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1. Evidence of H/D Exchange within Metal-Adducted Carbohydrates after Ion/Ion-Dissociation Reactions

   https://doi.org/10.1021/jacs.3c05793  

   Gass, Darren T.; Cordes, Michael S.; Alberti, Sebastian N.; Kim, H. Jamie; Gallagher, Elyssia S. (November 2023, Journal of the American Chemical Society)

   Tandem mass spectrometry (MS/MS) using fragmentation has become one of the most effective methods for gaining sequence and structural information of biomolecules. Ion/ion reactions are competitive reactions where either proton transfer (PT) or electron transfer (ET) can occur from interactions between multiply charged cations and singly charged anions. Utilizing ion/ion reactions with fluoranthene has offered a unique method of fragment formation for structural elucidation of biomolecules. Fluoranthene is considered an ideal anion reagent because it selectively causes electron transfer dissociation (ETD) and minimizes PT when interacting with peptides. However, limited investigations have sought to understand how fluoranthene – the primary, commercially available anion reagent – interacts with other biomolecules. Here, we apply deuterium labeling to investigate ion/ion reaction mechanisms between fluoranthene and divalent, metal-adducted carbohydrates (Ca2+, Mg2+, Co2+, and Ni2+). Deuterium labeling of carbohydrates allowed us to observe evidence of hydrogen/deuterium exchange (HDX) occurring after ion/ion dissociation reactions. The extent of deuterium loss is dependent on several factors, including the physical properties of the metal ion and the fragment structure. Based on the deuterium labeling data, we have proposed ETD, PTD, and intermolecular PT – also described as HDX - mechanisms. This research provides a fundamental perspective of ion/ion and ion/molecule reaction mechanisms and illustrates properties that impact ion/ion and ion/molecule reactions for carbohydrates. Together, this could improve the capability to distinguish complex and heterogenous biomolecules, such as carbohydrates. 

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2. A simplified coaxial ion trap mass analyzer: Characterization of the simplified toroidal ion trap with a rectilinear ion guide

   Sirbescu-Stanley, DV; Lemmer, KM; Austin, DE; Taylor, NR (October 2024, International journal of mass spectrometry)

   A new miniature coaxial ion trap mass analyzer with a rectilinear ion guide has been constructed using a combination of planar and cylindrical electrodes. The results reported here focus on characterizing the performance of the rectilinear ion guide and simplified toroidal ion trap components. The simplified toroidal ion trap was found to have an ion capacity in excess of 105 ions and mass spectral resolution of 0.5–0.6 when used as a mass analyzer. The ion storage efficiency within the toroidal trapping region was evaluated and found the stored ion population decreased exponentially with storage time. Ion losses depended slightly on the stored βz condition. Ion losses within the toroidal region are attributed primarily to field instabilities at the intersection point of the two components while charge exchange reactions were observed but considered a minor loss mechanism. The ability to mass selectively ejection ions of a specific mass from the toroidal trapping region was characterized and found to approach 100 % efficiency under appropriate ejection conditions. 

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3. Anion chemical composition of poly(ethylene oxide)-based sulfonylimide and sulfonate lithium ionomers controls ion aggregation and conduction

   https://doi.org/10.1039/D2TC02212E  

   Mei, Wenwen; Yu, Deyang; George, Christy; Madsen, Louis A.; Hickey, Robert J.; Colby, Ralph H. (October 2022, Journal of Materials Chemistry C)

   Maximizing ion conduction in single-ion-conducting ionomers is essential for their application in energy-related technologies such as Li-ion batteries. Understanding the anion chemical composition impacts on ion conduction offers new perspectives to maximize ion transport, since the current approach of lowering T g has apparently reached a limit (lowest T g ∼ 190 K, highest conductivity ∼10 −5 –10 −4 S cm −1 ). Here, a series of random ionomers are synthesized by copolymerizing poly(ethylene glycol)methacrylate with either sulfonylimide lithium methacrylate (MTLi) or sulfonate lithium methacrylate (MSLi) using reversible addition–fragmentation chain transfer (RAFT) polymerization. Li-Ion conduction and self-diffusion coefficients ( D Li + ) of the ionomers are characterized with dielectric relaxation spectroscopy (DRS) and pulsed-field-gradient (PFG) NMR diffusometry, respectively. Increasing ion content decreases the Li-ion conductivity and D Li + , as expected from the increased T g . Moreover, a considerably lower ionic conductivity and D Li + are observed for MSLi compared to MTLi at constant ion content and T g / T . As revealed from X-ray scattering, strong ion aggregation in MSLi results in much lower conductivity and D Li + compared with less aggregated MTLi based on the more delocalized sulfonylimide anion. These results emphasize the detrimental and molecularly specific role of ion aggregation in Li-ion conductivity, and highlight the necessity for minimizing ion aggregation via the rational choice of anion chemical composition. 

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4. Particle-in-cell simulations – ion beam instabilities and the generation of Alfvén and whistler waves in low β plasma

   https://doi.org/10.1093/mnras/stad2897  

   Che, H.; Benz, A_O; Zank, G_P (September 2023, Monthly Notices of the Royal Astronomical Society)

   ABSTRACT Ion beam-driven instabilities in a collisionless space plasma with low β, i.e. low plasma and magnetic pressure ratio, are investigated using particle-in-cell (PIC) simulations. Specifically, the effects of different ion drift velocities on the development of Buneman and resonant electromagnetic (EM) right-handed (RH) ion beam instabilities are studied. Our simulations reveal that both instabilities can be driven when the ion beam drift exceeds the theoretical thresholds. The Buneman instability, which is weakly triggered initially, dissipates only a small fraction of the kinetic energy of the ion beam while causing significant electron heating, owing to the small electron-ion mass ratio. However, we find that the ion beam-driven Buneman instability is quenched effectively by the resonant EM RH ion beam instability. Instead, the resonant EM RH ion beam instability dominates when the ion drift velocity is larger than the Alfvén speed, leading to the generation of RH Alfvén waves and RH whistler waves. We find that the intensity of Alfvén waves decreases with decrease of ion beam drift velocity, while the intensity of whistler waves increases. Our results provide new insights into the complex interplay between ion beams and plasma instabilities in low β collisionless space plasmas. 

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5. Structural Characteristics of Ion Holes in Plasma

   https://doi.org/10.3390/plasma4030032  

   Aravindakshan, Harikrishnan; Kakad, Amar; Kakad, Bharati; Yoon, Peter H. (September 2021, Plasma)

   Ion holes refer to the phase-space structures where the trapped ion density is lower at the center than at the rim. These structures are commonly observed in collisionless plasmas, such as the Earth’s magnetosphere. This paper investigates the role of multiple parameters in the generation and structure of ion holes. We find that the ion-to-electron temperature ratio and the background plasma distribution function of the species play a pivotal role in determining the physical plausibility of ion holes. It is found that the range of width and amplitude that defines the existence of ion holes splits into two separate domains as the ion temperature exceeds that of the electrons. Additionally, the present study reveals that the ion holes formed in a plasma with ion temperature higher than that of the electrons have a hump at its center. 

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