Tang Wen-Qi, Zhou Ye-Qin, Gao Xing-Yu, Li Wang, Xu Ming, Gu Zhi-Yuan
Jiangsu Key Laboratory of Biofunctional Materials, Jiangsu Collaborative Innovation Center of Biomedical Functional Materials, Jiangsu Key Laboratory of New Power Batteries, College of Chemistry and Materials Science, Nanjing Normal University, Nanjing 210023, China.
Jiangsu Key Laboratory of Biofunctional Materials, Jiangsu Collaborative Innovation Center of Biomedical Functional Materials, Jiangsu Key Laboratory of New Power Batteries, College of Chemistry and Materials Science, Nanjing Normal University, Nanjing 210023, China.
Talanta. 2025 May 15;287:127665. doi: 10.1016/j.talanta.2025.127665. Epub 2025 Jan 29.
The development of stable and high-performance stationary phases is essential for achieving high-resolution gas chromatographic (GC) isomer separation. This study demonstrated a simple and effective method for synthesizing a stable nano metal-organic framework (MOF) as an efficient stationary phase for GC separation. The introduction of weakly basic pyridine played a key role in modulating the generation rate of small crystal particles while inhibiting the aggregation of nanoparticles. By reducing particle size from micrometers to nanometers, the surface properties and mechanical strength of the material are significantly enhanced, leading to improved stability. The nano-sized MIL-103 (MIL-103-N) stationary phase exhibited a significantly longer lifetime than the micro one, with a lifespan of up to one month. The elution order of dichlorobenzenes followed p-, m-, and o-, which was consistented with the principle that a more negative ΔH (-49.1 ± 2.19 kJ/mol, -54.6 ± 0.390 kJ/mol, -57.4 ± 0.260 kJ/mol for p-, m-, and o-, respectively) value correlated with later elution. The standard curve for m-dichlorobenzene on the MIL-103-N column was y = 3.95 × 10x-3.12 × 10 (R-squared = 0.999). The MIL-103-N column showed high-resolution separations of a series of disubstituted benzene isomers, aromatic compounds, and alkanes. Notably, the resolution of the MIL-103-N column for dichlorobenzenes, dibromobenzenes, and trichlorobenzene isomers exceeded 1.50, achieving baseline separation. The exceptional performance of MIL-103-N can be attributed to its refined interactions with analytes and reduced diffusion barriers. This research offered a promising method for producing stable, efficient columns to separate isomer analytes.
开发稳定且高性能的固定相对实现高分辨率气相色谱（GC）异构体分离至关重要。本研究展示了一种简单有效的方法，用于合成一种稳定的纳米金属有机框架（MOF）作为GC分离的高效固定相。弱碱性吡啶的引入在调节小晶体颗粒的生成速率同时抑制纳米颗粒的聚集方面发挥了关键作用。通过将粒径从微米减小到纳米，材料的表面性质和机械强度得到显著增强，从而提高了稳定性。纳米尺寸的MIL-103（MIL-103-N）固定相的寿命明显长于微米级的固定相，使用寿命长达一个月。二氯苯的洗脱顺序为对、间、邻，这与更负的ΔH值（对、间、邻分别为-49.1±2.19kJ/mol、-54.6±0.390kJ/mol、-57.4±0.260kJ/mol）与较晚洗脱相关的原理一致。MIL-103-N柱上间二氯苯的标准曲线为y = 3.95×10x - 3.12×10（决定系数 = 0.999）。MIL-103-N柱对一系列二取代苯异构体、芳香族化合物和烷烃表现出高分辨率分离。值得注意的是，MIL-103-N柱对二氯苯、二溴苯和三氯苯异构体的分离度超过1.50，实现了基线分离。MIL-103-N的卓越性能可归因于其与分析物的精细相互作用以及降低的扩散障碍。本研究为生产稳定、高效的柱用于分离异构体分析物提供了一种有前景的方法。
