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J Phys Chem A 2022 Jul 29;126(27):4482-4496. Epub 2022 Jun 29.

National Institute of Advanced Industrial Science and Technology (AIST), 16-1 Onogawa, Tsukuba, Ibaraki 305-8569, Japan.

An attempt is made to evaluate the nonstatistical effects in the thermal decomposition of hydrogen peroxide (HO). Previous experimental studies on this reaction reported an unusual pressure dependence of the rate constant indicating broader falloff behavior than expected from conventional theory. In this work, the possibility that the rate constant is affected by nonstatistical effects is investigated based on classical trajectory calculations on the global potential energy surfaces of HO and HO + Ar. Read More

Acc Chem Res 2021 12 11;54(23):4410-4422. Epub 2021 Nov 11.

Department of Chemistry and Biochemistry, Brigham Young University, Provo, Utah 84602, United States.

Homogeneous metal-mediated organometallic reactions represent a very large and diverse reaction class. Density functional theory calculations are now routinely carried out and reported for analyzing organometallic mechanisms and reaction pathways. While density functional theory calculations are extremely powerful to understand the energy and structure of organometallic reactions, there are several assumptions in their use and interpretation to define reaction mechanisms and to analyze reaction selectivity. Read More

Science 2021 07;373(6551):208-212

Beckman Institute for Advanced Science and Technology, University of Illinois at Urbana-Champaign, Urbana, IL 61801, USA.

Dynamic effects are an important determinant of chemical reactivity and selectivity, but the deliberate manipulation of atomic motions during a chemical transformation is not straightforward. Here, we demonstrate that extrinsic force exerted upon cyclobutanes by stretching pendant polymer chains influences product selectivity through force-imparted nonstatistical dynamic effects on the stepwise ring-opening reaction. The high product stereoselectivity is quantified by carbon-13 labeling and shown to depend on external force, reactant stereochemistry, and intermediate stability. Read More

Eur Surg Res 2021 21;62(2):97-104. Epub 2021 May 21.

Daniel Swarovski Research Laboratory, Department of Visceral, Transplant and Thoracic Surgery, Center of Operative Medicine, Medical University of Innsbruck, Innsbruck, Austria.

Background: Postoperative pancreatic fistula (POPF) is a major complication in pancreatic surgery and can cause considerable postoperative morbidity. Advanced surgical-technical approaches to prevent POPF did not yield a substantial improvement. To investigate innovative treatments, experimental animal models of distal pancreatic resection and pancreaticoduodenectomy are of fundamental importance. Read More

J Am Chem Soc 2021 01 5;143(2):1088-1097. Epub 2021 Jan 5.

Department of Chemistry, University of California, Davis, One Shields Avenue, Davis, California 95616, United States.

Carbocation rearrangement reactions are of great significance to synthetic and biosynthetic chemistry. In pursuit of a scale of inherent migratory aptitude that takes into account dynamic effects, both uphill and downhill molecular dynamics (AIMD) simulations were used to examine competing migration events in a model system designed to remove steric and electronic biases. The results of these simulations were combined with detailed investigations of potential energy surface topography and variational transition state theory calculations to reveal the importance of nonstatistical dynamic effects on migratory aptitude. Read More