High-Sensitivity Elemental Mass Spectrometry of Fluorine by Ionization in Plasma Afterglow.

Fluorine elemental analysis using inductively coupled plasma mass spectrometry (ICPMS) is challenging because of low F ionization efficiency in the plasma and severe isobaric interferences. Notably, there is an increasing demand for ppb level fluorine measurements due to the rising importance of fluorinated compounds in pharmaceutical, environmental, and food analyses. Here, we report a new elemental ionization method where fluorinated analytes are introduced into an ICP to produce NaF followed by NaF formation in the atmospheric-pressure plasma afterglow.

A method for assessing and maintaining the reproducibility of mass spectrometric analyses of complex samples.

Direct injection mass spectrometric analysis of biological samples is potentially an attractive approach to the discovery of diagnostic patterns for specific pathophysiological conditions because of its speed and simplicity. Despite the possible benefits offered by such a method, its extensive application has been limited so far by several factors, including the inadequate reproducibility of the analytical results. We describe a method for monitoring and optimizing the performance of mass spectrometers used for biomarker discovery studies, based on the analysis of patterns of standardized spectral features.

A method for monitoring and controlling reproducibility of intensity data in complex electrospray mass spectra: a thermometer ion-based strategy.

Reproducibility in mass spectral data is important in both biomarker discovery and spectral database searching. We report a strategy, employing a series of substituted benzylpyridinium thermometer ions that can be used to monitor changes in performance of multiple aspects of an electrospray ionization source that impact the intensity axis of a spectrum. Performance attributes, which could confound even isotope-based quantification strategies, are readily assessed using a mixture of thermometer ions.

Chemical reaction interface mass spectrometry with high efficiency nebulization.

A high efficiency nebulizer (HEN) coupled to a heated spray chamber and a membrane desolvator is used for liquid sample introduction in chemical reaction interface mass spectrometry (CRIMS). Compared to the conventional thermospray nebulizer operated at solvent flow rate of 1 mL/min, the HEN provides small droplets at lower flow rates (10-100 microL/min), improving the desolvation and analyte transport efficiency. As a result, the sensitivity for carbon detection by CRIMS is improved by a factor of 4.

The role of esterification on detection of protonated and deprotonated peptide ions in matrix assisted laser desorption/ionization (MALDI) mass spectrometry (MS).

Esterification was used to investigate how introduction of aliphatic chains within the peptide structure affects the MALDI response of ions analyzed in both polarity regimes. In binary mixtures containing equimolar amounts of a peptide with its correspondent alkyl ester, derivatization of the carboxylic groups has the tendency to increase MALDI detection of the modified protonated peptide ions. This positive effect on ion yield is more pronounced when longer alcohols are employed.

A multi-enzyme cascade of hemoglobin proteolysis in the intestine of blood-feeding hookworms.

Blood-feeding pathogens digest hemoglobin (Hb) as a source of nutrition, but little is known about this process in multicellular parasites. The intestinal brush border membrane of the canine hookworm, Ancylostoma caninum, contains aspartic proteases (APR-1), cysteine proteases (CP-2), and metalloproteases (MEP-1), the first of which is known to digest Hb. We now show that Hb is degraded by a multi-enzyme, synergistic cascade of proteolysis.

Kinetic isotope effects in Ras-catalyzed GTP hydrolysis: evidence for a loose transition state.

A remote labeling method has been developed to determine (18)O kinetic isotope effects (KIEs) in Ras-catalyzed GTP hydrolysis. Substrate mixtures consist of (13)C-depleted GTP and [(18)O,(13)C]GTP that contains (18)O at phosphoryl positions of mechanistic interest and (13)C at all carbon positions of the guanosine moiety. Isotope ratios of the nonvolatile substrates and products are measured by using a chemical reaction interface/isotope ratio mass spectrometer.

In vitro performance of hemodialysis membranes after repeated processing.

Background: Dialyzers reprocessed with chlorine-based solutions have been associated with increases in ultrafiltration coefficient and middle-molecule removal. Increased pore size has been hypothesized as the mechanism for the latter phenomenon. Dialyzers exposed to Amukin-D (Amuchina Int Inc, Gaithersburg, MD), a chlorine-based reprocessing agent, were evaluated for changes in molecular weight (MW) cutoff and ultrafiltration properties.

Size-exclusion chromatography in multidimensional separation schemes for proteome analysis.

Size-exclusion chromatography (SEC) is a separation technique with a relatively low resolving power, compared to those usually utilized in proteomics. Therefore, it is often overlooked in experimental protocols, when the main goal is resolving complex biological mixtures. In this report, we introduce innovative multidimensional schemes for proteomics analysis, in which SEC plays a practical role.