Thrombin is a coagulation factor increased in pregnancy and further increased in preeclampsia (PE), a hypertensive disorder. Thrombin is also expressed in the brain and may have a nonhemostatic role. We characterized thrombin expression and vasoactivity in brain cerebral parenchymal arterioles (PAs) in rat models of pregnancy and PE.
View Article and Find Full Text PDFMesoporous silicon nitride (SiN) is a nontraditional support for the chemisorption of organometallic complexes with the potential for enhancing catalytic activity through features such as the increased Lewis basicity of nitrogen for heterolytic bond activation, increased ligand donor strength, and metal-ligand orbital overlap. Here, tetrabenzyl zirconium (ZrBn) was chemisorbed on SiN, and the resulting supported organometallic species was characterized by Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS), Dynamic Nuclear Polarization-enhanced Solid State Nuclear Magnetic Resonance (DNP-SSNMR), and X-ray Absorption Spectroscopy (XAS). Based on the hypothesis that the nitride might enable facile heterolytic C-H bond activation along the Zr-N bond, this material was found to be a highly active (1.
View Article and Find Full Text PDFSecond sphere coordination effects ubiquitous in enzymatic catalysis occur through direct interactions, either covalent or non-covalent, with reaction intermediates and transition states. We present herein evidence of indirect second sphere coordination effects in which ligation of water/alkanols far removed from the primary coordination sphere of the active site nevertheless alter energetic landscapes within catalytic redox cycles in the of direct physicochemical interactions with surface species mediating catalytic turnovers. Density functional theory, in situ X-ray absorption and infrared spectroscopy, and a wide array of steady-state and transient CO oxidation rate data suggest that the presence of peripheral water renders oxidation half-cycles within two-electron redox cycles over μ-oxo-bridged trimers in MIL-100(M) more kinetically demanding.
View Article and Find Full Text PDFTemperature is a major ecological driver of mosquito-borne diseases as it influences the life-history of both the mosquito and the pathogen harboured within it. Understanding the mosquitoes' thermal biology is essential to inform risk prediction models of such diseases. Mosquitoes can respond to temperatures by microhabitat selection through thermal preference.
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