Insight into the glycerol extraction from biodiesel using deep eutectic solvents.

CONTEXT: The main challenge of large-scale biofuel production is related to the extraction of its undesired impurities including glycerol, water, methanol, soap/catalyst, free fatty acids, glycerides, and others. There are many ways to remove glycerol, and herein, the one alternative is the extraction of glycerol from biodiesel by deep eutectic solvents. In this regard, the mixture of a choline chloride (ChCl) and urea, methyltriphenylphosphonium chloride (MTPPCl), and ethylene glycol (EGL), as a deep eutectic solvent (DES), is effective in removing glycerol from biofuel. METHODS: In this work, we have investigated the formation mechanism of ChCl and urea, and then MTPPCl and EGL, as a DES, and then extraction of glycerol from biofuel via DES implementing density functional theory (DFT) by Gaussian09 software, B3LYP basis set, and classical all-atom molecular dynamics (MD) simulations by Gromacs software, GROMOS force field. DFT approximation demonstrates that Cl ion plays an important binding role in the formation of complexes ChCl/urea-based DES + biofuel and in MTPPCl/EGL-based DES + biofuel. We have also considered the formation and change of hydrogen bonds upon the formation of these systems using the DFT method. Large HOMO-LUMO gaps in ChCl/urea-based DES + biofuel and in MTPPCl/urea-based DES + biofuel demonstrate the stability of the complexes. The results of MD work have stated that the chloride ion formed bonding with the choline/ethylene glycol EGL, while still weakly intermolecular interacting with the urea/methyltriphenylphosphonium in ChCl/urea- and MTPPCl/EGL-based DESs. Further results of MD simulations stated that the DESs had a higher intermolecular interaction with glycerol in comparison with biofuel, thereby favoring the extraction process of glycerol from model biofuel. HIGHLIGHTS: • Intermolecular interactions of choline chloride and urea, methyl triphenyl phosphonium chloride, and ethylene glycol-based DESs and their applications in the extraction of glycerol from biofuel studied by DFT calculations and classical all-atom molecular dynamics simulations. • Calculated outputs of DFT calculations and classical all-atom molecular dynamics simulations for DESs and their applications in the extraction of glycerol from biofuel were discussed in detail. • The molecular formation mechanism of choline and methyl triphenyl phosphonium-based DESs and their application in the extraction process of glycerol from biofuel were summarized.

Health Risk Assessment of Nitrate in Drinking Water with Potential Source Identification: A Case Study in Almaty, Kazakhstan.

Infant mortality in Kazakhstan is six times higher compared with the EU. There are several reasons for this, but a partial reason might be that less than 30% of Kazakhstan's population has access to safe water and sanitation and more than 57% uses polluted groundwater from wells that do not comply with international standards. For example, nitrate pollution in surface and groundwater continues to increase due to intensified agriculture and the discharge of untreated wastewater, causing concerns regarding environmental and human health. For this reason, drinking water samples were collected from the water supply distribution network in eight districts of Almaty, Kazakhstan, and water quality constituents, including nitrate, were analyzed. In several districts, the nitrate concentration was above the WHO and Kazakhstan's maximum permissible limits for drinking water. The spatial distribution of high nitrate concentration in drinking water was shown to be strongly correlated with areas that are supplied with groundwater, whereas areas with lower nitrate levels are supplied with surface water sources. Based on source identification, it was shown that groundwater is likely polluted by mainly domestic wastewater. The health risk for infants, children, teenagers, and adults was assessed based on chronic daily intake, and the hazard quotient (HQ) of nitrate intake from drinking water was determined. The non-carcinogenic risks increased in the following manner: adult < teenager < child < infant. For infants and children, the HQ was greater than the acceptable level and higher than that of other age groups, thus pointing to infants and children as the most vulnerable age group due to drinking water intake in the study area. Different water management options are suggested to improve the health situation of the population now drinking nitrate-polluted groundwater.

Studying the Formation of Choline Chloride- and Glucose-Based Natural Deep Eutectic Solvent at the Molecular Level.

The liquid waste is the major source of waste, which usually generated from academic laboratories and industry during the extraction, separation, chemical synthesis, and pretreatment processes. These chemical and engineering processes require more solvents. In this regard, there is a need to develop more environmentally friendly, cheaper, non-toxic solvents that are harmless to humans and the environment. In this regard, deep eutectic solvents (DES) and their derivatives so-called natural deep eutectic solvents (NADES) are a new field in the search for green alternative solvents. In our work, the formation of choline chloride-based NADESs using density functional theory (DFT) calculations, and classical all-atom molecular dynamics (MD) simulation was studied in detail using Gaussian09 and Gromacs software's. Next, the ground state geometry optimizations were performed in the gas phase using DFT B3LYP 6-31 + G(d) level of theory. Moreover, classical all-atom MD simulations were implemented using Gromos force field. After the modeling and simulations, the DFT calculation results revealed the formation of NADESs via formation (creation) of binding between chlorine and choline, and chlorine and glucose. At the same time, the results of classical all-atom MD simulations, based on the time average of the equilibrated production run of MD simulations, stated that the nitrogen atom of choline ion and chloride ion has greater interactions, while chloride ion has also greater interaction with glucose during formation of NADES. The outcomes of both DFT and classical all-atom MD simulations are in good agreements.

Synthesis, Characterization and Antibacterial Application of Copolymers Based on N,N-Dimethyl Acrylamide and Acrylic Acid.

Hydrogel copolymers based on N,N-dimethyl acrylamide (DMA) and acrylic acid (AAc) were synthesized using a solution polymerization technique with different monomer ratios and ammonium persulfate as an initiator. This paper investigates the thermal stability, physical and chemical properties of the hydrogel copolymer. Testing includes Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), scanning electron microscopy (SEM) and elemental analysis (CHNS). The copolymer composition was determined by elemental analysis, and the reactivity ratios of monomers were calculated through linearization methods such as Fineman-Ross (FR), inverted Fineman-Ross (IFR), Kelen-Tudos (KT) and Mayo-Lewis (ML). Good agreement was observed between the results of all four methods. The ratio of r1 and r2 were 0.38 (r1) and 1.45 (r2) (FR), 0.38 (r1) and 1.46 (r2) (IFR), 0.38 (r1) and 1.43 (r2) (KT), and 0.38 (r1) and 1.45 (r2) (ML). Hydrogel copolymers exhibited good thermal stability, and SEM showed three-dimensional porous structures. Antibiotic-free and antibiotic-loaded hydrogels demonstrated antimicrobial properties against both Gram-positive and Gram-negative bacteria. As the ratio of DMA in hydrogel copolymer increased, the activity of copolymer against bacteria enhanced. The results indicated that these hydrogels have the potential to be used as antibacterial materials.