Induzierte Chiralität in achiralen Lösungsmitteln – mysteriöse Solvenseffekte, aufgeklärt mit theoretischen Methoden

Neugebauer, Johannes

doi:10.1002/ange.200702858

Cited by 9 publications

(8 citation statements)

References 32 publications

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“…The situation may be considered as complementary to the recently discovered phenomenon of solvent imprinting, [8,9] in which the contribution of chiral solute to the net OR is negligible in comparison with that of solvent molecules organized in a chiral fashion around the solute. The situation may be considered as complementary to the recently discovered phenomenon of solvent imprinting, [8,9] in which the contribution of chiral solute to the net OR is negligible in comparison with that of solvent molecules organized in a chiral fashion around the solute.…”

Section: Light Scattering Experimentsmentioning

confidence: 99%

“…Although such supramers (especially those formed in dilute solutions) contain mostly achiral water molecules along with a few chiral solute molecules, their OR may be considerable in value and different from that for supramers formed in different concentration ranges. The situation may be considered as complementary to the recently discovered phenomenon of solvent imprinting, [8,9] in which the contribution of chiral solute to the net OR is negligible in comparison with that of solvent molecules organized in a chiral fashion around the solute. Moreover, the presence of different solute conformations in such supramers cannot be definitely ruled out, which makes the situation even more complex.…”

Section: Light Scattering Experimentsmentioning

confidence: 99%

“…in solution. [3][4][5] A third possibility, by far less considered in the literature, [6][7][8][9][10] is related to the solvent distribution around the solute molecules, which is also dependent on concentration. Perhaps by a heritage of the models developed for ideal solutions, such distribution is assumed almost always to be homogeneous.…”

Section: Introductionmentioning

confidence: 99%

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Polarimetry as a Tool for the Study of Solutions of Chiral Solutes

et al. 2013

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Optical rotation of aqueous solutions of D-levoglucosan was studied experimentally in the 0.03-4.0 mol L(-1) concentration range and a nonlinear concentration dependence of specific optical rotation (SR) was revealed. Discontinuities observed in the concentration plot of SR (at 0.1, 0.3, 0.5, 1.0, and 2.0 mol L(-1)) are well correlated with those found by static and dynamic light scattering and identify concentration ranges in which different solution domains (supramers) may exist. The average SR experimental value for a D-levoglucosan aqueous solution ([α]D(28) -58.5±8.7 deg dm(-1) cm(-3) g(-1)) was found to be in good agreement with values obtained by theoretical calculation (TD-DFT/GIAO) of SR for 15 different conformers revealed by conformational sampling at the PCM/B3LYP/6-311++G(2d,2p)//B3LYP/6-31+G(d,p) level, which were shown to be strongly affected by the solvation microenvironment (0, 1, 2, and 3 explicit solvent molecules considered) due to local geometrical changes induced in the solute molecule. This exceptionally high sensitivity of SR makes polarimetry a unique method capable of sensing changes in the structure of supramers detected in this study.

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Section: Light Scattering Experimentsmentioning

confidence: 99%

Section: Light Scattering Experimentsmentioning

confidence: 99%

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Polarimetry as a Tool for the Study of Solutions of Chiral Solutes

et al. 2013

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“… Markus R. Heinrich (TU München) for his work on organic radical and photochemistry,3a Jens Bredenbeck (University of Frankfurt) for his investigations into biophysical problems using ultrafast spectroscopic methods,3b and Johannes Neugebauer (ETH Zurich, now at the University of Leiden) for his theoretical investigations of functional molecular aggregates and Raman spectroscopy 3c …”

Section: Awarded…︁mentioning

confidence: 99%

German Congress of Chemistry Lecturers: Prizes to H.‐U. Blaser and D. Scheschkewitz

2009

Angew Chem Int Ed

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“…refs. [4,5]). In order to understand such phenomena, it is important to have the necessary theoretical tools at hand that allow one to describe the relevant interactions in the assembly and the resulting effects on the properties of the system.…”

Section: Introductionmentioning

confidence: 97%

Subsystem‐Based Theoretical Spectroscopy of Biomolecules and Biomolecular Assemblies

Neugebauer

2009

ChemPhysChem

Self Cite

123

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The absorption properties of chromophores in biomolecular systems are subject to several fine-tuning mechanisms. Specific interactions with the surrounding protein environment often lead to significant changes in the excitation energies, but bulk dielectric effects can also play an important role. Moreover, strong excitonic interactions can occur in systems with several chromophores at close distances. For interpretation purposes, it is often desirable to distinguish different types of environmental effects, such as geometrical, electrostatic, polarization, and response (or differential polarization) effects. Methods that can be applied for theoretical analyses of such effects are reviewed herein, ranging from continuum and point-charge models to explicit quantum chemical subsystem methods for environmental effects. Connections to physical model theories are also outlined. Prototypical applications to optical spectra and excited states of fluorescent proteins, biomolecular photoreceptors, and photosynthetic protein complexes are discussed.

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Induzierte Chiralität in achiralen Lösungsmitteln – mysteriöse Solvenseffekte, aufgeklärt mit theoretischen Methoden

Cited by 9 publications

References 32 publications

Polarimetry as a Tool for the Study of Solutions of Chiral Solutes

Polarimetry as a Tool for the Study of Solutions of Chiral Solutes

German Congress of Chemistry Lecturers: Prizes to H.‐U. Blaser and D. Scheschkewitz

Subsystem‐Based Theoretical Spectroscopy of Biomolecules and Biomolecular Assemblies

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