Araujo Marques Isabela, Campos de Paula Hauster Maximiler, Fonseca Silva Camilla, Soares Nascimento Clebio, Coelho Yara Luiza, Dos Santos Pires Ana Clarissa, Mendes da Silva Luis Henrique
Advanced Thermokinetics of Molecular Systems (ATOMS) Group, Chemistry Department, Federal University of Viçosa, Viçosa-MG 36570-000, Brazil.
Theoretical and Computational Chemistry (LQTC) Laboratory, Department of Natural Sciences (DCNAT), Federal University of São João Del Rei, Dom Bosco Campus, São João Del Rei-MG 36301-160, Brazil.
J Phys Chem B. 2024 Oct 3;128(39):9604-9612. doi: 10.1021/acs.jpcb.4c04516. Epub 2024 Sep 20.
This study examines the kinetics and thermodynamics of the inclusion complex (IC) formation between sodium dodecylbenzenesulfonate (SDBS) and amine-modified β-cyclodextrin (βCD-NH) using surface plasmon resonance (SPR) and theoretical analysis. We determined a binding constant of 10 L mol for the thermodynamically stable complex ([βCD-NH/SDBS]°) within the temperature range of 285.2-301.2 K. The thermodynamic analysis revealed a transition from entropy-driven to enthalpy-driven behavior with increasing temperature. The rate constant for IC formation was approximately 10 M s, with the residence time decreasing from 14.08 s at 285.2 K to 6.13 s at 301.2 K. We observed the formation of an activated complex ([βCD-NH/SDBS]), with energetic parameters indicating temperature dependence. At 285.2 K, the activated enthalpy change was positive, while at 301.2 K, it was negative. The dissociation energetic parameters remained temperature-independent. Additionally, increasing concentrations of the ionic liquid 1-butyl-3-methylimidazolium chloride influenced the SDBS tail's conformation and penetration into the βCD-NH cavity at the activated state. These findings provide insights into the complexation mechanism and the effects of the temperature and ionic liquids on IC formation.
本研究采用表面等离子体共振(SPR)和理论分析方法,考察了十二烷基苯磺酸钠(SDBS)与胺改性β-环糊精(βCD-NH)之间包合物(IC)形成的动力学和热力学。我们测定了在285.2 - 301.2 K温度范围内热力学稳定络合物([βCD-NH/SDBS]°)的结合常数为10 L/mol。热力学分析表明,随着温度升高,行为从熵驱动转变为焓驱动。IC形成的速率常数约为10 M/s,停留时间从285.2 K时的14.08 s降至301.2 K时的6.13 s。我们观察到了活化络合物([βCD-NH/SDBS])的形成,其能量参数表明与温度有关。在285.2 K时,活化焓变为正值,而在301.2 K时为负值。解离能量参数与温度无关。此外,离子液体1-丁基-3-甲基咪唑鎓氯化物浓度的增加会影响活化态下SDBS尾部的构象以及其向βCD-NH空腔的渗透。这些发现为络合机理以及温度和离子液体对IC形成的影响提供了见解。