The effect of mobile phase pH on positive ionization process and retention time of nine pharmaceuticals on ultra-performance liquid chromatography-electrospray–tandem mass spectrometry (LC-MS/MS) was discussed. The effective use of high and low mobile phase pH in LC-MS/MS qualitative analyses method was also evaluated by comparing the instrument detection limit, quantification limit, precision, linearity and signal to noise (S/N) under low and high mobile phase pH. In this work, six mobile phase pH that ranged between pH 2 and pH 10 were used to evaluate the effect of the mobile phase pH changes on the ionization process in electrospray ionization. Results revealed that high mobile phase pH ionized more pharmaceuticals molecules and gave a higher signal than low mobile phase pH in positive ionization mode. The results proved that ammonium ion was better as a proton donor in high pH mobile phase than the hydronium ion in acidic mobile phase. The results revealed that the qualitative LC-MS/MS analyses method by using high mobile phase pH has better performance for most analytes in terms of sensitivity, precision, linearity and S/N than the low mobile phase pH.
Electrospray ionization (ESI) and desorption electrospray ionization (DESI) are common soft ionization method of mass spectrometry (MS). However, recent studies revealed that some chemical reactions can be induced or greatly accelerated in the sprayed microdroplets compared to the same reaction in the bulk. These open a new area in using microdroplet MS to explore new chemistry and develop new applications. This minireview will introduce microdroplet chemistries and explore various microdroplet techniques most of which are ESI‐ or DESI‐based extensions by incorporating transfer tube, supersonic nebulizing gas, droplet fusion, spray extraction, laser irradiation, or laser ablation for online/offline MS analysis. Potential applications associated with new techniques, including real‐time reaction monitoring, high‐throughput reaction screening, protein identification, and protein characterization, are also described. Future outlook, such as coupling microdroplet MS with separation techniques, is proposed and discussed.
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