A versatile method to fingerprint and compare the oxidative behaviour of lipids beyond their oxidative stability

: In this work we propose the use of isothermal thermogravimetry to evaluate the oxidative stability of a lipid and to evaluate how the glyceride composition affects the entire oxidative process, to quantify the oxidation undertaken by the lipid, and numerically compare the oxidative behaviour of different lipids. The innovative aspect of the present method lies in the acquisition of a prolonged "oxygen uptake" curve (4000-10,000 min) of a lipid under oxygen and in the development of a semi-empirical fitting equation for the experimental data. This provides the induction period (oxidative stability), and allows to evaluate the rate of oxidation, the rate and the magnitude of oxidative degradation, the overall mass loss and the mass of oxygen taken by the lipid upon time. The proposed approach is used to characterize the oxidation of different edible oils with different degrees of unsaturation (linseed oil, sunflower oil, and olive oil) as well as chemically simpler compounds used in the literature to model the autoxidation of vegetable oils and lipids in general: triglycerides (glyceryl trilinolenate, glyceryl trilinoleate and glyceryl trioleate) and methyl esters (methyl linoleate and methyl linolenate). The approach proves very robust and very sensitive to changes in the sample composition

Investigation of the LCST-Thermoresponsive Behavior of Novel Oligo(Ethylene Glycol)-Modified Pentafluorostyrene Homopolymers

Amphiphilic tetrafluorostyrene monomers (EFS8) carrying in the para position an oligoethylene glycol chain containing 8 oxyethylenic units on average were synthesized and used for preparation via activator regenerated by electron transfer atom transfer radical polymerization (ARGET-ATRP) of the corresponding amphiphilic homopolymers (pEFS8-x) with different degrees of polymerization (x = 26 and 46). Combining light transmittance and nano-differential scanning calorimetry (n-DSC) measurements revealed that pEFS8-x homopolymers displayed a lower critical solution temperature (LCST) thermoresponsive behavior in water solutions. Moreover, n-DSC measurements revealed the presence in heating scans of a broad endothermic peak ascribable to the dehydration process of the polymer single chains (unimers) and their collapse into aggregates. Consistently, dynamic light scattering (DLS) measurements showed below the LCST the presence of small nanostructures with a hydrodynamic diameter size Dh of 6–7 nm, which collapsed into concentration-dependent larger multichain aggregates (Dh = 300–3000 nm) above LCST. Interestingly, n-DSC data showed that the unimer-aggregate transition was reversible up to a specific temperature (Trev) of each homopolymer, which in any case was higher than Tmax. When heating above Trev the transition was no longer reversible, causing the shift of Tonset and Tmax at lower values, thus suggesting an increase in hydrophobicity of the polymer systems associated with a temperature-dependent dehydration process

Interactions between inorganic pigments and rabbit skin glue in reference paint reconstructions

The thermal degradation of rabbit skin glue, a collagen-based proteinaceous material used as a paint binder in paintings, was investigated in this paper. Paint reconstructions of the glue on its own or mixed with azurite (Cu3(CO3)2(OH)2), calcium carbonate (CaCO3), hematite (Fe2O3nH2O) and red lead (Pb3O4) were analysed using a thermoanalytical approach. This method enabled us to investigate the interactions between the glue and pigments before and after artificial indoor light ageing. The study was carried out using differential scanning calorimetry, thermogravimetry and thermogravimetry/FTIR analysis already successfully employed to characterize the paint binders. The results highlighted that all the inorganic pigments interact with rabbit skin glue, thus decreasing the thermal stability of the binder. Light ageing further decreased the thermal stability of pigmented paint replicas, suggesting a moderate increase in the rate of the degradation

Guidelines for a correct evaluation of deep eutectic solvents thermal stability

Deep eutectic solvents (DESs) are a class of versatile and green emerging materials. Despite the huge amounts of applications proposed in the last years, studies on their thermal stability are often missing. In this short review, we propose a guide for a correct evaluation of DES thermal stability, conducted mainly by dynamical thermogravimetry (TGA). We collected all the data reported in the literature on choline chloride (ChCl)-based DESs, as proof of concept to show the potentialities of the technique, highlighting all the parameters that need to be considered for a correct analysis, with particular attention to the possible sources of misleading interpretations (e.g. the adsorbed water, or the formation of undesired products during DES preparation). In many cases, the additional use of isothermal TGA, or TGA coupled with online techniques such as Fourier Infra-Red Spectroscopy or Mass Spectrometry, may help for the data interpretation. Besides, we summarize in a graph the degradation temperatures of many DESs and their precursors, intended as an operative guide to choosing the correct DES for different applications. The findings reported to date, highlight the potentialities of thermal analysis on DESs, as a powerful tool to obtain essential information on their applicability, and to implement the knowledge of their nanostructure from a molecular point of view

20 years of microwave technology developments using a coaxial antenna: From human health to green chemistry applications

The global interest on microwave assisted chemistry (MAC) is due to the important benefits for the sustainable growth of green chemical industries and environmentally friendly progress of society. MAC has been firstly developed using oven-type microwaves (MWs) assisted reactors, which requires difficult and expensive industrial scale-up. In 2002, the development of coaxial dipole antenna allowed a direct application of MWs in situ in the reaction media, opening a crucial, novel versatile technological solution, making MW-assisted processes feasible in any configuration at any industrial level. Here, we present an overview of the technological development of 20 years research using a coaxial MW antenna for green chemistry and human health applications. The major MW technology breakthroughs described in these short-review are: i) MW-induced thermoablation machine, ii) in situ MW heating in open glassware chemical reactors, iii) electrodeless MW/ultraviolet (UV) lamps and photoreactors, iv) MW-high pressure reactor and v) solventless/simultaneous MW/UV/ultrasound (US) configurations. Applications for the synthesis of nanocatalysts, nanoparticles and polymers, advanced oxidative decomposition photochemical processes, solvothermal extraction of valuable products and biomass processing are discussed. Remarks on the scaling up of the extraction processes and frontier applications addressed to the treatment of current and future outbreak pandemic emergences are also shown

Aquazol as a binder for retouching paints. An evaluation through analytical pyrolysis and thermal analysis

Aquazol poly (2-ethyl-oxazoline) is a tertiary aliphatic amide, with physical and chemical properties that are exploited in a variety of ways, from pharmaceutical applications to the conservation of cultural heritage. In this study, we evaluated the use of Aquazol as a new binder for retouching paint in the restoration of artworks. Aquazol 500 admixed with various formulations of organic red pigments was used to prepare paint replicas which were artificially aged and investigated by a multi-analytical approach based on analytical pyrolysis coupled with gas chromatography and mass spectrometry (Py-GC/MS), and thermogravimetry (TG), complemented by FTIR and LIBS spectroscopy. This is the first study on the ageing phenomena of Aquazol 500 using analytical pyrolysis and thermogravimetric analysis. The influence of the pigments' components on the pyrolysis behavior of Aquazol was also investigated. The paint replicas did not show significant modifications during artificial ageing. This thus highlights the optimal properties of Aquazol 500 as a binder for retouching, in addition to its already established suitability as a filler or consolidant in the restoration of artifacts. Interestingly, when Aquazol 500 is used in formulations containing organic pigments, Aquazol-pigment interactions are observed, strongly depending on the pigment used

Enthalpies of solution of organic compounds in water/octan-1-ol mixtures. II. Bifunctional saturated compounds

Limiting enthalpies of solution of several bifunctional compounds (1,2-dimethoxyethane, 2-methoxyethanamine, 2-methoxyethanol, 2-aminoethanol, 1,4-dioxane, morpholine, 4-methylmorpholine, 1-methylpiperazine) in water/octan-1-ol mixtures, with water content ranging from zero to saturation, have been determined at 25degreesC. The observed phenomenology has been interpreted according to a model of microphase transition involving the solvent medium. In the low water content range, water acts as prevailingly monodispersed, whereas above 0.1 mole fraction water the formation of pseudomicellar water aggregates can be inferred and a simple model of phase distribution can be applied to describe the observed trends