Li Xi, Sawada Keisuke, Shioji Hirotaka
Organic Analysis Laboratory, Toray Research Center, Inc., Otsu, Shiga, Japan.
Research and Development Planning Department, Toray Research Center, Inc., Otsu, Shiga, Japan.
Rapid Commun Mass Spectrom. 2023 Dec 30;37(24):e9649. doi: 10.1002/rcm.9649.
The structures of metal complexes determine their stable functioning in product performance. Electrospray ionization mass spectrometry (ESI-MS) is used in studying metal complexes despite exhibiting limitations in analyzing labile complexes. Therefore, identifying a method for detecting unstable complexes and evaluating their stabilities is necessary, providing a theoretical basis for material selection and performance evaluation.
The standard complexes Zn(BTZ) , Fe(acac) , and Sn(Oct) were analyzed using nanoESI quadrupole orbitrap MS (nanoESI-MS) and compared with ESI-MS for two temperature modes. The three complexes and alkylamine-Ag complexes were analyzed using nanoESI and collision-induced dissociation MS/MS (CID-MS/MS). Breakdown plots of the survival yield against collision energies expressed in terms of the center-of-mass were constructed according to the obtained product ion spectra. Quantum chemical calculations based on density functional theory were performed to calculate the binding energies between the alkylamines and Ag .
The three standard complexes were detected in the native structures using nanoESI-MS, confirming the advantage of nanoESI over ESI for detecting unstable complexes. The gas-phase stabilities of the amine-Ag complexes, estimated using the breakdown plots constructed by plotting the data obtained via nanoESI and CID-MS/MS, were consistent with the established theories, previous studies, and binding energies calculated using computational methods.
NanoESI-MS is suitable for detecting labile complexes and enables the structural analyses of unknown complex additives. A novel approach based on nanoESI and CID-MS/MS was developed to determine the gas-phase stabilities of complexes, enabling their quantification and comparison and providing a technical basis for product improvement, which is essential in developing industrial materials.
金属配合物的结构决定了它们在产品性能中的稳定功能。尽管电喷雾电离质谱（ESI-MS）在分析不稳定配合物时存在局限性，但仍用于研究金属配合物。因此，有必要确定一种检测不稳定配合物并评估其稳定性的方法，为材料选择和性能评估提供理论依据。
使用纳米电喷雾四极杆轨道阱质谱（nanoESI-MS）分析标准配合物Zn(BTZ)、Fe(acac)和Sn(Oct)，并与ESI-MS在两种温度模式下进行比较。使用纳米电喷雾和碰撞诱导解离串联质谱（CID-MS/MS）分析这三种配合物和烷基胺-银配合物。根据获得的产物离子光谱，构建以质心表示的碰撞能量与存活产率的分解图。进行基于密度泛函理论的量子化学计算，以计算烷基胺与银之间的结合能。
使用纳米电喷雾质谱在天然结构中检测到这三种标准配合物，证实了纳米电喷雾在检测不稳定配合物方面优于电喷雾电离质谱。使用通过纳米电喷雾和CID-MS/MS获得的数据绘制的分解图估算的胺-银配合物的气相稳定性，与既定理论、先前研究以及使用计算方法计算的结合能一致。
纳米电喷雾质谱适用于检测不稳定配合物，并能够对未知配合物添加剂进行结构分析。开发了一种基于纳米电喷雾和CID-MS/MS的新方法来确定配合物的气相稳定性，实现其定量和比较，并为产品改进提供技术基础，这在开发工业材料中至关重要。
