Synthesis, structure, electrochemistry and magnetism of cobalt-, nickel- and zinc-containing [M4(OH)3(H2O)2(α-SiW10O36.5)2]13- (M = Co2+, Ni2+, and Zn2+).

Interaction of the trilacunary 9-tungstosilicate [A-α-SiW9O34]10- with cobalt(ii), nickel(ii) and zinc(ii) ions in pH 9 aqueous medium at room temperature led to the formation of the respective M4-containing heteropolytungstates [M4(OH)3(H2O)2(α-SiW10O36.5)2]13- (M = Co2+ (1), Ni2+ (2), and Zn2+ (3)). Polyanions 1-3 were characterized in the solid state by single-crystal XRD, FT-IR spectroscopy, and thermogravimetric and elemental analyses. Electrochemical studies showed that the Co2+ ions in 1 can be oxidized to Co3+ and the CVs of the WVI centers of the polyanions feature well-defined and chemically reversible reduction waves. Magnetic measurements on 1 and 2 showed paramagnetism with complex ferromagnetic and antiferromagnetic interactions. A model was presented for extracting the exchange constants for the magnetic exchange interaction.

Atmospheric-Pressure Dielectric Barrier Discharge as an Elemental Ion Source for Gas Chromatographic Analysis of Organochlorines.

Atmospheric-pressure dielectric barrier discharge (AP-DBD) plasma has emerged in recent years as a versatile plasma for molecular ionization and elemental spectroscopy. However, its capabilities as an elemental ion source have been less explored, partly because of difficulties in the detection of positive elemental ions from this low-gas-temperature plasma. In this work, we investigate the detection of negative elemental ions to enable elemental mass spectrometry (MS) using AP-DBD. A gas chromatograph is coupled to a helium AP-DBD apparatus and positioned in front of an atmospheric-pressure-sampling mass spectrometer with no modifications to the ion sampling interface. We demonstrate that Cl- ions are detected with a compound-independent efficiency, enabling elemental quantification of organochlorines. Further, addition of oxygen at low concentration (11 ppm, v/v) to the helium plasma improves the analytical performance by reducing postcolumn peak broadening, whereas high oxygen concentrations (>110 ppm, v/v) lead to loss of the compound-independent response. The optimized GC-AP-DBD-MS setup shows close to 2 orders of magnitude of linearity for its compound-independent Cl response and offers detection limits of 0.5-1 pg of Cl on column (0.6 pg/s), suitable for analysis of organochlorines in food samples. We demonstrate this capability by analyzing orange juice spiked with pesticides at 9 µg/L and a single internal standard. Importantly, we demonstrate that a quick, easy, cheap, effective, rugged, and safe (QuEChERS) extraction followed by GC-AP-DBD-MS quantification using the single standard provides acceptable recoveries (80-120%). These results highlight uniform QuEChERS extraction of a range of compounds and the compound-independent response of AP-DBD for Cl, making the combination of the two methods desirable for the rapid quantification of organochlorines. Furthermore, we discuss ionization matrix effects in AP-DBD for chlorine detection and offer strategies to flag matrix-impacted analytes. These results suggest that AP-DBD has the potential to become a unified ion source for both elemental quantification and molecular identification of GC eluents on a single MS platform.

Elemental quantitation of carbon via production of polyatomic anions in gas chromatography-plasma assisted reaction chemical ionization mass spectrometry.

Elemental mass spectrometry offers quantitation and isotopic analysis without the need for compound-specific standards. We have recently introduced plasma assisted reaction chemical ionization (PARCI) as an efficient elemental ionization method for halogens. Here, we report a new ionization chemistry in PARCI for facile quantitation of elemental carbon in gas chromatography eluates. We demonstrate that in-plasma reactions of organic compounds followed by afterglow ionization lead to formation of polyatomic anions (CN-, OCN-, and CO3-), among which CN- offers the best analytical sensitivity with a detection limit of ~25 pg (21 pg/s) carbon on column. Using a mixture of pesticides with wide variations in structures and heteroatom content, we demonstrate that CN- ion response is quantitatively correlated with the carbon concentration over two orders of magnitude (r 2 = 0.985). We show that the novel GC-PARCI-MS method provides recoveries within 80-120% using a single standard for all analytes, highlighting the strength of elemental quantitation. Further, the ability of GC-PARCI-MS to identify 13C-tagged molecules without a priori knowledge of chemical formulas of analytes is demonstrated. Graphical abstract ᅟ.