Water Dramatically Accelerates the Decomposition of α-Hydroxyalkyl-Hydroperoxides in Aerosol Particles.
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ABSTRACT:
SUBMITTER: Qiu J
PROVIDER: S-EPMC6778917 | biostudies-literature |
REPOSITORIES: biostudies-literature
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Project description:Organic hydroperoxides (ROOHs) play key roles in the atmosphere as a reactive intermediate species. Due to the low volatility and high hydrophilicity, ROOHs are expected to reside in atmospheric condensed phases such as aerosols, fogs, and cloud droplets. The decomposition mechanisms of ROOHs in the liquid phase are, however, still poorly understood. Here we report a temperature-dependent kinetics and theoretical calculation study of the aqueous-phase decompositions of C12 or C13 α-alkoxyalkyl-hydroperoxides (α-AHs) derived from ozonolysis of α-terpineol in the presence of 1-propanol, 2-propanol, and ethanol. We found that the temporal profiles of α-AH signals, detected as chloride-adducts by negative ion electrospray mass spectrometry, showed single-exponential decay, and the derived first-order rate coefficient k for α-AH decomposition increased as temperature increased, e.g., k(288 K) = (5.3 ± 0.2) × 10-4 s-1, k(298 K) = (1.2 ± 0.3) × 10-3 s-1, k(308 K) = (2.1 ± 1.4) × 10-3 s-1 for C13 α-AHs derived from the reaction of α-terpineol Criegee intermediates with 1-propanol in the solution at pH 4.5. Arrhenius plot analysis yielded an activation energy (E a) of 12.3 ± 0.6 kcal mol-1. E a of 18.7 ± 0.3 and 13.8 ± 0.9 kcal mol-1 were also obtained for the decomposition of α-AHs (at pH 4.5) derived from the reaction of α-terpineol Criegee intermediates with 2-propanol and with ethanol, respectively. Based on the theoretical kinetic and thermodynamic calculations, we propose that a proton-catalyzed mechanism plays a central role in the decomposition of these α-AHs in acidic aqueous organic media, while water molecules may also participate in the decomposition pathways and affect the kinetics. The decomposition of α-AHs could act as a source of H2O2 and multifunctionalized species in atmospheric condensed phases.
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Project description:O-(1-Carboxy-1-alkyloxycarbonyl) hydroxamates were found to spontaneously decarboxylate in aqueous neutral buffer to form O-(2-hydroxyalkylcarbonyl) hydroxamates. While the former molecules do not react rapidly with serine β-lactamases, the latter are quite good substrates of representative class A and C, but not D, enzymes, and particularly of a class C enzyme. The enzymes catalyze hydrolysis of these compounds to a mixture of the α-hydroxy acid and hydroxamate. Analogous compounds containing aryloxy leaving groups rather that hydroxamates are also substrates. Structure-activity experiments showed that the α-hydroxyl group was required for any substantial substrate activity. Although both d- and l-α-hydroxy acid derivatives were substrates, the former were preferred. The response of the class C activity to pH and to alternative nucleophiles (methanol and d-phenylalanine) suggested that the same active site functional groups participated in catalysis as for classical substrates. Molecular modeling was employed to explore how the α-hydroxy group might interact with the class C β-lactamase active site. Incorporation of the α-hydroxyalkyl moiety into novel inhibitors will be of considerable interest.
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Project description:α-Mangostin, the extract from pericarp of Garcinia mangostana L . or mangosteen fruit, has been applied in various biomedical products because of its minimal skin irritation, and prominent anti-inflammatory, antimicrobial and immune-modulating activities. Owing to its low water solubility, the particle formulations are necessary for the applications of α-mangostin in aqueous media. The particle formulations are usually prepared using surfactants and/or polymers, usually at a larger amount of these auxiliaries than the amount of α-mangostin itself. Here, we show the self-assembly of α-mangostin molecules into water-dispersible particles without a need of any polymers/surfactants. Investigations on chemical structure, crystallinity and thermal properties of the obtained α-mangostin particles, in comparison to the conventional α-mangostin crystalline solid, confirm no formation of the new compound during the particle formation and suggest changes in intermolecular interactions among α-mangostin molecules and significantly more hydroxyl functionality positioned at the particles' surface. The ability of the water suspension of the α-mangostin to inhibit the growth of Propionibacterium acnes, the acne-causing bacteria, is similar to that of the solution of the conventional α-mangostin in 5% dimethyl sulfoxide. Moreover, at 12.7 ppm in an aqueous environment of RAW 264.7 cell culture, α-mangostin suspension exhibits five times higher anti-inflammatory activity than the conventional α-mangostin solution, with the same acceptable cytotoxicity of less than 20% cell death.
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Project description:Advancements in designing complex models for atmospheric aerosol science and aerosol-cloud interactions rely vitally on accurately measuring the physicochemical properties of microscopic particles. Optical tweezers are a laboratory-based platform that can provide access to such measurements as they are able to isolate individual particles from an ensemble. The surprising ability of a focused beam of light to trap and hold a single particle can be conceptually understood in the ray optics regime using momentum transfer and Newton's second law. The same radiation pressure that results in stable trapping will also exert a deforming optical stress on the surface of the particle. For micron-sized aqueous droplets held in the air, the deformation will be on the order of a few nanometers or less, clearly not observable through optical microscopy. In this study, we utilize cavity-enhanced Raman scattering and a phenomenon known as thermal locking to measure small deformations in optically trapped droplets. With the aid of light-scattering calculations and a model that balances the hydrostatic pressure, surface tension, and optical pressure across the air-droplet interface, we can accurately determine surface tension from our measurements. Our approach is applied to 2 systems of atmospheric interest: aqueous organic and inorganic aerosol.
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Project description:Large increases in the number of low earth orbit satellites are projected in the coming decades [L. Schulz, K.-H. Glassmeier, Adv. Space Res. 67, 1002-1025 (2021)] with perhaps 50,000 additional satellites in orbit by 2030 [GAO, Large constellations of satellites: Mitigating environmental and other effects (2022)]. When spent rocket bodies and defunct satellites reenter the atmosphere, they produce metal vapors that condense into aerosol particles that descend into the stratosphere. So far, models of spacecraft reentry have focused on understanding the hazard presented by objects that survive to the surface rather than on the fate of the metals that vaporize. Here, we show that metals that vaporized during spacecraft reentries can be clearly measured in stratospheric sulfuric acid particles. Over 20 elements from reentry were detected and were present in ratios consistent with alloys used in spacecraft. The mass of lithium, aluminum, copper, and lead from the reentry of spacecraft was found to exceed the cosmic dust influx of those metals. About 10% of stratospheric sulfuric acid particles larger than 120 nm in diameter contain aluminum and other elements from spacecraft reentry. Planned increases in the number of low earth orbit satellites within the next few decades could cause up to half of stratospheric sulfuric acid particles to contain metals from reentry. The influence of this level of metallic content on the properties of stratospheric aerosol is unknown.
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