Anisotropy Spectra of Amino Acids

Meinert, Cornelia; Bredehöft, Jan Hendrik; Filippi, Jean‐Jacques; Baraud, Yannick; Nahon, Laurent; Wien, Frank; Jones, Nykola C.; Hoffmann, Søren Vrønning; Meierhenrich, Uwe J.

doi:10.1002/anie.201108997

Cited by 58 publications

(109 citation statements)

References 46 publications

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“…The CD spectra for amino acids all indicate that cpl is differentially absorbed by D-and L-enantiomers. Additionally, the anisotropy spectra of amino acids measured to date all indicate that >1% ee can be induced by photochemical exposure to cpl [52]. Asymmetric photochemistry could therefore have induced a non-racemic bias under prebiotic conditions.…”

Section: And Anisotropy Spectroscopy Of Amino Acids: Applicationsmentioning

confidence: 97%

“…Therefore systematic understanding of enantioselective photolysis reactions cannot exclusively rely on CD data and requires the recording of the anisotropy factor as a function of wavelength, or g(λ). These measurements are now known as anisotropy spectroscopy [52].…”

Section: Anisotropy Spectroscopymentioning

confidence: 99%

“…As outlined above, these influences are more directly provided by the anisotropy factor, g. This is given by the equation g ¼ Δε/ε, which utilizes the differential extinction coefficient recorded during CD measurements as well as the extinction coefficient recorded during absorption measurements. For a given wavelength of cpl, g can be determined from CD and absorption spectra: for a known extent of reaction ξ for the asymmetric photochemical process, the maximum ee inducible by the process can be predicted using [52] ee ! 1 À ð1 À ξÞ…”

Section: Anisotropy Spectroscopy Of Small Molecules: Theorymentioning

confidence: 99%

“…By determining g for every wavelength of cpl measured during CD spectroscopy, it becomes possible to generate plots of anisotropy spectra that afford full and direct characterization of the photochemical interactions of cpl with a given small molecule [52]. Anisotropy spectra therefore provide a means for directly predicting photochemical differentiation between enantiomers at given wavelengths of light and provide a unique methodology for tuning photochemical behavior to produce enantiomeric excesses that can be amplified using alternative chemical means [61][62][63][64].…”

Section: Anisotropy Spectroscopy Of Small Molecules: Theorymentioning

confidence: 99%

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Anisotropy Spectra for Enantiomeric Differentiation of Biomolecular Building Blocks

Evans

Meinert

Bredehöft

et al. 2013

Topics in Current Chemistry

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All biopolymers are composed of homochiral building blocks, and both D-sugars and L-amino acids uniquely constitute life on Earth. These monomers were originally enantiomerically differentiated under prebiotic conditions. Particular progress has recently been made in support of the photochemical model for this differentiation: the interaction of circularly polarized light with racemic molecules is currently thought to have been the original source for life's biological homochirality. The differential asymmetric photoreactivity of particular small molecules can be characterized by both circular dichroism and anisotropy spectroscopy. Anisotropy spectroscopy, a novel derivative of circular dichroism spectroscopy, records the anisotropy factor g = Δε/ε as a function of the wavelength. Anisotropy spectroscopy promisingly affords the wavelength-dependent determination of the enantiomeric excess (ee) inducible into chiral organic molecules by photochemical irradiation with circularly polarized light. Anisotropy spectra of small molecules therefore provide unique means for characterizing the different photochemical behaviors between enantiomers upon exposure to various wavelengths of circularly polarized light. This chapter will: (1) present the theory and configuration of anisotropy spectroscopy; (2) explain experimentally recorded anisotropy spectra of selected chiral biomolecules such as amino acids; and (3) discuss the relevance of these spectra for the investigation of the origin of the molecular homochirality observed in living organisms. This review describes a new chiroptical technique that is of significance for advances in asymmetric photochemistry and that is also highly relevant for the European Space Agency Rosetta Mission, which will determine enantiomeric excesses (ees) in chiral organic molecules in cometary ices when it lands on Comet 67P/Churyumov-Gerasimenko in November 2014.

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Section: And Anisotropy Spectroscopy Of Amino Acids: Applicationsmentioning

confidence: 97%

Section: Anisotropy Spectroscopymentioning

confidence: 99%

Section: Anisotropy Spectroscopy Of Small Molecules: Theorymentioning

confidence: 99%

Section: Anisotropy Spectroscopy Of Small Molecules: Theorymentioning

confidence: 99%

See 2 more Smart Citations

Anisotropy Spectra for Enantiomeric Differentiation of Biomolecular Building Blocks

Evans

Meinert

Bredehöft

et al. 2013

Topics in Current Chemistry

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“…One such external influence is circularly polarized light (CPL), which is inherently chiral and has been regarded as one source for the origin of homochirality in nature 8 . Left-and right-handed CPL have been used to induce the enantioselective photodecomposition of chiral organic compounds; however, only a small enantiomeric excess (o4%) could be obtained due to their very small anisotropy (g) factors 9,10 . Recently, Professor Iwamoto and our group demonstrated the synthesis of helical PDA through asymmetric polymerization with CPL 11 .…”

mentioning

confidence: 99%

Enantioselective synthesis of helical polydiacetylene by application of linearly polarized light and magnetic field

Yang

Xia

et al. 2014

Nat Commun

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Magnetic optical activity, which can occur in all media and is induced by longitudinal magnetic field, causes the difference in absorption coefficients of left and right circularly polarized light and has the potential for magnetically induced enantioselectivity in chemical reactions. Compared with the well-established technique with circularly polarized light, there are few reports on the production of helical conjugated polymers in a photochemical reaction based on above magnetochiral anisotropy mechanism. Herein, we demonstrate experimentally that the enantioselective polymerization of diacetylene derivative can be achieved in the liquid crystal phase by application of linearly polarized light under a parallel or antiparallel magnetic field. The screw direction of predominant helical polydiacetylene chain can be rigorously controlled with the relative orientation of linearly polarized light and the magnetic field. Moreover, the prepared helical polydiacetylene assemblies can serve as a direct visual probe for the enantioselective recognition of D-or L-lysine.

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The Asymmetry of Life

2014

Comets and Their Origin

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Anisotropy Spectra of Amino Acids

Abstract: International audienc

Cited by 58 publications

References 46 publications

Anisotropy Spectra for Enantiomeric Differentiation of Biomolecular Building Blocks

Anisotropy Spectra for Enantiomeric Differentiation of Biomolecular Building Blocks

Enantioselective synthesis of helical polydiacetylene by application of linearly polarized light and magnetic field

The Asymmetry of Life

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