Policy-makers and researchers have been considering a shift from conventional fossil fuels to renewable sources due to the growing concerns over global warming and diminishing oil reserves. Biodiesel, a renewable bio-driven fuel, can be derived from vegetable oils and animal fats, and is considered to be bio-degradable, non-toxic and environmentally friendly. The cetane number and calorific power of biodiesel are quite similar to those of conventional diesel. Crude glycerol of about 10–20% by volume appears as a byproduct in biodiesel production. The increasing demand for biodiesel has led to a substantial increase of glycerol supply in the global market and a dramatic fall in the price of glycerol which has warranted alternative uses of glycerol. One potential way to deal with the crude glycerol overflow is to convert it to glycerol carbonate (GC) and use GC as a fuel or fuel additive. Prior studies have indicated that carbonate esters can significantly reduce particulate emissions during engine combustion. In this work, we have explored possible reaction pathways in the initial stage of glycerol carbonate pyrolysis. Ab initio/RRKM-master equation methods are employed to differentiate various reaction pathways and to obtain the pressure- and temperature-dependence of the major channels. We have found that glycerol carbonate decomposes almost exclusively to produce CO₂ and 3-hydroxypropanal over 800–2000 K and radical forming channels are unimportant. As 3-hydroxypropanal is one of the main products of GC decomposition, and aldehydes are known to have a very high impact on soot reduction, we conclude that GC has great potential for cleaner combustion as a fuel additive.

A kinetic and mechanistic investigation of the alcoholysis of phenyl isocyanate using 1-propanol as the alcohol was undertaken. A molecular mechanism of urethane formation in both alcohol and isocyanate excess is explored using a combination of an accurate fourth generation Gaussian thermochemistry (G4MP2) with the Solvent Model Density (SMD) implicit solvent model. These mechanisms were analyzed from an energetic point of view. According to the newly proposed two-step mechanism for isocyanate excess, allophanate is an intermediate towards urethane formation via six-centered transition state (TS) with a reaction barrier of 62.6 kJ/mol in the THF model. In the next step, synchronous 1,3-H shift between the nitrogens of allophanate and the cleavage of the C–N bond resulted in the release of the isocyanate and the formation of a urethane bond via a low-lying TS with 49.0 kJ/mol energy relative to the reactants. Arrhenius activation energies of the stoichiometric, alcohol excess and the isocyanate excess reactions were experimentally determined by means of HPLC technique. The activation energies for both the alcohol (measured in our recent work) and the isocyanate excess reactions were lower compared to that of the stoichiometric ratio, in agreement with the theoretical calculations.

A simplified, fast, and effective production method has been developed for the synthesis of manganese ferrite (MnFe₂O₄) magnetic nanoparticles (MNPs). In addition to the wide applicability of MnFe₂O₄ MNPs, this work also reports their application in DNA isolation for the first time. An ultrasonic-cavitation-assisted combustion method was applied in the synthesis of MnFe₂O₄ MNPs at different furnace temperatures (573 K, 623 K, 673 K, and 773 K) to optimize the particles’ properties. It was shown that MnFe₂O₄ nanoparticles synthesized at 573 K consist of a spinel phase only with adequate size and zeta potential distributions and superparamagnetic properties. It was also demonstrated that superparamagnetic manganese ferrite nanoparticles bind DNA in buffer with a high NaCl concentration (2.5 M), and the DNA desorbs from the MNPs by decreasing the NaCl concentration of the elution buffer. This resulted in a DNA yield comparable to that of commercial DNA extraction products. Both the DNA concentration measurements and electrophoresis confirmed that a high amount of isolated bacterial plasmid DNA (pDNA) with adequate purity can be extracted with MnFe₂O₄ (573 K) nanoparticles by applying the DNA extraction method proposed in this article.

The adsorption of formamide is studied both at the surface of crystalline (Ih) ice at 200 K and at the surface of low density amorphous (LDA) ice in the temperature range of 50 200 K by grand canonical Monte Carlo (GCMC) simulation. These systems are characteristic to the upper troposphere and to the interstellar medium (ISM), respectively. Our results reveal that, while no considerable amount of formamide is dissolved in the bulk ice phase in any case, the adsorption of formamide at the ice surface under these conditions is a very strongly preferred process, which has to be taken into account when studying the chemical reactivity in these environments. The adsorption is found to lead to the formation of multimolecular adsorption layer, the occurrence of which somewhat precedes the saturation of the first molecular layer. Due to the strong lateral interaction acting between the adsorbed formamide molecules, the adsorption isotherm does not follow the Langmuir shape. Adsorption is found to be slightly stronger on LDA than Ih ice under identical thermodynamic conditions, due to the larger surface area exposed to the adsorption. Indeed, the monomolecular adsorption capacity of the LDA and Ih ice surfaces is found to be 10.5 ± 0.7 micromol/m2 and 9.4 micromol/m2, respectively. The first layer formamide molecules are very strongly bound to the ice surface, forming typically four hydrogen bonds with each other and the surface water molecules. The heat of adsorption at infinitely low surface coverage is found to be 105.6 kJ/mol on Ih ice at 200 K.