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Fragment correlation mass spectrometry correlates ion pairs generated from the same fragmentation pathway, achieved by covariance mapping of tandem mass spectra generated with an unmodified linear ion trap without preseparation. We enable the identification of different precursors at different charge states in a complex mixture from a large isolation window, empowering an analytical approach for data-independent acquisition. The method resolves and matches isobaric fragments, internal ions, and disulfide bond fragments. We suggest that this method represents a major advance for analyzing structures of biopolymers in mixtures.
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We synthesized ammonia (NH3) by bubbling nitrogen (N2) gas into bulk liquid water (200 mL) containing 50 mg polytetrafluoroethylene (PTFE) particles (~5 µm in diameter) suspended with the help of a surfactant (Tween 20, ~0.05 vol.%) at room temperature (25 °C). Electron spin resonance spectroscopy and density functional theory calculations reveal that water acts as the proton donor for the reduction of N2. Moreover, isotopic labeling of the N2 gas shows that it is the source of nitrogen in the ammonia. We propose a mechanism for ammonia generation based on the activation of N2 caused by electron transfer and reduction processes driven by contact electrification. We optimized the pH of the PTFE suspension at 6.5 to 7.0 and employed ultrasonic mixing. We found an ammonia production rate of ~420 µmol L-1 h-1 per gram of PTFE particles for the conditions described above. This rate did not change more than 10% over an 8-h period of sustained reaction.
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Water microdroplets (7 to 11 µm average diameter, depending on flow rate) are sprayed in a closed chamber at ambient temperature, whose relative humidity (RH) is controlled. The resulting concentration of ROS (reactive oxygen species) formed in the microdroplets, measured by the amount of hydrogen peroxide (H2O2), is determined by nuclear magnetic resonance (NMR) and by spectrofluorimetric assays after the droplets are collected. The results are found to agree closely with one another. In addition, hydrated hydroxyl radical cations (â¢OH-H3O+) are recorded from the droplets using mass spectrometry and superoxide radical anions (â¢O2-) and hydroxyl radicals (â¢OH) by electron paramagnetic resonance spectroscopy. As the RH varies from 15 to 95%, the concentration of H2O2 shows a marked rise by a factor of about 3.5 in going from 15 to 50%, then levels off. By replacing the H2O of the sprayed water with deuterium oxide (D2O) but keeping the gas surrounding droplets with H2O, mass spectrometric analysis of the hydrated hydroxyl radical cations demonstrates that the water in the air plays a dominant role in producing H2O2 and other ROS, which accounts for the variation with RH. As RH increases, the droplet evaporation rate decreases. These two facts help us understand why viruses in droplets both survive better at low RH values, as found in indoor air in the wintertime, and are disinfected more effectively at higher RH values, as found in indoor air in the summertime, thus explaining the recognized seasonality of airborne viral infections.
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Water (H2O) microdroplets are sprayed onto a magnetic iron oxide (Fe3O4) and Nafion-coated graphite mesh using compressed N2 or air as the nebulizing gas. The resulting splash of microdroplets enters a mass spectrometer and is found to contain ammonia (NH3). This gas-liquid-solid heterogeneous catalytic system synthesizes ammonia in 0.2 ms. The conversion rate reaches 32.9 ± 1.38 nmol s-1 cm-2 at room temperature without application of an external electric potential and without irradiation. Water microdroplets are the hydrogen source for N2 in contact with Fe3O4. Hydrazine (H2NNH2) is also observed as a by-product and is suspected to be an intermediate in the formation of ammonia. This one-step nitrogen-fixation strategy to produce ammonia is eco-friendly and low cost, which converts widely available starting materials into a value-added product.
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Synthetic amorphous silica is a common food additive and a popular cosmetic ingredient. Mesoporous silica particles are also widely studied for their potential use in drug delivery and imaging applications because of their unique properties, such as tunable pore sizes, large surfaces areas, and assumed biocompatibility. Such a nanomaterial, when consisting of pure silicon dioxide, is generally considered to be chemically inert, but in this study, we showed that oxidation yields for different compounds were facilitated by simply incubating aqueous solutions with pure silica particles. Three thiol-containing molecules, L-cysteine, glutathione, and D-penicillamine, were studied separately, and it was found that more than 95% of oxidation happened after incubating any of these compounds with mesoporous silica particles in the dark for a day at room temperature. Oxidation increased over incubation time, and more oxidation was found for particles having larger surface areas. For nonporous silica particles at submicron ranges, yields of oxidation were different based on the structures of molecules, correlating with steric hindrance while accessing surfaces. We propose that the silyloxy radical (SiOâ¢) on silica surfaces is what facilitates oxidation. Density functional theory calculations were conducted for total energy changes for reactions between different aqueous species and silicon dioxide surfaces. These calculations identified two most plausible pathways of the lowest energy to generate SiO⢠radicals from water radical cations H2Oâ¢+ and hydroxyl radicals â¢OH, previously known to exist at water interfaces.
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Spontaneous generation of reactive oxygen species (ROS) in aqueous microdroplets or at a water vapor-silicate interface is a new source of redox chemistry. However, such generation occurs with difficulty in liquid water having a large ionic strength. We report that ROS is spontaneously produced when water vapor contacts hydrogen-bonded hydroxyl groups on a silicate surface. The evolution of hydrogen-bonded species such as hydroxyl groups was investigated by using two-dimensional, time-resolved FT-IR spectroscopy. The participation of water vapor in ROS generation is confirmed by investigating the reaction of D2O vapor and hydroxyl groups on a silicate surface. We propose a reaction pathway for ROS generation based on the change of the hydrogen-bonding network and corresponding electron transfer onto the silicate surface in the water vapor-solid contact process. Our observations suggest that ROS production from water vapor-silicate contact electrification could have contributed to oxidation during the Archean Eon before the Great Oxidation Event.
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Hydrogen peroxide (H2O2) plays a key role in environmental chemistry, biology, and medicine. H2O2 concentrations typically are 6 to 10 orders of magnitude lower than that of water, making its quantitative detection challenging. We demonstrate that optimized NMR spectroscopy allows direct, interference-free, quantitative measurements of H2O2 down to submicromolar levels in a wide range of fluids, ranging from exhaled breath and air condensate to rain, blood, urine, and saliva. NMR measurements confirm the previously reported spontaneous generation of H2O2 in microdroplets that form when condensing water vapor on a hydrophobic surface, which can interfere with atmospheric H2O2 measurements. Its antimicrobial activity and strong seasonal variation speculatively could be linked to the seasonality of respiratory viral diseases.
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Peróxido de Hidrógeno/análisis , Espectroscopía de Resonancia Magnética/métodos , Aire/análisis , Sangre , Análisis Químico de la Sangre , Líquidos Corporales/química , Espiración/fisiología , Heces/química , Humanos , Lluvia/química , Saliva/química , Orina/químicaRESUMEN
The anion of pyridine, C5H5N−, has been thought to be short lived in the gas phase and was only previously observed indirectly. In the condensed phase, C5H5N− is known to be stabilized by solvation with other molecules. We provide in this study striking results for the formation of isolated C5H5N− from microdroplets of water containing dissolved pyridine observed in the negative ion mass spectrum. The gas-phase lifetime of C5H5N− is estimated to be at least 50 ms, which is much longer than previously thought. The generated C5H5N− captured CO2 molecules to form a stable (Py-CO2)− complex, further confirming the existence of C5H5N−. We propose that the high electric field at the airwater interface of a microdroplet helps OH− to transfer an electron to pyridine to form C5H5N− and the hydroxyl radical â¢OH. Oxidation products of the Py reacting with â¢OH are also observed in the mass spectrum recorded in positive mode, which further supports this mechanism. The present study pushes the limits of the reducing and oxidizing power of water microdroplets to a new level, emphasizing how different the behavior of microdroplets can be from bulk water. We also note that the easy formation of C5H5N− in water microdroplets presents a green chemistry way to synthesize value-added chemicals.
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Contact electrification between water and a solid surface is crucial for physicochemical processes at water-solid interfaces. However, the nature of the involved processes remains poorly understood, especially in the initial stage of the interface formation. Here we report that H2O2 is spontaneously produced from the hydroxyl groups on the solid surface when contact occurred. The density of hydroxyl groups affects the H2O2 yield. The participation of hydroxyl groups in H2O2 generation is confirmed by mass spectrometric detection of 18O in the product of the reaction between 4-carboxyphenylboronic acid and 18O-labeled H2O2 resulting from 18O2 plasma treatment of the surface. We propose a model for H2O2 generation based on recombination of the hydroxyl radicals produced from the surface hydroxyl groups in the water-solid contact process. Our observations show that the spontaneous generation of H2O2 is universal on the surfaces of soil and atmospheric fine particles in a humid environment.
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Electricidad , Peróxido de Hidrógeno , Radical Hidroxilo , Agua , Atmósfera/química , Humedad , Peróxido de Hidrógeno/síntesis química , Peróxido de Hidrógeno/química , Radical Hidroxilo/química , Espectrometría de Masas , Isótopos de Oxígeno/análisis , Isótopos de Oxígeno/química , Tamaño de la Partícula , Suelo/química , Agua/químicaRESUMEN
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 D2O instead of H2O 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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Spraying water microdroplets containing 1,2,3-triazole (Tz) has been found to effectively convert gas-phase carbon dioxide (CO2), but not predissolved CO2, into formic acid (FA). Herein, we elucidate the reaction mechanism at the molecular level through quantum chemistry calculations and ab initio molecular dynamics (AIMD) simulations. Computations suggest a multistep reaction mechanism that initiates from the adsorption of CO2 by Tz to form a CO2-Tz complex (named reactant complex (RC)). Then, the RC either is reduced by electrons that were generated at the air-liquid interface of the water microdroplet and then undergoes intramolecular proton transfer (PT) or switches the reduction and PT steps to form a [HCO2-(Tz-H)]- complex (named PC-). Subsequently, PC- undergoes reduction and the C-N bond dissociates to generate COOH- and [Tz-H]- (m/z = 69). COOH- easily converts to HCOOH and is captured at m/z = 45 in mass spectroscopy. Notably, the intramolecular PT step can be significantly lowered by the oriented electric field at the interface and a water-bridge mechanism. The mechanism is further confirmed by testing multiple azoles. The AIMD simulations reveal a novel proton transfer mechanism where water serves as a transporter and is shown to play an important role dynamically. Moreover, the transient â¢COOH captured by the experiment is proposed to be partly formed by the reaction with Hâ¢, pointing again to the importance of the air-water interface. This work provides valuable insight into the important mechanistic, kinetic, and dynamic features of converting gas-phase CO2 to valuable products by azoles or amines dissolved in water microdroplets.
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Liquid water provides the largest hydrogen reservoir on the earth's surface. Direct utilization of water as a source of hydrogen atoms and molecules is fundamental to the evolution of the ecosystem and industry. However, liquid water is an unfavorable electron donor for forming these hydrogen species owing to its redox inertness. We report oil-mediated electron extraction from water microdroplets, which is easily achieved by ultrasonically spraying an oil-water emulsion. Based on charge measurement and electron paramagnetic resonance spectroscopy, contact electrification between oil and a water microdroplet is demonstrated to be the origin of electron extraction from water molecules. This contact electrification results in enhanced charge separation and subsequent mutual neutralization, which enables a â¼13-fold increase of charge carriers in comparison with an ultrapure water spray, leading to a â¼16-fold increase of spray-sourced hydrogen that can hydrogenate CO2 to selectively produce CO. These findings emphasize the potential of charge separation enabled by spraying an emulsion of liquid water and a hydrophobic liquid in driving hydrogenation reactions.
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We report a technique for the noninvasive detection of skin cancer by imprint desorption electrospray ionization mass spectrometry imaging (DESI-MSI) using a transfer agent that is pressed against the tissue of interest. By noninvasively pressing a tape strip against human skin, metabolites, fatty acids, and lipids on the skin surface are transferred to the tape with little spatial distortion. Running DESI-MSI on the tape strip provides chemical images of the molecules on the skin surface, which are valuable for distinguishing cancer from healthy skin. Chemical components of the tissue imprint on the tape strip and the original basal cell carcinoma (BCC) section from the mass spectra show high consistency. By comparing MS images (about 150-µm resolution) of same molecules from the tape strip and from the BCC section, we confirm that chemical patterns are successfully transferred to the tape stripe. We also used the technique to distinguish cherry angiomas from normal human skin by comparing the molecular patterns from a tape strip. These results demonstrate the potential of the imprint DESI-MSI technique for the noninvasive detection of skin cancers as well as other skin diseases before and during clinical surgery.
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Carcinoma Basocelular , Neoplasias Cutáneas , Humanos , Espectrometría de Masa por Ionización de Electrospray/métodos , Neoplasias Cutáneas/diagnóstico por imagen , Carcinoma Basocelular/diagnóstico , Ácidos GrasosRESUMEN
Water microdroplets containing dissolved ammonia (30-300 µM) are sprayed through a copper oxide mesh with a 200 µm average pore size, resulting in the formation of nitrate (NO3-) and the release of molecular hydrogen (H2). The products result from a redox process that takes place at the liquid-solid interface through contact electrification, where no external potential is applied. Oxidation is initiated by superoxide radical anions (O2-) that originate from the oxygen in the air surrounding the microdroplets and from the hydroxyl radicals (OHâ¢) originating from the water-air interface. Two spin traps (TEMPO and DMPO) capture these radicals as well as NH2OH+â¢, HNO, NOâ¢, NO2â¢, and NOOH, which are detected by mass spectrometry. We also directly observed N2O2-⢠by the same means. We found that the hydrogen atom from the ammonia molecule can be set free not only in the form of H⢠but also as H2, which is detected using a residue gas analyzer. The oxidation process can be significantly enhanced by a factor of 3 when the sprayed microdroplets are irradiated with ultraviolet light (265 nm, 5 W). 35% of 300 µM ammonia can be degraded within 20 µs, and the nitrate conversion rate is estimated to be 15 nmol·mg-1·h-1.
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Water droplets are spraying into air using air as a nebulizing gas, and the droplets pass between two parallel metal plates with opposite charges. A high-speed camera records droplet trajectories in the uniform electric field, providing visual evidence for the Lenard effect, that is, smaller droplets are negatively charged whereas larger droplets are positively charged. By analyzing the velocities of the droplets between the metal plates, the charges on the droplets can be estimated. Some key observations include: (1) localized electric fields with intensities on the order of 109 V/m are generated, and charges are expected to jump (micro-lightening) between a positively charged larger droplet and the negatively charged smaller droplet as they separate; (2) the strength of the electric field is sufficiently powerful to ionize gases surrounding the droplets; and (3) observations in an open-air mass spectrometer reveal the presence of ions such as N2+, O2+, NO+, and NO2+. These findings provide new insight into the origins of some atmospheric ions and have implications for understanding ionization processes in the atmosphere and chemical transformations in water droplets, advancing knowledge in the field of aerosol science and water microdroplet chemistry.
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We report examples of C(sp2 )-N, C(sp2 )-S, and C(sp2 )-P bond-forming transformations in water microdroplets at room temperature and atmospheric pressure using N2 as a nebulizing gas. When an aqueous solution of vinylic acid and amine is electrosprayed (+3â kV), the corresponding C(sp2 )-N product is formed in a single step, which was characterized using mass spectrometry (MS) and tandem mass spectrometry (MS2 ). The scope of this reaction was extended to other amines and other unsaturated acids, including acrylic (CH2 =CHCOOH) and crotonic (CH3 CH=CHCOOH) acids. We also found that thiols and phosphines are viable nucleophiles, and the corresponding C(sp2 )-S and C(sp2 )-P products are observed in positive ion mode using MS and MS2 .
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Previous studies have shown that hydroxyl radicals can be formed at the water-gas surface of water microdroplets. We report the use of in situ generated hydroxyl radicals to carry out an organic transformation in one step, namely, the formation of anilines from aryl acids as well as both ammonia and primary/secondary amines via decarboxylation. Benzoic acids and amines are dissolved in water, and the solution is sprayed to form microdroplets whose chemical contents are analyzed mass spectrometrically. All intermediates and products are determined using mass spectrometry (MS) as well as in some cases tandem mass spectrometry (MS2). These results support the following reaction mechanism: NR2OH, formed via reaction of the amine with â¢OH, reacts with benzoic acid to form an isocyanate via a Lossen rearrangement. Hydrolysis followed by liberation of CO2 then delivers the aniline product. Notably, the scope of this transformation includes a variety of amines and aromatic acids and enables their conversion into aniline and N-substituted anilines, all in a single step. Additionally, this reaction occurs at room temperature and does not require metal catalysts or organic solvents.
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Ácidos Carboxílicos , Agua , Aminación , Ácidos Carboxílicos/química , Compuestos de Anilina/química , Aminas/química , Radical Hidroxilo , CatálisisRESUMEN
This paper describes the nature of the hydrogen bond (HB), B:---H-A, using valence bond theory (VBT). Our analysis shows that the most important HB interactions are polarization and charge transfer, and their corresponding sum displays a pattern that is identical for a variety of energy decomposition analysis (EDA) methods. Furthermore, the sum terms obtained with the different EDA methods correlate linearly with the corresponding VB quantities. The VBT analysis demonstrates that the total covalent-ionic resonance energy (RECS) of the HB portion (B---H in B:---H-A) correlates linearly with the dissociation energy of the HB, ΔEdiss. In principle, therefore, RECS(HB) can be determined by experiment. The VBT wavefunction reveals that the contributions of ionic structures to the HB increase the positive charge on the hydrogen of the corresponding external/free O-H bonds in, for example, the water dimer compared with a free water molecule. This increases the electric field of the external O-H bonds of water clusters and contributes to bringing about catalysis of reactions by water droplets and in water-hydrophobic interfaces.
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The properties of water microdroplets strikingly differ from bulk water. Using room-temperature water microdroplets, we find that toluene can react with CO2 to form phenylacetic acid in one step without any catalyst with negative high voltage applied at the sprayer source. The chemical components of these microdroplets are identified by mass spectrometry, and product structures are confirmed by tandem mass spectrometry. In this manner, we generate three drug molecules in a single step: 4-aminophenylacetic acid (epithelial peptide transporter PepT1 inhibitor), 3,4-dihydroxyphenylacetic acid (dopamine metabolite neurotransmitter), and phenylacetic acid (sodium salt form; treatment of urea cycle disorder). Mechanistic studies show that benzyl radicals formed from hydroxyl radicals at the water microdroplet interface drive these carboxylation reactions. This water microdroplet chemistry is general, allowing activation and subsequent carboxylation of aryl α-C-H groups.