Application of time domain nuclear magnetic resonance (TD-NMR) for study of the distillation curve of petroleum

Crude oil distillates are a highly useful industrial product, mainly for energy generation. Unfortunately, they are rarely studied, mainly due to the low accessibility to products directly obtained from the distillation process, which is a laborious, expensive, and time-consuming operation. This work presents and discusses the use of time-domain nuclear magnetic resonance (TD-NMR) as a simple, affordable, and straightforward tool for the development of correlations supported on the transverse relaxation time (T₂) and boiling temperature. The results point out a high convergence between TD-NMR experimental data and the ASTM D2892 method for distillates from light, medium, and heavy oils, with up to 52.20% of accumulated mass and boiling point temperature (T_b) up to 400°C. Furthermore, an unprecedented relationship between T₂ values and the accumulated mass of the distillates is first demonstrated. This new insight opens new perspectives for future prediction of accumulated mass for unknown crude oils, placing the TD-NMR relaxometry as an appeal spectroscopy approach with a potential to meaningfully contribute to the daily refining petrochemical industry field operations.     

Organic-Inorganic Hybrid Materials with the Ability to Bind Metal Ions: Calorimetric Properties and Thermostability

Organic-inorganic hybrid materials with excellent heavy metal ions chelating properties were synthesized by covalent bonding of multifunctional polymers of polyamidoamine (PAA) type onto silica. Two series of polyamidoamine-silica hybrid materials differing in the PAA chemical structure were prepared and their thermal properties were investigated. Differential Scanning Calorimetry was used to study the effects of chain immobilization and ion chelation on the glass-transition temperature (Tg) of the polymers. The Tg of PAA-hybrid materials was elevated with respect to ungrafted PAAs. Complex formation with metal ions such as Cu⁺⁺ or Co⁺⁺ caused total suppression of Tg for both linear polymers as well as the corresponding hybrid materials. Finally, the silica particles slightly influenced the decomposition temperatures of linear polymers increasing their thermal stability.     

Diffusion of Organic Vapors in Materials for Gas Sensing Application

Mass-variation measurements were carried out on carbon black (CB)-poly(vinyl chloride) (PVC) composite film with 40% by weight of di(2-ethylhexyl)-phthalate (DOP), cast on resonant piezo-layer (RPL) elements of lead zirconat titanate (PZT). Even if anomalous diffusion is predicted by fitting the data with M_t/M_∞=kt^α, the fractional uptake M_t/M_∞ is linear with the square root of the time up to M_t/M_∞=0.6, suggesting Fickian behavour. The anomalous values of α are probably due to experimental time lag. A dependence of the diffusion on the morphology of the material and the penetrant shape and flexibility has been found.     

Ligand-Free Pd-Catalyzed Reductive Mizoroki-Heck Reaction Strategy for the One-Pot Synthesis of Functionalized Oxygen Heterocycles in Deep Eutectic Solvents

A Deep Eutectic Solvent, choline chloride/glycerol (1 : 2 mol mol⁻¹), proved to be an effective and sustainable reaction medium to promote telescoped, one-pot Mizoroki-Heck cross-coupling/reduction processes between 2,3-dihydrofuran or 3,4-dihydro-2H-pyran and several (hetero)aryl halides to easily access valuable 2-(hetero)aryl tetrahydrofuran (THF) or tetrahydropyran derivatives in up to 95 % yield. Notably, the whole transformation takes place under aerobic conditions, in the absence of additional ligands, and with a good substrate scope. The practicability of the method is also exemplified by the sustainable synthesis of two key THF derivatives, which are side chains of pharmacologically relevant inhibitors of Kv1.2 channel.     

Blends Based on Polystyrene and Statistical Aromatic Copolycarbonates

The compatibility of polystyrene (PS) with aromatic copolycarbonates containing bisphenol A (BPA) and tetramethyl bisphenol A (TMBPA) was investigated. The simple prevision scheme developed by Sonja Krause was employed to evaluate the effect of the copolymer molecular structure on the miscibility with polystyrene. These prevision data were used to select copolycarbonates of potential interest. Statistical copolycarbonates (CPC) containing different BPA/TMBPA molar ratios were synthesised by polycondensation reaction between a mixture of the two monomers and phosgene. PS/polycarbonates blends, prepared by casting from chloroform solution, were studied with differential scanning calorimetry and optical microscopy to evaluate the components compatibility, which increases with the TMBPA copolymer content.