Elucidating the Structure, Dynamics, and Interaction of a Choline Chloride and Citric Acid Based Eutectic System by Spectroscopic and Molecular Modeling Investigations.
Elucidating the Structure, Dynamics, and Interaction of a Choline Chloride and Citric Acid Based Eutectic System by Spectroscopic and Molecular Modeling Investigations.
复制标题
DOI：
10.1021/acsomega.3c04570
复制
发表时间：
2023-10-17
期刊：
影响因子：
4.1
通讯作者：
Halim, Mohammad A.
中科院分区：
文献类型：
--
作者：
Ali, Md Ackas;Kaium, Md Abdul;Uddin, Sayed Nesar;Uddin, Md Jaish;Olawuyi, Oluseyi;Campbell Jr, Albert D.;Saint-Louis, Carl Jacky;Halim, Mohammad A.
铕溶剂体系是已发现广泛用于许多应用中的通用溶剂。传统的溶剂是均相的，只有一种组分，它们的化学性质相对简单，但也有一些例外。另一方面，深共熔溶剂（DES）包含二元组分，通常是具有不同比例的氢键的供体和受体。在DES中，参与氢键的给体和受体之间的相互作用化学是复杂的。尽管大量的研究集中在DES的合成和应用上，但很少有研究阐明DES的复杂结构和动力学行为以及相互作用。本研究采用量热法、振动光谱技术（包括FTIR和拉曼）以及核磁共振技术，研究了氯化胆碱（ChCl）和柠檬酸（CA）在形成DES过程中的结构特征和非共价键接触。1：1的ChCl/CA低共熔体系显示出相变和熔融峰，在156.22 °C处具有最显著的峰，表明DES在比ChCl和CA的熔融温度更低的温度下熔融。除了红外光谱和拉曼光谱的研究结果，1H NMR研究表明，氢键分子间相互作用的ChCl和CA，支持1：1的ChCl/CA DES的形成的基础上的质子的去屏蔽化学位移的CH。氯阴离子与甲基质子（H4）和亚甲基质子（H3）的ChCl的相互作用，以及强烈的氢键之间的相互作用的ChCl的羟基氢（H1）与CA的羰基氧之一，都支持构象E的形成。此外，采用密度泛函理论（DFT）和分子动力学方法，在ω B 97 XD理论和6-311++G（d，p）基组下，对DES的结构和相互作用进行了可视化研究.实验和理论红外光谱、拉曼光谱和结构分析都证明了DES是通过氢键形成的。这些多方面的实验和计算研究提供了ChCl/CA DES的结构和分子间相互作用的细节。
Eutectic solvent systems are versatile solvents that have found widespread use in numerous applications. Traditional solvents are homogeneous, having only one component, and their chemistry is relatively simple, with some exceptions. On the other hand, deep eutectic solvents (DESs) comprise binary components, generally a donor and an acceptor in hydrogen bonding with varying ratios. The interaction chemistry among the donor and acceptor involved in hydrogen bonding in DESs is complicated. Although numerous research is focused on the synthesis and application of DESs, few studies are reported to elucidate the complex structure and dynamic and interaction behavior of DESs. In this study, we employed calorimetry, vibrational spectroscopy techniques including FTIR and Raman, and nuclear magnetic resonance to derive insight into the structural feature and noncovalent contact of choline chloride (ChCl) and citric acid (CA) while they formed DESs. The 1:1 ChCl/CA eutectic system showed phase transitions and melting peaks with the most pronounced peak at 156.22 °C, suggesting the DESs melting at a lower temperature than the melting temperatures of ChCl and CA. In addition to IR and Raman findings, 1H NMR investigations demonstrate hydrogen bonding intermolecular interactions between ChCl and CA, supporting the formation of 1:1 ChCl/CA DESs based on the deshielded chemical shifts of the proton for Ch. The interaction of the chloride anion with the methyl protons (H4) and methylene protons (H3) of ChCl as well as the strong hydrogen bonding interactions between the hydroxyl hydrogen (H1) of ChCl with one of CA’s carbonyl oxygens both supported the formation of conformer E. In addition, molecular dynamics followed by the density functional theory (DFT) was employed to visualize the structure and interaction of DESs using the ωB97XD theory and 6-311++G (d,p) basis set. Both experimental and theoretical IR, Raman, and structural analyses provided evidence of the formation of DESs by possessing hydrogen bonds. These multifaceted experimental and computational investigations provide details of structural and intermolecular interactions of ChCl/CA DESs.
登录
查看更多内容
影响因子：
3
作者：
Krieger E;Vriend G
通讯作者：
Vriend G
影响因子：
2.9
作者：
Ali, Md Ackas;Rahman, Md Sajjadur;Halim, Mohammad A.
通讯作者：
Halim, Mohammad A.
影响因子：
15
作者：
Abbott, AP;Boothby, D;Rasheed, RK
通讯作者：
Rasheed, RK
DOI：
10.1016/j.jpba.2022.114709
发表时间：
2022-05-30
影响因子：
3.4
作者：
Achanta, Prabhakar S.;Niemitz, Matthias;Friesen, J. Brent;Tadjimukhamedov, Fatkhulla K.;Bzhelyansky, Anton;Giancaspro, Gabriel, I;Chen, Shao-Nong;Pauli, Guido F.
通讯作者：
Pauli, Guido F.
基于氯化胆碱的深共晶溶剂的热不稳定性及其对毒性的影响--作为可持续材料的 DES 的重要局限性
影响因子：
4.2
作者：
Marchel, Mateusz;Cieslinski, Hubert;Boczkaj, Grzegorz
通讯作者：
Boczkaj, Grzegorz