金屬有機骨架及其衍生材料於表面輔助雷射脫附游離質譜儀之應用

傅崇瑋

doi:10.6840/cycu201800119

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金属有机骨架及其衍生材料於表面辅助雷射脱附游离质谱仪之应用

The Application of Metal-Organic Frameworks and its Derived Materials for Surface-Assisted Laser Desorption Ionization-Mass Spectrometry

傅崇玮 , 博士　　导师：林嘉和;刘婉舲　　

英文 DOI： 10.6840/cycu201800119

金属有机骨架；表面辅助雷射脱附游离质谱仪；奈米复合材料；奈米孔洞碳材； Metal-organic framework ； surface-assisted laser desorption ionization-mass spectrometry ； nanocomposite ； nanoporous carcon

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摘要 │ 参考文献 (66) │ 国际计量

摘要〈TOP〉

基质辅助雷射脱附游离质谱法(matrix-assisted laser desorption/ionization-mass spectrometry, MALDI-MS)为现代科学非常重要的一个软性离子化(soft ionization)技术，在此技术的辅助下，可在短时间内轻易地藉由质谱仪直接检测分析物既有的分子量，达到直接定性与定量的效果，目前已被广泛应用於合成高分子、蛋白质体学已及代谢质体学之研究。然而，在传统的MALDI-MS中，常由於基质分子吸收雷射而自身离子化导致小分子的检测往往受到背景的严重干扰。有别於往，本研究中以新颖孔洞材，金属有机骨架(Metal-Organic Frameworks, MOFs)，及其衍生材料取代传统MALDI中所使用的有机酸化合物(α-cyano-4-hydroxycinnamic acid or 2,5-dihydroxybezoic acid)，藉由表面辅助雷射脱附游离质谱法(Surface-assisted laser desorption ionization, SALDI-MS)，提高小分子於质谱仪之侦测灵敏度。
第一部份：本实验将五种金属有机骨架(MIL-100(Fe)、MIL-100(Al)、MIL-100(Cr)、MIL-101(Cr)及UiO-66)应用於表面辅助雷射脱附游离质谱法，分析多种单、双醣、胜肽及环糊精等亲水性小分子化合物，相较於传统有机基质的分析结果，MOFs基质之图谱较少背景干扰。其中MIL-100(Fe)基质的分析结果具有最低的讯号变异性，其讯杂比之相对标准偏差小於11%，同时可检测胜肽与环糊精等多种亲水性化合物，此外，也藉由二次质谱(MS/MS)所得到的图谱来区分不同醣类异构物。最後，本实验以MIL-100(Fe)作为基质时，可直接检测未经任何处理之淀粉水解後所产生的麦芽糖，并藉由二次质谱达到进一步的定性分析。
第二部分：本实验将两种以铜为中心金属之金属有机骨架(HKUST-1 and NENU-3)结合磁性奈米粒子(Fe3O4 nanoparticles)，合成磁性金属有机骨架复合材料(Fe3O4@HKUST-1 and Fe3O4@NENU-3)，并作为基质应用於表面辅助雷射脱附游离质谱仪中，检测亲水的醣类小分子及疏水的邻苯二甲酸酯(phthalate esters, PAEs)与多环芳香烃(polycyclic aromatic hydrocarbon, PAHs)。研究中比较了奈米复合材料之形貌与离子化效能之影响，结果指出，相较於核壳状的Fe3O4@HKUST-1，无定型包覆的Fe3O4@NENU-3具有较佳的离子化效能，而磁性奈米粒子与金属有机骨架间的协同效应(synergistic effect)也大幅增加其讯号强度与再现性。此外，水稳定高的Fe3O4@NENU-3不仅可作为基质，也可当作吸附剂对环境污染物PAEs (1 ppm)及PAHs (0.5 ppm)进行固相萃取，PAEs侦测极限从50 – 187.5 µg L-1降至3.6 – 9.5 µg L-1，而PAHs的LOD可达7 – 18 µg L-1。
第三部分：本实验将两种铝为中心金属之金属有机骨架(MIL-53(Al) and CYCU-3(Al))在高温下进行碳化，煅烧出新颖的奈米孔洞碳材，碳化金属有机骨架(carbonized MOFs, cMOFs)，藉由此煅烧过程开发出亲水性的碳材并应於表面辅助雷射脱附游离质谱仪检测醣类、胜肽、PAEs、PAHs及酚酸等不同亲疏水性化合物。通常市售孔洞碳材因为本身非极性结构，在样品制备上容易因自身团聚而生成不均匀的共结晶，导致讯号再现性不佳的情况，相对的，cMOFs具有良好的亲水性，能与分析物形成较均匀的共结晶，且具有较强作用力，因此大幅提升了分析物在正、负电模式下的离子化效率。同时，cMOFs可用以萃取河水样品中的DEHP，其侦测极限可达4.0 µg L-1.

并列摘要〈TOP〉

Matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) is one of the most popular soft ionization techniques in mass spectrometry. With the assistance of this technique, the parent ion of compounds could be easily detected by the MS that would be beneficial for both qualitative and quantitative analyses. To date, MALDI-MS has been widely used in synthetic polymer, proteomics and metabolomics analysis. However, serious background interference is often encountered when traditional MALDI-MS is applied due to the self-ionization of matrix molecules, and thus restricting its application towards the analysis of small molecules. In this study, novel porous materials, such as metal-organic frameworks (MOFs) and MOF-derived materials, were employed to replace the traditional matrix (α-cyano-4-hydroxycinnamic acid or 2,5-dihydroxybezoic acid) via surface-assisted laser desorption/ionization (SALDI-MS) and to further enhance the sensitivity of detecting small molecules in MS.
For the first part of this study, five MOFs namely MIL-100(Fe), MIL-100(Al), MIL-100(Cr), MIL-101(Cr) and UiO-66 were utilized as matrix for SALDI-MS analyses of hydrophilic small molecules such as mono-, disaccharides, peptides and cyclodextrins. Compared to the results obtained in traditional matrices, MOFs demonstrated lower background interferences. Among them, the MIL-100(Fe) displayed the lowest signal variation for the analysis of carbohydrates with relative standard deviation (RSD) values for signal-to-noise ratio (S/N ratio) of lower than 11%. Besides, it could also be utilized to detect the peptides and cyclodextrins. The MS/MS spectra were also applied to distinguish the carbohydrate isomers. Finally, maltose obtained from hydrolyzed starch were directly detected without any pretreatment when MIL-100(Fe) was utilized as matrix.
For the second part of this study, two magnetic MOF composites, which were constructed from copper-based MOFs (HKUST-1 and NENU-3) and magnetic nanoparticles (Fe3O4), were developed and employed as matrices for the detection of carbohydrates, phthalate esters (PAEs) and polycyclic aromatic hydrocarbon (PAHs). Herein, the effect of morphology for both nanocomposites in the ionization performance was investigated. Compared to Fe3O4@HKUST-1, which has core-shell morphology, the Fe3O4@NENU-3, which was developed by embedding Fe3O4 within NENU-3, demonstrated better ionization performance and reproducibility due the synergistic effect between Fe3O4 and MOFs. The Fe3O4@NENU-3 not only serves as matrix for SALDI-MS but also useful as adsorbent for solid phase extraction of trace-level PAEs (1 mg mL-1) and PAHs (0.5 mg mL-1) in river water samples. Hence, the limit of detections (LODs) of PAEs were lower from 50 – 187.5 µg L-1 to 3.6 – 9.5 µg L-1, and LODs of PAHs in the range from 7 – 18 μg L-1 were achieved.
Lastly, novel nanoporous carbons derived from MOFs (cMOFs) were developed via direct carbonization of two aluminum-based (MIL-53(Al) and CYCU-3(Al)). Through carbonization process, hydrophilic carbonaceous materials were developed and subsequently employed as matrices for analyses of carbohydrates, peptides, PAEs, PAHs and phenolic acids in SALDI-MS application. For useful comparison, various commercial nanoporous materials, which were deemed highly nonpolar, were also utilized as matrices for SALDI-MS analyses. However, these nanoporous materials exhibited poor signal reproducibilities due to self-aggregation and afforded inhomogeneous co-crystalline phase during the sample preparation. In contrast, the cMOFs, which demonstrated good hydrophilicities, formed homogeneous co-crystalline phase leading to the enhancement of their interactions with the target analytes, which further enhanced their ionization performances for under both positive and negative modes. Among the cMOFs, the cMIL-53 was found useful as adsorbent for solid phase extraction of trap trace-level DEHP with LOD of 4.0 µg L-1.

参考文献 ( 66 ) 〈TOP〉

[142] J. W. Yoon, Y.-K. Seo, Y. K. Hwang, J.-S. Chang, H. Leclerc, S. Wuttke, P. Bazin, A. Vimont, M. Daturi, E. Bloch, P. L. Llewellyn, C. Serre, P. Horcajada, J.-M. Grenèche, A. E. Rodrigues, G. Férey, Angewandte Chemie International Edition 2010, 49, 5949-5952.
连结：
[143] C. D. Mowry, M. V. Johnston, The Journal of Physical Chemistry 1994, 98, 1904-1909.
连结：
[146] X. Yang, L. Qiao, W. Dai, Chinese Journal of Catalysis 2015, 36, 1875-1885.
连结：
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连结：
[152] J. Zhang, X. Dong, J. Cheng, J. Li, Y. Wang, Journal of The American Society for Mass Spectrometry 2011, 22, 1294-1298.
连结：

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使用DOI作为永久连结

引用含有DOI的文献

DOI可强化引用精确性、增强学术圈连结，并给予使用者跨平台的良好使用经验，目前在全世界已有超过五千万个对象申请DOI。 如想对DOI的使用与概念有进一步了解，请参考 （ ） 。

DOI可强化引用精确性、增强学术圈连结，并给予使用者跨平台的良好使用经验，目前在全世界已有超过五千万个对象申请DOI。如想对DOI的使用与概念有进一步了解，请参考（）。