PMID: 11902884Mar 21, 2002Paper

Using equilibrium isotope effects to detect intramolecular OH/OH hydrogen bonds: structural and solvent effects

Journal of the American Chemical Society
Thomas E VasquezDaniel J O'Leary

Abstract

A comparative (1)H NMR study of partially deuterated 1,3- and 1,4-diols has demonstrated that intramolecular hydrogen bonds of different geometry can give rise to equilibrium isotope shifts of opposite sign in hydrogen-bond-accepting solvents such as DMSO-d(6), acetone-d(6), and THF-d(8). The sign inversion is interpreted in terms of the ability of solvent molecules to form competitive intermolecular hydrogen bonds with the diol and in terms of the limiting chemical shifts for the interior and exterior hydroxyl groups. Deuterium is shown to prefer the intermolecular solvent hydrogen bond by 10.9 +/- 0.5 cal/mol for 1,4-diol 3 dissolved in DMSO-d(6) at room temperature. Pyridine-d(5) is shown to be capable of amplifying positive (downfield) isotope shifts measured in DMSO-d(6), in some cases by as much as a factor of 3. Its use is demonstrated for the assignment of the syn or anti relative configuration of 2,4-pentanediol and for the amplification of isotope shifts used to detect intramolecular hydrogen bonds in alpha- and beta-cyclodextrin. Studies in apolar solvents such as CD(2)Cl(2) and benzene-d(6) reveal that the isotope shift is negative (upfield) for all hydrogen bond geometries studied. Larger isotope shifts are measure...Continue Reading

References

Feb 19, 2000·Current Opinion in Chemical Biology·P Colas
Jul 13, 2000·Organic Letters·M FiermanD J O'Leary

❮ Previous
Next ❯

Citations

Jan 1, 2010·Acta Crystallographica. Section E, Structure Reports Online·Rajshekhar KarpoormathGlenn E M Maguire
May 13, 2014·Progress in Nuclear Magnetic Resonance Spectroscopy·Marcos D BattistelDarón I Freedberg
Feb 10, 2016·Journal of the American Chemical Society·Guillaume PelletierScott J Miller
Dec 21, 2016·The Journal of Physical Chemistry. B·Marcos D BattistelDarón I Freedberg
Aug 14, 2018·Physical Chemistry Chemical Physics : PCCP·Jan Jadżyn, Jolanta Swiergiel
Nov 30, 2007·Magnetic Resonance in Chemistry : MRC·Birgit HakkarainenCorine Sandström
Oct 2, 2015·Beilstein Journal of Organic Chemistry·Sambasivarao KothaGaddamedi Sreevani
Jun 21, 2013·Magnetic Resonance in Chemistry : MRC·John S Lomas
Feb 4, 2015·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Poul Erik Hansen
Nov 15, 2008·The Journal of Organic Chemistry·Lev Kuno, Silvio E Biali
Dec 10, 2009·The Journal of Organic Chemistry·Daniel J O'LearyPoul Erik Hansen
Dec 21, 2013·The Journal of Physical Chemistry. B·Consuelo N BeecherCynthia K Larive
Mar 28, 2013·The Journal of Physical Chemistry. B·Marcos D BattistelDarón I Freedberg
Jan 31, 2012·The Journal of Physical Chemistry. B·Olga SwiechRenata Bilewicz
Nov 17, 2021·The Journal of Organic Chemistry·Kavoos KolahdouzanDaniel J O'Leary

❮ 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.