A screening method for heavy metals in consumer goods using reactive desorption electrospray ionization mass spectrometry.

RATIONALE: Contamination of everyday goods with heavy metals such as nickel, cadmium, and lead known to be hazardous to the health of customers is an ongoing problem. METHOD: Here, a mass spectrometric screening method based on reactive desorption electrospray ionization (DESI) is presented for the analysis of metals in consumer goods such as jewelry, tableware, and paintings. The method detects oxidized species of lead, nickel, cadmium, copper, and iron from the surface of objects without sample preparation. Positively charged metal ions form singly and doubly negatively charged complexes with ethylenediaminetetraacetic acid added to the DESI solvent, which are analyzed by a mass spectrometer. RESULTS: Qualitative and quantitative performance of the method was elucidated with metal salt standards. Subsequently, authentic samples were analyzed qualitatively. Reactive DESI-MS was able to detect lead and cadmium in eight out of nine consumer goods. For tableware, these heavy metals were found to be localized in the print as determined by reactive DESI imaging. In addition, mockup paintings generated from modern and historical pigments of Pb, Cu, Cd, and Fe in various media (acrylic binder, egg tempera, and linseed oil) were measured to show the suitability of the method for art authentication and conservation. CONCLUSION: The developed method expands the range of analytes accessible by DESI-MS to metal ions. Hence, DESI becomes a suitable ionization technique for an increasing number of analyte classes, which are of interest in chemical screening of consumer goods.

Direct Monitoring of the Reaction between Photochemically Generated Nitric Oxide and Mycobacterium tuberculosis Truncated Hemoglobin N Wild Type and Variant Forms: An Assessment of Computational Mechanistic Predictions.

The previously reported nitric oxide precursor [Mn(PaPy2Q)NO]ClO4 (1), where (PaPy2QH) is N,N-bis(2-pyridylmethyl)-amine-N-ethyl-2-quinoline-2-carboxamide, was used to investigate the interaction between NO and the protein truncated hemoglobin N (trHbN) from the pathogen Mycobacterium tuberculosis. Oxy-trHbN is exceptionally efficient at converting NO to nitrate, with a reported rate constant of 7.45 × 10(8) M(-1) s(-1) [Ouellet, H., et al. (2002) Proc. Natl. Acad. Sci. U.S.A. 99, 5902] compared to 4 × 10(7) M(-1) s(-1) for oxy-myoglobin [Eich, R. F., et al. (1996) Biochemistry 35, 6976]. This work analyzed the NO dioxygenation kinetics of wild type oxy-trHbN and a set of variants, as well as the nitrosylation kinetics for the reduced (red-trHbN) forms of these proteins. The NO dioxygenation reaction was remarkably insensitive to mutations, even within the active site, while nitrosylation was somewhat more sensitive. Curiously, the most profound change to the rate constant for nitrosylation was effected by deletion of a 12-amino acid dangling N-terminal sequence. The deletion mutant exhibited first-order kinetics with respect to NO but was zero-order with respect to protein concentration; by contrast, all other variants exhibited second-order rate constants of >10(8) M(-1) s(-1). trHbN boasts an extensive tunnel system that connects the protein exterior with the active site, which is likely the main contributor to the protein's impressive NO dioxygenation efficiency. The results herein suggest that N-terminal deletion abolishes a large scale conformational motion, in the absence of which NO can still readily enter the tunnel system but is then prevented from binding to the heme for an extended period of time.

Evolution of Li2O2 growth and its effect on kinetics of Li-O2 batteries.

Lithium peroxide (Li2O2), the solid and intrinsically electronic insulating discharge product of Li-O2 batteries strongly influences the discharge and charge kinetics. In a series of experiments, we investigated the growth of Li2O2 upon discharge and the corresponding reduction and oxidation processes by varying the depth of discharge. The results indicate that insulating Li2O2 particles with a disc-like shape were formed during the initial discharge stage. Afterward, the nucleation and growth of Li2O2 resulted in the formation of conducting Li2O2 shells. When the discharge voltage dropped below 2.65 V, the Li2O2 discs evolved to toroid-shaped particles and defective superoxide-like phase presumably with high conductivity was formed on the rims of Li2O2 toroids. Both Li2O2 and the superoxide-like phase are unstable in ether-based electrolytes resulting in the degradation of the corresponding cells. Nevertheless, by controlling the growth of Li2O2, the chemical reactivity of the discharge product can be suppressed to improve the reversibility of Li-O2 batteries.