Chemical forms of phosphorus (P) in airborne particulate matter (PM) are poorly known and do not correlate with solubility or extraction measurements commonly used to infer speciation. Selleckchem Adavosertib We used P X-ray absorption near-edge structure (XANES) and 31P nuclear magnetic resonance (NMR) spectroscopies to determine P species in PM collected at four mountain sites (Colorado and California). Organic P species dominated samples from high elevations, with organic P estimated at 65-100% of total P in bulk samples by XANES and 79-88% in extracted fractions (62-84% of total P) by NMR regardless of particle size (≥10 or 1-10 μm). Phosphorus monoester and diester organic species were dominant and present in about equal proportions, with low fractions of inorganic P species. By comparison, PM from low elevation contained mixtures of organic and inorganic P, with organic P estimated at 30-60% of total P. Intercontinental PM transport determined from radiogenic lead (Pb) isotopes varied from 0 to 59% (mean 37%) Asian-sourced Pb at high elevation, whereas stronger regional PM inputs were found at low elevation. Airborne flux of bioavailable P to high-elevation ecosystems may be twice as high as estimated by global models, which will disproportionately affect net primary productivity.A highly stable and luminescent 3D metal-organic framework (MOF), [Zn4(μ3-OH)2(BTC)2(BBI4PY)2]·10H2On (Zn-MOF), with a rare [Zn4(μ3-OH)2]6+ core has been synthesized using a new rigid and functionalized pillar linker, 2,6-bis(pyridin-4-yl)-1,7-dihydrobenzo[1,2-d4,5-d’]diimidazole (BBI4PY) in combination with Zn(OAc)2·2H2O and 1,3,5-benzenetricarboxylic acid (H3BTC) under solvothermal conditions. Unlike other MOFs with the [Zn4(μ3-OH)2]6+ core, Zn-MOF was synthesized without using an external base, as the intrinsic basicity of BBI4PY served the purpose. Furthermore, it retains crystallinity and phase purity up to 350 °C on the basis of TGA and in situ variable temperature PXRD, correlating with its solid-state structure. Using the dehydrated Zn-MOF, water sorption studies show uptake of 220 cm3 g-1 (corresponds to 10 water molecules). A large hysteresis in desorption isotherm signifies strong interactions between adsorbed water and Lewis basic sites present in the framework. The reversible nature of water sorption was further manifested by TGA and PXRD studies. As an example of its application, the highly fluorescent and electron-rich nature of Zn-MOF has been utilized for the selective sensing of Fe3+ and 2,4,6-trinitrophenol (TNP) in water with detection limits of 3.7 and 1.8 ppm, respectively. The mechanistic details for the turn-off quenching have been elucidated with the help of Stern-Volmer plots, spectral overlap, lifetime studies, and density functional theory calculations. This mechanistic evidence reveals that a combination of strong hydrogen bonding with resonance energy transfer and photoinduced electron transfer (PET) processes is synchronously responsible for the quenching of the fluorescence intensity of Zn-MOF.Hydrogen bonding has profound effects on the behavior of molecules. Fourier Transform infrared spectroscopy (FTIR) is the technique most commonly used to qualitatively identify hydrogen bonding moieties present in a chemical sample. However, quantitative analysis of infrared (IR) spectra is nontrivial for the hydroxyl stretching region where hydrogen bonding is most prominently expressed in organic alcohols and water. Specifically, the breadth and extreme overlap of the O-H stretching bands, and the order of magnitude variability of their IR attenuation coefficients complicates the analysis. In the present work, sequential molecular dynamics (MD) simulations and quantum mechanical (QM) calculations are used to develop a function to relate the integrated IR attenuation coefficient to the vibrational frequencies of hydroxyl bands across the O-H stretching region. This relationship is then used as a guide to develop an attenuation coefficient scaling function to quantitatively determine concentrations of alcohols in hydrocarbon solution from experimental IR spectra by integration across the entire hydroxyl frequency range.Selenium (Se) is an important micronutrient for living organisms, since it is involved in several physiological and metabolic processes. Se intake in humans is often low and very seldom excessive, and its bioavailability depends also on its chemical form, with organic Se as the most available after ingestion. The main dietary source of Se for humans is represented by plants, since many species are able to metabolize and accumulate organic Se in edible parts to be consumed directly (leaves, flowers, fruits, seeds, and sprouts) or after processing (oil, wine, etc.). Countless studies have recently investigated the Se biofortification of plants to produce Se-enriched foods and elicit the production of secondary metabolites, which may benefit human health when incorporated into the diet. Moreover, feeding animals Se-rich diets may provide Se-enriched meat. This work reviews the most recent literature on the nutraceutical profile of Se-enriched foods from plant and animal sources.Modern photoredox catalysis has traditionally relied upon metal-to-ligand charge-transfer (MLCT) excitation of metal polypyridyl complexes for the utilization of light energy for the activation of organic substrates. Here, we demonstrate the catalytic application of ligand-to-metal charge-transfer (LMCT) excitation of cerium alkoxide complexes for the facile activation of alkanes utilizing abundant and inexpensive cerium trichloride as the catalyst. As demonstrated by cerium-catalyzed C-H amination and the alkylation of hydrocarbons, this reaction manifold has enabled the facile use of abundant alcohols as practical and selective hydrogen atom transfer (HAT) agents via the direct access of energetically challenging alkoxy radicals. Furthermore, the LMCT excitation event has been investigated through a series of spectroscopic experiments, revealing a rapid bond homolysis process and an effective production of alkoxy radicals, collectively ruling out the LMCT/homolysis event as the rate-determining step of this C-H functionalization.