Attractive Interactions between Heteroallenes and the Cucurbituril Portal

Journal of the American Chemical Society
Ofer ReanyEhud Keinan

Abstract

In this paper, we report on the noteworthy attractive interaction between organic azides and the portal carbonyls of cucurbiturils. Five homologous bis-α,ω-azidoethylammonium alkanes were prepared, where the number of methylene groups between the ammonium groups ranges from 4 to 8. Their interactions with cucurbit[6]uril were studied by NMR spectroscopy, IR spectroscopy, X-ray crystallography, and computational methods. Remarkably, while the distance between the portal plane and most atoms at the guest end groups increases progressively with the molecular size, the β-nitrogen atoms maintain a constant distance from the portal plane in all homologues, pointing at a strong attractive interaction between the azide group and the portal. Both crystallography and NMR support a specific electrostatic interaction between the carbonyl and the azide β-nitrogen, which stabilizes the canonical resonance form with positive charge on the β-nitrogen and negative charge on the γ-nitrogen. Quantum computational analyses strongly support electrostatics, in the form of orthogonal dipole-dipole interaction, as the main driver for this attraction. The alternative mechanism of n → π* orbital delocalization does not seem to play a significant role in...Continue Reading

References

Jul 20, 1973·Science·C B Anfinsen
Dec 26, 2001·Chemical Reviews·K Müller-Dethlefs, P Hobza
Mar 30, 2002·Science·George M Whitesides, Bartosz Grzybowski
May 31, 2002·Acta Crystallographica. Section B, Structural Science·Frank H Allen, W D Samuel Motherwell
Dec 20, 2002·Angewandte Chemie·Thomas Steiner
Mar 20, 2003·Angewandte Chemie·Emmanuel A MeyerFrançois Diederich
Feb 12, 2005·Angewandte Chemie·Ralph PauliniFrançois Diederich
Jul 30, 2005·Angewandte Chemie·Jason LagonaLyle Isaacs
Aug 2, 2008·The Journal of Physical Chemistry. B·Kwang-Im OhMinhaeng Cho
Apr 17, 2010·Journal of the American Chemical Society·Erin R JohnsonWeitao Yang
Jul 10, 2010·The Journal of Chemical Physics·Edward G Hohenstein, C David Sherrill
Oct 20, 2010·Proceedings of the National Academy of Sciences of the United States of America·Robert R Knowles, Eric N Jacobsen
Mar 22, 2012·Chemistry : a European Journal·Mantosh K SinhaEhud Keinan
Nov 21, 2012·The Journal of Organic Chemistry·Kimberli J KamerRonald T Raines
Mar 2, 2013·Physical Chemistry Chemical Physics : PCCP·Peter PolitzerTimothy Clark
Jan 1, 2014·Protein Science : a Publication of the Protein Society·Robert W NewberryRonald T Raines
Feb 22, 2014·ACS Chemical Biology·Robert W Newberry, Ronald T Raines
Mar 13, 2014·The Journal of Chemical Physics·Trent M ParkerC David Sherrill
Mar 29, 2014·Journal of the American Chemical Society·Kang-Da ZhangJulius Rebek
Apr 2, 2014·Chemical Communications : Chem Comm·Kang-Da ZhangJulius Rebek
May 8, 2014·Journal of Chemical Theory and Computation·Amanda LiMichael K Gilson
Jun 14, 2014·Organic Letters·Amit ChoudharyRonald T Raines
Sep 10, 2014·The Journal of Chemical Physics·Andreas Heßelmann, Tatiana Korona
Oct 16, 2014·Chemical Society Reviews·Khaleel I Assaf, Werner M Nau
Nov 14, 2015·Chemical Reviews·Steven J BarrowOren A Scherman
Feb 26, 2016·Chemical Communications : Chem Comm·Volodymyr SashukOksana Danylyuk
Jun 18, 2016·Chemical Communications : Chem Comm·Wei LiAdam R Urbach
Jul 20, 2016·Journal of the American Chemical Society·Sebastian BenzStefan Matile
Jun 1, 2016·Chemical Science·Xiaoxi LingEric Masson

❮ Previous
Next ❯

Citations

Jan 14, 2021·Physical Chemistry Chemical Physics : PCCP·Song XiaoGuang-Yan Sun
Oct 21, 2020·Chemistry : a European Journal·Markus BurschDaniel B Werz
May 16, 2019·Molecular Pharmaceutics·Marcello Martinez MoralesJeremy P Derrick
Aug 17, 2021·Angewandte Chemie·Mithun C MadhusudhananKana M Sureshan

❮ 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.