Conformational Distributions of Phenyl β-D-Glucopyranoside and Gastrodin in Solution by Vibrational Optical Activity and Theoretical Calculations DOI Creative Commons
Mutasem Alshalalfeh, Ningjie Sun,

Amanda Hanashiro Moraes

et al.

Molecules, Journal Year: 2023, Volume and Issue: 28(10), P. 4013 - 4013

Published: May 10, 2023

The conformational landscapes of two highly flexible monosaccharide derivatives, namely phenyl β-D-glucopyranoside (ph-β-glu) and 4-(hydroxymethyl)phenyl β-D-glucopyranoside, also commonly known as gastrodin, were explored using a combined experimental theoretical approach. For the infrared, Raman, associated vibrational optical activity (VOA), i.e., circular dichroism Raman activity, experiments these compounds in DMSO water carried out. Extensive systematic searches performed recently developed searching tool called CREST (conformer-rotamer ensemble sampling tool) solvents. Fourteen twenty-four low-energy conformers identified at DFT level for ph-β-glu respectively. spectral simulations individual done B3LYP-D3BJ/def2-TZVPD with polarizable continuum model VOA features exhibit much higher specificity to differences than their parent infrared Raman. excellent agreements achieved between simulated spectra allow extraction distributions carbohydrates solution directly. percentage abundances based on hydroxymethyl (at pyranose ring) conformations G+, G-, T obtained be 15%, 75%, 10% 53%, 40%, 7% water, respectively, comparison previously reported gas phase values 68%, 25%, 7%, highlighting important role solvents preferences. corresponding gastrodin are 56%, 22%, 22% 70%, 21%, 9% water.

Language: Английский

Modelling solute–solvent interactions in VCD spectra analysis with the micro-solvation approach DOI
Christian Merten

Physical Chemistry Chemical Physics, Journal Year: 2023, Volume and Issue: 25(43), P. 29404 - 29414

Published: Jan. 1, 2023

Strong solute–solvent interactions can affect VCD spectral signatures in various ways. In this perspective, we discuss the micro-solvation approach to simulate solvent effects.

Language: Английский

Citations

13
Assessing Nonbonded Aggregates Populations: Application to the Concentration-Dependent IR O–H Band of Phenol DOI

Josefa Gálvez,

José Zúñiga, Javier Cerezo

et al.

Journal of Chemical Theory and Computation, Journal Year: 2025, Volume and Issue: unknown

Published: April 14, 2025

In this work, we present two alternative computational strategies to determine the populations of nonbonded aggregates. One approach extracts these from molecular dynamics (MD) simulations, while other employs quantum mechanical partition functions for most relevant minima multimolecular potential energy surfaces (PESs), identified by automated conformational sampling. both cases, adopt a common graph-theory-based framework, introduced in identifying aggregate conformations, which enables consistent comparative assessment methodologies and provides insight into underlying approximations. We apply investigate phenol aggregates, up tetramer, at different concentrations phenol/carbon tetrachloride mixtures. Subsequently, simulate concentration-dependent OH stretching IR region averaging harmonic Infrared (IR) spectra aggregates using predicted each strategy. Our results indicate that extracted MD trajectories yield signals closely follow experimental trends, outperforming obtained systematic searches. Such better performance is attributed description entropic contributions. Moreover, proposed protocol not only successfully addresses very challenging problem but also offers benchmark assess accuracy intermolecular force fields.

Language: Английский

Citations

0
Influence of microsolvation on vibrational circular dichroism spectra in dimethyl sulfoxide solvent: A Bottom-Up approach using Quantum cluster growth DOI
Andrew R. Puente, Prasad L. Polavarapu

Spectrochimica Acta Part A Molecular and Biomolecular Spectroscopy, Journal Year: 2023, Volume and Issue: 303, P. 123231 - 123231

Published: Aug. 2, 2023

Language: Английский

Citations

6
Vibrational circular dichroism spectra of proline in water at different pH values DOI Creative Commons
Deborah A. Drost, Christian Merten

Physical Chemistry Chemical Physics, Journal Year: 2024, Volume and Issue: 26(25), P. 17753 - 17759

Published: Jan. 1, 2024

The computed VCD spectra of proline–water clusters depend on the orientation water molecules in solvation shell. We thus use an MD-based solvent-shell approach to sample configurational space solvent shell around solute.

Language: Английский

Citations

1
Conformational Distributions of Phenyl β-D-Glucopyranoside and Gastrodin in Solution by Vibrational Optical Activity and Theoretical Calculations DOI Creative Commons
Mutasem Alshalalfeh, Ningjie Sun,

Amanda Hanashiro Moraes

et al.

Molecules, Journal Year: 2023, Volume and Issue: 28(10), P. 4013 - 4013

Published: May 10, 2023

The conformational landscapes of two highly flexible monosaccharide derivatives, namely phenyl β-D-glucopyranoside (ph-β-glu) and 4-(hydroxymethyl)phenyl β-D-glucopyranoside, also commonly known as gastrodin, were explored using a combined experimental theoretical approach. For the infrared, Raman, associated vibrational optical activity (VOA), i.e., circular dichroism Raman activity, experiments these compounds in DMSO water carried out. Extensive systematic searches performed recently developed searching tool called CREST (conformer-rotamer ensemble sampling tool) solvents. Fourteen twenty-four low-energy conformers identified at DFT level for ph-β-glu respectively. spectral simulations individual done B3LYP-D3BJ/def2-TZVPD with polarizable continuum model VOA features exhibit much higher specificity to differences than their parent infrared Raman. excellent agreements achieved between simulated spectra allow extraction distributions carbohydrates solution directly. percentage abundances based on hydroxymethyl (at pyranose ring) conformations G+, G-, T obtained be 15%, 75%, 10% 53%, 40%, 7% water, respectively, comparison previously reported gas phase values 68%, 25%, 7%, highlighting important role solvents preferences. corresponding gastrodin are 56%, 22%, 22% 70%, 21%, 9% water.

Language: Английский

Citations

2