Physiologic-insensitive Left Ventricular Assist Predisposes Right-sided Circulatory Failure: a Pilot Simulation and Validation Study

Right-sided circulatory failure (RSCF) is a serious complication in 15–30% of patients receiving a left ventricular assist device (LVAD). It is hypothesized that left ventricular support which lacks physiologic properties predisposes to RSCF. An integral computer simulation and experimental validation protocol was performed. The results suggest that with conventional insensitive left ventricular support right-sided circulatory function is compromised, which may form a substrate for the onset or progress of RSCF. Feedback control of the LVAD could provide a means to counter this problem. A control concept for the LVAD which aims to preserve right-sided circulatory function, while supporting peripheral perfusion, is propose

Discounting and Reciprocity in an Iterated Prisoner’s Dilemma

animal care and breeding, T. Wiltshire for preliminary mapping of the Opn4 locus, F. A. J. M. van de Klundert for help in generating the targeting vector, and the anonymous reviewers for their valuable comments

Structural and Spectroscopic Consequences of Hexacoordination of a Bacteriochlorophyll Cofactor in the Rhodobacter sphaeroides Reaction Center

The structural and functional consequences of changing the coordination state of one of the bacteriochlorophyll (BChl) cofactors in the purple bacterial reaction center have been explored. A combination of steady state spectroscopy and X-ray crystallography was used to demonstrate that mutagenesis of residue 181 of the L-polypeptide from Phe to Arg (FL181R) causes the BChl at the accessory (BB) position on the so-called inactive cofactor branch to become hexacoordinated, with no significant changes to the structure of the surrounding protein. This change was accompanied by the appearance of a distinctive absorbance band at 631 nm in the room-temperature absorbance spectrum. The ligand donor was not the Arg side chain but rather an intervening water molecule, and contrary to expectations, the Mg of BB did not adopt a more in-plane geometry in response to hexacoordination. The mutation caused a disturbance to the detailed conformation of the BChl macrocycle that manifested in a number of subtle changes to the resonance Raman spectrum. Hexacoordination of BB produced a small increase in the lifetime of the excited electronic state of the primary donor bacteriochlorophylls (P*), indicating some disturbance to light-driven energy and/or electron transfer events on the time scale of a few picoseconds after light excitation. The BB bacteriochlorophyll returned to a pentacoordinated state in a double mutant where the FL181R mutation was combined with removal of the native axial ligand through mutation of His M182 to Leu. Experimental evidence of hexacoordinated bacteriochlorophylls in the literature on antenna proteins is considered, and possible reasons why hexacoordinated bacteriochlorophylls and chlorophylls appear to be avoided in photosynthetic proteins are discussed

Electrochemical and spectroscopic methods for evaluating molecular electrocatalysts

© 2017 Macmillan Publishers Limited. Modern energy challenges have amplified interest in transition metal-based molecular electrocatalysts for fuel-forming reactions. The activity of these homogeneous electrocatalysts, and the mechanisms by which they operate, can be uncovered using state-of-the-art electrochemical methods. Catalyst performance can be benchmarked according to metrics obtainable from cyclic voltammograms by analysis of catalytic plateau currents and peak potentials, as well as by foot-of-the-wave analysis. The application of complementary spectroscopic techniques, including spectroelectrochemistry, stopped-flow rapid mixing and transient absorption, are also discussed. In this Review, we present case studies highlighting the utility of these analytical methods in the context of renewable energy. Alongside these examples is a discussion of the theoretical underpinnings of each method, outlining the conditions necessary for the analysis to be rigorous and the type of information that can then be extracted