Mosermccormick8938

Global climate change and the industrial revolution have increased the concentration of tropospheric ozone, a photochemical air pollutant that can negatively affect plant growth and crop production. In the present study, we investigated the effects of O3 on the metabolites and transcripts of tartary buckwheat. A total of 36 metabolites were identified by gas chromatography coupled with time-of-flight mass spectrometry, and principal component analysis was performed to verify the metabolic differences between nontreated and O3-treated tartary buckwheat. The content of threonic acid increased after 2 days of the O3 treatment, whereas it decreased after 4 days of exposure, after which it gradually increased until the eighth day of exposure. In addition, the levels of most metabolites decreased significantly after the O3 treatment. On the contrary, the levels of two anthocyanins, cyanidin-3-O-glucoside and cyanidin-3-O-rutinoside, increased more than 11.36- and 11.43-fold, respectively, after the O3 treatment. To assess the effect of O3 on the genomic level, we analyzed the expression of anthocyanin biosynthesis pathway genes in O3-treated and nontreated buckwheat using quantitative real-time reverse transcription polymerase chain reaction (PCR). We found that the expression of all anthocyanin pathway genes increased significantly in the O3-treated buckwheat compared to that in the nontreated buckwheat. Altogether, our results suggested that O3 affected the transcripts and metabolites of tartary buckwheat, which would eventually cause phenotypic changes in plants.The fluorescence of most organic chromophore is emitted from the ππ* state, whereas the nπ* state, as a dark state, plays an important role in quenching the fluorescence when its energy is close to the ππ* state. Herein, we report a theoretical study on the fluorescence quenching of 8-methoxy-4-methyl-2H-benzo[g]chromen-2-one by the nπ* state and propose a new mechanism for describing the vibronic coupling between the ππ* and nπ* states. By applying extended multistate complete-active-space second-order perturbation theory (XMS-CASPT2) to optimize the geometries, the geometry distortion of the ππ* state along the out-of-plane mode is observed. This geometry distortion causes the stretching vibration of the carbonyl group to be coupled with the C-C bonds of the pyran ring, which become a Franck-Condon active mode upon photoexcitation and provides a driving force for nonradiative decay from the nπ* state, even if it is energetically unfavorable. This mechanism is significantly different from the previously proposed "proximity effect" and cannot be captured by the popularly used time-dependent density functional theory (TDDFT) and complete-active-space self-consistent field (CASSCF) methods.Asphaltenes have been suggested to play an important role in the remarkable stability of some water-in-crude oil emulsions, although the precise mechanisms by which they act are not yet fully understood. Being one of the more polar fractions in crude oils, asphaltenes are surface active and strongly adsorb at the oil/water interface, and as the interface becomes densely packed, solid-like mechanical properties emerge, which influence many typical interfacial experiments. The present work focuses on purposefully measuring the rheology in the limit of an insoluble, spread Langmuir monolayer in the absence of adsorption/desorption phenomena. Moreover, the changes in surface tension are deconvoluted from the purely mechanical contribution to the surface stress by experiments with precise interfacial kinematics. Compression "isotherms" are combined with the measurement of both shear and dilatational rheological properties to evaluate the relative contributions of mechanical versus thermodynamic aspects, i.e., to evaluate the "interfacial rheological" versus the standard interfacial activity. The experimental results suggest that asphaltene nanoaggregates are not very efficient in lowering interfacial tension but rather impart significant mechanical stresses. Interestingly, physical aging effects are not observed in the spread layers, contrary to results for adsorbed layers. By further studying asphaltene fractions of different polarity, we investigate whether mere packing effects or strong interactions determine the mechanical response of the dense asphaltene systems as either soft glassy or gel-like responses have been reported. The compressional and rheological data reflect the dense packing, and the behavior is captured well by the soft glassy rheology model, but a more complicated multilayer structure may develop as coverage is increased. Potential implications of the experimental observations on these model and insoluble interfaces for water-in-crude oil emulsion stability are briefly discussed.We present a new approach for characterizing drug-polymer interactions in aqueous media, using sedimentation velocity analytical ultracentrifugation (AUC). We investigated the potential interaction of ketoconazole (KTZ), a poorly water-soluble drug, with polyacrylic acid (PAA) and a polyvinyl caprolactam-polyvinyl acetate-polyethylene glycol graft copolymer (Soluplus) in aqueous buffers. The effect of the polymer on the sedimentation coefficient of the drug was the observable metric. The drug alone, when subjected to AUC, exhibited a very narrow sedimentation peak at 0.2 Svedberg (S), in agreement with the expectation for a monomeric drug with a molar mass less then 1000 Dalton. Conversely, the neat polymers showed broad profiles with higher sedimentation coefficients, reflecting their larger more heterogeneous size distributions. The sedimentation profiles of the drug-polymer mixtures were expectedly different from the profile of the neat drug. With KTZ-Soluplus, a complete shift to faster sedimentation times (indicative of an interaction) was observed, while with KTZ-PAA, a split peak indicated the existence of the drug in both free and interacting states. The sedimentation profile of carbamazepine, a second model drug, in the presence of hydroxypropyl methyl cellulose acetate succinate (HPMCAS, another polymer) revealed multiple "populations" of drug-polymer species, very similar to the sedimentation profile of neat HPMCAS. The interactions probed by AUC were compared with the results from isothermal titration calorimetry. buy BDA-366 In vitro dissolution tests performed on amorphous solid dispersions prepared with the same drug-polymer pairs suggested that the interactions may play a role in prolonging drug supersaturation. The results show the possibility of characterizing drug-polymer interactions in aqueous solution with high hydrodynamic resolution, addressing a major challenge frequently encountered in the mechanistic investigations of the dissolution behavior of amorphous solid dispersions.