OAGB is a valid alternative for complete DM2 remission no matter if it is not accompanied by some degree of obesity, since in this case the length of the biliopancreatic limb and common channel is modified to make a less malabsorptive procedure.Crystallization of active pharmaceutical ingredients (APIs) from the supercooled liquid state is an important issue in determining the stability of amorphous pharmaceutical dispersions. In the present study, the isothermal crystallization from the supercooled liquid state of the pharmaceutical compound nifedipine was investigated by both rheological and differential scanning calorimetry (DSC) measurements, and the crystallization kinetics was fitted to the Johnson-Mehl-Avrami (JMA) equation. Both the crystallization induction time and completion time from the two methods were used to construct the time-temperature-transformation (TTT) diagram for nifedipine. A model based on a modification of classical homogeneous nucleation and crystal growth theory was employed to fit the induction and completion time curves. Both DSC and rheological methods give similar results for the crystallization kinetics of the nifedipine. From the crystallization kinetics modeling, the solid-liquid interfacial surface tension σSL of nifedipine was estimated and the value was found to be consistent with prior results obtained from melting point depression measurements as a function of crystal size. Evidence is shown that for temperatures below 110 °C, at the early stage of nucleation, NIF first nucleates into the metastable β’-form and later converts into the stable α-form during the isothermal crystallization. We are also able to report the heat of fusion of the γ’-NIF based on the calorimetric experiments.We report switching of molecular conductance at finite bias in a binuclear organometallic complex and its cation which were previously experimentally analyzed at low voltages to see the signature of Kondo resonance. The variational reduced density matrix theory is applied to show that the system is strongly multireferenced especially in its charged form. We also study the molecular conductance of both forms using recently developed current-constrained two-electron reduced density matrix theory which is capable of handling strong electronic correlation. We compare the results against an uncorrelated 1-electron reduced density matrix version of conductance calculations using Hartree-Fock molecular orbitals. We observe that despite quantitative disagreements, the qualitative trend in the conductance is correctly predicted to be favorable for the cationic partner by both methods. We explain the results using the inherently high density of states for the low-lying excited states in the cationic partner which is also replicable from uncorrelated electronic structure methods. Our results not only indicate that the low-bias conductance trend is maintained even beyond the Kondo regime and produces quantitative agreement with that of the experiment but also identifies important physical markers that are responsible for the high conductance of the charged species.We describe the effective rhodium(I)-catalyzed [2+2+1] carbonylative cycloaddition of diynes, yielding cyclopentadienes (CPDs), under photoirradiation. The catalysis involves the promotion of the photodissociation of the product CPD, with the simultaneous production of an essential vacant coordination site on the rhodium for an unreacted substrate. The combined use of cationic [Rh(cod)2]BF4 as a catalyst and photoirradiation was also found to give various CPDs in high yields (≤96%).DNA-based detection methods are highly promising for risk assessment in the food sector, such as tracing the existence of food allergens. However, due to the complexity of food matrices, cumbersome protocols are often needed to isolate the DNA components, which hinder the achievement of rapid and on-site detection. Herein, an instant and multiple DNA extraction method was developed based on the poly(vinyl alcohol) microneedle (MN) patch. With simple press and peel-off operations within 1 min, samples suitable for DNA-based analysis such as polymerase chain reaction (PCR) could be collected. By further combining with the recombinase polymerase amplification assay, rapid screening of the allergenic risks in complex samples such as shrimp ball and cheesecake could be achieved within 30 min. The MN-based DNA extraction method not only was a potential alternative to the traditional DNA extraction method but provided a transformative approach in realizing rapid, on-site detection of foodborne hazards in collaborating with fast DNA-based assays.Expansion of the scope of the 1,3-diaza-Claisen rearrangement beyond bridged-bicyclic tertiary allylic amines has been investigated through a tethering strategy. Isothioureas tethered to tertiary allylic amines are converted to carbodiimides through a reaction with AgOTf/Et3N. Intramolecular cyclization of the tertiary allylic amine to the carbodiimide equilibrates with a zwitterionic intermediate. Heating the carbodiimide/zwitterion affords a rearrangement product. Heating carbodiimide/zwitterion with a deuterated allyl group results in the scrambling of the deuterium label, which is consistent with an ionic mechanism involving heterolytic cleavage of the allylic C-N bond, followed by trapping of the allyl cation at either terminal carbon. The ionic mechanism is attributed to silver salt contamination since pushing deuterium-labeled carbodiimide/zwitterion through silica gel prior to heating results in clean deuterium transposition consistent with a sigmatropic mechanism, and adding back silver salts results in deuterium scrambling. Overall, the tethering strategy broadens the scope of the rearrangement to simpler allylic substrates. selleck kinase inhibitor Density functional theory (DFT) calculations of the sigmatropic rearrangement are in agreement with reactivity trends observed with reactions run under silver-free conditions.The transfer of excitation energy in photosynthetic light-harvesting complexes has inspired growing interest for its scientific and engineering significance. Recent experimental findings have suggested that spatially correlated environmental fluctuations may account for the existence of long-lived quantum coherent energy transfer observed even at physiological temperature. In this paper, we investigate the effects of spatial correlations on the excitation energy transfer dynamics by including a nonequilibrium initial bath in a simulated donor-acceptor model. The initial bath state, which is assumed to be either equilibrium or nonequilibrium, is expanded in powers of coupling strength within the polaron formalism of a quantum master equation. The spatial correlations of bath fluctuations strongly influence the decay of coherence in the dynamics. The role of a nonequilibrium initial bath is also influenced by spatial correlations and becomes the most conspicuous for certain degrees of spatial correlations from which we propose a picture that the spatial correlations of bath fluctuations open up new energy transfer pathways, playing a role of protecting coherence.