Chemical Detection by Analyte-Induced Change in Electrophoretic Deposition of Gold Nanoparticles

The electrophoretic deposition (EPD) of citrate-stabilized Au nanoparticles (cit-Au NPs) occurs on indium tin oxide (ITO)-coated glass electrodes upon electrochemical oxidation of hydroquinone (HQ) due to the release of hydronium ions. Anodic stripping voltammetry (ASV) for Au oxidation allows the determination of the amount of Au NP deposition under a specific EPD potential and time. The binding of Cr3+ to the cit-Au NPs inhibits the EPD by inducing aggregation and/or reducing the negative charge, which could lower the effective NP concentration of the cit-Au NPs and/or lower the electrophoretic mobility. This lowers the Au oxidation charge in the ASV, which acts as an indirect signal for Cr3+. The binding of melamine to cit-Au NPs similarly leads to aggregation and/or lowers the negative charge, also resulting in reduction of the ASV Au oxidation peak. The decrease in Au oxidation charge measured by ASV increases linearly with increasing Cr3+ and melamine concentration. The limit of detection (LOD) for Cr3+ is 21.1 ppb and 16.0 ppb for 15.1 and 4.1 nm diameter cit-Au NPs, respectively. Improving the sensing conditions allows for as low as 1 ppb detection of Cr3+. The LOD for melamine is 45.7 ppb for 4.1 nm Au NPs.

Alkali metal cations can inhibit non-covalent catalysis

The study concerns the effect of inorganic salts on supramolecular catalysis. The model reaction is the acid hydrolysis of the ammonium phenyl acetate derivative promoted by cucurbit[7]uril macrocycle. When salt is absent, the macrocycle is insensitive to the ionic strength of the solution, and the reaction rate linearly depends on the concentration of hydronium ions (H3O+). After the addition of inorganic salts, in particular, Na+ and K+ ions, the catalytic effect of the macrocycle is suppressed. The kinetic and binding data collected by us evidence the formation of the ternary complexes between the cations, macrocycle, and substrate, which are less prone to H3O+ attack. This type of inhibition corresponds to a rare uncompetitive model in contrast to a more common competitive one that relies on the displacement of the substrate. This study shows that special care must be taken when studying catalysis in solutions that contain metal cations, such as regular water and inorganic buffers.

Generation of ultrafast, transient, highly acidic pH spikes in the radiolysis of water at very high dose rates. Relevance for FLASH radiotherapy.

Monte Carlo multi-track chemistry simulations were carried out to study the effects of high dose rates on the transient yields of hydronium ions (H₃O⁺) formed during low linear energy transfer (LET) radiolysis of both pure, deaerated and aerated liquid water at 25 °C, in the interval ~1 ps–10 μs. Our simulation model consisted of randomly irradiating water with <i>N</i> interactive tracks of 300-MeV incident protons (LET ~ 0.3 keV/μm), which simultaneously impact perpendicularly on the water within a circular surface. The effect of the dose rate was studied by varying <i>N</i>. Our calculations showed that the radiolytic formation of H₃O⁺ causes the entire irradiated volume to temporarily become very acidic. The magnitude and duration of this abrupt “acid-spike” response depend on the value of <i>N</i>. It is most intense at times less than ~10–100 ns, equal to ~3.4 and 2.8 for <i>N</i> = 500 and 2000 (<i>i.e.</i>, for dose rates of ~1.9 × 10⁹ and 8.7 × 10⁹ Gy/s, respectively). At longer times, the pH gradually increases for all <i>N</i> values and eventually returns to the neutral value of seven, which corresponds to the non-radiolytic, pre-irradiation concentration of H₃O⁺. It is worth noting that these early acidic pH responses are very little dependent on the presence or absence of oxygen. Finally, given the importance of pH for many cellular functions, this study suggests that these acidic pH spikes may contribute to the normal tissue-sparing effect of FLASH radiotherapy.

Effects of Hydration and Temperature on the Microstructure and Transport Properties of Nafion Polyelectrolyte Membrane: A Molecular Dynamics Simulation

To investigate the effects of temperature and hydration on the microstructure of polymer electrolyte membrane and the transport of water molecules and hydronium ions, molecular dynamics simulations are performed on Nafion 117 for a series of water contents at different temperatures. The interactions among the sulfonate groups, hydronium ions, and water molecules are studied according to the analysis of radial distribution functions and coordination numbers. The sizes and connectivity of water clusters are also discussed, and it is found that the hydration level plays a key role in the phase separation of the membrane. However, the effect of the temperature is slight. When the water content increases from 3.5 to 16, the size of water clusters in the membrane increases, and the clusters connect to each other to form continuous channels for diffusion of water molecules and hydronium ions. The diffusion coefficients are estimated by studying the mean square displacements. The results show that the diffusion of water molecules and hydronium ions are both enhanced by the increase of the temperature and hydration level. Furthermore, the diffusion coefficient of water molecules is always much larger than that of hydronium ions. However, the ratio of the diffusion coefficient of water molecules to that of hydronium ions decreases with the increase of water content.

Expansive Growth vs. pH Reflects a Poisson Point Process of Binding/Unbinding Events in Plant Cell Walls

The paramount role of $$\mathrm{pH}$$ pH and temperature $$\left(T\right)$$ T in the expansive growth of a plant coleoptile/hypocotyl non-meristematic zone or plant and fungal cells was examined within the framework of the underlying chemical bond statistics in order to reproduce an experimental plot of growth vs. $$\mathrm{pH}$$ pH . Here, according to the definition, $$\mathrm{pH}=\mathrm{pH}\left({\mu }_{{\mathrm{H}}^{+}}\left(T\right), T\right)$$ pH = pH μ H + T , T is considered as a function of the chemical potential of the H+ (hydronium) ions ($${\mu }_{{\mathrm{H}}^{+}})$$ μ H + ) , as well as an implicit and explicit function of $$T$$ T . The derivation of the $$\mathrm{pH}$$ pH and $$T$$ T dependent expansive growth distribution from the Poisson statistics of the “tethers” that reproduce the chemical bonds between microfibrils was determined. The probability distribution for the attachment/detachment/reattachment events of the tethers that are connected to the microfibrils in the elongation zone was obtained. The two distinct but interrelated modes of the expansive growth, which are known as “acid growth” and “auxin growth” were distinguished in the analytic model, while the acid growth hypothesis was verified and confirmed at the semi-empirical and microscopic levels for the first time. Moreover, further perspectives, in which the macroscopic variables $$\left(P, V, T\right)$$ P , V , T with $$P$$ P standing for the turgor pressure and $$V$$ V for the cell volume, and the microscopic variables, $${E}^{{\varvec{d}},{\varvec{r}}}$$ E d , r , which represent the binding energies of the detachment/reattachment events at the expense of ATP energy, and $${\mu }_{{\mathrm{H}}^{+}}$$ μ H + can occur simultaneously, were identified. With a few assumptions that are partly based on experimental data it was possible to synthesise a link between the microscopic, explicit statistical explanation of bond dynamics and the macroscopic rheological properties of the cell wall at a given $$\mathrm{pH}$$ pH and temperature. A statistical description that predicted the importance of $$\mathrm{pH}$$ pH and temperature-dependent chemical potential of the H+ ions in microscopic events that result in growth would be supposedly applicable across scales.

Confinement effects and acid strength in zeolites

Chemical reactivity and sorption in zeolites are coupled to confinement and—to a lesser extent—to the acid strength of Brønsted acid sites (BAS). In presence of water the zeolite Brønsted acid sites eventually convert into hydronium ions. The gradual transition from zeolite Brønsted acid sites to hydronium ions in zeolites of varying pore size is examined by ab initio molecular dynamics combined with enhanced sampling based on Well-Tempered Metadynamics and a recently developed set of collective variables. While at low water content (1–2 water/BAS) the acidic protons prefer to be shared between zeolites and water, higher water contents (n > 2) invariably lead to solvation of the protons within a localized water cluster adjacent to the BAS. At low water loadings the standard free energy of the formed complexes is dominated by enthalpy and is associated with the acid strength of the BAS and the space around the site. Conversely, the entropy increases linearly with the concentration of waters in the pores, favors proton solvation and is independent of the pore size/shape.

Solvent molecules form surface redox mediators in situ and cocatalyze O2 reduction on Pd

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.

Proton Transfer in Bulk Water using the Full Adaptive QM/MM Method: Integration of Solute- and Solvent-Adaptive Approaches

<div><div>The quantum mechanical/molecular mechanical (QM/MM) method is a hybrid molecular simulation technique that increases the accessibility of local electronic structures of large systems.</div><div> The technique combines the benefit of accuracy found in the QM method and that of cost efficiency found in the MM method.</div><div> However, it is difficult to directly apply the QM/MM method to the dynamics of solution systems, particularly for proton transfer. </div><div> As explained in the Grotthuss mechanism, proton transfer is a structural interconversion between hydronium ions and solvent water molecules. </div><div> Hence, when the QM/MM method is applied, an adaptive treatment, namely on-the-fly revisions on molecular definitions, is required for both the solute and solvent. </div><div> Although several solvent-adaptive methods have been proposed, a full adaptive framework, which is an approach that also considers adaptation for solutes, remains untapped. In this paper, we propose a new numerical expression for the coordinates of the excess proton and its control algorithm.</div><div> Furthermore, we confirm that this method can stably and accurately simulate proton transfer dynamics in bulk water.</div></div>