are technical fellows at Pratt and Whitney. Both provided extensive guidance on the research plan. Ian Agoos and Tyler Englerth are engineers in the Systems Engineering and Validation group at Pratt and Whitney. Both provided extensive guidance on the research plan and facilitated weekly technical discussions.

The feasibility of more than one mechanism was established for the fragmentation of β-substituted propanoates. The contribution of each mechanistic pathway to the formation of the substituent anion was influenced by structural variations and conformational constraints, but mostly depended on the nature of the substituent. Copyright © 2016 John Wiley & Sons, Ltd.

No abstract

We recently identified three novel thioredoxin-like genes in the genome of the protozoan parasite Plasmodium that belong to the Phosducin-like family of proteins (PhLP). PhLPs are small cytosolic proteins hypothesized to function in G-protein signaling and protein folding. Although PhLPs are highly conserved in eukaryotes from yeast to mammals, only a few representatives have been experimentally characterized to date. In addition, while PhLPs contain a thioredoxin domain, they lack a CXXC motif, a strong indicator for redox activity, and it is unclear whether members of the PhLP family are enzymatically active. Here, we describe PbPhLP-3 as the first phosducin-like protein of a protozoan organism, Plasmodium berghei. Initial transcription analysis revealed continuous low-level expression of pbphlp-3 throughout the complex Plasmodium life cycle. Attempts to knockout pbphlp-3 in P. berghei did not yield live parasites, suggesting an essential role for the gene in Plasmodium. We cloned, expressed and purified PbPhLP-3 and determined that the recombinant protein is redox active in vitro in a thioredoxin-coupled redox assay. It also has the capacity to reduce the organic compound tert-Butyl hydroperoxide (TBHP) in vitro, albeit at low efficiency. Sequence analysis, structural modeling, and site-directed mutagenesis revealed a conserved cysteine in the thioredoxin domain to be the redox active residue. Lastly, we provide evidence that recombinant human PhLP-3 exhibits redox activity similar to that of PbPhLP-3 and suggest that redox activity may be conserved in PhLP-3 homologs of other species. Our data provide new insight into the function of PhLP-3, which is hypothesized to act as co-chaperones in the folding and regulation of cytoskeletal proteins. We discuss the potential implications of PhLP-3 as a thioredoxin-target protein and possible links between the cellular redox network and the eukaryotic protein folding machinery.

A comprehensive and efficient post-processing framework is presented for obtaining aerodynamics measurements of three-component velocity, static temperature, and static density using filtered Rayleigh scattering (FRS). This framework contains several steps which culminate in an optimization process for iterative minimization of errors between the experimentally measured FRS spectra and spectra generated by models, providing an inverse solution to determine the local measurement values. Robustness is gained using a multi-level processing technique for successive spatial resolution refinement of measurements. An assessment of the speed and spectral outputs of several published laser Rayleigh scattering models is provided and resulted in the recommendation that Doll's analytic Tenti-S6 model be adopted as the best trade-off in speed and consistency. A distinguishing feature of the approach is the inclusion of methods for interpreting FRS spectra that contain significant scattering contributions from particles and surfaces. The performance of the methods has been quantified for uncertainties using Monte Carlo simulations, while planar results from two experiments are presented for validation and demonstration of robustness, respectively: a benchtop free jet and the exhaust plume of a miniature turbojet engine. Monte Carlo simulations show that at a signal-to-noise ratio (SNR) of 30 dB the approximate uncertainty in scattering angle is 0.3°, 2.5 K for static temperature, 1.5 m/s for velocity, 0.01 kg/m3 for static density, and 0.01 for both Mie and background scattering intensity ratios. The free jet results show differences of 1.5 K for total temperature, 1 m/s for axial velocity, 0.005 kg/m3 for total density, and 200 Pa for total pressure when compared to probe data. All results fall within the 95% confidence bounds of the a priori uncertainties. The small turbojet (JetCat) results are included to show that the processor is robust and accurate even when used with non-ideal data sets from realistic applications such as vitiated exhausts. The JetCat results show differences of 20 K for total temperature, 8 m/s for axial velocity, 0.01 kg/m3 for total density, and 500 Pa for total pressure when compared to probe data. All results except near the edge of the jet plume fall within the 95% confidence bounds of the a priori uncertainties.