The relative contributions to ionization efficiency by three molecular chemical properties have been examined for field-free and field-enabled capillary vibrating sharp-edge spray ionization (cVSSI) using mass spectrometry (MS) analysis. Ion intensities have been recorded for model compounds under each operational ionization mode as well as for aqueous and nonaqueous (methanol) solvent systems. Multiple regression analysis suggests that for field-free cVSSI, ion intensity is mostly associated with the log of the base dissociation constant (pKb) and proton affinity (PA) for both aqueous and methanol solutions. Comparatively, for field-enabled cVSSI using aqueous solutions, the dominant factor correlated with ion intensity is the log of the partition coefficient (log P). To a lesser degree, this is observed for methanol solutions as well. For ESI, pKb is the dominant factor associated with ion signal levels from methanol and aqueous solutions. These results are supported by studies conducted on two different mass spectrometers employing different cVSSI emitter tips. The relationship of ion intensity and pKb in ESI is supported by multiple studies; however, the shift to other chemical properties with the addition of cVSSI suggests the possibility that a different (or combinations of) ionization mechanism(s) may be operative for these ionization modes. These results are briefly considered in light of the different ESI mechanisms.

中文翻译：

---

毛细管振动锐边喷雾电离 (cVSSI) 中电离效率与物理化学性质的相关性。

已经使用质谱 (MS) 分析检查了无场和场启用毛细管振动锐边喷雾电离 (cVSSI) 的三种分子化学性质对电离效率的相对贡献。在每种操作电离模式以及水和非水（甲醇）溶剂系统下，模型化合物的离子强度均已记录。多元回归分析表明，对于无场 cVSSI，离子强度主要与水溶液和甲醇溶液的碱基解离常数 (pKb) 和质子亲和力 (PA) 的对数有关。相比之下，对于使用水溶液的场启用 cVSSI，与离子强度相关的主要因素是分配系数的对数 (log P)。在较小程度上，甲醇溶液也会出现这种情况。对于 ESI，pKb 是与来自甲醇和水溶液的离子信号水平相关的主要因素。这些结果得到了对使用不同 cVSSI 发射器尖端的两种不同质谱仪进行的研究的支持。多项研究支持 ESI 中离子强度和 pKb 的关系；然而，添加 cVSSI 后向其他化学性质的转变表明，不同的（或组合的）电离机制可能对这些电离模式起作用。根据不同的 ESI 机制简要考虑了这些结果。多项研究支持 ESI 中离子强度和 pKb 的关系；然而，添加 cVSSI 后向其他化学性质的转变表明，不同的（或组合的）电离机制可能对这些电离模式起作用。根据不同的 ESI 机制简要考虑了这些结果。多项研究支持 ESI 中离子强度和 pKb 的关系；然而，添加 cVSSI 后向其他化学性质的转变表明，不同的（或组合的）电离机制可能对这些电离模式起作用。根据不同的 ESI 机制简要考虑了这些结果。