An Unusual Salt Effect in an Interfacial Nucleophilic Substitution Reaction

Langmuir : the ACS Journal of Surfaces and Colloids
Shuheng Li, Milan Mrksich

Abstract

This paper reports a kinetic characterization of the interfacial reaction of N-methylpyrrolidine with a self-assembled monolayer presenting an iodoalkyl group. SAMDI (self-assembled monolayers for matrix-assisted laser desorption/ionization) mass spectrometry was used to determine the extent of reaction for monolayers that were treated with a range of concentrations of the nucleophile for a range of times. These data revealed a second-order rate constant for the reaction that was approximately 100-fold greater than that for the analogous solution-phase reaction. However, addition of sodium iodide to the reaction mixture resulted in a 7-fold decrease in the reaction rate. Addition of bromide and chloride salts also gave slower rate constants for the reaction, but only at 100- and 1000-fold higher concentrations than was observed with iodide, respectively. The corresponding solution-phase reactions, by contrast, had rate constants that were unaffected by the concentration of halide salts. This work provides a well-characterized example illustrating the extent to which the kinetics and properties of an interfacial reaction can depart substantially from their better-understood solution-phase counterparts.

References

Oct 16, 1999·Proceedings of the National Academy of Sciences of the United States of America·N HoranD Kahne
Aug 3, 2001·Nature Cell Biology·A Schulze, J Downward
Sep 11, 2003·Chemical Reviews·Maurizio BenagliaFranco Cozzi
Nov 26, 2004·Journal of the American Chemical Society·Ellen S Gawalt, Milan Mrksich
Sep 21, 2005·Angewandte Chemie·Steffen OnclinDavid N Reinhoudt
Jun 24, 2006·Drug Discovery Today·David CastelXavier Gidrol
Jul 21, 2006·Proceedings of the National Academy of Sciences of the United States of America·Xuefeng GuoColin Nuckolls
Oct 6, 2007·Langmuir : the ACS Journal of Surfaces and Colloids·Jing LiMilan Mrksich
Oct 24, 2007·Journal of the American Chemical Society·Paul H J Kouwer, Timothy M Swager
Feb 1, 2008·Physical Review Letters·Dominik Horinek, Roland R Netz
Mar 3, 2009·Acta Biomaterialia·Milan Mrksich
Oct 13, 2009·Chemistry : a European Journal·Xiaoli LiaoMilan Mrksich
Jun 7, 2011·ACS Combinatorial Science·Zachary A Gurard-LevinMilan Mrksich
Jul 24, 2012·Nature Chemical Biology·Lan BanMilan Mrksich
Nov 8, 2012·Langmuir : the ACS Journal of Surfaces and Colloids·Shuheng LiMilan Mrksich

❮ Previous
Next ❯

Citations

Jun 3, 2020·Proceedings of the National Academy of Sciences of the United States of America·Alison A BaylyKarl A Scheidt
Jul 15, 2021·Dalton Transactions : an International Journal of Inorganic Chemistry·Maxime LauransSascha Ott

❮ Previous
Next ❯

Related Concepts

Trending Feeds

COVID-19

Coronaviruses encompass a large family of viruses that cause the common cold as well as more serious diseases, such as the ongoing outbreak of coronavirus disease 2019 (COVID-19; formally known as 2019-nCoV). Coronaviruses can spread from animals to humans; symptoms include fever, cough, shortness of breath, and breathing difficulties; in more severe cases, infection can lead to death. This feed covers recent research on COVID-19.

Blastomycosis

Blastomycosis fungal infections spread through inhaling Blastomyces dermatitidis spores. Discover the latest research on blastomycosis fungal infections here.

Nuclear Pore Complex in ALS/FTD

Alterations in nucleocytoplasmic transport, controlled by the nuclear pore complex, may be involved in the pathomechanism underlying multiple neurodegenerative diseases including Amyotrophic Lateral Sclerosis and Frontotemporal Dementia. Here is the latest research on the nuclear pore complex in ALS and FTD.

Applications of Molecular Barcoding

The concept of molecular barcoding is that each original DNA or RNA molecule is attached to a unique sequence barcode. Sequence reads having different barcodes represent different original molecules, while sequence reads having the same barcode are results of PCR duplication from one original molecule. Discover the latest research on molecular barcoding here.

Chronic Fatigue Syndrome

Chronic fatigue syndrome is a disease characterized by unexplained disabling fatigue; the pathology of which is incompletely understood. Discover the latest research on chronic fatigue syndrome here.

Evolution of Pluripotency

Pluripotency refers to the ability of a cell to develop into three primary germ cell layers of the embryo. This feed focuses on the mechanisms that underlie the evolution of pluripotency. Here is the latest research.

Position Effect Variegation

Position Effect Variagation occurs when a gene is inactivated due to its positioning near heterochromatic regions within a chromosome. Discover the latest research on Position Effect Variagation here.

STING Receptor Agonists

Stimulator of IFN genes (STING) are a group of transmembrane proteins that are involved in the induction of type I interferon that is important in the innate immune response. The stimulation of STING has been an active area of research in the treatment of cancer and infectious diseases. Here is the latest research on STING receptor agonists.

Microbicide

Microbicides are products that can be applied to vaginal or rectal mucosal surfaces with the goal of preventing, or at least significantly reducing, the transmission of sexually transmitted infections. Here is the latest research on microbicides.