Coupling of complex aromatic ring vibrations to solvent through hydrogen bonds

Effect of varied on-ring and off-ring hydrogen-bonding substitutions

Nathaniel Nucci, J. Nathan Scott, Jane M. Vanderkooi

Research output: Contribution to journalArticle

6 Citations (Scopus)

Abstract

In this study, we examine the coupling of a complex ring vibration to solvent through hydrogen-bonding interactions. We compare phenylalanine, tyrosine, L-dopa, dopamine, norepinephrine, epinephrine, and hydroxyl-DL-dopa, a group of physiologically important small molecules that vary by single differences in H-bonding substitution. By examination of the temperature dependence of infrared absorptions of these molecules, we show that complex, many-atom vibrations can be coupled to solvent through hydrogen bonds and that the extent of that coupling is dependent on the degree of both on- and off-ring H-bonding substitution. The coupling is seen as a temperature-dependent frequency shift in infrared spectra, but the determination of the physical origin of that shift is based on additional data from temperature-dependent optical experiments and ab initio calculations. The optical experiments show that these small molecules are most sensitive to their immediate H-bonding environment rather than to bulk solvent properties. Ab initio calculations demonstrate H-bond-mediated vibrational coupling for the system of interest and also show that the overall small molecule solvent dependence is determined by a complex interplay of specific interactions and bulk solvation characteristics. Our findings indicate that a full understanding of biomolecule vibrational properties must include consideration of explicit hydrogen-bonding interactions with the surrounding microenvironment.

Original languageEnglish (US)
Pages (from-to)4022-4035
Number of pages14
JournalJournal of Physical Chemistry B
Volume112
Issue number13
DOIs
StatePublished - Apr 3 2008

Fingerprint

Hydrogen bonds
Substitution reactions
substitutes
hydrogen bonds
vibration
Molecules
dopa
rings
hydrogen
Norepinephrine
molecules
norepinephrine
Dihydroxyphenylalanine
epinephrine
Solvation
Infrared absorption
Levodopa
Biomolecules
Phenylalanine
dopamine

All Science Journal Classification (ASJC) codes

  • Materials Chemistry
  • Surfaces, Coatings and Films
  • Physical and Theoretical Chemistry

Cite this

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abstract = "In this study, we examine the coupling of a complex ring vibration to solvent through hydrogen-bonding interactions. We compare phenylalanine, tyrosine, L-dopa, dopamine, norepinephrine, epinephrine, and hydroxyl-DL-dopa, a group of physiologically important small molecules that vary by single differences in H-bonding substitution. By examination of the temperature dependence of infrared absorptions of these molecules, we show that complex, many-atom vibrations can be coupled to solvent through hydrogen bonds and that the extent of that coupling is dependent on the degree of both on- and off-ring H-bonding substitution. The coupling is seen as a temperature-dependent frequency shift in infrared spectra, but the determination of the physical origin of that shift is based on additional data from temperature-dependent optical experiments and ab initio calculations. The optical experiments show that these small molecules are most sensitive to their immediate H-bonding environment rather than to bulk solvent properties. Ab initio calculations demonstrate H-bond-mediated vibrational coupling for the system of interest and also show that the overall small molecule solvent dependence is determined by a complex interplay of specific interactions and bulk solvation characteristics. Our findings indicate that a full understanding of biomolecule vibrational properties must include consideration of explicit hydrogen-bonding interactions with the surrounding microenvironment.",
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Coupling of complex aromatic ring vibrations to solvent through hydrogen bonds : Effect of varied on-ring and off-ring hydrogen-bonding substitutions. / Nucci, Nathaniel; Scott, J. Nathan; Vanderkooi, Jane M.

In: Journal of Physical Chemistry B, Vol. 112, No. 13, 03.04.2008, p. 4022-4035.

Research output: Contribution to journalArticle

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