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1. The role of charge in microdroplet redox chemistry

   https://doi.org/10.1038/s41467-024-47879-0  

   Heindel, Joseph_P; LaCour, R_Allen; Head-Gordon, Teresa (April 2024, Nature Communications)

   Abstract In charged water microdroplets, which occur in nature or in the lab upon ultrasonication or in electrospray processes, the thermodynamics for reactive chemistry can be dramatically altered relative to the bulk phase. Here, we provide a theoretical basis for the observation of accelerated chemistry by simulating water droplets of increasing charge imbalance to create redox agents such as hydroxyl and hydrogen radicals and solvated electrons. We compute the hydration enthalpy of OH⁻and H⁺that controls the electron transfer process, and the corresponding changes in vertical ionization energy and vertical electron affinity of the ions, to create OH^•and H^•reactive species. We find that at ~ 20 − 50% of the Rayleigh limit of droplet charge the hydration enthalpy of both OH⁻and H⁺have decreased by >50 kcal/mol such that electron transfer becomes thermodynamically favorable, in correspondence with the more favorable vertical electron affinity of H⁺and the lowered vertical ionization energy of OH⁻. We provide scaling arguments that show that the nanoscale calculations and conclusions extend to the experimental microdroplet length scale. The relevance of the droplet charge for chemical reactivity is illustrated for the formation of H₂O₂, and has clear implications for other redox reactions observed to occur with enhanced rates in microdroplets. 

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2. Dendronized fluorosurfactant for highly stable water-in-fluorinated oil emulsions with minimal inter-droplet transfer of small molecules

   https://doi.org/10.1038/s41467-019-12462-5  

   Chowdhury, Mohammad Suman; Zheng, Wenshan; Kumari, Shalini; Heyman, John; Zhang, Xingcai; Dey, Pradip; Weitz, David A.; Haag, Rainer (December 2019, Nature Communications)

   null (Ed.)

   Abstract Fluorosurfactant-stabilized microfluidic droplets are widely used as pico- to nanoliter volume reactors in chemistry and biology. However, current surfactants cannot completely prevent inter-droplet transfer of small organic molecules encapsulated or produced inside the droplets. In addition, the microdroplets typically coalesce at temperatures higher than 80 °C. Therefore, the use of droplet-based platforms for ultrahigh-throughput combination drug screening and polymerase chain reaction (PCR)-based rare mutation detection has been limited. Here, we provide insights into designing surfactants that form robust microdroplets with improved stability and resistance to inter-droplet transfer. We used a panel of dendritic oligo-glycerol-based surfactants to demonstrate that a high degree of inter- and intramolecular hydrogen bonding, as well as the dendritic architecture, contribute to high droplet stability in PCR thermal cycling and minimize inter-droplet transfer of the water-soluble fluorescent dye sodium fluorescein salt and the drug doxycycline. 

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3. Plasma-droplet interaction study to assess transport limitations and the role of ^⋅ OH, O ^⋅ ,H ^⋅ ,O ₂ (a ¹ Δ _g ),O ₃ , He(2 ³ S) and Ar(1s ₅ ) in formate decomposition

   https://doi.org/10.1088/1361-6595/ac2676  

   Nayak, Gaurav; Oinuma, Gaku; Yue, Yuanfu; Santos Sousa, João; Bruggeman, Peter J (November 2021, Plasma Sources Science and Technology)

   Abstract Plasmas interacting with liquid microdroplets are gaining momentum due to their ability to significantly enhance the reactivity transfer from the gas phase plasma to the liquid. This is, for example, critically important for efficiently decomposing organic pollutants in water. In this contribution, the role of ⋅ OH as well as non- ⋅ OH-driven chemistry initiated by the activation of small water microdroplets in a controlled environment by diffuse RF glow discharge in He with different gas admixtures (Ar, O 2 and humidified He) at atmospheric pressure is quantified. The effect of short-lived radicals such as O ⋅ and H ⋅ atoms, singlet delta oxygen (O 2 ( a 1 Δ g )), O 3 and metastable atoms of He and Ar, besides ⋅ OH radicals, on the decomposition of formate dissolved in droplets was analyzed using detailed plasma diagnostics, droplet characterization and ex situ chemical analysis of the treated droplets. The formate decomposition increased with increasing droplet residence time in the plasma, with ∼70% decomposition occurring within ∼15 ms of the plasma treatment time. The formate oxidation in the droplets is shown to be limited by the gas phase ⋅ OH flux at lower H 2 O concentrations with a significant enhancement in the formate decomposition at the lowest water concentration, attributed to e − /ion-induced reactions. However, the oxidation is diffusion limited in the liquid phase at higher gaseous ⋅ OH concentrations. The formate decomposition in He/O 2 plasma was similar, although with an order of magnitude higher O ⋅ radical density than the ⋅ OH density in the corresponding He/H 2 O plasma. Using a one-dimensional reaction–diffusion model, we showed that O 2 ( a 1 Δ g ) and O 3 did not play a significant role and the decomposition was due to O ⋅ , and possibly ⋅ OH generated in the vapor containing droplet-plasma boundary layer. 

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4. Tandem droplet locomotion in a uniform electric field

   https://doi.org/10.1017/jfm.2022.875  

   Sorgentone, Chiara; Vlahovska, Petia M. (November 2022, Journal of Fluid Mechanics)

   An isolated charge-neutral droplet in a uniform electric field experiences no net force. However, a droplet pair can move in response to field-induced dipolar and hydrodynamic interactions. If the droplets are identical, the centre of mass of the pair remains fixed. Here, we show that if the droplets have different properties, the pair experiences a net motion due to non-reciprocal electrohydrodynamic interactions. We analyse the three-dimensional droplet trajectories using asymptotic theory, assuming spherical droplets and large separations, and numerical simulations based on a boundary integral method. The dynamics can be quite intricate depending on the initial orientation of the droplets line-of-centres relative to the applied field direction. Drops tend to migrate towards a configuration with line-of-centres either parallel or perpendicular to the applied field direction, while either coming into contact or indefinitely separating. We elucidate the conditions under which these different interaction scenarios take place. Intriguingly, we find that in some cases droplets can form a pair (tandem) that translates either parallel or perpendicular to the applied field direction. 

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5. Spray Mechanism of Contained-Electrospray Ionization

   https://doi.org/10.1021/jasms.0c00044  

   Miller, Colbert F.; Burris, Benjamin J.; Badu-Tawiah, Abraham K. (January 2020, Journal of the American Society for Mass Spectrometry)

   Analytical characteristics of contained electrospray ionization (ESI) are summarized in terms of its potential to modify the analyte solution during the stages of droplet formation to provide opportunities to generate native versus denatured biomolecular gas-phase ions, without the need for bulk-phase analyte modifications. The real-time modification of the charged microdroplets occurs in a cavity that is included in the outlet of the contained-ESI ion source. Close examination of the inside of the cavity using a high-speed camera revealed the formation of discrete droplets as well as thin liquid films in the droplets wake. When operated at 20 psi N2 pressure, the droplets were observed to move at an average speed of 8 mm/s providing ∼1 s mixing time in a 10 mm cavity length. Evidence is provided for the presence of highly reactive charged droplets based on myoglobin charge state distribution, apo-myoglobin contents, and ion mobility drift time profiles under different spray conditions. Mechanistic insights for the capture of vapor-phase reagents and droplet dynamics as influenced by different operational modes are also described. 

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