Quantitative Analysis of Nitrotoluene Isomer Mixtures Using Femtosecond Time-Resolved Mass Spectrometry

Discrimination of isomers in a mixture is a subject of ongoing interest in biology, pharmacology, and forensics. We demonstrate that femtosecond time-resolved mass spectrometry (FTRMS) effectively quantifies mixtures of ortho-, para-, and meta-nitrotoluenes, the first two of which are common explosive degradation products. The key advantage of the FTRMS approach to mixture quantification lies in the ability of the pump-probe laser control scheme to capture distinct fragmentation dynamics of each nitrotoluene cation isomer on femtosecond timescales, thereby allowing for discrimination of the isomers using only the signal of the parent molecular ion at m/z 137. Upon measurement of reference dynamics of each individual isomer, the molar fractions of binary and ternary mixtures can be predicted to within similar to 5 and similar to 7% accuracy, respectively.

Automated summary

The discrimination of isomers in mixtures using femtosecond time-resolved mass spectrometry (FTRMS) has been effectively demonstrated in this study. The unique advantage lies in the ability to capture distinct fragmentation dynamics of each isomer and predict the molar fractions of mixtures with high accuracy.