Visualizing partial solvation at the air–water interface

Judd, Kenneth D.; Parsons, Sean W.; Eremin, Dmitry B.; Fokin, Valery V.; Dawlaty, Jahan M.

doi:10.1039/d4sc01311e

Cited by 4 publications

(1 citation statement)

References 85 publications

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“…These results underscore the presence of partial solvation at the interface and underscore the intricate interplay between hydrogen bonding and electrostatic potential, which can either facilitate or hinder the polarization of reactants, intermediates, or products at the interface. Understanding and fine-tuning interfacial reactivity hinges upon recognizing these dynamics. , We previously demonstrated the spontaneous formation of hydrogen peroxide in microdroplets and recently investigated the effect of relative humidity on this process, highlighting the importance of the gas–liquid interface in microdroplet chemistry . Organic peroxides (POs), consisting of organic compounds featuring peroxide (−O–O−) bonds, are commonly represented by the generic formula ROOR′, with R representing an organic group (e.g., alkyl, aryl, or acyl substituent), or R′ can be either a hydrogen atom for organic hydroperoxides (ROOH, which is also referred to as an HPO).…”

Section: Introductionmentioning

confidence: 99%

Water Microdroplets Surrounded by Alcohol Vapor Cause Spontaneous Oxidation of Alcohols to Organic Peroxides

Mofidfar,

Mehrgardi,

Zare

2024

J. Am. Chem. Soc.

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Using real-time mass spectrometric (MS) monitoring, we demonstrate one-step, catalyst-free spontaneous oxidation of various alcohols (ROH) to key reactive intermediates for the formation of ROO − compounds on the surface of water microdroplets surrounded by alcohol vapor, carried out under ambient conditions. These organic peroxides (POs) can act as important secondary organic aerosols (SOA). We used hydrogen− deuterium exchange by spraying D 2 O instead of H 2 O to learn about the reaction mechanism, and the results demonstrate the crucial role of the water−air interface in microdroplet chemistry. We find that the formation of POs relies on electron transfer occurring at the microdroplet interface, which generates hydrogen atoms and hydroxyl radicals that lead to a cascade of radical reactions. This electron transfer is believed to be driven by two factors: (1) the emergence of a strong electrostatic potential on the microdroplet's surface; and (2) the partial solvation of ions at the interface. Mass spectra reveal that the formation of POs is dependent on the alcohol structure, with tertiary alcohols showing a higher tendency to form organic peroxides than secondary alcohols, which in turn are more reactive than primary alcohols.

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Section: Introductionmentioning

confidence: 99%

Water Microdroplets Surrounded by Alcohol Vapor Cause Spontaneous Oxidation of Alcohols to Organic Peroxides

Mofidfar,

Mehrgardi,

Zare

2024

J. Am. Chem. Soc.

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Hybrid Planar Copolymer Membranes with Dual Functionality against Bacteria Growth

Bina,

Coats,

Skowicki

et al. 2024

Langmuir

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Antibacterial surfaces can be classified into two categories: passive surfaces, which repel bacteria by affecting surface wettability, and active surfaces, which have bactericidal properties that disrupt cell membranes upon contact. With the increasing demand for effective antibacterial solutions that combine these properties, advanced strategies are concentrating on developing surfaces with dual antimicrobial functionalities. Here, we present surfaces with nanotexture resulting from the phase separation of two different amphiphilic block copolymers displaying efficient dual functionality against bacteria growth. This approach combines the inherent antifouling properties of poly(ethylene oxide) as the hydrophilic domain of one copolymer with the antimicrobial effect of a peptide covalently attached to the hydrophilic domain of the second copolymer. The planar membranes are generated by self-assembly of the amphiphilic copolymer mixture deposited by Langmuir−Blodgett and Langmuir−Schaffer methods on a solid support, followed by covalent attachment of the antimicrobial peptides to one of the copolymers, specifically functionalized. Combining both copolymers, in terms of their properties and functionalities on the same surface, significantly limitsEscherichia colibiofilm formation and effectively eradicates bacteria during short-term incubation. While such multifunctional antimicrobial planar polymer membranes show promising potential in the design of fine coatings for small surgical or implantable devices, they are not limited to this application. Their use can be completely changed by attaching other active molecules or assemblies to induce specific multifunctionality for the targeted application.

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Rapid Exploration of Chemical Space by High-Throughput Desorption Electrospray Ionization Mass Spectrometry

Huang,

Morato,

Feng

et al. 2024

J. Am. Chem. Soc.

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This study leverages accelerated reactions at the solution/air interface of microdroplets generated by desorption electrospray ionization (DESI) to explore the chemical space. DESI is utilized to synthesize drug analogs at an overall rate of 1 reaction mixture per second, working on the low-nanogram scale. Transformations of multiple drug molecules at specific functionalities (phenol, hydroxyl, amino, carbonyl, phenyl, thiophenyl, and alkenyl) are achieved using electrophilic/nucleophilic, redox, C−H functionalization, and coupling reactions. These transformations occur under ambient conditions on the millisecond time scale with direct detection of products being successful in all but three of the reaction types studied. The large scope (22 bioactive compounds, >20 chemical transformations, and >300 functionalization reagents) and high speed (>3000 reactions/hour) provide access to a wide array of drug analogs that can be used for bioactivity testing. A total of ∼6800 unique reactions were examined through a data-driven workflow, and more than 3000 unique derivatives (∼44%) were identified tentatively by the m/z value and signal-to-control ratio in single-stage mass spectrometry (MS) analysis, with over 1000 being further characterized by tandem MS. The speed of the DESI-MS reaction screen provides potential advantages for emerging machine learning-based predictions of organic synthesis, and it sets the stage for future online DESI-MS bioassays and scaled-up microdroplet synthesis before formal characterization of hit compounds is sought using traditional methods of drug discovery.

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Visualizing partial solvation at the air–water interface

Abstract: To understand the solvation environment at the air–water interface, we use an azide vibrational reporter. The probe is sensitive to hydrogen bonding and electrostatics of the interface.

Cited by 4 publications

References 85 publications

Water Microdroplets Surrounded by Alcohol Vapor Cause Spontaneous Oxidation of Alcohols to Organic Peroxides

Water Microdroplets Surrounded by Alcohol Vapor Cause Spontaneous Oxidation of Alcohols to Organic Peroxides

Hybrid Planar Copolymer Membranes with Dual Functionality against Bacteria Growth

Rapid Exploration of Chemical Space by High-Throughput Desorption Electrospray Ionization Mass Spectrometry

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