As miniaturization of electrospray continues to become more prevalent in the mass spectrometry arsenal, numerous types of conductive coatings have been developed with miniaturized electrospray emitters. Different conductive coatings have different properties that may lead to differences in analytical performance. This paper investigates and compares the analytical properties of a series of applied conductive coatings for low-flow electrospray ionization developed in this laboratory vs. commercially-available types. Evaporated graphite is thoroughly compared with commercially available polyaniline (PANI) coated emitters and metal coated emitters. Each set of emitters was investigated to determine various performance characteristics, including susceptibility to electrical discharge in both positive and negative ionization modes, as well as emitter reproducibility and generation of a standard curve to determine each emitter coating's limit of detection and limit of quantitation. Furthermore, evaporated graphite and polyaniline coated fused silica capillaries were investigated to determine which coating is more stable over long-term analyses and during electrical discharge.
Fourier transform mass spectrometry (FTMS), long-known for its capabilities in structural characterization of molecules, is an emerging tool in quantification, and quantification methods using external and internal standards with electrospray ionization (ESI) FTMS have recently been demonstrated. Here, commercial ESI-FTMS is used to quantify the opioid pentapeptide methionine enkephalin using an internal standard. Linear working curves over three orders of magnitude are obtained using the internal standard, an improvement of one order of magnitude over the previous external standard ESI-FTMS quantification method for enkephalins. Low coefficients of variation (generally <6%) are observed, and inter-day and intra-day assays are compared and found to possess similar linearity and precision. The high mass accuracy advantage of FTMS can be exploited to give molecular specificity. Efforts to improve mass accuracy using internal mass calibration generally provide mass accuracies within 2.5 ppm.
Fourier transform mass spectrometry (FTMS), long-known for its capabilities in structural characterization of molecules, is an emerging tool in quantification, and quantification methods using external and internal standards with electrospray ionization (ESI) FTMS have recently been demonstrated. Here, commercial ESI-FTMS is used to quantify the opioid pentapeptide methionine enkephalin using an internal standard. Linear working curves over three orders of magnitude are obtained using the internal standard, an improvement of one order of magnitude over the previous external standard ESI-FTMS quantification method for enkephalins. Low coefficients of variation (generally <6%) are observed, and inter-day and intra-day assays are compared and found to possess similar linearity and precision. The high mass accuracy advantage of FTMS can be exploited to give molecular specificity. Efforts to improve mass accuracy using internal mass calibration generally provide mass accuracies within 2.5 ppm.
The formation of disulfide-bonds is vital for the proper folding of most secreted proteins and the stabilization of the final protein structure, including many of medical importance. The determination of disulfide-bonds is an important aspect of gaining a comprehensive understanding of the chemical structure of a protein. A long-term goal of ours is to examine the mechanism of disulfide-bond formation in aqueous solution and the potential role hydrogen bonds play in this process. Here, we report preliminary results from a method that utilizes the oxidizing power of iodine to generate disulfide bonds from synthesized model compounds, which is followed by nanoelectrospray ionization (nanoESI)- mass spectrometry (MS). By continuously monitoring the reaction mixture during disulfide formation, this nanoESI approach provides insight on the sequence of intermediate species formed, and how hydrogen-bonding donor/acceptor pairs may promote disulfide bond formation.
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