Damborgkoch0965

The addition-type ozone oxidation of silylalkenes is a highly efficient reaction to provide synthetically versatile α-silylperoxy carbonyl compounds. To gain insight into the reaction mechanism, we performed a computational study, which revealed that the reaction proceeds via [1,2]-Brook rearrangement-type silyl migration of primary ozonide. In sharp contrast to the addition-type reactions, the ozone oxidation of α-alkoxysilylalkenes proceeds in a cleavage-type manner to afford excellent yields of silacarboxylic acid esters via the 1,3-cycloelimination of primary ozonide prior to 1,2-silyl migration.The potential of oxide-supported rhodium single atom catalysts (SACs) for heterogeneous hydroformylation was investigated both theoretically and experimentally. Using high-level domain-based local-pair natural orbital coupled cluster singles doubles with perturbative triples contribution (DLPNO-CCSD(T)) calculations, both stability and catalytic activity were investigated for Rh single atoms on different oxide surfaces. Atomically dispersed, supported Rh catalysts were synthesized on MgO and CeO2. While the CeO2-supported rhodium catalyst is found to be highly active, this is not the case for MgO, most likely due to increased confinement, as determined by extended X-ray absorption fine structure spectroscopy (EXAFS), that diminishes the reactivity of Rh complexes on MgO. This agrees well with our computational investigation, where we find that rhodium carbonyl hydride complexes on flat oxide surfaces such as CeO2(111) have catalytic activities comparable to those of molecular complexes. For a step edge on a MgO(301) surface, however, calculations show a significantly reduced catalytic activity. At the same time, calculations predict that stronger adsorption at the higher coordinated adsorption site leads to a more stable catalyst. Keeping the balance between stability and activity appears to be the main challenge for oxide supported Rh hydroformylation catalysts. In addition to the chemical bonding between rhodium complex and support, the confinement experienced by the active site plays an important role for the catalytic activity.Polyphenol extracts derived from gastrointestinal digestates of buckwheat (Fagopyrum Mill) were studied for their intestinal transport and lipid-lowering effects in Caco 2/HepG2 coculture models. The relative amounts of all phenolic compounds throughout the digestion and intestinal absorption process were determined by UHPLC-Q-Orbitrap MS. The digestible and easily transported phenolic compounds in buckwheat extract were identified. Herein, four main phenolic compounds and their metabolites were found on both the apical and basolateral sides of the Caco-2 cell Transwell model. The transepithelial transport rates in the Caco-2 cell monolayer were scoparone (0.97) > hydroxycinnamic acid (0.40) > rutin (0.23) > quercetin (0.20). The main metabolism of hydroxycinnamic acid, quercetin and scoparone in transepithelial transport was found to be methylation. Furthermore, results indicated that the triglyceride, low-density lipoprotein cholesterol, total cholesterol, aspartate aminotransferase and alanine aminotransferase levels in HepG2 cells on the basolateral side of coculture models can be suppressed by 53.64%, 23.44%, 36.49%, 27.98%, and 77.42% compared to the oleic acid-induced group (p less then 0.05). In addition, the mRNA expression of Fabp4 relative to control was found to be significantly upregulated (85.82±10.64% to 355.18±65.83%) by the easily transported buckwheat polyphenol components in HepG2 cells (p less then 0.01).Hydrogen-deuterium exchange mass spectrometry (HDX-MS) is becoming a popular technique for interrogating biological systems. In recent years, advancements have been made to increase peptide coverage for proteins that resist digestion such as antibodies and membrane proteins. These methods commonly include using alternative digestion enzymes or longer chromatographic gradients, which may be expensive or time-consuming to implement. Here, we recommend an efficient proteomics-based approach to increase peptide confidence and coverage. A major filtering parameter for peptides in HDX is the number of product ions detected; this is a result of the collision energy (CE) applied within the MS. A traditional linear ramp achieves optimal CE for only short periods of time. More product ions will be created and detected if optimal CE can be achieved for a longer period of time. As a result, the coverage, redundancy, and data confidence are all increased. We achieved this by implementing a mobility-dependent CE look up table (LUT) which increases the CE as a function of mobility. We developed a program to calculate the optimal CE for a set of peptides and MS settings based on initial reference samples. We demonstrated the utility of the CE LUT on three protein samples including the soluble phosphorylase B, IgG2, and the membrane-stabilized AcrB. We showed that applying a CE LUT provided 8.5-50% more peptides compared to a linear CE ramp. selleck The results demonstrate that a time-dependent CE LUT is a quick and inexpensive method to increase data confidence and peptide abundance for HDX-MS experiments.Proanthocyanidins (PAs) are mainly composed of epicatechin (EC) or catechin (C) subunits. C-type catechins (C and GC) are generally considered to be catalyzed by leucocyanidin reductase (LAR). In this study, we re-evaluated the function of LAR. LcLAR1 was isolated from Lotus corniculatus, which is rich in C-type catechins. Overexpression of LcLAR1 in tobacco resulted in a significantly increased content of EC and EC-glucoside. Overexpression of LcLAR1 in Arabidopsis thaliana promoted the accumulation of soluble PAs, including EC, PA dimers, and PA trimers. However, in the transgenic ans mutant overexpressing LcLAR1, the contents of C and C-glucoside were increased. In addition, overexpression of LcLAR1 in L. corniculatus resulted in a significant increase of C levels. Taken together, the products of LcLAR1 depended on the substrates, which revealed the substrate diversity of LcLAR1. Our study provides new insights into the flavonoid pathway, especially the role of LAR.