Total synthesis of (+/-)-mersicarpine

The first total synthesis of the indole alkaloid mersicarpine is reported. Key steps include a beta-dicarbonyl radical cyclization, as well as an oxidation of the benzopyrrole moiety to establish the masked 1,2-dicarbonyl functionality. An X-ray crystal structure and discussion of the 1H NMR behavior of the natural product are also presented.     

A Simple Primary Amide for the Selective Recovery of Gold from Secondary Resources

Waste electrical and electronic equipment (WEEE) such as mobile phones contains a plethora of metals of which gold is by far the most valuable. Herein a simple primary amide is described that achieves the selective separation of gold from a mixture of metals typically found in mobile phones by extraction into toluene from an aqueous HCl solution; unlike current processes, reverse phase transfer is achieved simply using water. Phase transfer occurs by dynamic assembly of protonated and neutral amides with [AuCl₄]^? ions through hydrogen bonding in the organic phase, as shown by EXAFS, mass spectrometry measurements, and computational calculations, and supported by distribution coefficient analysis. The fundamental chemical understanding gained herein should be integral to the development of metal‐recovery processes, in particular through the use of dynamic assembly processes to build complexity from simplicity.     

Structure conditioned velocity statistics in a high pressure swirl flame

A piloted, partially premixed, liquid-fueled swirl burner is operated at high pressure (1 MPa). High-speed (6 KHz) stereoscopic PIV is used to investigate the characteristics of the stagnation line separating the pilot jet and the central recirculation zone (CRZ) with varying pilot-main ratio and global equivalence ratio. The mean curvature of the stagnation line displayed a large spatial scale pattern that was present for all operating conditions. All three components of velocity, in-plane shear, and swirling strength are conditioned upon the instantaneous stagnation line. Mean distributions of the velocity normal to the stagnation line show that velocity is oriented towards the CRZ when the stagnation line is found nearer the centerline of the combustor. The conditioned out-of-plane velocity (w) shows a distinct concentration of large mean and fluctuation RMS values towards the center of the measurement domain. Varying fuel flow does not significantly change this spatial structure, only the magnitudes of the w statistics. The in-plane shear stress was the largest for the pilot biased condition as a stronger shear layer develops. For the leanest flame, large fluctuation RMS values of shear stress were confined to a region where the pilot jet begins to interact more heavily with the main jet. Operating with less pilot fuel flow enhanced the mean conditional swirling strength indicating that the pilot shear layer was shedding more intense eddies. Disregarding spatial relations, a scatter plot of w, shear stress, and swirling strength displayed trends between the variables. The largest swirling strength values coincide with highest magnitude shear stresses and the widest range of w. These conditioned statistics highlight how certain aspects of the combustor flow field are invariant with fuel distribution. This is desirable for aeropropulsive combustors that must maintain stable ignition from a range of conditions from landing/take-off to cruise.     

Microfluidically-unified cell culture, sample preparation, imaging and flow cytometry for measurement of cell signaling pathways with single cell resolution

We have developed a microfluidic platform that enables, in one experiment, monitoring of signaling events spanning multiple time-scales and cellular locations through seamless integration of cell culture, stimulation and preparation with downstream analysis. A combination of two single-cell resolution techniques-on-chip multi-color flow cytometry and fluorescence imaging provides multiplexed and orthogonal data on cellular events. Automated, microfluidic operation allows quantitatively- and temporally-precise dosing leading to fine time-resolution and improved reproducibility of measurements. The platform was used to profile the toll-like receptor (TLR4) pathway in macrophages challenged with lipopolysaccharide (LPS)-beginning with TLR4 receptor activation by LPS, through intracellular MAPK signaling, RelA/p65 translocation in real time, to TNF-α cytokine production, all in one small macrophage population (< 5000 cells) while using minute reagent volume (540 nL/condition). The platform is easily adaptable to many cell types including primary cells and provides a generic platform for profiling signaling pathways.     

Wavelets and molecular structure

Summary The wavelet method offers possibilities for display, editing, and topological comparison of proteins at a user-specified level of detail. Wavelets are a mathematical tool that first found application in signal processing. The multiresolution analysis of a signal via wavelets provides a hierarchical series of best lower-resolution approximations. B-spline ribbons model the protein fold, with one control point per residue. Wavelet analysis sets limits on the information required to define the winding of the backbone through space, suggesting a recognizable fold is generated from a number of points equal to 1/4 or less the number of residues. Wavelets applied to surfaces and volumes show promise in structure-based drug design.This paper is based on a presentation given at the 14th Molecular Graphics and Modelling Society Conference, held in Cairns, Australia, August 27–September 1, 1995.