Three closely related previously synthesized monoaza[5]helicenes have been resolved into their en... more Three closely related previously synthesized monoaza[5]helicenes have been resolved into their enantiomers via enantioselective HPLC using a cellulose-derivative Chiralcel OD column. Circular dichroism (CD) spectra of the enantiomerically enriched samples have been recorded and assigned. The spectra were analyzed as a function of time, and different rate constants were found in the kinetics of racemization for the three molecules. Ab initio DFT calculations for the ground electronic states were employed to determine minima and saddle point structures and to understand the racemization process. The theoretical geometries compared well with those from X-ray structures. CD spectra were calculated by TD-DFT ab initio methods, and compared with experimental data.
Near-infrared vibrational circular dichroism (VCD) spectra in the region 1500-850 nm are recorded... more Near-infrared vibrational circular dichroism (VCD) spectra in the region 1500-850 nm are recorded for both enantiomers of camphor and fenchone using a home-built dispersive instrument. Two CH-stretching overtone regions and two CH-stretching/HCH-bending combination regions are investigated. The near-infrared VCD data are examined and compared with the corresponding previously published data of (3R)-(+)-methylcyclopentanone and (3R)-(+)-methylcyclohexanone. The absorption spectra of both the fundamental and overtone regions are also considered, and the fundamental CH-stretching VCD data are taken into account, where possible. An empirical assignment of the spectra is first considered, with special regard to the second CHstretching overtone region. This region is then investigated by a heuristic approach based on DFT calculations, using the hybrid functional B3LYP at the 6-31G** basis set level. Subsequently rotational strengths have been evaluated by use of a classical model based on the contribution of polarizable groups to the optical activity. The same models are also used to interpret the VCD spectra between 2000 and 3000 wavenumbers for (3R)-(+)-methylcyclopentanone-d 4 .
Journal of Radioanalytical and Nuclear Chemistry Articles, 1994
The electrochemical reductions of hexavalent and tetravalent uranium are reported in "t-butyrolac... more The electrochemical reductions of hexavalent and tetravalent uranium are reported in "t-butyrolactone, ~t-valerolactone, ~-octanoiclactone and in the mixed solvent y-butyrolactone/tetrahydrofuran. The transient techniques foresee either the formation of uranium dioxide or uranium metal according to a two-step reduction but the presence of these cathodic products is difficult to ascertain in controlled potential electrolysis. While mixing a lactone with tetrahydrofuran, the reversibility of the electrode reactions increases. The conducting salt noticeably determines the current yield of uranium deposition. A s additional kinetic phenomena nre made clear, we found that sampled polarography is the best method to gain a full understanding of the electrode mechanisms.
The electronic circular dichroism spectra of achiral product ''Lumogen F Red'' (ROT-300) in four ... more The electronic circular dichroism spectra of achiral product ''Lumogen F Red'' (ROT-300) in four different chiral solvents are recorded at different temperatures. DFT calculations allow to identify two enantiomeric conformers for ROT-300. In vacuo they are equally populated; in chiral solvents one enantiomer prevails. Thermodynamic quantities involved in the chiral preference are derived. Chirality 23:910-915, 2011. V
Ultraviolet (UV), Circular Dichroism (CD), Fluorescence, and Circularly Polarized Luminescence (C... more Ultraviolet (UV), Circular Dichroism (CD), Fluorescence, and Circularly Polarized Luminescence (CPL) spectra were recorded for mixed chloroform/methanol and chloroform/ butanol solutions of regioregular poly[3-((S)-2-methylbutyl)-thiophene]. An evaluation of the chiral and nonchiral components in solution is proposed on the basis of the UV and CD spectra. The fluorescence and CPL spectra are observed in a wavelength range where some UV and CD activity still appears. For this reason, the observed CPL features are strongly influenced by CD. A general procedure for evaluating true CPL spectra is proposed, when absorption and emission coexist.
Molecular dynamics (MD) has been used to simulate a dilute aqueous solution of a 50-units oligome... more Molecular dynamics (MD) has been used to simulate a dilute aqueous solution of a 50-units oligomer model for the thermoresponsive polymer poly(N-isopropylacrylamide) at 300 and 310 K, i.e., below and above its lower critical solution temperature (LCST) in water. Statistical analyses of the system trajectories show that at 310 K the oligomer exhibits a more compact conformation than at 300 K, in qualitative agreement with experiments, and that it is surrounded by a smaller number of first-hydrationshell water molecules.
The absolute configuration of a newly designed, letrozole-based chiral aromatase inhibitor that c... more The absolute configuration of a newly designed, letrozole-based chiral aromatase inhibitor that could not be defined by crystallographic techniques has been determined by means of vibrational and electronic circular dichroism and by optical rotation measurements combined with density functional theory calculations on possible conformers. The same absolute configurational assignment can be applied to the individual enantiomeric sulfamate esters, which are derived from the corresponding enantiomers of the chirally separated parent phenols, based on the similarity of the ECD spectrum of the sulfamate derivative to that of its phenolic precursor. The two enantiomeric sulfamate esters studied here are the first examples of nonsteroidal dual aromatase-sulfatase inhibitor whose activities have been evaluated on optically resolved enantiomers.
Three closely related previously synthesized monoaza[5]helicenes have been resolved into their en... more Three closely related previously synthesized monoaza[5]helicenes have been resolved into their enantiomers via enantioselective HPLC using a cellulose-derivative Chiralcel OD column. Circular dichroism (CD) spectra of the enantiomerically enriched samples have been recorded and assigned. The spectra were analyzed as a function of time, and different rate constants were found in the kinetics of racemization for the three molecules. Ab initio DFT calculations for the ground electronic states were employed to determine minima and saddle point structures and to understand the racemization process. The theoretical geometries compared well with those from X-ray structures. CD spectra were calculated by TD-DFT ab initio methods, and compared with experimental data.
Near-infrared vibrational circular dichroism (VCD) spectra in the region 1500-850 nm are recorded... more Near-infrared vibrational circular dichroism (VCD) spectra in the region 1500-850 nm are recorded for both enantiomers of camphor and fenchone using a home-built dispersive instrument. Two CH-stretching overtone regions and two CH-stretching/HCH-bending combination regions are investigated. The near-infrared VCD data are examined and compared with the corresponding previously published data of (3R)-(+)-methylcyclopentanone and (3R)-(+)-methylcyclohexanone. The absorption spectra of both the fundamental and overtone regions are also considered, and the fundamental CH-stretching VCD data are taken into account, where possible. An empirical assignment of the spectra is first considered, with special regard to the second CHstretching overtone region. This region is then investigated by a heuristic approach based on DFT calculations, using the hybrid functional B3LYP at the 6-31G** basis set level. Subsequently rotational strengths have been evaluated by use of a classical model based on the contribution of polarizable groups to the optical activity. The same models are also used to interpret the VCD spectra between 2000 and 3000 wavenumbers for (3R)-(+)-methylcyclopentanone-d 4 .
Journal of Radioanalytical and Nuclear Chemistry Articles, 1994
The electrochemical reductions of hexavalent and tetravalent uranium are reported in "t-butyrolac... more The electrochemical reductions of hexavalent and tetravalent uranium are reported in "t-butyrolactone, ~t-valerolactone, ~-octanoiclactone and in the mixed solvent y-butyrolactone/tetrahydrofuran. The transient techniques foresee either the formation of uranium dioxide or uranium metal according to a two-step reduction but the presence of these cathodic products is difficult to ascertain in controlled potential electrolysis. While mixing a lactone with tetrahydrofuran, the reversibility of the electrode reactions increases. The conducting salt noticeably determines the current yield of uranium deposition. A s additional kinetic phenomena nre made clear, we found that sampled polarography is the best method to gain a full understanding of the electrode mechanisms.
The electronic circular dichroism spectra of achiral product ''Lumogen F Red'' (ROT-300) in four ... more The electronic circular dichroism spectra of achiral product ''Lumogen F Red'' (ROT-300) in four different chiral solvents are recorded at different temperatures. DFT calculations allow to identify two enantiomeric conformers for ROT-300. In vacuo they are equally populated; in chiral solvents one enantiomer prevails. Thermodynamic quantities involved in the chiral preference are derived. Chirality 23:910-915, 2011. V
Ultraviolet (UV), Circular Dichroism (CD), Fluorescence, and Circularly Polarized Luminescence (C... more Ultraviolet (UV), Circular Dichroism (CD), Fluorescence, and Circularly Polarized Luminescence (CPL) spectra were recorded for mixed chloroform/methanol and chloroform/ butanol solutions of regioregular poly[3-((S)-2-methylbutyl)-thiophene]. An evaluation of the chiral and nonchiral components in solution is proposed on the basis of the UV and CD spectra. The fluorescence and CPL spectra are observed in a wavelength range where some UV and CD activity still appears. For this reason, the observed CPL features are strongly influenced by CD. A general procedure for evaluating true CPL spectra is proposed, when absorption and emission coexist.
Molecular dynamics (MD) has been used to simulate a dilute aqueous solution of a 50-units oligome... more Molecular dynamics (MD) has been used to simulate a dilute aqueous solution of a 50-units oligomer model for the thermoresponsive polymer poly(N-isopropylacrylamide) at 300 and 310 K, i.e., below and above its lower critical solution temperature (LCST) in water. Statistical analyses of the system trajectories show that at 310 K the oligomer exhibits a more compact conformation than at 300 K, in qualitative agreement with experiments, and that it is surrounded by a smaller number of first-hydrationshell water molecules.
The absolute configuration of a newly designed, letrozole-based chiral aromatase inhibitor that c... more The absolute configuration of a newly designed, letrozole-based chiral aromatase inhibitor that could not be defined by crystallographic techniques has been determined by means of vibrational and electronic circular dichroism and by optical rotation measurements combined with density functional theory calculations on possible conformers. The same absolute configurational assignment can be applied to the individual enantiomeric sulfamate esters, which are derived from the corresponding enantiomers of the chirally separated parent phenols, based on the similarity of the ECD spectrum of the sulfamate derivative to that of its phenolic precursor. The two enantiomeric sulfamate esters studied here are the first examples of nonsteroidal dual aromatase-sulfatase inhibitor whose activities have been evaluated on optically resolved enantiomers.
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