Vibrational circular dichroism as a probe of solid‐state organisation of derivatives of cyclic β‐amino acids: Cis ‐ and trans ‐2‐aminocyclobutane‐1‐carboxylic acid
| Autor: | David J. Aitken, Anne Zehnacker, Régis Guillot, Valérie Declerck, Michel Mons, Ariel Pérez-Mellor |
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| Přispěvatelé: | Institut des Biomolécules Max Mousseron [Pôle Chimie Balard] (IBMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), Université Paris-Sud - Paris 11 (UP11)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Francis PERRIN (LFP - URA 2453), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Moléculaires d'Orsay (ISMO), Université Paris-Sud - Paris 11 (UP11)-Centre National de la Recherche Scientifique (CNRS), SYSIPHE, Université Paris-Sud - Paris 11 (UP11)-Centre National de la Recherche Scientifique (CNRS)-Université Paris-Sud - Paris 11 (UP11)-Centre National de la Recherche Scientifique (CNRS), ANR-17-CE29-0008,TUNIFOLD-S,Le soufre pour contrôler la flexibilité de briques moléculaires(2017), Université Paris-Sud - Paris 11 (UP11)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM) |
| Rok vydání: | 2019 |
| Předmět: |
crystal structure
Absorption spectroscopy Carboxylic acid Amino Acids Cyclic Infrared spectroscopy Crystallography X-Ray 010402 general chemistry 01 natural sciences Catalysis Analytical Chemistry β peptide Spectroscopy Fourier Transform Infrared Drug Discovery Density Functional Theory ComputingMilieux_MISCELLANEOUS Spectroscopy Pharmacology chemistry.chemical_classification 010405 organic chemistry Chemistry Hydrogen bond Circular Dichroism Organic Chemistry Intermolecular force Hydrogen Bonding Stereoisomerism VCD Amides 0104 chemical sciences [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry Crystallography IR spectroscopy Vibrational circular dichroism Density functional theory Gases Cis–trans isomerism |
| Zdroj: | Chirality Chirality, 2019, 31 (8), pp.547-560. ⟨10.1002/chir.23083⟩ Chirality, Wiley, 2019, 31 (8), pp.547-560. ⟨10.1002/chir.23083⟩ |
| ISSN: | 1520-636X 0899-0042 |
| DOI: | 10.1002/chir.23083 |
| Popis: | Peptide models built from cis- and trans-2-aminocyclobutane-1-carboxylic acids (ACBCs) are studied in the solid phase by combining Fourier-transform infrared spectroscopy (FTIR) absorption spectroscopy, vibrational circular dichroism (VCD), and quantum chemical calculations using density functional theory (DFT). The studied systems are N-tert-butyloxycarbonyl (Boc) derivatives of 2-aminocyclobutanecarboxylic acid (ACBC) benzylamides, namely Boc-(cis-ACBC)-NH-Bn and Boc-(trans-ACBC)-NH-Bn. These two diastereomers show very different VCD signatures and intensities, which of the trans-ACBC derivative being one order of magnitude larger in the region of the ν (CO) stretch. The spectral signature of the cis-ACBC derivative is satisfactorily reproduced by that of the monomer extracted from the solid-state geometry of related ACBC derivatives, which shows that no long-range effects are implicated for this system. In terms of hydrogen bonds, the geometry of this monomer is intermediate between the C6 and C8 structures (exhibiting a 6- or 8-membered cyclic NH⋯O hydrogen bond) previously evidenced in the gas phase. The benzyl group must be in an extended geometry to reproduce satisfactorily the shape of the VCD spectrum in the ν (CO) range, which qualifies VCD as a potential probe of dispersion interaction. In contrast, reproducing the IR and VCD spectrum of the trans-ACBC derivative requires clusters larger than four units, exhibiting strong intermolecular H-bonding patterns. A qualitative agreement is obtained for a tetramer, although the intensity enhancement is not reproduced. These results underline the sensitivity of VCD to the long-range organisation in the crystal. |
| Databáze: | OpenAIRE |
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