Dynamic path bifurcation for the Beckmann reaction: observation and implication

The reaction of oximes to amides, known as the Beckmann rearrangement, may undergo fragmentation to form carbocations + nitriles instead of amides when the cations have reasonable stability. The reactions of oxime derivatives of 1-substituted-phenyl-2-propanones and 3-substituted-phenyl-2-butanones in aqueous solvents gave both rearrangement and fragmentation products, the ratio of which was dependent on substituents. Transition state (TS) optimizations and intrinsic reaction coordinate (IRC) calculations for the reaction of 1-phenyl-2-propanone oximes showed that there is a single TS for each substituted compound. The IRC path from the TS either led to a rearrangement product or a fragmentation product depending on the substituent; the IRC path changes from rearrangement to fragmentation when substituent X becomes more electron donating. Ab initio dynamics simulations were found to follow the IRC path for X = p-NH2 and p-MeO giving fragmentation products, and almost so for X = p-NO2 giving the rearrangement products. However, in a borderline case where X is less donating than p-MeO or less withdrawing than p-NO2, the trajectories did not follow the minimum energy path on the potential energy surface, but gave both rearrangement and fragmentation products directly from the single TS. This is a novel example of path bifurcation for a closed shell anionic reaction. It was concluded that a reactivity-selectivity argument based on the traditional TS theory may not always be applicable even to a well-known textbook organic reaction

\u3ci\u3eAb Initio\u3c/i\u3e Study of Formazan and 3-Nitroformazan

Formazan and 3-nitroformazan have been investigated at abinitio level (MP2/6-31G** and B3LYP/6-31G**) in all their possible conformations, for studying the various possibilities of intramolecular hydrogen bonding formation. The trans-syn-s-cis (TSSC), known also asyellowform, has been found to be the most stable conformer (at least in the gas phase) in both compounds. This particular structure is strongly stabilized by a N–H···N hydrogen bridge, which gives rise to a hexatomic chelate ring, with the possibility of a proton transfer process.This closely resembles that of malondialdehyde, previously studied, in the evolution of the potential energy shape but with a greater barrier height. Various approaches for obtaining a quantitative estimate of the energy of the hydrogen bridges are discussed. The electronic structures of the most favoured TSSC, TSST (trans-syn-s-trans) and TAST (trans-anti-s-trans) conformations of formazan have been compared with those of the corresponding forms of 1,5-diphenylformazan, in order to account for the UV spectra available in the literature and the different colours exhibited by the molecule on passing from one conformation to another

Dynamic patterns of expertise: The case of orthopedic medical diagnosis

The aim of this study was to analyze dynamic patterns for scanning femoroacetabular impingement (FAI) radiographs in orthopedics, in order to better understand the nature of expertise in radiography. Seven orthopedics residents with at least two years of expertise and seven board-certified orthopedists participated in the study. The participants were asked to diagnose 15 anteroposterior (AP) pelvis radiographs of 15 surgical patients, diagnosed with FAI syndrome. Eye tracking data were recorded using the SMI desk-mounted tracker and were analyzed using advanced measures and methodologies, mainly recurrence quantification analysis. The expert orthopedists presented a less predictable pattern of scanning the radiographs although there was no difference between experts and non-experts in the deterministic nature of their scan path. In addition, the experts presented a higher percentage of correct areas of focus and more quickly made their first comparison between symmetric regions of the pelvis. We contribute to the understanding of experts' process of diagnosis by showing that experts are qualitatively different from residents in their scanning patterns. The dynamic pattern of scanning that characterizes the experts was found to have a more complex and less predictable signature, meaning that experts' scanning is simultaneously both structured (i.e. deterministic) and unpredictable

Integrated Computational Chemistry System for Catalysts Design

The understanding of valuable catalytic and adsorptive properties of heterogeneous catalysts at atomic and electronic levels is essential for the design of novel catalysts. Computer simulation studies can significantly contribute to provide a rational interpretation of the observed experimental results and suggest modification of new catalysts. Our recent work on the application of integrated computer simulation methods to investigate the structure and catalytic properties of solid surfaces including zeolites, transition metals and their oxides have been reviewed in this paper. We have emphasized the effectivity and applicability of integrated computer simulation system to solve the problems in a variety of targets of industrial and academic importance

Treatment With Naringenin Elevates the Activity of Transcription Factor Nrf2 to Protect Pancreatic β-Cells From Streptozotocin-Induced Diabetes in vitro and in vivo

Chronic hyperglycemia and unusually high oxidative stress are the key contributors for diabetes in humans. Since nuclear factor E2-related factor 2 (Nrf2) controls the expression of antioxidant- and detoxification genes, it is hypothesized that targeted activation of Nrf2 using phytochemicals is likely to protect pancreatic β-cells, from oxidative damage, thereby mitigates the complications of diabetes. Naringenin is one such activator of Nrf2. However, it is currently not known whether the protective effect of naringenin against streptozotocin (STZ) induced damage is mediated by Nrf2 activation. Hence, the potential of naringenin to activate Nrf2 and protect pancreatic β-cells from STZ-induced damage in MIN6 cells is studied. In MIN6 cells, naringenin could activate Nrf2 and its target genes GST and NQO1, thereby inhibit cellular apoptosis. In animals, administration of 50 mg/kg body weight naringenin, for 45 days, significantly decreased STZ-induced blood glucose levels, normalized the lipid profile, and augmented the levels of antioxidants in pancreatic tissues. Immunohistochemical analysis measuring the number of insulin-positive cells in pancreas showed restoration of insulin expression similar to control animals. Furthermore, naringenin promoted glycolysis while inhibiting gluconeogenesis. In conclusion, naringenin could be a good anti-diabetic agent, which works by promoting Nrf2 levels and by decreasing cellular oxidative stress

Health and Human Rights in Chin State, Western Burma: A Population-Based Assessment Using Multistaged Household Cluster Sampling

Sollom and colleagues report the findings from a household survey study carried out in Western Burma; they report a high prevalence of human rights violations such as forced labor, food theft, forced displacement, beatings, and ethnic persecution

Upcycling Single-Use Polyethylene into High-Quality Liquid Products

Our civilization relies on synthetic polymers for all aspects of modern life; yet, inefficient recycling and extremely slow environmental degradation of plastics are causing increasing concern about their widespread use. After a single use, many of these materials are currently treated as waste, underutilizing their inherent chemical and energy value. In this study, energy-rich polyethylene (PE) macromolecules are catalytically transformed into value-added products by hydrogenolysis using well-dispersed Pt nanoparticles (NPs) supported on SrTiO3 perovskite nanocuboids by atomic layer deposition. Pt/SrTiO3 completely converts PE (Mn = 8000− 158,000 Da) or a single-use plastic bag (Mn = 31,000 Da) into high-quality liquid products, such as lubricants and waxes, characterized by a narrow distribution of oligomeric chains, at 170 psi H2 and 300 °C under solvent-free conditions for reaction durations up to 96 h. The binding of PE onto the catalyst surface contributes to the number averaged molecular weight (Mn) and the narrow polydispersity (Đ) of the final liquid product. Solidstate nuclear magnetic resonance of 13C-enriched PE adsorption studies and density functional theory computations suggest that PE adsorption is more favorable on Pt sites than that on the SrTiO3 support. Smaller Pt NPs with higher concentrations of undercoordinated Pt sites over-hydrogenolyzed PE to undesired light hydrocarbons