An official website of the United States government
Abstract The chemical stability of 2D MXene nanosheets in aqueous dispersions must be maintained to foster their widespread application. MXene nanosheets react with water, which results in the degradation of their 2D structure into oxides and carbon residues. The latter detrimentally restricts the shelf life of MXene dispersions and devices. However, the mechanism of MXene degradation in aqueous environment has yet to be fully understood. In this work, the oxidation kinetics is investigated of Ti3C2Txand Ti2CTxin aqueous media as a function of initial pH values, ionic strengths, and nanosheet concentrations. The pH value of the dispersion is found to change with time as a result of MXene oxidation. Specifically, MXene oxidation is accelerated in basic media by their reaction with hydroxyl anions. It is also demonstrated that oxidation kinetics are strongly dependent on nanosheet dispersion concentration, in which oxidation is accelerated for lower MXene concentrations. Ionic strength does not strongly affect MXene oxidation. The authors also report that citric acid acts as an effective antioxidant and mitigates the oxidation of both Ti3C2Txand Ti2CTxMXenes. Reactive molecular dynamic simulations suggest that citric acid associates with the nanosheet edge to hinder the initiation of oxidation.
more »
« less
This content will become publicly available on June 9, 2026
Evaluation of pH and concentration effects on the antioxidant and pro-oxidant activities of lysine- and lysine methyl ester-based antioxidant tetramers, each containing four units of either syringaldehyde or vanillin
Previous studies indicated that antioxidant (AO)/pro-oxidant (PO) activities could depend on pH/concentrations. In this study, we examined how antioxidants with multiple hindered phenol rings are influenced by pH levels and concentrations.
more »
« less
- Award ID(s):
- 2320737
- PAR ID:
- 10627133
- Publisher / Repository:
- Royal Society of Chemistry
- Date Published:
- Journal Name:
- New Journal of Chemistry
- Volume:
- 49
- Issue:
- 23
- ISSN:
- 1144-0546
- Page Range / eLocation ID:
- 9779 to 9797
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
null (Ed.)Abstract Variation in soil organic C (%OC) concentration has been associated with the concentration of reactive Fe- and Al-oxyhydroxide phases and exchangeable Ca, with the relative importance of these two stabilizing components shifting as soil pH moves from acid to alkaline. However, it is currently unknown if this pattern is similar or different with regard to measures of soil C persistence. We sampled soils from 3 horizons (uppermost A, uppermost B, C or lowest B horizons) across a pH gradient of 11 grass-dominated and 13 deciduous/mixed forest-dominated NEON sites to examine similarities and differences in the drivers of C concentration and persistence. Variation in C concentrations in all soils could be linked to abundances of Fe, Al and Ca, but were not significantly linked to variation in soil C persistence. Though pH was related to variation in Δ 14 OC, higher persistence was associated with more alkaline pH values. In forested soils, depth explained 75% of the variation in Δ 14 OC ( p < 0.0001), with no significant additional correlations with extractable metal phases. In grasslands, soil organic C persistence was not associated with exchangeable Ca concentrations, but instead was explained by depth and inorganic C concentrations (R 2 = 0.76, p < 0.0001), implying stabilization of organic C through association with carbonate precipitation. In grasslands, measures of substrate quality suggested greater persistence is also associated with a more advanced degree of decomposition. Results suggest that explanatory variables associated with C concentrations differ from those associated with persistence, and that reactive Fe- and Al-oxyhydroxide phases may not be present in high enough concentrations in most soils to offer any significant protective capacity. These results have significant implications for our understanding of how to model the soil C cycle and may suggest previously unrecognized stabilization mechanisms associated with carbonates and forms of extractable Si.more » « less
-
Quantifying the Antioxidant Capacity of Inorganic Nanoparticles: Challenges and Analytical SolutionsAntioxidant properties of inorganic nanoparticles in aqueous media are attracting growing interest due to their high surface reactivity. Materials such as cerium oxide, iron oxide, silver, and gold exhibit distinct radical-scavenging behaviors at the nanoscale, but reliable quantification remains challenging. Conventional assays developed for molecular antioxidants cannot be directly applied because probes such as 2,2-diphenyl-1-picrylhydrazyl (DPPH) require methanol–water mixtures and are unstable in aqueous nanoparticle suspensions, while other assays are affected by nanoparticle-induced absorption or fluorescence changes. Here we demonstrate strategies to correct these interferences by independently measuring nanoparticle optical properties after oxidation and customizing assay conditions to account for the dilute, per-particle concentrations of nanomaterials. Using a high-throughput 96-well format, four adapted assays revealed that silver, ceria, and iron oxide nanoparticles possess substantially higher antioxidant capacities than Trolox, while gold showed negligible activity. This optimized approach enables reproducible comparison of nanoparticle antioxidants and provides a platform for tailoring nanostructures with enhanced radical-scavenging properties.more » « less
-
We show by extensive experimental characterization combined with molecular simulations that pH has a major impact on the assembly mechanism and properties of poly( l -lysine) (PLL) and poly( l -glutamic acid) (PGA) complexes. A combination of dynamic light scattering (DLS) and laser Doppler velocimetry (LDV) is used to assess the complexation, charge state, and other physical characteristics of the complexes, isothermal titration calorimetry (ITC) is used to examine the complexation thermodynamics, and circular dichroism (CD) is used to extract the polypeptides’ secondary structure. For enhanced analysis and interpretation of the data, analytical ultracentrifugation (AUC) is used to define the precise molecular weights and solution association of the peptides. Molecular dynamics simulations reveal the associated intra- and intermolecular binding changes in terms of intrinsic vs. extrinsic charge compensation, the role of hydrogen bonding, and secondary structure changes, aiding in the interpretation of the experimental data. We combine the data to reveal the pH dependency of PLL/PGA complexation and the associated molecular level mechanisms. This work shows that not only pH provides a means to control complex formation but also that the associated changes in the secondary structure and binding conformation can be systematically used to control materials assembly. This gives access to rational design of peptide materials via pH control.more » « less
-
An investigation has been carried out to understand the solution chemistry of the Cu-NH−-SO4−2 system, focusing on the effect of pH on the solubility of copper in the solution and maximizing the Cu(I):Cu(II) ratio. A Pourbaix diagram for the Cu-N-S system has also been created using the HSC Chemistry software for a wide range of Cu-NH3 species, unlike most other studies that focused only on Cu(NH3)42+ and Cu(NH3)52+ (Cu(II)) as the dominant species. The Pourbaix diagram demonstrated that the Cu(I) exists as Cu(NH3)2+, while the Cu(II) species are present in the system as Cu(NH3)42+ and Cu(NH3)52+, depending upon the Eh and pH of the solution. Copper precipitation was observed in the electrolyte at pH values less than 8.0, and the precipitation behavior increased as the pH became acidic. The highest Cu(I):Cu(II) ratio was observed at higher pH values of 10.05 due to the higher solubility of copper at higher alkaline pH. The maximum Cu(II) concentration can be achieved at 4.0 M NH4OH and 0.76 M (NH4)2SO4. In the case of low pH, the highest Cu(I):Cu(II) ratio obtained was 0.91 against the 4.0 M and 0.25 M concentrations of NH4OH and (NH4)2SO4, respectively. Meanwhile, at high pH, the maximum Cu(I):Cu(II) ratio was 15.11 against the 0.25 M (NH4)2SO4 and 4.0 M NH4OH. Furthermore, the low pH experiments showed the equilibrium constant (K) K < 1, and the high pH experiments demonstrated K > 1, which justified the lower and higher copper concentrations in the solution, respectively.more » « less
