An official website of the United States government
Cold atmospheric pressure plasma (CAPP) is widely used in medicine for the treatment of diseases and disinfection of bio-tissues due to its antibacterial, antiviral, and antifungal properties. In agriculture, CAPP accelerates the imbibition and germination of seeds and significantly increases plant productivity. Plasma is also used to fix molecular nitrogen. CAPP can produce reactive oxygen and nitrogen species (RONS). Plasma treatment of bio-tissue can lead to numerous side effects such as lipid peroxidation, genotoxic problems, and DNA damage. The mechanisms of occurring side effects when treating various organisms with cold plasma are unknown since RONS, UV-Vis light, and multicomponent biological tissues are simultaneously involved in a heterogeneous environment. Here, we found that CAPP can induce in vitro oxidation of the most common water-soluble redox compounds in living cells such as NADH, NADPH, and vitamin C at interfaces between air, CAPP, and water. CAPP is not capable of reducing NAD+ and 1,4-benzoquinone, despite the presence of free electrons in CAPP. Prolonged plasma treatment of aqueous solutions of vitamin C, 1,4-hydroquinone, and 1,4-benzoquinone respectively, leads to their decomposition. Studies of the mechanisms in plasma-induced processes can help to prevent side effects in medicine, agriculture, and food disinfection.
more »
« less
This content will become publicly available on December 1, 2025
Electrochemical Reactions at the Boundary Areas Between Cold Atmospheric Pressure Plasma, Air, and Water
A cold atmospheric-pressure He-plasma jet (CAPPJ) interacts with air and water, producing reactive oxygen and nitrogen species (RONS), including biologically active ions, radicals, and molecules such as NOx, H2O2, HNO3, HNO2, and O3. These compounds can activate interfacial redox processes in biological tissues. The CAPPJ can oxidize N2 to HNO3 and water to H2O2 at the interface between plasma and water. It can also induce the oxidation of water-soluble redox compounds in various organisms and in vitro. This includes salicylic acid, hydroquinone, and mixtures of antioxidants such as L (+)-ascorbic acid sodium salt with NADPH. It can react with redox indicators, such as ferroin, in a three-phase system consisting of air, CAPPJ, and water. Without reducing agents in the water, the CAPPJ will oxidize the water and decrease the pH of the solution. When antioxidants such as ascorbate, 1,4-hydroquinone, or NADPH are present in the aqueous phase, the CAPPJ oxidizes these substances first and then oxidizes water to H2O2. The multielectron mechanisms of the redox reactions in the plasma-air/water interfacial area are discussed and analyzed.
more »
« less
- PAR ID:
- 10573713
- Publisher / Repository:
- Plasma
- Date Published:
- Journal Name:
- Plasma
- Volume:
- 7
- Issue:
- 4
- ISSN:
- 2571-6182
- Page Range / eLocation ID:
- 891 to 903
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
We report on the sensitivity of enhanced ozone (O3) production, observed during lake breeze circulation along the coastline of Lake Michigan, to the concentrations of nitrogen oxides (NOx = NO + NO2) and volatile organic compounds (VOCs). We assess the sensitivity of O3 production to NOx and VOC on a high O3 day during the Lake Michigan Ozone Study 2017 (LMOS 2017) using an observationally-constrained chemical box model that implements the Master Chemical Mechanism (MCM v3.3.1) and recent emission inventories for NOx and VOCs. The MCM model is coupled to a backward air mass trajectory analysis from a ground supersite in Zion, IL where an extensive series of measurements of O3 precursors and their oxidation products, including hydrogen peroxide (H2O2), nitric acid (HNO3), and particulate nitrates (NO3-) serve as model constraints. We evaluate the chemical evolution of the Chicago-Gary urban plume as it advects over Lake Michigan and demonstrate how modeled indicators of VOC- vs. NOx- sensitive regimes can be constrained by measurements at the trajectory endpoint. Using the modeled ratio of the instantaneous H2O2 and HNO3 production rates (PH2O2 / PHNO3), we suggest that O3 production over the urban source region is strongly VOC-sensitive and progresses towards a more NOx-sensitive regime as the plume advects north along the Lake Michigan coastline on this day. We also demonstrate that ground-based measurements of the mean concentration ratio of H2O2 to HNO3 describe the sensitivity of O3 production to VOC and NOx as the integral of chemical production along the plume path.more » « less
-
Probing Real Time Redox Events in Human Airway Epithelial Cells Exposed to an Environmental PeroxideAir pollutants such as ozone, particulate matter, and secondary organic aerosols (SOA) induce intracellular oxidative stress via the generation of reactive oxygen species (ROS). While ROS play important roles in regulating signaling pathways, supra-physiological levels disrupt redox homeostasis and potentiate inappropriate oxidation of regulatory thiols. We examined the effect of isoprene hydroxy hydroperoxide (ISOPOOH), an environmentally derived peroxide that contributes to SOA, on the interplay between bioenergetics and intracellular redox status. We used live cell imaging of human airway epithelial cells (HAECs) expressing the genetically encoded ratiometric biosensors roGFP, iNAP1, and HyPER, to monitor changes in the glutathione redox potential (EGSH), NADPH and H2O2, respectively. Non-cytotoxic exposure to ISOPOOH induced transient increases in EGSH in HAECs that were markedly potentiated by glucose deprivation. ISOPOOH-induced changes in EGSH were not driven by intracellular H2O2. Following ISOPOOH exposure, the addition of 1 mM glucose rapidly restored baseline EGSH and reversed ISOPOOH-induced reductions in NADPH levels, while lower concentrations of glucose (30 uM) induced a bi-modal EGSH recovery. Alternatively, the addition of the glycolytic inhibitor 2-deoxyglucose (2-DG) did not block recovery of NADPH levels nor EGSH restoration. To impair the recovery of EGSH and NADPH levels, we employed a lentiviral vector system to knockdown glucose-6-phosphate dehydrogenase (G6PD), a key enzyme involved in NADPH synthesis. The resulting G6PD knockdown (~50%) did not block glucose-mediated recovery of EGSH, implicating that a partial knockdown of G6PD may not be sufficient to manipulate NADPH levels and thereby EGSH. These findings underscore early mechanisms involved in the cellular response to ISOPOOH while providing a unique live view of the dynamic regulation of redox homeostasis in the human lung during exposure to environmental oxidants. THIS ABSTRACT OF A PROPOSED PRESENTATION DOES NOT NECESSARILY REFLECT EPA POLICY.more » « less
-
null (Ed.)Palladium(II)-catalyzed allylic acetoxylation has been the focus of extensive development and investigation. Methods that use molecular oxygen (O2) as the terminal oxidant typically benefit from the use of benzoquinone (BQ) and a transition-metal (TM) cocatalyst, such as Co(salophen), to support oxidation of Pd0 during catalytic turnover. We previously showed that Pd(OAc)2 and 4,5-diazafluoren-9-one (DAF) as an ancillary ligand catalyze allylic oxidation with O2 in the absence of cocatalysts. Herein, we show that BQ enhances DAF/Pd(OAc)2 catalytic activity, nearly matching the performance of reactions that include both BQ and Co(salophen). These observations are complemented by mechanistic studies of DAF/Pd(OAc)2 catalyst systems under three different oxidation conditions: (1) O2 alone, (2) O2 with cocatalytic BQ, and (3) O2 with cocatalytic BQ and Co(salophen). The beneficial effect of BQ in the absence of Co(salophen) is traced to the synergistic roles of O2 and BQ, both of which are capable of oxidizing Pd0 to PdII. The reaction of O2 generates H2O2 as a byproduct, which can oxidize hydroquinone to quinone in the presence of PdII. NMR spectroscopic studies, however, show that hydroquinone is the predominant redox state of the quinone cocatalyst in the absence of Co(salophen), while inclusion of Co(salophen) maintains oxidized quinone throughout the reaction, resulting in better reaction performance.more » « less
-
Abstract. We present a novel photolytic source of gas-phase NO3 suitable for use in atmospheric chemistry studies that has several advantages over traditional sources that utilize NO2 + O3 reactions and/or thermal dissociation of dinitrogen pentoxide (N2O5). The method generates NO3 via irradiation of aerated aqueous solutions of ceric ammonium nitrate (CAN, (NH4)2Ce(NO3)6) and nitric acid (HNO3) or sodium nitrate (NaNO3). We present experimental and model characterization of the NO3 formation potential of irradiated CAN / HNO3 and CAN / NaNO3 mixtures containing [CAN] = 10−3 to 1.0 M, [HNO3] = 1.0 to 6.0 M, [NaNO3] = 1.0 to 4.8 M, photon fluxes (I) ranging from 6.9 × 1014 to 1.0 × 1016 photons cm−2 s−1, and irradiation wavelengths ranging from 254 to 421 nm. NO3 mixing ratios ranging from parts per billion to parts per million by volume were achieved using this method. At the CAN solubility limit, maximum [NO3] was achieved using [HNO3] ≈ 3.0 to 6.0 M and UVA radiation (λmax = 369 nm) in CAN / HNO3 mixtures or [NaNO3] ≥ 1.0 M and UVC radiation (λmax = 254 nm) in CAN / NaNO3 mixtures. Other reactive nitrogen (NO2, N2O4, N2O5, N2O6, HNO2, HNO3, HNO4) and reactive oxygen (HO2, H2O2) species obtained from the irradiation of ceric nitrate mixtures were measured using a NOx analyzer and an iodide-adduct high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS). To assess the applicability of the method for studies of NO3-initiated oxidative aging processes, we generated and measured the chemical composition of oxygenated volatile organic compounds (OVOCs) and secondary organic aerosol (SOA) from the β-pinene + NO3 reaction using a Filter Inlet for Gases and AEROsols (FIGAERO) coupled to the HR-ToF-CIMS.more » « less
