Communication Dans Un Congrès Année : 2024

Crystallographic analysis of amylose (3,5-dimethylphenylcarbamate) (ADMPC)

Résumé

Chirality plays a crucial role in the physiologic actions of biologically-active compounds such as pharmaceuticals and agrochemicals. For example, (S)-naproxen exhibits therapeutic anti-inflammatory properties, while its enantiomer (R)-naproxen lacks analgesic effects and causes liver toxicity. Thus, chiral resolution by high-performance liquid chromatography [1] has been widely used to analyze the enantiopurity of chiral molecules. Our group has recently developed an alternative approach for chiral resolution by filtration through enantioselective membranes prepared by electrospinning of cellulose- and amylose-based chiral selectors (CSs) [2]. The present project aimed at elucidating the mechanism of chiral resolution at the molecular scale by crystallographic analysis of the polysaccharidic CSs and their complexes with chiral molecules. Amylose (3,5-dimethylphenyl carbamate) (ADMPC) [3] (Figure 1), a widely used CS in chiral chromatography columns, was crystallized for the first time from dilute solutions using controlled precipitation methods involving various solvents (ethyl acetate, 1,4-dioxane, dimethylformamide, etc.) and precipitants (mainly alcohols). Depending on the crystallization setup and protocol, three-dimensional flower-like assemblies of lamellar crystals (Figure 2a) or more individual hexagonal lamellae, involving chain-folding, similar to those obtained with flexible polymers, were observed (Figure 2b). Using transmission electron microscopy (TEM) images, wide-angle X-ray scattering (WAXS) and electron diffraction (ED) data from tilted crystals, we identified a potential hexagonal or orthorhombic unit cell, providing preliminary insights into the structural arrangement of ADMPC chains in the dry state. These findings lay the groundwork for future studies of structural modifications of ADMPC crystallized in the presence of enantiomers and further clarify the mechanisms of chiral discrimination. References [1] Ikai, T.; Okamoto, Y. Chem. Rev. 2009, 109 (11), 6077–6101. https://doi.org/10.1021/cr8005558. [2] Otsuka, I.; Pandey, K.; Ahmadi-Nohadani, H.; Nono-Tagne, S. ACS Macro Lett. 2021, 10 (7), 921–925. https://doi.org/10.1021/acsmacrolett.1c00349. [3] Chankvetadze, B.; Yashima, E.; Okamoto, Y. J. Chromatogr. A 1995, 694 (1), 101–109. https://doi.org/10.1016/0021-9673(94)00729-S. [4] Ye, Y. K.; Bai, S.; Vyas, S.; Wirth, M. J., J. Phys. Chem. B 2007, 111, 1189–1198.

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Dates et versions

hal-04885792 , version 1 (14-01-2025)

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  • HAL Id : hal-04885792 , version 1

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Maëlle Fischer, Issei Otsuka, Jean-Luc Putaux. Crystallographic analysis of amylose (3,5-dimethylphenylcarbamate) (ADMPC). Colloque SFµ Juniors 2024, Société Française des Microscopies, Nov 2024, Grenoble, France. ⟨hal-04885792⟩
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