The controlled reversal of supramolecular helical chirality in protein fibrils is reported for the first time. Normal or reversed insulin fibrils were grown by precise adjustment of pH. AFM images show two polymorphs corresponding to opposite senses of helical twist of the supramolecular structure with the same cross-β-sheet core.

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We report the first mid-infrared observation of vibrational circular birefringence (VCB) arising from individual chiral molecules. VCB can also be called vibrational optical rotatory dispersion (VORD) and is the Kramers-Kronig transform of vibrational circular dichroism (VCD). The method of measurement involves a simple change in the optical set-up and electronic processing of a VCD spectrometer such that the VCB spectrum appears at twice the polarization modulation frequency as a pseudo vibrational linear dichroism (VLD) spectrum. VCB spectra are also calculated with density function theory (DFT) for the first time using a commercially available program for rotational strengths where the calculated intensities are convolved with the real, dispersive part of a normalized complex Lorentzian lineshape rather than the imaginary, absorptive part, normally used for IR and VCD intensity calculations. Comparison of the measured and calculated VCB, VCD, and IR spectra of (1)-R-limonene and (2)-S-apinene show close agreement and confirm the validity of the new VCB measurements. Chirality 21:E277-E286, 2009. V

Enantioenriched square-pyramidal oxo- and sulfidorhenium(v) complexes have been prepared and their stereochemistry studied by vibrational circular dichroism (VCD) spectroscopy.

The infrared and vibrational circular dichroism (VCD) spectra of six chiral oxorhenium(V) complexes, bearing a hydrotris(1-pyrazolyl)borate (Tp) ligand, have been investigated. These complexes are promising candidates for observation of parity violation (symmetry breaking due to the weak nuclear force). New chiral oxorhenium complexes have been synthesized, namely, [TpReO(eta2-O(CH3)CH2CH2O-O,O)] (4a and 4b) diastereomers and [TpReO(eta2-N(CH3)CH2CH2O-N,O)] (5) and [TpReO(eta2-N(tBu)CH2CH2O-N,O)] (6) enantiomers. All compounds could be obtained in enantiomerically pure form by using either column chromatography or HPLC over chiral columns. VCD spectroscopy of these compounds and of [TpReO(eta2-N(CH3)CH(CH3)CH(Ph)O-N,O)] (2) and [TpReO(eta2-N(CH2)3CHCO2-N,O)] (3) (with chiral bidentate ligands derived, respectively, from ephedrine and proline) were studied. This allowed the absolute configuration determination of all compounds together with their conformational analysis, by comparing calculated and experimental spectra. This is the first VCD study of rhenium complexes which further demonstrates the applicability of VCD spectroscopy in determining the chirality of inorganic complexes.