采用四极杆/静电场轨道阱高分辨质谱，通过正负离子快速切换的全扫描分析，实现了对92种工业染料的分子离子峰的离子化规律的探究。结果表明：碱性染料中氯或硫元素的存在状态决定了染料分子离子峰的存在形式，其中，氯元素以氯化氢形式存在的含氯染料是通过丢掉氯化氢形成[^*M+H]⁺分子离子峰，氯元素以Cl^-存在且含有强极性基团（分子中氮原子呈现带有4个键的正离子状态）的染料分子离子峰通过丢掉Cl^-后形成[^*M]⁺分子离子峰；对于含有硫元素的碱性染料，当硫元素是以HSO₄^-的形式存在且含有强极性基团（分子中氮原子呈现带有4个键的正离子状态）的碱性染料是通过丢掉HSO₄^-形成[^*M]⁺分子离子峰；酸性染料准分子离子峰的类型与分子结构中Na⁺、磺酸基的数目相关，倾向失去所有的Na⁺，从溶剂中获得氢原子结合在磺酸基上，形成一系列[（M-xNa+yH）/（x-y）]^-离子，含有多个磺酸基染料的多以二价准分子离子峰为基峰；苏丹染料和分散染料作为含电负性基团的弱极性染料，更易形成[M+H]⁺分子离子峰。

A probe into the regularities of ionization of molecular ion peaks of 92 industrial dyestuffs was accomplished by Q-orbitrap-high resolution mass spectrometry in the analytical mode of full scanning of positive and negative ions with rapid switching. It was found that the existing forms of molecular ion peaks of basic dyestuffs were determined by the existing forms of the elements of chlorine or sulfur in the molecules of the dyestuffs. Cl-containing basic dyestuffs with chlorine present as hydrogen chloride formed molecular ionic peaks of[^*M+H]^- by giving up hydrogen chloride, Cl-containing basic dyestuffs with chlorine present as chloride, and having strongly polar groups (N in the molecule appears in positive ionic state having 4 valency bonds) formed molecular ionic peaks of[^*M]⁺ by giving up their Cl^-. For S-containing basic dyestuffs with sulfur present as HSO₄^-, and having also the strong polar groups of N⁺ as above, their molecular ionic peaks transformed into[^*M]⁺ by giving up the HSO₄^- ion. For acidic dyestuffs, forms of their quasi-molecular ionic peak were related to the numbers of Na⁺ and sulfonate group in their molecules, and were tending to give up all the Na⁺ ions and to combine the H⁺ from the solvent to the sulfonate radicals, forming a series of anions conforming to the formula[(M-xNa+yH)/(x-y)]^-, and giving mainly divalent quasi-molecular ionic peaks for dyestuffs containing 2 and more sulfonate radicals. Dispersed dyestuffs and sudan dyestuffs were weakly polar dyestuffs containing electronegative groups and were tending to form molecular ionic peaks of[M+H]⁺ more easily.