Mechanistic studies of pyridinium electrochemistry: alternative chemical pathways in the presence of CO2

2016 ◽  
Vol 18 (3) ◽  
pp. 1578-1586 ◽  
Author(s):  
A. G. Peroff ◽  
E. Weitz ◽  
R. P. Van Duyne

Pyridinium has been described as a catalyst for CO2 reduction, however with low faradaic efficiency. This article discusses a series of electrochemistry experiments to study other chemical processes occurring during pyridinium electrochemistry which might provide insight into the low faradaic efficiency.

2016 ◽  
Vol 45 (6) ◽  
pp. 2554-2561 ◽  
Author(s):  
Nicolas A. McLeod ◽  
Lyudmila G. Kuzmina ◽  
Ilia Korobkov ◽  
Judith A. K. Howard ◽  
Georgii I. Nikonov

The β-SiH agostic complex (ArN)2Mo{η3-N(tBu)SiMe2–H}H is a pre-catalyst for hydrosilylation of carbonyls. Mechanistic studies revealed a non-hydride mechanism, with the benzoxy complex 8 being the resting state.


2018 ◽  
Vol 39 (01) ◽  
pp. 003-011 ◽  
Author(s):  
Theo Moraes ◽  
Malcolm Sears ◽  
Padmaja Subbarao

AbstractAsthma is a heterogeneous disorder with a complex etiology. Prevalence rates for asthma have been increasing in many countries over the past few decades. While it is unclear why this increase is occurring, the variation reported in asthma prevalence and severity associated with ethnicity offers some insight into the determinants of asthma. In this chapter, we discuss the data linking asthma to ethnicity and some of the factors that may explain this association. These include socioeconomic status, environmental exposures, the host microbiome, and genetics. A better understanding of these processes may inform future mechanistic studies and identify modifiable risk factors for targeted health care interventions.


2019 ◽  
Vol 5 (8) ◽  
pp. eaaw0513 ◽  
Author(s):  
Zhe Chen ◽  
Arash Khajeh ◽  
Ashlie Martini ◽  
Seong H. Kim

Friction occurs through a complex set of processes that act together to resist relative motion. However, despite this complexity, friction is typically described using a simple phenomenological expression that relates normal and lateral forces via a coefficient, the friction coefficient. This one parameter encompasses multiple, sometimes competing, effects. To better understand the origins of friction, here, we study a chemically and topographically well-defined interface between silica and graphite with a single-layer graphene step edge. We identify the separate contributions of physical and chemical processes to friction and show that a single friction coefficient can be separated into two terms corresponding to these effects. The findings provide insight into the chemical and topographic origins of friction and suggest means of tuning surfaces by leveraging competing frictional processes.


2014 ◽  
Vol 12 (36) ◽  
pp. 7059-7067 ◽  
Author(s):  
Nicholas K. Pinkin ◽  
Marcey L. Waters

Iterative monomer redesign leads to a Kme3-peptide receptor with 10-fold tighter affinity and 5-fold improved selectivity over Kme2 than the original receptor. Thermodynamic analysis provides insight into this improvement.


1991 ◽  
Vol 02 (C2) ◽  
pp. C2-155-C2-165
Author(s):  
M. E. PEMBLE ◽  
D. S. BUHAENKO ◽  
H. PATEL ◽  
A. STAFFORD ◽  
A. G. TAYOR

1994 ◽  
Author(s):  
R.J. Waganet ◽  
John Duxbury ◽  
Uri Mingelgrin ◽  
John Hutson ◽  
Zev Gerstl

Pesticide leaching in heterogeneous field soils is relatively unstudied and is the focus of this project. A wide variety of heterogeneous soils exist, characterized by processes that result from the presence of structural cracks, worm holes, and other preferred pathways within which the majority of transport can occur (called physical non-equilibrium processes), along with the presence of sorption processes that are both equilibrium and kinetic (chemical non-equilibrium processes). Previous studies of pesticide leaching have focused primarily on relatively homogeneous soils, which are less widely distributed in nature, but more studied due to the relative ease with which quantitative theory can be applied to interpret experimental results. The objectives of the proposed project were: first, to gain greater insight into the basic physical and chemical processes that characterize non-equilibrium systems, second, to improve our ability to predict pesticide leaching in heterogeneous field soils, and third, to estimate the consequences of non-equilibrium processes at the field scale by conducting an analysis of the probability of pesticide leaching when non-equilibrium processes prevail. The laboratory, theoretical and modelling aspects of the project were successful; the field aspects less so. We gained greater insight into basic processes in heterogeneous field soils, and we improved and tested tools (simulation models) and the methodology of using such tools for assessing the probability of pesticide leaching as a contribution to broader risk analysis efforts.


2021 ◽  
Author(s):  
Sii Hong Lau ◽  
Meredith Borden ◽  
Talia Steiman ◽  
Lucy Wang ◽  
Marvin Parasram ◽  
...  

A Ni/photoredox-catalyzed enantioselective reductive coupling of styrene oxides and aryl iodides is reported. This reaction affords access to enantioenriched 2,2-diarylalcohols from racemic epoxides via a stereoconvergent mechanism. Multivariate linear regression (MVLR) analysis with 29 bioxazoline (BiOx) and biimidazoline (BiIm) ligands revealed that enantioselectivity correlates with electronic properties of the ligands, with more electron-donating ligands affording higher ee’s. Mechanistic studies were conducted, lending support to the hypothesis that the electronic character of the ligands influences the enantioselectivity by altering the position of the transition state structure along the reaction coordinate. This study demonstrates the benefits of utilizing statistical modeling as a platform for mechanistic understanding and provides new insight into an emerging class of chiral ligands for stereoconvergent Ni and Ni/photoredox cross-coupling.


2019 ◽  
Author(s):  
Isaac Omari ◽  
Parmissa Randhawa ◽  
Jaiya Randhawa ◽  
Jenny Yu ◽  
J Scott McIndoe

<p>The abundance of an ion in an electrospray ionization mass spectrum is dependent on many factors beyond just solution concentration. Even in cases where the ions are permanently charged and do not rely on protonation or other chemical processes to acquire the necessary charge, factors such as cation structure, molecular weight, solvent, and the identity of the anion can perturb results. Screening of a variety of combinations of cation, anion and solvent provided insight into some of the more important factors. Rigid cations and high conductivity anions tended to provide the highest responses, while acetonitrile was the most accurate solvent for reflecting solution composition. Functional groups that had affinity for the solvent tended to depress response. These observations will provide predictive power when accounting for ions that for reasons of high reactivity can not be isolated.</p><br>


Author(s):  
Diogo Sousa ◽  
Nuno Basílio ◽  
Joana Oliveira ◽  
Victor de Freitas ◽  
Fernando Pina

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