Theoretical design of transition metal-doped oxo-triarylmethyl as a disposable platform for adsorption of ibuprofen.

Emerging environmental contaminants have become a crucial environmental issue because of the highly toxic effluents emitted by factories. Ibuprofen (IBP), as a typical anti-inflammatory drug, is frequently detected in water sources. Therefore, its removal using various adsorbents has drawn great interest. Herein, the structural, electronic, energetic, and optical properties of pristine oxo-triarylmethyl (oxTAM) and transition metal-doped oxo-triarylmethyl (TM@oxTAM, TM = Sc, Ti, V, Cr, and Mn) for adsorption of the IBU drug were investigated using density functional theory (DFT) calculations implemented in Gaussian and VASP codes. Frontier molecular orbital (FMO), density of states (DOS), and electronic band structure results demonstrated that transition metal-doped oxTAM causes a significant reduction in the energy band gap (Eg) value of pristine oxTAM, with the highest decrease (30.14 %) in the case of Mn@oxTAM. It was found that transition metal doping onto oxTAM leads to an increase in the adsorption energies (1.20-2.64 eV) and charge density between transition metal and IBU. Natural bond orbital (NBO) analysis revealed that charge was effectively transferred from the IBU towards the transition metal, which was further analyzed by charge decomposition analysis (CDA). Furthermore, quantum theory of atoms in molecules (QTAIM), interaction region indicator (IRI), electron localization function (ELF), and radial distribution function (RDF) analyses revealed that the IBU is adsorbed on the Sc@oxTAM surface via covalent interactions, while electrostatic with partially covalent interactions are dominated in other IBU/TM@oxTAM complexes. The results suggest that TM doping on the oxTAM provides a new insight for developing photocatalyst-based covalent organic frameworks (COFs) to remove emerging pollutants in wastewater.

Chitosan-based adsorptive membrane modified by carboxymethyl cellulose for heavy metal ion adsorption: Experimental and density functional theory investigations.

Low adsorption capacity and weak mechanical stability are the main drawbacks of chitosan (CS)-based adsorptive membranes for heavy metal ion removal. Polyvinyl alcohol (PVA) has been used to improve the mechanical stability of CS membranes, but adsorption capacity is disregarded. In the current study, the surface of the chitosan/polyvinyl alcohol (CP) membrane was modified using carboxymethyl cellulose (CMC) to increase its heavy metal ion adsorption capacity. Experimental and density functional theory (DFT) calculations were used to evaluate the heavy metal ion (As3+ and Cr3+) adsorption capabilities of CP and carboxymethyl cellulose-functionalized CP (CMC-CP) membranes. The batch adsorption process presented a higher heavy metal adsorption capacity of the CMC-CP membrane (As3+/CMC-CP = 234.78 mg/g and Cr3+/CMC-CP = 230.12 mg/g) compared to the CP membrane (As3+/CP = 89.02 mg/g and Cr3+/CP = 75.61 mg/g). The heavy metal/CMC-CP complexes confirmed higher adsorption energies (As3+/CMC-CP = -23.62 kcal/mol and Cr3+/CMC-CP = -23.21 kcal/mol) than the heavy metal/CP complexes (As3+/CP = -3.47 kcal/mol and Cr3+/CP = -2.92 kcal/mol). The electronic band structure was higher for CMC-CP (5.42 eV) compared to CP (4.43 eV). Experimental and theoretical findings were close, implying that the CMC-CP membrane has superior heavy metal adsorption capability than the CP membrane.

Aftershocks and Fluctuating Diffusivity.

The Omori-Utsu law shows the temporal power-law-like decrease of the frequency of earthquake aftershocks and, interestingly, is found in a variety of complex systems/phenomena exhibiting catastrophes. Now, it may be interpreted as a characteristic response of such systems to large events. Here, hierarchical dynamics with the fast and slow degrees of freedom is studied on the basis of the Fokker-Planck theory for the load-state distribution to formulate the law as a relaxation process, in which diffusion coefficient in the space of the load state is treated as a fluctuating slow variable. The evolution equation reduced from the full Fokker-Planck equation and its Green's function are analyzed for the subdynamics governing the load state as the fast degree of freedom. It is shown that the subsystem has the temporal translational invariance in the logarithmic time, not in the conventional time, and consequently the aging phenomenon appears.

γ-Iron Phase Stabilized at Room Temperature by Thermally Processed Graphene Oxide.

Stabilizing nanoparticles on surfaces, such as graphene, is a growing field of research. Thereby, iron particle stabilization on carbon materials is attractive and finds applications in charge-storage devices, catalysis, and others. In this work, we describe the discovery of iron nanoparticles with the face-centered cubic structure that was postulated not to exist at ambient conditions. In bulk, the γ-iron phase is formed only above 917 °C, and transforms back to the thermodynamically favored α-phase upon cooling. Here, with X-ray diffraction and Mössbauer spectroscopy we unambiguously demonstrate the unexpected room-temperature stability of the γ-phase of iron in the form of the austenitic nanoparticles with low carbon content from 0.60% through 0.93%. The nanoparticles have controllable diameter range from 30 nm through 200 nm. They are stabilized by a layer of Fe/C solid solution on the surface, serving as the buffer controlling carbon content in the core, and by a few-layer graphene as an outermost shell.