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1. Reductive Amination for LC–MS Signal Enhancement and Confirmation of the Presence of Caribbean Ciguatoxin-1 in Fish

   https://doi.org/10.3390/toxins14060399  

   Kryuchkov, Fedor ; Robertson, Alison ; Mudge, Elizabeth M. ; Miles, Christopher O. ; Van Gothem, Soetkien ; Uhlig, Silvio ( June 2022 , Toxins)

   Ciguatera poisoning is a global health concern caused by the consumption of seafood containing ciguatoxins (CTXs). Detection of CTXs poses significant analytical challenges due to their low abundance even in highly toxic fish, the diverse and in-part unclarified structures of many CTX congeners, and the lack of reference standards. Selective detection of CTXs requires methods such as liquid chromatography coupled to tandem mass spectrometry (LC–MS/MS) or high-resolution MS (LC–HRMS). While HRMS data can provide greatly improved resolution, it is typically less sensitive than targeted LC–MS/MS and does not reliably comply with the FDA guidance level of 0.1 µg/kg CTXs in fish tissue that was established for Caribbean CTX-1 (C-CTX-1). In this study, we provide a new chemical derivatization approach employing a fast and simple one-pot derivatization with Girard’s reagent T (GRT) that tags the C-56-ketone intermediate of the two equilibrating C-56 epimers of C-CTX-1 with a quaternary ammonium moiety. This derivatization improved the LC–MS/MS and LC–HRMS responses to C-CTX-1 by approximately 40- and 17-fold on average, respectively. These improvements in sensitivity to the GRT-derivative of C-CTX-1 are attributable to: the improved ionization efficiency caused by insertion of a quaternary ammonium ion; the absence of adduct-ions and water-loss peaks for themore »GRT derivative in the mass spectrometer, and; the prevention of on-column epimerization (at C-56 of C-CTX-1) by GRT derivatization, leading to much better chromatographic peak shapes. This C-CTX-1–GRT derivatization strategy mitigates many of the shortcomings of current LC–MS analyses for C-CTX-1 by improving instrument sensitivity, while at the same time adding selectivity due to the reactivity of GRT with ketones and aldehydes.« less
2. Solution- and gas-phase behavior of decavanadate: implications for mass spectrometric analysis of redox-active polyoxidometalates

   https://doi.org/10.1039/d1qi01618k  

   Favre, Daniel ; Bobst, Cedric E. ; Eyles, Stephen J. ; Murakami, Heide ; Crans, Debbie C. ; Kaltashov, Igor A. ( March 2022 , Inorganic Chemistry Frontiers)

   Decavanadate (V 10 O 28 6− or V10) is a paradigmatic member of the polyoxidometalate (POM) family, which has been attracting much attention within both materials/inorganic and biomedical communities due to its unique structural and electrochemical properties. In this work we explored the utility of high-resolution electrospray ionization (ESI) mass spectrometry (MS) and ion exclusion chromatography LC/MS for structural analysis of V10 species in aqueous solutions. While ESI generates abundant molecular ions representing the intact V10 species, their isotopic distributions show significant deviations from the theoretical ones. A combination of high-resolution MS measurements and hydrogen/deuterium exchange allows these deviations to be investigated and interpreted as a result of partial reduction of V10. While the redox processes are known to occur in the ESI interface and influence the oxidation state of redox-active analytes, the LC/MS measurements using ion exclusion chromatography provide unequivocal evidence that the mixed-valence V10 species exist in solution, as extracted ion chromatograms representing V10 molecular ions at different oxidation states exhibit distinct elution profiles. The spontaneous reduction of V10 in solution is seen even in the presence of hydrogen peroxide and has not been previously observed. The susceptibility to reduction of V10 is likely to be shared bymore »other redox active POMs. In addition to the molecular V10 ions, a high-abundance ionic signal for a V 10 O 26 2− anion was displayed in the negative-ion ESI mass spectra. None of the V 10 O 26 cations were detected in ESI MS, and only a low-abundance signal was observed for V 10 O 26 anions with a single negative charge, indicating that the presence of abundant V 10 O 26 2− anions in ESI MS reflects gas-phase instability of V 10 O 28 anions carrying two charges. The gas-phase origin of the V 10 O 26 2− anion was confirmed in tandem MS measurements, where mild collisional activation was applied to V10 molecular ions with an even number of hydrogen atoms (H 4 V 10 O 28 2− ), resulting in a facile loss of H 2 O molecules and giving rise to V 10 O 26 2− as the lowest-mass fragment ion. Water loss was also observed for V 10 O 28 anions carrying an odd number of hydrogen atoms ( e.g. , H 5 V 10 O 28 − ), followed by a less efficient and incomplete removal of an OH˙ radical, giving rise to both HV 10 O 26 − and V 10 O 25 − fragment ions. Importantly, at least one hydrogen atom was required for ion fragmentation in the gas phase, as no further dissociation was observed for any hydrogen-free V10 ionic species. The presented workflow allows a distinction to be readily made between the spectral features revealing the presence of non-canonical POM species in the bulk solution from those that arise due to physical and chemical processes occurring in the ESI interface and/or the gas phase.« less
3. Molecular investigation of the multi-phase photochemistry of Fe( iii )–citrate in aqueous solution

   https://doi.org/10.1039/D1EM00503K  

   West, Christopher P. ; Morales, Ana C. ; Ryan, Jackson ; Misovich, Maria V. ; Hettiyadura, Anusha P. ; Rivera-Adorno, Felipe ; Tomlin, Jay M. ; Darmody, Andrew ; Linn, Brittany N. ; Lin, Peng ; et al ( February 2023 , Environmental Science: Processes & Impacts)

   Iron (Fe) is ubiquitous in nature and found as Fe II or Fe III in minerals or as dissolved ions Fe 2+ or Fe 3+ in aqueous systems. The interactions of soluble Fe have important implications for fresh water and marine biogeochemical cycles, which have impacts on global terrestrial and atmospheric environments. Upon dissolution of Fe III into natural aquatic systems, organic carboxylic acids efficiently chelate Fe III to form [Fe III –carboxylate] 2+ complexes that undergo a wide range of photochemistry-induced radical reactions. The chemical composition and photochemical transformations of these mixtures are largely unknown, making it challenging to estimate their environmental impact. To investigate the photochemical process of Fe III –carboxylates at the molecular level, we conduct a comprehensive experimental study employing UV-visible spectroscopy, liquid chromatography coupled to photodiode array and high-resolution mass spectrometry detection, and oil immersion flow microscopy. In this study, aqueous solutions of Fe III –citrate were photolyzed under 365 nm light in an experimental setup with an apparent quantum yield of ( φ ) ∼0.02, followed by chemical analyses of reacted mixtures withdrawn at increment time intervals of the experiment. The apparent photochemical reaction kinetics of Fe 3+ –citrates (aq) were expressed as twomore »generalized consecutive reactions of with the experimental rate constants of j 1 ∼ 0.12 min −1 and j 2 ∼ 0.05 min −1 , respectively. Molecular characterization results indicate that R and I consist of both water-soluble organic and Fe–organic species, while P compounds are a mixture of water-soluble and colloidal materials. The latter were identified as Fe–carbonaceous colloids formed at long photolysis times. The carbonaceous content of these colloids was identified as unsaturated organic species with low oxygen content and carbon with a reduced oxidation state, indicative of their plausible radical recombination mechanism under oxygen-deprived conditions typical for the extensively photolyzed mixtures. Based on the molecular characterization results, we discuss the comprehensive reaction mechanism of Fe III –citrate photochemistry and report on the formation of previously unexplored colloidal reaction products, which may contribute to atmospheric and terrestrial light-absorbing materials in aquatic environments.« less
4. On structure and phase transformation of uranium doped La ₂ Hf ₂ O ₇ nanoparticles as an efficient nuclear waste host

   https://doi.org/10.1039/c8qm00266e  

   Abdou, Maya ; Gupta, Santosh K. ; Zuniga, Jose P. ; Mao, Yuanbing ( November 2018 , Materials Chemistry Frontiers)

   The design and development of efficient and stable nuclear waste hosts has drawn intensive interest for long-lived lanthanides and actinides. A detailed investigation of their structure and potential structural evolution are crucial. In this study, we have synthesized lanthanum hafnate La 2 Hf 2 O 7 nanoparticles (NPs) doped with uranium at different concentrations (0–10%) and investigated their structural transition. We have discovered that in our La 2 Hf 2 O 7 :U NPs, the uranium dopants are stabilized at both U 4+ and U 6+ oxidation states in which the U 6+ oxidation state exists in octahedral uranate UO 6 6− form. We also confirmed that the U 4+ ions substituted the Hf 4+ ions with a lifetime of ∼1.0 μs and the UO 6 6− ions resided at the La 3+ sites with a lifetime of ∼9.0 μs. More interestingly, the proportion of the U 4+ ions in the La 2 Hf 2 O 7 :U NPs was higher than that of the UO 6 6− ions at low doping level, but at the doping level higher than 2.5%, the fraction of the UO 6 6− ions was greater than that of the U 4+ ions. Furthermore, wemore »studied the structural phase transformation from order pyrochlore to cotunnite of these La 2 Hf 2 O 7 :U NPs with increasing uranium doping level, and found that ordered pyrochlore phase favors the U 4+ ions whereas disordered cotunnite phase favors the UO 6 6− ions. We further used in situ Raman spectroscopy to confirm the reversible cotunnite to pyrochlore phase transformation of the La 2 Hf 2 O 7 :10%U NPs at 900 °C. Therefore, this work demonstrated the successful development of uranium doped La 2 Hf 2 O 7 NPs and thorough characterization of the fundamental spectra of uranium ions, doping induced phase transformation, and structure–optical property correlation.« less
5. Effect of relative humidity on the composition of secondary organic aerosol from the oxidation of toluene

   https://doi.org/10.5194/acp-18-1643-2018  

   Hinks, Mallory L. ; Montoya-Aguilera, Julia ; Ellison, Lucas ; Lin, Peng ; Laskin, Alexander ; Laskin, Julia ; Shiraiwa, Manabu ; Dabdub, Donald ; Nizkorodov, Sergey A. ( January 2018 , Atmospheric Chemistry and Physics)

   The effect of relative humidity (RH) on the chemical composition of secondary organic aerosol (SOA) formed from low-NO_x toluene oxidation in the absence of seed particles was investigated. SOA samples were prepared in an aerosol smog chamber at < 2 % RH and 75 % RH, collected on Teflon filters, and analyzed with nanospray desorption electrospray ionization high-resolution mass spectrometry (nano-DESI–HRMS). Measurements revealed a significant reduction in the fraction of oligomers present in the SOA generated at 75 % RH compared to SOA generated under dry conditions. In a separate set of experiments, the particle mass concentrations were measured with a scanning mobility particle sizer (SMPS) at RHs ranging from < 2 to 90 %. It was found that the particle mass loading decreased by nearly an order of magnitude when RH increased from < 2 to 75–90 % for low-NO_x toluene SOA. The volatility distributions of the SOA compounds, estimated from the distribution of molecular formulas using the molecular corridor approach, confirmed that low-NO_x toluene SOA became more volatile on average under high-RH conditions. In contrast, the effect of RH on SOA mass loading was found to be much smaller for high-NO_x toluene SOA. The observed increase in the oligomer fraction and particle mass loading under dry conditions were attributed to the enhancement of condensation reactions,more »which produce water and oligomers from smaller compounds in low-NO_x toluene SOA. The reduction in the fraction of oligomeric compounds under humid conditions is predicted to partly counteract the previously observed enhancement in the toluene SOA yield driven by the aerosol liquid water chemistry in deliquesced inorganic seed particles.« less