Different impact of menthol chirality on ideal and deep eutectic solvents: Thermal and structural insights

IF 5.3 2区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Molecular Liquids Pub Date : 2025-04-29 DOI:10.1016/j.molliq.2025.127676

Giorgia Mannucci , Matteo Busato , Eva Pietropaoli , Matteo Palluzzi , Paolo Casu , Angela Capocefalo , Claudia Fasolato , Paolo Postorino , Paola D'Angelo

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引用次数: 0

Abstract

Although chiral molecules are common components of deep eutectic solvents (DESs), the impact of precursor chirality on the fundamental aspects of these solvents is far from being systematically explored. Here, the effect of chirality on the eutectic mixtures formed by the optically active menthol (MEN) with thymol (TYM) and butylated hydroxytoluene (BHT) has been investigated. To this purpose, we resorted to a combined thermal and structural analysis by means of differential scanning calorimetry measurements aided by the COSMO-RS solvation model, Raman spectroscopy, small- and wide-angle X-ray scattering, and molecular dynamics simulations. A slightly different thermal behavior and self-association are observed for the levorotatory enantiomer (L-MEN) as compared to the dextrorotatory one (D-MEN) and the racemate (D/L-MEN) in the pure MEN system. This behavior is preserved in the BHT:MEN 1:3 ideal eutectic as the interaction with the BHT molecules is hampered due to the presence of the bulky substituents. On the other hand, the precursor chirality has no detectable influence on the overall properties of the TYM:MEN 1:1 DES due to strong interactions with the non-chiral counterpart. These findings have important implications for the design and employment of chiral DESs for enantioselective purposes.

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薄荷醇手性对理想溶剂和深度共晶溶剂的不同影响：热学和结构见解

虽然手性分子是深共晶溶剂（DESs）的常见组分，但前体手性对这些溶剂的基本方面的影响还远未被系统地探索。本文研究了手性对光学活性薄荷醇（MEN）与百里酚（TYM）和丁基羟基甲苯（BHT）形成共晶混合物的影响。为此，我们借助于cosmos - rs溶剂化模型、拉曼光谱、小角和广角x射线散射以及分子动力学模拟，采用差示扫描量热法进行了热学和结构分析。在纯MEN体系中，左旋对映体（L-MEN）与右旋对映体（D-MEN）和外消旋对映体（D/L-MEN）的热行为和自缔合略有不同。这种行为在BHT:MEN 1:3理想共晶中得以保留，因为与BHT分子的相互作用由于大体积取代基的存在而受到阻碍。另一方面，由于前体手性与非手性对应物的强相互作用，前体手性对TYM:MEN 1:1 DES的整体性能没有明显的影响。这些发现对手性DESs的设计和应用具有重要意义。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Journal of Molecular Liquids 化学-物理：原子、分子和化学物理

CiteScore

10.30

自引率

16.70%

发文量

2597

审稿时长

78 days

期刊介绍： The journal includes papers in the following areas: – Simple organic liquids and mixtures – Ionic liquids – Surfactant solutions (including micelles and vesicles) and liquid interfaces – Colloidal solutions and nanoparticles – Thermotropic and lyotropic liquid crystals – Ferrofluids – Water, aqueous solutions and other hydrogen-bonded liquids – Lubricants, polymer solutions and melts – Molten metals and salts – Phase transitions and critical phenomena in liquids and confined fluids – Self assembly in complex liquids.– Biomolecules in solution The emphasis is on the molecular (or microscopic) understanding of particular liquids or liquid systems, especially concerning structure, dynamics and intermolecular forces. The experimental techniques used may include: – Conventional spectroscopy (mid-IR and far-IR, Raman, NMR, etc.) – Non-linear optics and time resolved spectroscopy (psec, fsec, asec, ISRS, etc.) – Light scattering (Rayleigh, Brillouin, PCS, etc.) – Dielectric relaxation – X-ray and neutron scattering and diffraction. Experimental studies, computer simulations (MD or MC) and analytical theory will be considered for publication; papers just reporting experimental results that do not contribute to the understanding of the fundamentals of molecular and ionic liquids will not be accepted. Only papers of a non-routine nature and advancing the field will be considered for publication.