Versatile scaffold applications based on MoS2 quantum dots for imaging mitochondrial pH in living cells.

Sensitive and accurate detection and imaging of mitochondrial pH have become significant methods in biological and biomedical research to elucidate the biological functions of mitochondria. Herein, a mitochondria-targeted ratiometric fluorescent nanoprobe was developed to image mitochondrial pH in living cells. This nanoprobe was prepared by covalently linking a mitochondria-targeted ligand (triphenylphosphonium, TPP) and a pH recognition fluorescent indicator (rhodamine, RhB) onto the surface of MoS2 quantum dots (QDs). In this multifunctional fluorescent nanoprobe, MoS2 QDs serve not only as nanocarrier for the targeting ligand and pH fluorescent indicator, but also as a fluorescent reference for the ratiometric signal. Indeed, the fluorescence intensity of the MoS2 QDs is highly resistant to increasing proton concentrations, while that of RhB is sensitive to pH. Ratiometric detection of pH was carried out by comparing the pH-sensitive fluorescence of the RhB-based group with the pH-resistant fluorescence of MoS2 QDs. After uptake in living cells, the nanoprobe could stain mitochondria specifically, and allowed to image and monitor pH in mitochondria in a satisfactory manner.

A Hierarchical Theoretical Study of the Hydrogen Abstraction Reactions of H2/C1-C4 Molecules by the Methyl Peroxy Radical and Implications for Kinetic Modeling.

The hydrogen atom abstraction by the methyl peroxy radical (CH3O2) is an important reaction class in detailed chemical kinetic modeling of the autoignition properties of hydrocarbon fuels. Systematic theoretical studies are performed on this reaction class for H2/C1-C4 fuels, which is critical in the development of a base model for large fuels. The molecules include hydrogen, alkanes, alkenes, and alkynes with a carbon number from 1 to 4. The B2PLYP-D3/cc-pVTZ level of theory is employed to optimize the geometries of all of the reactants, transition states, and products and also the treatments of hindered rotation for lower frequency modes. Accurate benchmark calculations for abstraction reactions of hydrogen, methane, and ethylene with CH3O2 are performed by using the coupled cluster method with explicit inclusion of single and double electron excitations and perturbative inclusion of triple electron excitations (CCSD(T)), the domain-based local pair-natural orbital coupled cluster method (DLPNO-CCSD(T)), and the explicitly correlated CCSD(T)-F12 method with large basis sets. Reaction rate constants are computed via conventional transition state theory with quantum tunneling corrections. The computed rate constants are compared with literature values and those employed in detailed chemical kinetic mechanisms. The calculated rate constants are implemented into the recently developed NUIGMECH1.1 base model for kinetic modeling of ignition properties.

Benchmark calculations for bond dissociation energies and enthalpy of formation of chlorinated and brominated polycyclic aromatic hydrocarbons.

Thermodynamic properties, i.e., bond dissociation energies and enthalpy of formation, of chlorinated and brominated polycyclic aromatic hydrocarbons play a fundamental role in understanding their formation mechanisms and reactivity. Computational electronic structure calculations routinely used to predict thermodynamic properties of various species are limited for these compounds due to large computational cost to obtain accurate results by employing high-level wave function theory methods. In this work, a number of composite model chemistry methods (CBS-QB3, G3MP2, G3, and G4) are used to compute bond dissociation energies and enthalpies of formation of small to medium-size chlorinated and brominated polycyclic aromatic hydrocarbon compounds. The enthalpy of formation is derived via the atomization method and compared against the recommended values. Statistical analysis indicates that G4 is the best method. For comparison, three commonly used density functional theory (DFT) methods (M06-2X, ωB97X-D and B2PLYP-D3) with various basis sets including 6-311++G(d, p), cc-pVTZ, and cc-pVQZ in the prediction of bond dissociation energies and enthalpies of formation have been tested using the optimized geometries at the same M06-2X/6-311++G(d, p) level of theory. It is found that ωB97X-D/6-311++G(d, p) shows the best performance in computing the bond dissociation energies, while ωB97X-D/cc-pVTZ exhibits the best prediction in enthalpy of formation of the studied reaction systems. The structural effect on the bond dissociation energies and enthalpy of formation of chlorinated and brominated polycyclic aromatic hydrocarbons are then systematically analyzed. Based on comparisons of the various methods, reliable DFT methods are recommended for future theoretical studies on large chlorinated and brominated polycyclic aromatic hydrocarbons considering both accuracy and computational cost. This work, to the authors' knowledge, is the first to systematically benchmark theoretical methods for the accurate prediction of thermodynamic properties for chlorinated and brominated polycyclic aromatic hydrocarbons.

Hyperbranched molecules having multiple functional groups as effective corrosion inhibitors for Al alloys in aqueous NaCl.

Hyperbranched molecules are a kind of promising materials due to their unique structures. In this work, two hyperbranched molecules (GON and GOH) are used as effective inhibitors for Al alloys in NaCl solution. Their inhibitive performances are evaluated by electrochemical measurements and surface characterization. The results indicate that inhibition performances of GON and GOH are closely related to the concentrations, influenced by the combination of steric hindrance and bonding effects. At relatively low concentrations (0.03-0.10 mM), GON displays a more pronounced ability to inhibit corrosion than GOH, owing to more anchoring functional groups. Oppositely, GOH has good inhibition performance at higher concentrations (0.50-1.00 mM). The interaction between the Al electrode and GOH results in the formation of a more condenser protective film than GON at high concentrations. In addition, the adsorption mechanism of two hyperbranched molecules is revealed by theoretical calculations.

Experimental and Theoretical Studies on the Corrosion Inhibition of Carbon Steel by Two Indazole Derivatives in HCl Medium.

In this work, two indazole derivatives, namely 5-aminoindazole (AIA) and 5-nitroindazole (NIA), were investigated as corrosion inhibitors for carbon steel in 1 M HCl solution by experimental and density functional theory (DFT) methods. The electrochemical results indicate that the inhibition ability follows the order of AIA > NIA, which is due to the stronger electron-donating effect of -NH2 of the AIA group than the -NO2 group of NIA. Besides, the frontier orbital theory shows that the AIA exhibits higher reaction activity than NIA, and a more negative adsorption energy for AIA was also obtained, which is consistent with the analysis of the electrochemical measurements. We draw the conclusion that the electron-donating effect makes it easier for AIA to donate electrons to iron atoms to form a stronger protective layer than NIA.

Experimental and theoretical studies on the corrosion inhibition of copper by two indazole derivatives in 3.0% NaCl solution.

Corrosion experiments and theoretical calculations were performed to investigate the inhibition mechanism of indazole (IA) and 5-aminoindazole (AIA) for copper in NaCl solution. The results obtained from weight loss and electrochemical experiments are in good agreement, and reveal that these compounds are high-efficiency inhibitors with inhibition efficiency order: AIA>IA, which was further confirmed by field emission scanning electronic microscope (FESEM) observation. Besides, the quantum chemical calculations and molecular dynamics (MD) simulation showed that both studied inhibitors are adsorbed strongly on the copper surface in parallel mode. The adsorption of these molecules on copper substrate was found to obey Langmuir isotherm.