Ab initio and DFT cation affinity study of selected neurosteroids

Anthony A. Morrison; Mitchell C. Paul; Carl H. Parsons; Michael B. Calford; E. von Nagy-Felsobuki

Ab initio and DFT cation affinity study of selected neurosteroids

Anthony A. Morrison, Mitchell C. Paul, Carl H. Parsons, Michael B. Calford, E. von Nagy-Felsobuki

Research output: Contribution to journal › Article

Abstract

Full 3N-6 optimization electronic structure calculations using the HF 6-31G(d)//HF 6-31G(d) and B3LYP 6-31G(d)//B3LYP 6-31G(d) levels of theory have been employed to determine the theoretical gas-phase cation affinities of 5-pregnen-3ÃŽÂ²-ol-20-one, 5-androsten-3ÃŽÂ²-ol-17-one, 4-pregnen-3,20-dione, 5ÃŽÂ±-pregnan-3, 20-dione, 5ÃŽÂ±-pregnan-3ÃŽÂ±-ol-20-one and 5ÃŽÂ±-pregnan-3ÃŽÂ²-ol-20-one. For all the selected neurosteroids both theoretical methods predicted the trend of cation affinity as: H+ &MGT; Li+ > Na+ > K+. The bonding interactions occur at the carbonyl group of the neurosteroids. The large cation affinities of the neurosteroid-proton adduct was found to be indicative of the formation of a stable complex via a relatively strong polar-covalent mechanism, while the lower cation affinity of the other adducts reflect the weaker ion-dipole mechanism.

Original language	English
Number of pages	9
Journal	Journal of Molecular Structure
Publication status	Published - 2004

Keywords

ab initio simulation
alkali metals
electronic structure
mass spectrometry
neurosteroids
thermochemistry

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@article{e1bd6d22a2b843628127413eb850c809,

title = "Ab initio and DFT cation affinity study of selected neurosteroids",

abstract = "Full 3N-6 optimization electronic structure calculations using the HF 6-31G(d)//HF 6-31G(d) and B3LYP 6-31G(d)//B3LYP 6-31G(d) levels of theory have been employed to determine the theoretical gas-phase cation affinities of 5-pregnen-3{\~A}{\v Z}{\^A}²-ol-20-one, 5-androsten-3{\~A}{\v Z}{\^A}²-ol-17-one, 4-pregnen-3,20-dione, 5{\~A}{\v Z}{\^A}±-pregnan-3, 20-dione, 5{\~A}{\v Z}{\^A}±-pregnan-3{\~A}{\v Z}{\^A}±-ol-20-one and 5{\~A}{\v Z}{\^A}±-pregnan-3{\~A}{\v Z}{\^A}²-ol-20-one. For all the selected neurosteroids both theoretical methods predicted the trend of cation affinity as: H+ &MGT; Li+ > Na+ > K+. The bonding interactions occur at the carbonyl group of the neurosteroids. The large cation affinities of the neurosteroid-proton adduct was found to be indicative of the formation of a stable complex via a relatively strong polar-covalent mechanism, while the lower cation affinity of the other adducts reflect the weaker ion-dipole mechanism.",

keywords = "ab initio simulation, alkali metals, electronic structure, mass spectrometry, neurosteroids, thermochemistry",

author = "Morrison, {Anthony A.} and Paul, {Mitchell C.} and Parsons, {Carl H.} and Calford, {Michael B.} and Nagy-Felsobuki, {E. von}",

year = "2004",

language = "English",

journal = "Journal of Molecular Structure",

issn = "0022-2860",

publisher = "Elsevier",

}

TY - JOUR

T1 - Ab initio and DFT cation affinity study of selected neurosteroids

AU - Morrison, Anthony A.

AU - Paul, Mitchell C.

AU - Parsons, Carl H.

AU - Calford, Michael B.

AU - Nagy-Felsobuki, E. von

PY - 2004

Y1 - 2004

N2 - Full 3N-6 optimization electronic structure calculations using the HF 6-31G(d)//HF 6-31G(d) and B3LYP 6-31G(d)//B3LYP 6-31G(d) levels of theory have been employed to determine the theoretical gas-phase cation affinities of 5-pregnen-3ÃŽÂ²-ol-20-one, 5-androsten-3ÃŽÂ²-ol-17-one, 4-pregnen-3,20-dione, 5ÃŽÂ±-pregnan-3, 20-dione, 5ÃŽÂ±-pregnan-3ÃŽÂ±-ol-20-one and 5ÃŽÂ±-pregnan-3ÃŽÂ²-ol-20-one. For all the selected neurosteroids both theoretical methods predicted the trend of cation affinity as: H+ &MGT; Li+ > Na+ > K+. The bonding interactions occur at the carbonyl group of the neurosteroids. The large cation affinities of the neurosteroid-proton adduct was found to be indicative of the formation of a stable complex via a relatively strong polar-covalent mechanism, while the lower cation affinity of the other adducts reflect the weaker ion-dipole mechanism.

AB - Full 3N-6 optimization electronic structure calculations using the HF 6-31G(d)//HF 6-31G(d) and B3LYP 6-31G(d)//B3LYP 6-31G(d) levels of theory have been employed to determine the theoretical gas-phase cation affinities of 5-pregnen-3ÃŽÂ²-ol-20-one, 5-androsten-3ÃŽÂ²-ol-17-one, 4-pregnen-3,20-dione, 5ÃŽÂ±-pregnan-3, 20-dione, 5ÃŽÂ±-pregnan-3ÃŽÂ±-ol-20-one and 5ÃŽÂ±-pregnan-3ÃŽÂ²-ol-20-one. For all the selected neurosteroids both theoretical methods predicted the trend of cation affinity as: H+ &MGT; Li+ > Na+ > K+. The bonding interactions occur at the carbonyl group of the neurosteroids. The large cation affinities of the neurosteroid-proton adduct was found to be indicative of the formation of a stable complex via a relatively strong polar-covalent mechanism, while the lower cation affinity of the other adducts reflect the weaker ion-dipole mechanism.

KW - ab initio simulation

KW - alkali metals

KW - electronic structure

KW - mass spectrometry

KW - neurosteroids

KW - thermochemistry

UR - http://handle.uws.edu.au:8081/1959.7/36870

M3 - Article

SN - 0022-2860

JO - Journal of Molecular Structure

JF - Journal of Molecular Structure

ER -

Ab initio and DFT cation affinity study of selected neurosteroids

Abstract

Keywords

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