Curtis Hubbard (pancolon0)

The chemical properties of actinide materials are often predefined and described based on the data available for isostructural species. This is the case for potassium plutonyl (PuVI) carbonate, K4PuVIO2(CO3)3(cr), a complex relevant for nuclear technology and the environment, of which the crystallographic and thermodynamic properties of which are still lacking. We report here the synthesis and characterization of PuVI achieved by single-crystal X-ray diffraction analysis and high-energy-resolution fluorescence-detected X-ray absorption near-edge structure at the Pu M4-edge coupled with electronic structure calculations. The crystallographic properties of PuVI are compared with isostructural uranium (U) and neptunium (Np) compounds. Actinyl (AnVI) axial bond lengths, [O-AnVI-O]2+, are correlated between solid, K4AnVIO2(CO3)3(cr), and aqueous, [AnVIO2(CO3)3]4-(aq) species for the UVI-NpVI-PuVI series. The spectroscopic data are compared to KPuVO2CO3(cr) and PuIVO2(cr) to tackle the trend in the electronic structure of PuVI regarding the oxidation state changes and local structural modifications around the Pu atom.An unusual chemoselective 1,1-addition of α-C2-bridged biphospholes to terminal alkynes is reported. The developed protocol provides simple access to the unknown 1,3-diphosphepines, which has potential applications in the coordination and catalyst chemistry. Their Pd and Mo complexes were studied by single-crystal X-ray diffraction analysis. This method features excellent chemoselectivity, high step and atom economy, mild reaction conditions, and wide substrate scope.Here we present plasmon-resonant vibrational sum frequency generation spectroscopy for use in electrochemical measurements. Using surface plasmon resonance we couple light through a CaF2 prism to Au films of >50 nm in order to reach the buried Au/electrolyte interface. The approach enables us to use bulk electrolyte, and high current densities (>1 mA/cm2), and therefore is suitable to probe active intermediates under relevant electrochemical reaction conditions. Fresnel factor modeling of the plasmon resonance for a three layer system (CaF2/Au/electrolyte) shows good agreement with experimental data. Off-angle momentum-matching to the surface plasmon resonance allows us to measure functional groups (-CH, -CD, -CN, -NO2) across a wide range of infrared frequencies by simply scanning the infrared wavelength without any angular realignment. Additionally we report a detection limit less then 1% of a monolayer for the Au/electrolyte interface. Using this method we observe an active intermediate during CO2 reduction on Au at catalytic currents. Consequently, we believe that this method will provide mechanistic understanding of electrochemical reactions.Caffeoylquinic acids (CQAs) are a broad class of secondary metabolites that have been found in edible and medicinal plants from various families. It has been 100 years since the discovery of chlorogenic acid in 1920. In recent years, a number of naturally derived CQAs have been isolated and structurally elucidated. Accumulated evidence demonstrate that CQAs have a wide range of biological activities, such as antioxidation, antibacterial, antiparasitic, neuroprotective, anti-inflammatory, anticancer, antiviral, and antidiabetic effects. Up to date, some meaningful progresses on the biosynthesis and total synthesis of CQAs have also been made. Therefore, it is necessary to comprehensively summarize the structure, biological activity, biosynthesis, and chemical synthesis of CQAs. This review provides extensive coverage of naturally occurring CQAs discovered from 1990 until 2020. Modern isolation techniques, chemical data (including structure, biosynthesis, and total synthesis), and bioactivity are summarized. This would be helpful for further research of CQAs as potential pharmaceutical agents.Mitochondrial fission is often associated with the development of oxidative stress related diseases, as the fragmentat