An official website of the United States government
This work reports a new ATP-independent bioluminescent probe (bor-DTZ) for detecting hydrogen peroxide that is compatible with the Nanoluciferase enzyme. The probe is designed with an arylboronate ester protecting group appended to a diphenylterazine core via a self-immolative phenolate linker. Reaction with hydrogen peroxide reveals diphenylterazine, which can then react with Nanoluciferase to produce a detectable bioluminescent signal. Bor-DTZ shows a dose-dependent response to hydrogen peroxide and selectivity over other biologically relevant reactive oxygen species and can be applied to detect either intra- or extracellular species. We further demonstrate the ability of this platform to monitor fluxes in extracellular hydrogen peroxide in a breast cancer cell line in response to the anticancer treatment, cisplatin.
more »
« less
Hydrogen Peroxide Interference in Chemical Oxygen Demand Assessments of Plasma Treated Waters
Plasma-driven advanced oxidation represents a potential technology to safely re-use waters polluted with recalcitrant contaminants by mineralizing organics via reactions with hydroxyl radicals, thus relieving freshwater stress. The process results in some residual hydrogen peroxide, which can interfere with the standard method for assessing contaminant removal. In this work, methylene blue is used as a model contaminant to present a case in which this interference can impact the measured chemical oxygen demand of samples. Next, the magnitude of this interference is investigated by dosing de-ionized water with hydrogen peroxide via dielectric barrier discharge plasma jet and by solution. The chemical oxygen demand increases with increasing concentration of residual hydrogen peroxide. The interference factor should be considered when assessing the effectiveness of plasma to treat various wastewaters.
more »
« less
- Award ID(s):
- 1747739
- PAR ID:
- 10107717
- Date Published:
- Journal Name:
- Plasma
- Volume:
- 2
- Issue:
- 3
- ISSN:
- 2571-6182
- Page Range / eLocation ID:
- 294 to 302
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Graphene with in-plane nanoholes, named holey graphene, shows great potential in electrochemical applications due to its fast mass transport and improved electrochemical activity. Scalable nanomanufacturing of holey graphene is generally based on chemical etching using hydrogen peroxide to form through-the-thickness nanoholes on the basal plane of graphene. In this study, we probe into the fundamental mechanisms of nanohole formation under peroxide etching via an integrated experimental and computational effort. The research results show that the growth of nanoholes during the etching of graphene oxide is achieved by a three-stage reduction–oxidation–reduction procedure. First, it is demonstrated that vacancy defects are formed via a partial reduction-based pretreatment. Second, hydrogen peroxide reacts preferentially with the edge-sites of defect areas on graphene oxide sheets, leading to the formation of various oxygen-containing functional groups. Third, the carbon atoms around the defects are removed along with the neighboring carbon atoms via reduction. By advancing the understanding of process mechanisms, we further demonstrate an improved nanomanufacturing strategy, in which graphene oxide with a high density of defects is introduced for peroxide etching, leading to enhanced nanohole formation.more » « less
-
Plasma-based water purification involves the transport of reactive species across the gas–liquid interface. This process is limited by slow diffusion driven mass transport of reactive species across the interface. Additionally, the plasma gas–liquid contact area is typically limited, contributing to reduced dose delivery. These key factors make it difficult to scale up the treatment process to input flows of industrial interest. In this work, turbulence is explored as a means to introduce a fine grain structure, thus greatly increasing the interfacial surface area, leading to large property gradients and more efficient mass transport. Such a fine scale structure can also enhance the local electric field. The test apparatus explored in this work is the packed bed reactor that places thin water jets into contact with plasma. It is theorized that introducing turbulence, via increasing Reynolds number in such thin jets, may enhance the effective plasma dose at fixed plasma power. In this work, changes in the flow regime, from laminar to turbulent, of water jets in a packed bed water reactor (PBR) configuration are investigated experimentally. Methylene blue dye, a model contaminant, was tested in the PBR to demonstrate enhanced treatment via reduced treatment times. Plasma surface morphology around the jets noticeably changed with the flow regime, and turbulent flow demonstrated a faster hydrogen peroxide uptake, along with slower temperature, electrical conductivity, and a pH change in a batch treatment process, compared to laminar flow. The dye was destroyed significantly faster in the turbulent flow, indicating an increased effective plasma dose.more » « less
-
The Earth’s environment is full of reactive chemicals that can cause harm to organisms. One of the most common is hydrogen peroxide, which is produced by several bacteria in concentrations high enough to kill small animals, such as the roundworm Caenorhabditis elegans . Forced to live in close proximity to such perils, C. elegans have evolved defenses to ensure their survival, such as producing enzymes that can break down hydrogen peroxide. However, this battle is compounded by other factors. For instance, rising temperatures can increase the rate at which the hydrogen peroxide produced by bacteria reacts with the molecules and proteins of C. elegans . In 2020, a group of researchers found that roundworms sense these temperature changes through special cells called sensory neurons and use this information to control the generation of enzymes that break down hydrogen peroxide. This suggests that C. elegans may pre-emptively prepare their defenses against hydrogen peroxide in response to higher temperatures so they are better equipped to shield themselves from this harmful chemical. To test this theory, Servello et al. – including some of the authors involved in the 2020 study – exposed C. elegans to a species of bacteria that produces hydrogen peroxide. This revealed that the roundworms were better at dealing with the threat of hydrogen peroxide when growing in warmer temperatures. Experiments done in C. elegans lacking a class of sensory cells, the AFD neurons, showed that these neurons increased the roundworms’ resistance to the chemical when temperatures increase. They do this by repressing the activity of INS-39, a hormone that stops C. elegans from switching on their defense mechanism against peroxides. This is the first example of a multicellular organism preparing its defenses to a chemical after sensing something (such as temperature) that enhances its reactivity. It is possible that other animals may also use this ‘enhancer sensing' strategy to anticipate and shield themselves from hydrogen peroxide and potentially other external threats.more » « less
-
Solvent molecules influence the reactions of molecular hydrogen and oxygen on palladium nanoparticles. Organic solvents activate to form reactive surface intermediates that mediate oxygen reduction through pathways distinct from reactions in pure water. Kinetic measurements and ab initio quantum chemical calculations indicate that methanol and water cocatalyze oxygen reduction by facilitating proton-electron transfer reactions. Methanol generates hydroxymethyl intermediates on palladium surfaces that efficiently transfer protons and electrons to oxygen to form hydrogen peroxide and formaldehyde. Formaldehyde subsequently oxidizes hydrogen to regenerate hydroxymethyl. Water, on the other hand, heterolytically oxidizes hydrogen to produce hydronium ions and electrons that reduce oxygen. These findings suggest that reactions of solvent molecules at solid-liquid interfaces can generate redox mediators in situ and provide opportunities to substantially increase rates and selectivities for catalytic reactions.more » « less
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.3390/plasma2030021
