(N-Alkyloxalamido)-Amino Acid Amides as the Superior Thixotropic Phase Selective Gelators of Petrol and Diesel Fuels.

(N-Alkyloxalamido)-amino acid amides 9-12 exhibit excellent gelation capacities toward some lipophilic solvents as well as toward the commercial fuels, petrol and diesel. Gelator 10 exhibits an excellent phase-selective gelation (PSG) ability and also possesses the highest gelation capacity toward petrol and diesel known to date, with minimum gelation concentration (MGC) values (%, w/v) as low as 0.012 and 0.015, respectively. The self-assembly motif of 10 in petrol and toluene gel fibres is determined from xerogel X-ray powder diffraction (XRPD) data via the simulated annealing procedure (SA) implemented in the EXPO2014 program and refined using the Rietveld method. The elucidated motif is strongly supported by the NMR (NOE and variable temperature) study of 10 toluene-d8 gel. It is shown that the triple unidirectional hydrogen bonding between gelator molecules involving oxalamide and carboxamide groups, together with their very low solubility, results in the formation of gel fibres of a very high aspect ratio (d = 10-30 nm, l = 0.6-1.3 µm), resulting in the as-yet unprecedented capacity of gelling commercial fuels. Rheological measurements performed at low concentrations of 10 confirmed the strength of the self-assembled network with the desired thixotropic properties that are advantageous for multiple applications. Instantaneous phase-selective gelation was obtained at room temperature through the addition of the 10 solution to the biphasic mixture of diesel and water in which the carrier solvent was congealed along with the diesel phase. The superior gelling properties and PSG ability of 10 may be used for the development of more efficient marine and surface oil spill recovery and waste water treatment technologies as well as the development of safer fuel storage and transport technologies.

Self-Healing Oxalamide Organogelators of Vegetable Oil.

The aim of this study was to assess the gelling potential of chiral oxalamide derivatives in vegetable oils. Special emphasis was given to the potential applications of the examined oil gels as sustained delivery systems and as fat substitutes in food products. The applicability of oil gelators is envisaged in food, cosmetics, and the pharmaceutical industry. The regulations requiring the elimination of saturated fats and rising concerns among consumers health motivated us to investigate small organic molecules capable of efficiently transforming from liquid oil to a gel state. The oxalamide organogelators showed remarkable gelation efficiency in vegetable oils, thermal and mechanical stability, self-healing properties, and a long period of stability. The physical properties of the gels were analysed by TEM microscopy, DSC calorimetry, and oscillatory rheology. The controlled release properties of acetylsalicylic acid, ibuprofen, and hydrocortisone were analysed by the LC-MS method. The influence of the oil type (sunflower, soybean, and olive oil) on gelation efficiency of diverse oxalamide derivatives was examined by oscillatory rheology. The oxalamide gelators showed thermoreversible and thixotropic properties in vegetable oils with a minimum gelation concentration of just 0.025 wt%. The substitution of palm fats with gelled sunflower oil applied in cocoa and milk spreads at gelator concentrations lower than 0.2 wt% have shown promising viscoelastic properties compared to that of the original food products.

Rheological, Microstructural and Thermal Properties of Magnetic Poly(Ethylene Oxide)/Iron Oxide Nanocomposite Hydrogels Synthesized Using a One-Step Gamma-Irradiation Method.

Magnetic polymer gels are a new promising class of nanocomposite gels. In this work, magnetic PEO/iron oxide nanocomposite hydrogels were synthesized using the one-step -irradiation method starting from poly(ethylene oxide) (PEO) and iron(III) precursor alkaline aqueous suspensions followed by simultaneous crosslinking of PEO chains and reduction of Fe(III) precursor. -irradiation dose and concentrations of Fe3+, 2-propanol and PEO in the initial suspensions were varied and optimized. With 2-propanol and at high doses magnetic gels with embedded magnetite nanoparticles were obtained, as confirmed by XRD, SEM and Mössbauer spectrometry. The quantitative determination of -irradiation generated Fe2+ was performed using the 1,10-phenanthroline method. The maximal Fe2+ molar fraction of 0.55 was achieved at 300 kGy, pH = 12 and initial 5% of Fe3+. The DSC and rheological measurements confirmed the formation of a well-structured network. The thermal and rheological properties of gels depended on the dose, PEO concentration and initial Fe3+ content (amount of nanoparticles synthesized inside gels). More amorphous and stronger gels were formed at higher dose and higher nanoparticle content. The properties of synthesized gels were determined by the presence of magnetic iron oxide nanoparticles, which acted as reinforcing agents and additional crosslinkers of PEO chains thus facilitating the one-step gel formation.

Chiral hexa- and nonamethylene-bridged bis(L-Leu-oxalamide) gelators: the first oxalamide gels containing aggregates with a chiral morphology.

Chiral amino acid- and amino alcohol-oxalamides are well-known as versatile and efficient gelators of various lipophilic and polar organic solvents and water. To further explore the capacity of the amino acid/oxalamide structural fragment as a gelation-generating motif, the dioxalamide dimethyl esters 1(6)Me and 1(9)Me, and dicarboxylic acid 2(6)OH/2(9)OH derivatives containing flexible methylene bridges with odd (9; n=7) and even (6; n=4) numbers of methylene groups were prepared. Their self-assembly motifs and gelation properties were studied by using a number of methods (FTIR, (1)H NMR spectroscopy, CD, TEM, DSC, XRPD, molecular modeling, MMFF94, and DFT). In contrast to the previously studied chiral bis(amino acid or amino alcohol) oxalamide gelators, in which no chiral morphology was ever observed in the gels, the conformationally more flexible 1(6)Me, 1(9)Me, 2(6)OH, and 2(9)OH provide gelators that are capable of forming diverse aggregates of achiral and chiral morphologies, such as helical fibers, twisted tapes, nanotubules, straight fibers, and tapes, in some cases coexisting in the same gel sample. It is shown that the differential scanning calorimetry (DSC)-determined gelation enthalpies could not be correlated with gelator and solvent clogP values. Spectroscopic results show that intermolecular hydrogen-bonding between the oxalamide units provides the major and self-assembly directing intermolecular interaction in the aggregates. Molecular modeling studies reveal that molecular flexibility of gelators due to the presence of the polymethylene bridges gives three conformations (zz, p1, and p2) close in energy, which could form oxalamide hydrogen-bonded layers. The aggregates of the p1 and p2 conformations tend to twist due to steric repulsion between neighboring iBu groups at chiral centers. The X-ray powder diffraction (XRPD) results of 1(6)Me and 1(9)Me, xerogels prove the formation of p1 and p2 gel aggregates, respectively. The latter results explain the formation of gel aggregates with chiral morphology and also the simultaneous presence of aggregates of diverse morphology in the same gel system.