A Confidence Level Algorithm for the Determination of Absolute Configuration Using Vibrational Circular Dichroism or Raman Optical Activity
| Autor: | Ewoud De Gussem, Wouter A. Herrebout, Patrick Bultinck, Rina K. Dukor, Elke Debie, Laurence A. Nafie |
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| Rok vydání: | 2011 |
| Předmět: |
Circular dichroism
Molecular Conformation Analytical chemistry chirality Similarity measure Spectrum Analysis Raman Measure (mathematics) Spectral line DENSITY-FUNCTIONAL THEORY symbols.namesake Similarity (network science) NATURAL-PRODUCTS ABSORPTION SPECTRA Physical and Theoretical Chemistry AB-INITIO configuration determination Chemistry Physics Circular Dichroism Stereoisomerism VCD Atomic and Molecular Physics and Optics circular dichroism THERMOCHEMISTRY Computational physics ACID Raman spectroscopy Vibrational circular dichroism IR symbols Raman optical activity Algorithms CONFORMATIONAL-ANALYSIS |
| Zdroj: | ChemPhysChem: a European journal of chemical physics and physical chemistry CHEMPHYSCHEM |
| ISSN: | 1439-4235 |
| DOI: | 10.1002/cphc.201100050 |
| Popis: | Spectral comparison is an important part of the assignment of the absolute configuration (AC) by vibrational circular dichroism (VCD), or equally by Raman optical activity (ROA). In order to avoid bias caused by personal interpretation, numerical methods have been developed to compare measured and calculated spectra. Using a neighbourhood similarity measure, the agreement between a computed and measured VCD or ROA spectrum is expressed numerically to introduce a novel confidence level measure. This allows users of vibrational optical activity (VOA) techniques (VCD and ROA) to assess the reliability of their assignment of the AC of a compound. To that end, a database of successful AC determinations is compiled along with neighbourhood similarity values between the experimental spectrum and computed spectra for both enantiomers. For any new AC determination, the neighbourhood similarities between the experimental spectrum and the computed spectra for both enantiomers are projected on the database allowing an interpretation of the reliability of their assignment. |
| Databáze: | OpenAIRE |
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