Reactive Thread Spray Mass Spectrometry for Localization of C═C Bonds in Free Fatty Acids: Applications for Obesity Diagnosis.

Cellulose thread substrates offer a platform for microsampling and reactive ionization of free fatty acid (FFA) isomers for direct differentiation by mass spectrometry. Ambient corona discharge forms when direct current high voltage is applied to the tiny subfibers on the thread substrate in the presence of a polar spray solvent (MeOH/H2O, 2:1, v/v), facilitating chemical reactions across a C═C bond of unsaturated fatty acids. The process was applied for diagnosis of obesity, which we observed to show better discriminatory power when compared to determinations based on body mass index. Overall, the integrated reactive thread-based platform is capable of (i) microsampling and dry-state, room-temperature storage (>30 days) of the biofluids, (ii) in-capillary liquid/liquid extraction, and (iii) in situ epoxidation reactions to locate the C═C bond position in unsaturated fatty acids via reactions with reactive oxygen species present in ambient corona discharge. The study showcased the ability to correctly characterize FFAs, including degree of unsaturation, and the determination of their relative concentrations in clinical biofluid samples.

A Proof-of-Concept, Two-Tiered Approach for Ricin Detection Using Ambient Mass Spectrometry.

Ricin is a naturally occurring, highly potent toxin native to castor bean plants that has recently been used as a biological weapon in cases of bioterrorism and suicide attempts. Difficulties with direct detection arise from large heterogeneities in ricin glycosylation, which leads to markedly different bioactivity, and the fact that carefully developed and laborious sample preparation steps are required to maintaining the activity of the protein during analysis. Herein, we present an alternative, two-tiered approach to identify the presence of ricin by detecting ricinoleic acid and ricinine, which are co-extracted with the protein. This direct mass spectrometric-based technique takes as little as 2 minutes, and we determined its sensitivity to be in the parts-per-trillion range. Our method is applicable to paper substrates from suspected contaminated envelopes and biofluids from at-risk patients. The fact that prior sample preparations are not needed in this procedure means that analysis can be performed in the field for emergency cases.