ArticleAnalytical chemistry2025
Uronium from X-ray-Desorbed Urea Enables Sustainable Ultrasensitive Detection of Amines and Semivolatiles.
Article in Analytical chemistry, 2025. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Not yet cited in PubMed.
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Abstract
Comprehensive mass spectrometric detection requires multiple ionization schemes. Chemical ionization (CI) at a low pressure is suitable for the detection of weakly polar volatile organic compounds (VOCs). Negative-mode ionization at ambient pressure delivers a superior performance for polar acidic compounds. Positive-mode CI has been explored to detect basic and polar neutral compounds for which negative polarity and low-pressure ionization techniques have shown insufficient performance. Several ion attachment reagents have been proposed for sensitive and soft ionization. These reagents are often reactive, toxic, and difficult to control, which impede their applicability and operability. Inspired by these challenges, we explored uronium, protonated urea, as an alternative for ionizing moderately oxygenated, basic, and polar neutral compounds at ambient pressure. Urea, a nontoxic solid with negligible vapor pressure, is desorbed by X-ray irradiation, forming the uronium ion. We experimentally determined the behavior of uronium ionization under different humidities for several semivolatile organic compounds (SVOCs), amines, and ammonia and explored the mechanism using theory. In laboratory measurements of α-pinene and dimethyl sulfide (DMS) oxidation systems, we characterized how uronium complements other ionization schemes. Excellent sensitivities were achieved for several key components (including amines, dimethyl sulfoxide (DMSO),
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