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1. Ion formation in droplet‐assisted ionization

   https://doi.org/10.1002/rcm.8227  

   Apsokardu, Michael J. ; Kerecman, Devan E. ; Johnston, Murray V. ( September 2018 , Rapid Communications in Mass Spectrometry)

   In droplet‐assisted ionization (DAI), intact molecular ions are generated from molecules in aerosol droplets by passing the droplets through a temperature‐controlled capillary inlet. Ion formation is explored through the effects of analyte mass flow, droplet solvent composition, and capillary temperature on ion signal intensity.

   A Waters SYNAPT G2‐S is adapted for DAI by reconfiguring the inlet with a temperature‐controlled capillary. Droplets are generated by atomization of a solution containing analyte and then sampled through the inlet. If desired, solvent can be removed from the droplets prior to analysis by sending the aerosol through a series of diffusion dryers. Size distributions of the dried aerosols allow the mass flow of analyte into the inlet to be determined.

   Analyte signal intensities are orders of magnitude higher from droplets containing a protic solvent (water) than an aprotic solvent (acetonitrile). The highest signal intensities for DAI are obtained with inlet temperatures above 500°C, though the optimum temperature is analyte dependent. At elevated temperatures, droplets are thought to undergo rapid solvent evaporation and bursting to produce ions. The lowest signal intensities are generally obtained in the 100–350°C range, where slow solvent evaporation is thought to inhibit ion formation. As the temperature decreases from 100°C down to 25°C, the signal intensity increases significantly. When 3‐nitrobenzonitrile, a common matrix for solid‐state matrix‐assisted ionization (MAI), is added to droplets consisting of 50/50 v/v water and acetonitrile, the matrix enhances ion formation to produce a signal intensity comparable to DAI in 100% water.

   The results are consistent with other inlet ionization techniques, suggesting that similar ion formation mechanisms are operative. Optimized ion yields (the combined effects of ionization probability and ion transmission) for DAI are currently in the 10⁻⁵to 10⁻⁶range, which is sufficient for many aerosol applications.

    

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2. Jet Formation After Droplet Impact on Microholed Hydrophilic Surfaces

   Md Nur E Alam and Hua Tan ( November 2022 , IMECE2022)

   Droplet impacts on solid surfaces produce a wide variety of phenomena such as spreading, splashing, jetting, receding, and rebounding. In microholed surfaces, downward jets through the hole can be caused by the high impact inertia during the spreading phase of the droplet over the substrate as well as the cavity collapse during recoil phase of the droplet. We investigate the dynamics of the jet formed through the single hole during the impacting phase of the droplet on a micro-holed hydrophilic substrate. The sub-millimeter circular holes are created on the 0.2 mm-thickness hydrophilic plastic films using a 0.5 mm punch. Great care has been taken to ensure that the millimeter-sized droplets of water dispensed by a syringe pump through a micropipette tip can impact directly over the micro-holes. A high-speed video photography camera is employed to capture the full event of impacting and jetting. A MATLAB code has been developed to process the captured videos for data analysis. We study the effect of impact velocity on the jet formation including jet velocity, ejected droplet volume, and breakup process. We find that the Weber number significantly affects outcomes of the drop impact and jetting mechanism. We also examine the dynamic contact angle of the contact line during the spreading and the receding phase. 

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3. Toward understanding the ionization mechanism of matrix‐assisted ionization using mass spectrometry experiment and theory

   https://doi.org/10.1002/rcm.8382  

   Lee, Chuping ; Inutan, Ellen D. ; Chen, Jien Lian ; Mukeku, Mutanu M. ; Weidner, Steffen M. ; Trimpin, Sarah ; Ni, Chi‐Kung ( March 2019 , Rapid Communications in Mass Spectrometry)

   Matrix‐assisted ionization (MAI) mass spectrometry does not require voltages, a laser beam, or added heat to initiate ionization, but it is strongly dependent on the choice of matrix and the vacuum conditions. High charge state distributions of nonvolatile analyte ions produced by MAI suggest that the ionization mechanism may be similar to that of electrospray ionization (ESI), but different from matrix‐assisted laser desorption/ionization (MALDI). While significant information is available for MAI using mass spectrometers operating at atmospheric and intermediate pressure, little is known about the mechanism at high vacuum.

   Eleven MAI matrices were studied on a high‐vacuum time‐of‐flight (TOF) mass spectrometer using a 266 nm pulsed laser beam under otherwise typical MALDI conditions. Detailed comparisons with the commonly used MALDI matrices and theoretical prediction were made for 3‐nitrobenzonitrile (3‐NBN), which is the only MAI matrix that works well in high vacuum when irradiated with a laser.

   Screening of MAI matrices with good absorption at 266 nm but with various degrees of volatility and laser energies suggests that volatility and absorption at the laser wavelength may be necessary, but not sufficient, criteria to explain the formation of multiply charged analyte ions. 3‐NBN produces intact, highly charged ions of nonvolatile analytes in high‐vacuum TOF with the use of a laser, demonstrating that ESI‐like ions can be produced in high vacuum. Theoretical calculations and mass spectra suggest that thermally induced proton transfer, which is the major ionization mechanism in MALDI, is not important with the 3‐NBN matrix at 266 nm laser wavelength. 3‐NBN:analyte crystal morphology is, however, important in ion generation in high vacuum.

   The 3‐NBN MAI matrix produces intact, highly charged ions of nonvolatile compounds in high‐vacuum TOF mass spectrometers with the aid of ablation and/or heating by laser irradiation, and shows a different ionization mechanism from that of typical MALDI matrices.

    

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4. The role of analyte concentration in accelerated reaction rates in evaporating droplets

   https://doi.org/10.1039/d3sc00259d  

   Chen, Casey J. ; Williams, Evan R. ( May 2023 , Chemical Science)

   Accelerated reactions in microdroplets have been reported for a wide range of reactions with some microdroplet reactions occurring over a million times faster than the same reaction in bulk solution. Unique chemistry at the air–water interface has been implicated as a primary factor for accelerated reaction rates, but the role of analyte concentration in evaporating droplets has not been as well studied. Here, theta-glass electrospray emitters and mass spectrometry are used to rapidly mix two solutions on the low to sub-microsecond time scale and produce aqueous nanodrops with different sizes and lifetimes. We demonstrate that for a simple bimolecular reaction where surface chemistry does not appear to play a role, reaction rate acceleration factors are between 10 2 and 10 7 for different initial solution concentrations, and these values do not depend on nanodrop size. A rate acceleration factor of 10 7 is among the highest reported and can be attributed to concentration of analyte molecules, initially far apart in dilute solution, but brought into close proximity in the nanodrop through evaporation of solvent from the nanodrops prior to ion formation. These data indicate that analyte concentration phenomenon is a significant factor in reaction acceleration where droplet volume throughout the experiment is not carefully controlled. 

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5. Resolving Isomers of Star-Branched Poly(Ethylene Glycols) by IMS-MS Using Multiply Charged Ions

   https://doi.org/10.1021/jasms.0c00045  

   Austin, Calvin A. ; Inutan, Ellen D. ; Bohrer, Brian C. ; Li, Jing ; Fischer, Joshua L. ; Wijerathne, Kanchana ; Foley, Casey D. ; Lietz, Christopher B. ; Woodall, Daniel W. ; Imperial, Lorelie F. ; et al ( January 2020 , Journal of the American Society for Mass Spectrometry)

   null (Ed.)

   Ion mobility spectrometry (IMS) mass spectrometry (MS) centers on the ability to separate gaseous structures by size, charge, shape, and followed by mass-to-charge (m/z). For oligomeric structures, improved separation is hypothesized to be related to the ability to extend structures through repulsive forces between cations electrostatically bonded to the oligomers. Here we show the ability to separate differently branched multiply charged ions of star-branched poly(ethylene glycol) oligomers (up to 2000 Da) regardless of whether formed by electrospray ionization (ESI) charged solution droplets or from charged solid particles produced directly from a surface by matrix-assisted ionization. Detailed structural characterization of isomers of the star-branched compositions was first established using a home-built high-resolution ESI IMS-MS instrument. The doubly charged ions have well-resolved drift times, achieving separation of isomers and also allowing differentiation of star-branched versus linear oligomers. An IMS-MS “snapshot” approach allows visualization of architectural dispersity and (im)purity of samples in a straightforward manner. Analyses capabilities are shown for different cations and ionization methods using commercially available traveling wave IMS-MS instruments. Analyses directly from surfaces using the new ionization processes are, because of the multiply charging, not only associated with the benefits of improved gas-phase separations, relative to that of ions produced by matrix-assisted laser desorption/ionization, but also provide the potential for spatially resolved measurements relative to ESI and other ionization methods. 

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