article · 29/03/2017
Raman scattering-based multiconformational analysis for probing the structural differences between acetylcholine and acetylthiocholine.
Résumé
Acetylcholine is the first discovered neurotransmitter that has received a great attention regarding its capability of binding to several cellular targets. The chemical composition of acetylcholine, including a positively charged trimethylammonium and a carbonyl group, as well as its conformational flexibility was pointed out as the key factors in the stabilization of its interactions. Here, the possibilities offered by a Raman scattering-based multiconformatioal analysis to access the most stable conformers of acetylcholine, is discussed. To control the validity of this protocol, acetylcholine and one of its closely structured analogues, acetylthiocholine, were simultaneously analyzed. Solution Raman spectra revealed distinct and well resolved strong markers for each molecule. Density functional theory calculations were consistent with the fact that the energy order of the low energy conformers is considerably affected by the acyloxy oxygen ? sulfur atom substitution. Raman spectra were calculated on the basis of the thermal average of the spectra arising from the low energy conformers. It has been evidenced that the carbonyl and trimethylammonium groups are the most favorable hydration sites in aqueous environment. Taking into account the large gap between the carbonyl bond-stretch and aliphatic bending bands, Raman spectra also allowed separation of the HOH bending vibrations arising from the bound and bulk water molecules.
Citer cet article
Hernández, B., Houzé, P., Pflüger, F., Kruglik, S.-G., & Ghomi, M. (2017). Raman scattering-based multiconformational analysis for probing the structural differences between acetylcholine and acetylthiocholine. Journal of Pharmaceutical and Biomedical Analysis, 138, 54-62. https://doi.org/10.1016/j.jpba.2017.01.049@article{Hernandez2017_144,
author = {Hernández, Belén and Houzé, Pascal and Pflüger, Fernando and Kruglik, Sergei G. and Ghomi, Mahmoud},
year = {2017},
month = {3},
title = {Raman scattering-based multiconformational analysis for probing the structural differences between acetylcholine and acetylthiocholine.},
journal = {Journal of Pharmaceutical and Biomedical Analysis},
volume = {138},
pages = {54-62},
abstract = {Acetylcholine is the first discovered neurotransmitter that has received a great attention regarding its capability of binding to several cellular targets. The chemical composition of acetylcholine, including a positively charged trimethylammonium and a carbonyl group, as well as its conformational flexibility was pointed out as the key factors in the stabilization of its interactions. Here, the possibilities offered by a Raman scattering-based multiconformatioal analysis to access the most stable conformers of acetylcholine, is discussed. To control the validity of this protocol, acetylcholine and one of its closely structured analogues, acetylthiocholine, were simultaneously analyzed. Solution Raman spectra revealed distinct and well resolved strong markers for each molecule. Density functional theory calculations were consistent with the fact that the energy order of the low energy conformers is considerably affected by the acyloxy oxygen ? sulfur atom substitution. Raman spectra were calculated on the basis of the thermal average of the spectra arising from the low energy conformers. It has been evidenced that the carbonyl and trimethylammonium groups are the most favorable hydration sites in aqueous environment. Taking into account the large gap between the carbonyl bond-stretch and aliphatic bending bands, Raman spectra also allowed separation of the HOH bending vibrations arising from the bound and bulk water molecules.},
url = {http://www.sciencedirect.com/science/article/pii/S0731708516309281},
doi = {10.1016/j.jpba.2017.01.049},
issn = {0731-7085},
}TY - JOUR
AU - Hernández, Belén
AU - Houzé, Pascal
AU - Pflüger, Fernando
AU - Kruglik, Sergei G.
AU - Ghomi, Mahmoud
PY - 2017
DA - 2017/03/29
TI - Raman scattering-based multiconformational analysis for probing the structural differences between acetylcholine and acetylthiocholine.
JO - Journal of Pharmaceutical and Biomedical Analysis
VL - 138
SN - 0731-7085
AB - Acetylcholine is the first discovered neurotransmitter that has received a great attention regarding its capability of binding to several cellular targets. The chemical composition of acetylcholine, including a positively charged trimethylammonium and a carbonyl group, as well as its conformational flexibility was pointed out as the key factors in the stabilization of its interactions. Here, the possibilities offered by a Raman scattering-based multiconformatioal analysis to access the most stable conformers of acetylcholine, is discussed. To control the validity of this protocol, acetylcholine and one of its closely structured analogues, acetylthiocholine, were simultaneously analyzed. Solution Raman spectra revealed distinct and well resolved strong markers for each molecule. Density functional theory calculations were consistent with the fact that the energy order of the low energy conformers is considerably affected by the acyloxy oxygen ? sulfur atom substitution. Raman spectra were calculated on the basis of the thermal average of the spectra arising from the low energy conformers. It has been evidenced that the carbonyl and trimethylammonium groups are the most favorable hydration sites in aqueous environment. Taking into account the large gap between the carbonyl bond-stretch and aliphatic bending bands, Raman spectra also allowed separation of the HOH bending vibrations arising from the bound and bulk water molecules.
SP - 54
EP - 62
DO - 10.1016/j.jpba.2017.01.049
UR - http://www.sciencedirect.com/science/article/pii/S0731708516309281
ER -