Second inflection point of supercooled water surface tension induced by hydrogen bonds: A molecular-dynamics study.

Surface tension of supercooled water is a fundamental property in various scientific processes. In this study, we perform molecular dynamics simulations with the TIP4P-2005 model to investigate the surface tension of supercooled water down to 220 K. Our results show a second inflection point (SIP) in the surface tension at temperature TSIP ≈ 267.5 ± 2.3 K. Using an extended IAPWS-E functional fit for the water surface tension, we calculate the surface excess internal-energy and entropy terms of the excess Helmholtz free energy. Similar to prior studies [Wang et al., Phys. Chem. Chem. Phys. 21, 3360 (2019); Gorfer et al., J. Chem. Phys. 158, 054503 (2023)], our results show that the surface tension is governed by two driving forces: a surface excess entropy change above the SIP and a surface excess internal-energy change below it. We study hydrogen-bonding near the SIP because it is the main cause of water's anomalous properties. With decreasing temperature, our results show that the entropy contribution to the surface tension reaches a maximum slightly below the SIP and then decreases. This is because the number of hydrogen bonds increases more slowly below the SIP. Moreover, the strengths and lifetimes of the hydrogen bonds also rise dramatically below the SIP, causing the internal-energy term to dominate the excess surface free energy. Thus, the SIP in the surface tension of supercooled TIP4P-2005 water is associated with an increase in the strengths and lifetimes of hydrogen bonds, along with a decrease in the formation rate (#/K) of new hydrogen bonds.

Dissociation Kinetics and Antimicrobial Activity of Ofloxacin Antibiotic in Artificial Tears Via 1H-NMR, Raman, and UV-Vis Spectroscopic Analysis.

Introduction: The hydrogen-bonded networks play a significant role in influencing several physicochemical properties of ofloxacin in artificial tears (ATs), including density, pH, viscosity, and self-diffusion coefficients. The activities of the ofloxacin antibiotic with Ats mixtures are not solely determined by their concentration but are also influenced by the strength of the hydrogen bonding network which highlight the importance of considering factors such as excessive tear production and dry eye conditions when formulating appropriate dosages of ofloxacin antibiotics for eye drops. Objectives: Investigating the physicochemical properties of ofloxacin-ATs mixtures, which serve as a model for understanding the impact of hydrogen bonding on the antimicrobial activity of ofloxacin antibiotic eye drops. Determine the antimicrobial activities of the ofloxacin-Ats mixture with different concentration of ofloxacin. Methods: The ofloxacin-ATs mixtures were analyzed using 1H-NMR, Raman, and UV-Vis spectroscopies, with variation of ofloxacin concentration to study its dissociation kinetics in ATs, mimicking its behavior in human eye tears. The investigation includes comprehensive analysis of 1H-NMR spectral data, self-diffusion coefficients, Raman spectroscopy, UV-Vis spectroscopy, liquid viscosity, and acidity, providing a comprehensive assessment of the physicochemical properties. Results: Analysis of NMR chemical shifts, linewidths, and self-diffusion coefficient curves reveals distinct patterns, with peaks or minima observed around 0.6 ofloxacin mole fraction dissociated in ATs, indicating a strong correlation with the hydrogen bonding network. Additionally, the pH data exhibits a similar trend to viscosity, suggesting an influence of the hydrogen bonding network on protonic ion concentrations. Antibacterial activity of the ofloxacin-ATs mixtures is evaluated through growth rate analysis against Salmonella typhimurium, considering varying concentrations with mole fractions of 0.1, 0.4, 0.6, 0.8, and 0.9. Conclusions: The antibiotic-ATs mixture with a mole fraction of 0.6 ofloxacin exhibited lower activity compared to mixtures with mole fractions of 0.1 and 0.4, despite its lower concentration. The activities of the mixtures are not solely dependent on concentration but are also influenced by the strength of the hydrogen bonding network. These findings emphasize the importance of considering tear over-secretion and dry eye problems when designing appropriate doses of ofloxacin antibiotics for eye drop formulations.

Surface Atomic Arrangement of Aluminum Ultra-Thin Layers Grown on Si(111).

Surface atomic arrangement and physical properties of aluminum ultrathin layers on c-Si(111)-7 × 7 and hydrogen-terminated c-Si(111)-1 × 1 surfaces deposited using molecular beam epitaxy were investigated. X-ray photoelectron spectroscopy spectra were collected in two configurations (take-off angle of 0° and 45°) to precisely determine the surface species. Moreover, 3D atomic force microscopy (AFM) images of the air-exposed samples were acquired to investigate the clustering formations in film structure. The deposition of the Al layers was monitored in situ using a reflection high-energy electron diffraction (RHEED) experiments to confirm the surface crystalline structure of the c-Si(111). The analysis of the RHEED patterns during the growth process suggests the settlement of aluminum atoms in Al(111)-1 × 1 clustered formations on both types of surfaces. The surface electrical conductivity in both configurations was tested against atmospheric oxidation. The results indicate differences in conductivity based on the formation of various alloys on the surface.

Treatment of olive mill effluent by adsorption on titanium oxide nanoparticles.

Olive mills wastewater (OMW) causes a serious environmental problem in the olive oil producing countries. This is due to its high organic matter content (COD), acidic pH values, suspended solids and high content of phytotoxic and antibacterial phenolic compounds. In this study, titanium dioxide (TiO2) as an adsorbent to reduce the COD value of the olive mill wastewater was investigated. Several variables were studied including the removal efficiency, effect of the initial COD value, amount of TiO2, temperature and pH value. The results revealed that the adsorption reached equilibrium within <120 min. Isotherm studies showed that the adsorption equilibrium data is in agreement with Freundlich isotherm. In addition, the results showed that the adsorption process was spontaneous and exothermic. The kinetic study indicated that adsorption did follow a pseudo-second order reaction. Variation of the amount of the TiO2 showed that using of 1.5 and 2 g/L of TiO2 caused the COD to drop from 1000 ppm to about 100 ppm (equilibrium concentration) in about 120 min. However, the use of 1 g/L of TiO2 exhibited almost the same effect on the COD-uptake, and the equilibrium concentration was about 400 ppm. The COD uptake was found to be inversely proportional with the temperature, pH value and the addition of salts such as sodium chloride (NaCl) and potassium chloride (KCl).

Anodic oxidation of slaughterhouse wastewater on boron-doped diamond: process variables effect.

A non-sacrificial boron-doped diamond electrode was prepared in the laboratory and used as a novel anode for electrochemical oxidation of poultry slaughterhouse wastewater. This wastewater poses environmental threats as it is characterized by a high content of recalcitrant organics. The influence of several process variables, applied current density, initial pH, supporting electrolyte nature, and concentration of electrocoagulant, on chemical oxygen demand (COD) removal, color removal, and turbidity removal was investigated. Results showed that raising the applied current density to 3.83 mA/cm2 has a positive effect on COD removal, color removal, and turbidity removal. These parameters increased to 100%, 90%, and 80% respectively. A low pH of 5 favored oxidants generation and consequently increased the COD removal percentage to reach 100%. Complete removal of COD had occurred in the presence of NaCl (1%) as supporting electrolyte. Na2SO4 demonstrated lower efficiency than NaCl in terms of COD removal. The COD decay kinetics follows the pseudo-first-order reaction. The simultaneous use of Na2SO4 and FeCl3 decreased the turbidity in wastewater by 98% due to electrocoagulation.