injection (LDI) combustor is carried out by resolving the entire inlet flow path through the swirl vanes and the combustor. A localized dynamic subgrid closure is combined with a subgrid mixing and combustion model so that no adjustable parameters are required for both non-reacting and reacting LES. Time-averaged velocity predictions compare well with the measured data. The unsteady flow features that play a major role in spray dispersion, fuel–air mixing and flame stabilization are identified from the simulation data. It is shown that the vortex breakdown bubble (VBB) is smaller with more intense reverse flow when there is heat release. The swirling shear layer plays a major role in spray dispersion and the VBB provides an efficient flameholding mechanism to stabilize the flame.     

1,3-Dipolar cycloaddition of nitrile oxides to (R)-1-(1-phenylethyl)-3,5-bis[(E)-arylmethylidene]tetrahydro-4(1H)-pyridinones: synthesis and antimycobacterial evaluation of novel enantiomerically pure di- and trispiroheterocycles

Enantiomerically pure (R)-(1-phenylethyl)-3,5-bis[(E)-arylmethylidene]tetrahydro-4(1H)-pyridinones were synthesized for the first time, and their 1,3-dipolar cycloaddition with nitrile oxides affording di- and trispiroheterocycles regio- and stereoselectively in moderate yields was investigated. These compounds were evaluated against Mycobacterium tuberculosis H37Rv (MTB) and multi-drug-resistant M. tuberculosis (MDR-TB). Among the compounds screened, the dispiroheterocycle, namely, (5R,6R,10S)-3,9-bis(4-chlorophenyl)-10-(2,4-dichlorophenyl)-14-[(E)-(2,4-dichlorophenyl)methylidene]-12-[(R)-1-phenylethyl]-1,4,7-trioxa-2,8,12-tri-azadispiro[4.0.4.4]tetradeca-2,8-diene 5m was found to possess the maximum activity with MIC of 0.49 μM against MTB, being 9.6 and 15.6 times more potent than ciprofloxacin and ethambutol, respectively. Against MDR-TB, 5m displayed maximum activity with an MIC of 0.49 μM, with it thus being more active than rifampicin, isoniazid, ciprofloxacin and ethambutol by 7.8, 23, 77 and 124 times, respectively.     

Cysteine‐capped ZnSe quantum dots as affinity and accelerating probes for microwave enzymatic digestion of proteins via direct matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometric analysis

Fluorescent semiconductor quantum dots (QDs) exhibit great potential and capability for many biological and biochemical applications. We report a simple strategy for the synthesis of aqueous stable ZnSe QDs by using cysteine as the capping agent (ZnSe‐Cys QDs). The ZnSe QDs can act as affinity probes to enrich peptides and proteins via direct matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry (MALDI‐TOFMS) analysis. This nanoprobe could significantly enhance protein signals (insulin, ubiquitin, cytochrome c, myoglobin and lysozyme) in MALDI‐TOFMS by 2.5–12 times compared with the traditional method. Additionally, the ZnSe‐Cys QDs can be applied as heat absorbers (as accelerating probes) to speed up microwave‐assisted enzymatic digestion reactions and also as affinity probes to enrich lysozyme‐digested products in MALDI‐TOFMS. Furthermore, after the enrichment experiments, the solutions of ZnSe‐Cys QDs mixed with proteins can be directly deposited onto the MALDI plates for rapid analysis. This approach shows a simple, rapid, efficient and straightforward method for direct analysis of proteins or peptides by MALDI‐TOFMS without the requirement for further time‐consuming separation processes, tedious washing steps or laborious purification procedures. The present study has demonstrated that ZnSe‐Cys QDs are reliable and potential materials for rapid, selective separation and enrichment of proteins as well as accelerating probes for microwave‐digested reactions for proteins than the regular MALDI‐MS tools. Additionally, we also believe that this work may also inspire investigations for applications of QDs in the field of MALDI‐MS for proteomics. Copyright © 2009 John Wiley & Sons, Ltd.