title: Charged tag founded in N-(1-chloroalkyl)pyridinium quaternization for quantification of fatty aldehydes.
abstract: N-(1-chloroalkyl)pyridinium quaternization was developed for the derivatization of fatty aldehydes. Differing from common pre-charged reagents, non-charged pyridine and thionyl chloride were designed to add permanently charged tag on aldehydes. Pyridine was far less competitive than charged derivatives in ionization. Thionyl chloride in excess was quenched by deionized water, converting into less residual sulfur dioxide bubbles. Thus solutions could be tested directly by mass spectrometry without further post-treatments. Pyridine-d5 labeled fatty aldehydes were prepared as internal standards. Mixed derivatives were then analyzed by high performance liquid chromatography coupled to positive electrospray ionization tandem mass spectrometry (HPLC-ESI-MS/MS). Analytical parameters including reaction yield, stability, precision, linearity, and detection limits (LODs < 0.3 pg mL(-1)) were carefully validated. This method facilitated the analysis low content (ng mL(-1)) levels of free aliphatic aldehydes (C6C18) in human thyroid carcinoma and para-carcinoma tissue with a simple pretreatment procedure. Content of long chain nonvolatile aldehydes (C10C18) remarkably increased in thyroid carcinoma tissues (p < 0.05).
authors: National Center for Organic Mass Spectrometry in Shanghai, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, PR China; Corporate Research Analytical Lab, 3M China R&D Center, 222 Tianlin Road, Shanghai 200236, PR China.
authors: Yanjing
authors: Y
authors: Cao
authors: Department of Head and Neck Surgery, Fudan University Shanghai Cancer Center (FUSCC), PR China; Department of Oncology, Shanghai Medical College, Fudan University, 200032 Shanghai, PR China.
authors: Qing
authors: Q
authors: Guan
authors: Department of Head and Neck Surgery, Fudan University Shanghai Cancer Center (FUSCC), PR China; Department of Oncology, Shanghai Medical College, Fudan University, 200032 Shanghai, PR China. Electronic address: tuanqisun@163.com.
authors: Tuanqi
authors: T
authors: Sun
authors: National Center for Organic Mass Spectrometry in Shanghai, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, PR China.
authors: Wanshu
authors: W
authors: Qi
authors: National Center for Organic Mass Spectrometry in Shanghai, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, PR China. Electronic address: ylguo@sioc.ac.cn.
authors: Yinlong
authors: Y
authors: Guo
mesh_terms: D000447:Aldehydes / Q000032:analysis*; D006801:Humans; D015394:Molecular Structure; D011726:Pyridinium Compounds / Q000737:chemistry*; D013964:Thyroid Neoplasms / Q000175:diagnosis*
chemical_list: D000447:Aldehydes; D011726:Pyridinium Compounds
keywords: Fatty aldehydes; Isotope labeling; N-(1-chloroalkyl)pyridinium quaternization; Select reaction monitoring; Thyroid carcinoma