Quantum effects in CH activation with [CuO] complexes.

We investigate the mechanism of primary alkane CH bond activation with dioxo-dicopper ([CuO]) complexes, which serve as model catalysts for enzymes capable of activating CH bonds under mild conditions. As large H/D kinetic isotope effects (KIEs) are observed in enzymes and their synthetic mimics, we employ density functional theory along with variational transition-state theory with multidimensional tunneling to estimate reaction rate coefficients. By systematically varying ligand electrophilicity and substrate chain length, we examine trends in rate coefficients and kinetic isotope effects for the two proposed CH activation pathways - one-step oxo-insertion and two-step radical recombination.

A configuration sampling study of reaction intermediates constituting catalytic cycles for CO oxidation with Pt1/TiO2.

We combine ab initio molecular dynamics (AIMD) simulations with an unsupervised machine learning approach to automate the search for possible configurations of CO oxidation reaction intermediates catalyzed by the atomically dispersed Pt1/TiO2 catalyst. Following the example of Roncoroni and co-workers [Phys. Chem.

Intra-gastric balloon with lifestyle modification: a promising therapeutic option for overweight and obese patients with metabolic dysfunction-associated steatotic liver disease.

Background: Data on effects of intra-gastric balloon (IGB) on metabolic dysfunction-associated steatotic liver disease (MASLD) are scarce, in part with contradictory results, and mainly obtained in tertiary care patients with diabetes and other comorbidities. We here explore effects of IGB in patients with MASLD referred to a first-line obesity clinic.

Methods: In this prospective cohort study, patients with at least significant fibrosis (≥ F2) and/or severe steatosis (S3) according to screening transient elastography (FibroScan®) were offered a second FibroScan® after 6 months lifestyle modification with or without IGB (based on patient preference).

Controlling selectivity for dechlorination of poly(vinyl chloride) with (xantphos)RhCl.

Reaction of poly(vinyl chloride) (PVC) with 5 equiv. of triethyl silane in THF, in the presence of generated (xantphos)RhCl catalyst, results in partial reduction of PVC hydrodechlorination to yield poly(vinyl chloride--ethylene). Increasing catalyst loading or using ,-dimethylacetamide (DMA) as a solvent both diminished selectivity for hydrodechlorination, promoting competitive dehydrochlorination reactions.

Recent Advances toward Efficient Calculation of Higher Nuclear Derivatives in Quantum Chemistry.

In this paper, we provide an overview of state-of-the-art techniques that are being developed for efficient calculation of second and higher nuclear derivatives of quantum mechanical (QM) energy. Calculations of nuclear Hessians and anharmonic terms incur high costs and memory and scale poorly with system size. Three emerging classes of methods─machine learning (ML), automatic differentiation (AD), and matrix completion (MC)─have demonstrated promise in overcoming these challenges.