Ab initio and DFT cation affinity study of selected neurosteroids

Anthony A. Morrison; Mitchell C. Paul; Carl H. Parsons; Mike B. Calford; Ellak I. Von Nagy-Felsobuki

doi:10.1016/j.theochem.2005.02.019

Ab initio and DFT cation affinity study of selected neurosteroids

Anthony A. Morrison
, Mitchell C. Paul
, Carl H. Parsons
, Mike B. Calford
, Ellak I. Von Nagy-Felsobuki

University of Newcastle

Research output: Contribution to journal › Article › peer-review

2 Citations (Scopus)

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-3β-ol-20-one, 5-androsten-3β-ol-17-one, 4-pregnen-3,20- dione, 5α-pregnan-3, 20-dione, 5α-pregnan-3α-ol-20-one and 5α-pregnan-3β-ol-20-one. For all the selected neurosteroids both theoretical methods predicted the trend of cation affinity as: H ⁺≫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
Pages (from-to)	85-93
Number of pages	9
Journal	Journal of Molecular Structure: THEOCHEM
Volume	723
Issue number	1-3
DOIs	https://doi.org/10.1016/j.theochem.2005.02.019
Publication status	Published - 20 May 2005
Externally published	Yes

Keywords

Ab initio
Cation affinities
Neurosteroids
Optimized geometries

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10.1016/j.theochem.2005.02.019

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@article{5d505ebaef4f4484a1e02eaa4c6fe34d,

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-3β-ol-20-one, 5-androsten-3β-ol-17-one, 4-pregnen-3,20- dione, 5α-pregnan-3, 20-dione, 5α-pregnan-3α-ol-20-one and 5α-pregnan-3β-ol-20-one. For all the selected neurosteroids both theoretical methods predicted the trend of cation affinity as: H +≫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, Cation affinities, Neurosteroids, Optimized geometries",

author = "Morrison, \{Anthony A.\} and Paul, \{Mitchell C.\} and Parsons, \{Carl H.\} and Calford, \{Mike B.\} and \{Von Nagy-Felsobuki\}, \{Ellak I.\}",

year = "2005",

month = may,

day = "20",

doi = "10.1016/j.theochem.2005.02.019",

language = "English",

volume = "723",

pages = "85--93",

journal = "Journal of Molecular Structure: THEOCHEM",

issn = "0166-1280",

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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, Mike B.

AU - Von Nagy-Felsobuki, Ellak I.

PY - 2005/5/20

Y1 - 2005/5/20

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-3β-ol-20-one, 5-androsten-3β-ol-17-one, 4-pregnen-3,20- dione, 5α-pregnan-3, 20-dione, 5α-pregnan-3α-ol-20-one and 5α-pregnan-3β-ol-20-one. For all the selected neurosteroids both theoretical methods predicted the trend of cation affinity as: H +≫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-3β-ol-20-one, 5-androsten-3β-ol-17-one, 4-pregnen-3,20- dione, 5α-pregnan-3, 20-dione, 5α-pregnan-3α-ol-20-one and 5α-pregnan-3β-ol-20-one. For all the selected neurosteroids both theoretical methods predicted the trend of cation affinity as: H +≫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

KW - Cation affinities

KW - Neurosteroids

KW - Optimized geometries

UR - https://www.scopus.com/pages/publications/18244397687

U2 - 10.1016/j.theochem.2005.02.019

DO - 10.1016/j.theochem.2005.02.019

M3 - Article

AN - SCOPUS:18244397687

SN - 0166-1280

VL - 723

SP - 85

EP - 93

JO - Journal of Molecular Structure: THEOCHEM

JF - Journal of Molecular Structure: THEOCHEM

IS - 1-3

ER -

Ab initio and DFT cation affinity study of selected neurosteroids

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Keywords

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