High-field asymmetric waveform ion mobility spectrometry (FAIMS) is shown to be capable of resolving isomeric and isobaric glycosaminoglycan negative ions, and to have great utility for the analysis of this class of molecules when combined with Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) and tandem mass spectrometry. Electron detachment dissociation (EDD) and other ion activation methods for tandem mass spectrometry can be used to determine the sites of labile sulfate modifications and for assigning the stereochemistry of hexuronic acid residues of GAGs. However, mixtures with overlapping mass-to-charge values present a challenge, as their precursor species cannot be resolved by a mass analyzer prior to ion activation. FAIMS is shown to resolve two types of mass-to-charge overlaps. A mixture of chondroitin sulfate A (CSA) oligomers with 4–10 saccharides units produces ions of a single mass-to-charge by electrospray ionization, as the charge state increases in direct proportion to the degree of polymerization for these sulfated carbohydrates. FAIMS is shown to resolve the overlapping charge. A more challenging type of mass-to-charge overlap occurs for mixtures of diastereomers. FAIMS is shown to separate two sets of epimeric GAG tetramers. For the epimer pairs, the complexity of the separation is reduced when the reducing end is alkylated, suggesting that anomers are also resolved by FAIMS. The resolved components were activated by EDD and the fragment ions were analyzed by FTICR-MS. The resulting tandem mass spectra were able to distinguish the two epimers from each other.
The effect of acute exercise on natural killer (NK) activity and on the distribution of phenotypic characteristics of peripheral blood lymphocytes was examined. Trained and sedentary individuals underwent a standard progressive exercise test on a cycle ergometer using an incremental work load of 15 W (90 kpm), increased every minute. Each subject was encouraged to exercise to exhaustion, and total ventilation and mixed expired O2 and CO2 were measured every 30 sec. All subjects reached the "anaerobic" threshold as judged by the deflection of ventilation at a work load near VO2max. NK activity against K562 reached maximum levels immediately after exercise, dropped to a low point 120 min later, then slowly came back to preexercise levels within 20 hr. No significant differences were observed between the trained and the sedentary groups. Furthermore, immediately after exercise the proportion of OKT-3+ and OKT-4+ cells was reduced by 29.8 +/- 3.6 and 33.6 +/- 5.4%, respectively; the percentage Leu-7+ and Leu-11a+ cells was increased by 53.9 +/- 1.7 and 57.3 +/- 2.9%, respectively. The percentage OKT-8+ cells was not significantly altered. When the percentage binding of effector to target cells was examined, it was highest at 0 min post-exercise (19 +/- 6.2%) and lowest at 120 min postexercise (7 +/- 3.9%), but the absolute number of NK cells remained unchanged. The source of serum used in the lytic assay had no effect on the NK activity, as fetal calf serum and autologous sera drawn at different time intervals during exercise gave similar results.(ABSTRACT TRUNCATED AT 250 WORDS)
Trapped ion mobility spectrometry coupled to mass spectrometry (TIMS-MS) was utilized for the separation and identification of familiar explosives in complex mixtures. For the first time, molecular adduct complex lifetimes, relative stability, binding energies and candidate structures are reported for familiar explosives. Experimental and theoretical results showed that the adduct size and reactivity, complex binding energy and the explosive structure tailors the stability of the molecular adduct complex. TIMS flexibility to adapt the mobility separation as a function of the molecular adduct complex stability (i.e., short or long IMS experiments / low or high IMS resolution) permits targeted measurements of explosives in complex mixtures with higher confidence levels.
Molecular characterization of compounds presents in highly complex mixtures such as petroleum is proving to be one of the main analytical challenges. Heavy fractions, such as asphaltenes, exhibit immense molecular...
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.