Reagents and methods are disclosed for detection of oxidizers and inorganic salts and other analytes of interest. The reagents can interact with their target analytes, especially oxidizer compositions or oxidizer-based explosives, to selectively enhance their ionization yield, interacting by chemical reaction or by forming an associative adduct which facilitates their detection. For example, the reagents can adduct with the counter-ion of the intended analyte for improved direct detection and/or react chemically via acid-base reactions to produce a new product for detection. In another aspect of the invention, reactive reagents and methods are also disclosed that facilitate indirect detection of the analyte at lower temperatures based on reduction-oxidation (redox) chemistry. These reagents are particularly useful in detecting oxidizer analytes.