Cyclodextrin derivatives in enantiomer GC separation of volatiles. Part XXI: Complexation of some terpenoids with 2‐O‐acetyl‐3‐O‐methyl‐ and 2‐O‐methyl‐3‐O‐acetyl‐6‐O‐t‐hexyldimethylsilyl‐γ‐cyclodextrins: Molecular Mechanics and Molecular Dynamics

Bicchi, Carlo; Brunelli, Claudio; Cravotto, Giancarlo; Rubiolo, Patrizia; Galli, Mario; Mendicuti, Francisco

doi:10.1002/jssc.200301560

Cited by 9 publications

(3 citation statements)

References 35 publications

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“…Cyclodextrin derivatives endowed with silyl/alkanoyl or alkyl/alkanoyl derivatizing groups represent popular chiral auxiliaries for gas chromatographic applications in the area of the enantiodiscrimination of chiral substrates lacking in hydrogen bond donor groups, which constitute challenging systems for the majority of the enantioseparation methods [ 19 , 20 , 21 ]. As an example, the gas chromatographic separation of the two enantiomers of 1,1,1,3,3-pentafluoro-2-(fluoromethoxy)-3-methoxypropane (compound B), a chiral degradation product of the fluorinated anesthetic sevoflurane [ 22 ], was achieved with high efficiency by selecting heptakis(2,3-di- O -acetyl-6- O - tert -butyldimethylsilyl)-β-cyclodextrin (AcSiCD7) as the chiral agent [ 23 ].…”

Section: Introductionmentioning

confidence: 99%

Chiral Discrimination Mechanisms by Silylated-Acetylated Cyclodextrins: Superficial Interactions vs. Inclusion

Balzano

Barretta

Sicoli

et al. 2022

IJMS

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Cyclodextrin derivatives constitute a powerful class of auxiliary agents for the discrimination of apolar chiral substrates. Both host–guest inclusion phenomena and interactions with the derivatizing groups located on the surface of the macrocycle could drive the enantiodiscrimination; thus, it is important to understand the role that these processes play in the rational design of new chiral selectors. The purpose of this study is to compare via nuclear magnetic resonance (NMR) spectroscopy the efficiency of silylated-acetylated α-, β-, and γ-cyclodextrins in the chiral discrimination of 1,1,1,3,3-pentafluoro-2-(fluoromethoxy)-3-methoxypropane (compound B) and methyl 2-chloropropionate (MCP). NMR DOSY (Diffusion Ordered SpectroscopY) experiments were conducted for the determination of the bound molar fractions and the association constants, whereas ROESY (Rotating-frame Overhauser Enhancement SpectroscopY) measurements provided information on the hosts’ conformation and on the interaction phenomena with the guests. Compound B, endowed with fluorinated moieties, is not deeply included due to attractive Si-F interactions occurring at the external surface of the cyclodextrins. Therefore, a low selectivity toward the size of cyclodextrin cavity is found. By contrast, enantiodiscrimination of MCP relies on the optimal fitting between the size of the guest and that of the cyclodextrin cavity.

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Section: Introductionmentioning

confidence: 99%

Chiral Discrimination Mechanisms by Silylated-Acetylated Cyclodextrins: Superficial Interactions vs. Inclusion

Balzano

Barretta

Sicoli

et al. 2022

IJMS

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“…Both menthol and menthol-substituted ILs have been the subject of several studies employing computational chemistry methods—either molecular dynamics (MD) or quantum chemistry [ 7 – 13 ]. However, to the authors’ best knowledge, none of the earlier works has developed a force field designed and validated specifically for the menthol molecule.…”

Section: Introductionmentioning

confidence: 99%

Parameterization and optimization of the menthol force field for molecular dynamics simulations

Jasik

Szefczyk

2016

J Mol Model

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Menthol’s various biological properties render it a useful component for medical and cosmetological applications, while its three centers of asymmetry mean that it can be used in a range of organic reactions. Menthol-substituted ionic liquids (ILs) have been found to exhibit promising antimicrobial and antielectrostatic properties, as well as being useful in organic catalysis and biochemical studies. However, so far, a force field designed and validated specifically for the menthol molecule has not been constructed. In the present work, the validation and optimization of force field parameters with regard to the ability to reproduce the macroscopic properties of menthol is presented. The set of optimized potentials for liquid simulations all atom (OPLS-AA) compatible parameters was tested and carefully tuned. The refinement of parameters included fitting of partial atomic charges, optimization of Lennard-Jones parameters, and recalculation of the dihedral angle parameters needed to reproduce quantum energy profiles. To validate the force field, a variety of physicochemical properties were calculated for liquid menthol. Both thermodynamic and kinetic properties were taken into account, including density, surface tension, enthalpy of vaporization, and shear viscosity. The obtained force field was proven to accurately reproduce the properties of the investigated compound while being fully compatible with the OPLS-AA force field.Electronic supplementary materialThe online version of this article (doi:10.1007/s00894-016-3082-1) contains supplementary material, which is available to authorized users.

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“…Bicchi et al [8,9] demonstrated the highest enantioselectivity in GC separation for octakis(2-O-methyl-3-O-acetyl-6-O-tert-hexyldimethylsilyl)-c-CD in comparison with octakis(2-Oacetyl-3-O-methyl-6-O-tert-hexyldimethylsilyl)-c-CD, octakis(2,3-di-O-acetyl-6-O-tert-hexyldimethylsilyl)-c-CD and octakis(2,3-di-O-methyl-6-O-tert-hexyldimethylsilyl)-c-CD. Busby and Vigh [10] have successfully used the sodium salt of heptakis(2-O-methyl-3-O-acetyl-6-O-sulpho)-b-CD for capillary electrophoretic enantioseparation.…”

Section: Introductionmentioning

confidence: 99%

Enantiomer separation on monolithic silica HPLC columns using chemically bonded methylated and methylated/acetylated 6-O-tert-butyldimethyl- silylated β-cyclodextrin

Bayer

Hänsel

Mosandl³

2006

J. Sep. Sci.

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A new 2,3-methylated 3*-monoacetylated 6-O-tert-butyldimethylsilylated beta-CD derivative was synthesized and chemically bonded onto aminopropyl derivatized monolithic silica HPLC columns. In this CD derivative, only one of seven methyl groups in 3-position was substituted by an acetyl group. Its applicability as a chiral stationary phase for HPLC was tested and compared with exclusively 2,3-methylated 6-O-tert-butyldimethylsilylated beta-CD immobilized onto aminopropyl-modified monoliths. Thirty-two chiral compounds from different chemical classes and different functionalities were tested under RP conditions. Fourteen compounds were resolved into their enantiomers by methylated 6-O-tert-butyldimethylsilylated beta-CD. By use of methylated/acetylated 6-O-tert-butyldimethylsilylated beta-CD as the chiral stationary phase 7 analytes were successfully stereodifferentiated.

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Cyclodextrin derivatives in enantiomer GC separation of volatiles. Part XXI: Complexation of some terpenoids with 2‐O‐acetyl‐3‐O‐methyl‐ and 2‐O‐methyl‐3‐O‐acetyl‐6‐O‐t‐hexyldimethylsilyl‐γ‐cyclodextrins: Molecular Mechanics and Molecular Dynamics

Cited by 9 publications

References 35 publications

Chiral Discrimination Mechanisms by Silylated-Acetylated Cyclodextrins: Superficial Interactions vs. Inclusion

Chiral Discrimination Mechanisms by Silylated-Acetylated Cyclodextrins: Superficial Interactions vs. Inclusion

Parameterization and optimization of the menthol force field for molecular dynamics simulations

Enantiomer separation on monolithic silica HPLC columns using chemically bonded methylated and methylated/acetylated 6-O-tert-butyldimethyl- silylated β-cyclodextrin

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