Nanostructured Poly-l-lactide and Polyglycerol Adipate Carriers for the Encapsulation of Usnic Acid: A Promising Approach for Hepatoprotection.

The present study investigates the utilization of nanoparticles based on poly-l-lactide (PLLA) and polyglycerol adipate (PGA), alone and blended, for the encapsulation of usnic acid (UA), a potent natural compound with various therapeutic properties including antimicrobial and anticancer activities. The development of these carriers offers an innovative approach to overcome the challenges associated with usnic acid's limited aqueous solubility, bioavailability, and hepatotoxicity. The nanosystems were characterized according to their physicochemical properties (among others, size, zeta potential, thermal properties), apparent aqueous solubility, and in vitro cytotoxicity. Interestingly, the nanocarrier obtained with the PLLA-PGA 50/50 weight ratio blend showed both the lowest size and the highest UA apparent solubility as well as the ability to decrease UA cytotoxicity towards human hepatocytes (HepG2 cells). This research opens new avenues for the effective utilization of these highly degradable and biocompatible PLLA-PGA blends as nanocarriers for reducing the cytotoxicity of usnic acid.

A Comprehensive Review on the Thermal Stability Assessment of Polymers and Composites for Aeronautics and Space Applications.

This review article provides an exhaustive survey on experimental investigations regarding the thermal stability assessment of polymers and polymer-based composites intended for applications in the aeronautical and space fields. This review aims to: (1) come up with a systematic and critical overview of the state-of-the-art knowledge and research on the thermal stability of various polymers and composites, such as polyimides, epoxy composites, and carbon-filled composites; (2) identify the key factors, mechanisms, methods, and challenges that affect the thermal stability of polymers and composites, such as the temperature, radiation, oxygen, and degradation; (3) highlight the current and potential applications, benefits, limitations, and opportunities of polymers and composites with high thermal stability, such as thermal control, structural reinforcement, protection, and energy conversion; (4) give a glimpse of future research directions by providing indications for improving the thermal stability of polymers and composites, such as novel materials, hybrid composites, smart materials, and advanced processing methods. In this context, thermal analysis plays a crucial role in the development of polyimide-based materials for the radiation shielding of space solar cells or spacecraft components. The main strategies that have been explored to improve the processability, optical transparency, and radiation resistance of polyimide-based materials without compromising their thermal stability are highlighted. The combination of different types of polyimides, such as linear and hyperbranched, as well as the incorporation of bulky pendant groups, are reported as routes for improving the mechanical behavior and optical transparency while retaining the thermal stability and radiation shielding properties. Furthermore, the thermal stability of polymer/carbon nanocomposites is discussed with particular reference to the role of the filler in radiation monitoring systems and electromagnetic interference shielding in the space environment. Finally, the thermal stability of epoxy-based composites and how it is influenced by the type and content of epoxy resin, curing agent, degree of cross-linking, and the addition of fillers or modifiers are critically reviewed. Some studies have reported that incorporating mesoporous silica micro-filler or microencapsulated phase change materials (MPCM) into epoxy resin can enhance its thermal stability and mechanical properties. The mesoporous silica composite exhibited the highest glass transition temperature and activation energy for thermal degradation among all the epoxy-silica nano/micro-composites. Indeed, an average activation energy value of 148.86 kJ/mol was recorded for the thermal degradation of unfilled epoxy resin. The maximum activation energy range was instead recorded for composites loaded with mesoporous microsilica. The EMC-5p50 sample showed the highest mean value of 217.6 kJ/mol. This remarkable enhancement was ascribed to the polymer invading the silica pores and forging formidable interfacial bonds.

Efficiency of municipal packaging waste recovery chain and suitability of separated residual waste fractions for use in alternative fuels production.

Due to the sheer quantity and quality of material, packaging waste is separately collected by municipal waste management systems, with a primary goal of its use in material recovery. The residual waste, i.e. rejected waste in the separation process can be energy recovered. Both recovery options have specific input material quality requirements. Therefore, it is important to know the characteristics of individual waste streams. This research analysed the composition and morphological characteristics of separately collected packaging waste from municipal waste management system, residual (rejected) waste fractions after separation steps and produced refuse-derived fuel (RDF). The efficiency of primary and secondary (manual) waste separation, as well as of the RDF production step, are tracked. Results show that primary waste separation produces material with under 7% of contaminants and secondary manual waste separation efficiency ranges between 45% and 55%. Physico-chemical comparison of simulated RDF strongly coincides with analysed properties of RDF as a final product which indicates very high separation efficiency in the RDF production. From the energy recovery/conversion standpoint, this can be quantified through deviations in the lower heating value (LHV) and the effective H/C molar ratio between simulated and real RDF samples, which are on the level of 1.8% and 1.1% respectively. The following conclusion can be made from the estimated relation between changes in separation efficiency and RDF energy-related characteristics; the separation efficiency of individual components plays important role in alternative fuel production as chemical compositions directly influence suitability for high-quality liquid fuel production. Results of this analysis shed a light on the connection between aspirations to increase material recovery share and the suitability of produced residual waste for further recovery and valorisation. The material and energetic valorisation are competitors, and further evaluation should be done to understand the investments needed to increase valuable fractions of wastes separation that, in turn, could diminish the energetic value of residual fractions and, therefore, the economic viability of energy recovery facilities.

Thermodynamic Study of Formamidinium Lead Iodide (CH5N2PbI3) from 5 to 357 K.

In the present study, the molar heat capacity of solid formamidinium lead iodide (CH5N2PbI3) was measured over the temperature range from 5 to 357 K using a precise automated adiabatic calorimeter. In the above temperature interval, three distinct phase transitions were found in ranges from 49 to 56 K, from 110 to 178 K, and from 264 to 277 K. The standard thermodynamic functions of the studied perovskite, namely the heat capacity C°p(T), enthalpy [H0(T) - H0(0)], entropy S0(T), and [G°(T) - H°(0)]/T, were calculated for the temperature range from 0 to 345 K based on the experimental data. Herein, the results are discussed and compared with those available in the literature as measured by nonclassical methods.

Thermodynamic and Kinetic Aspects of Formamidinium Lead Iodide Thermal Decomposition.

We report the results of a multi-technique study on the thermodynamics and kinetics of formamidinium lead iodide (FAPI) thermal decomposition. Thermodynamics was investigated by means of Knudsen effusion techniques. Kinetics was studied either by temperature-controlled powder X-ray diffraction or by two isoconversional treatments of differential scanning calorimetry data. FAPI appears to be much more thermally stable compared to methylammonium lead iodide, as predictable from the lower acidity of the formamidinium cation compared to methylammonium. The chemical processes responsible for its thermal degradation appear to be quite complex as highlighted by the composition of the gaseous phase evolved during the process. The apparent activation energy values of the decomposition obtained from X-ray diffraction (XRD) (112 ± 9 kJ/mol) and differential scanning calorimetry (DSC) measurements (205 ± 20 and 410 ± 20 kJ/mol, respectively, for the first and second decomposition steps identified by the deconvolution procedure) reflect the different steps of the process observed by the two techniques. The thermodynamic properties of the more important decomposition channels and the enthalpy of formation of FAPI were estimated by combining the results of Knudsen effusion measurements.

Synthesis, Structural, Morphological and Thermal Characterization of Five Different Silica-Polyethylene Glycol-Chlorogenic Acid Hybrid Materials.

The present study investigated the structure, morphology, thermal behavior, and bacterial growth analysis of novel three-component hybrid materials synthesized by the sol-gel method. The inorganic silica matrix was weakly bonded to the network of two organic components: a well-known polymer such as polyethylene glycol (PEG, average molar mass of about 4000 g/mol), and an antioxidant constituted by chlorogenic acid (CGA). In particular, a first series was made by a 50 wt% PEG-based (CGA-free) silica hybrid along with two 50 wt% PEG-based hybrids containing 10 and 20 wt% of CGA (denoted as SP50, SP50C10 and SP50C20, respectively). A second series contained a fixed amount of CGA (20 wt%) in silica-based hybrids: one was the PEG-free material (SC20) and the other two contained 12 and 50 wt% of PEG, respectively (SP12C20 and SP50C20, respectively), being the latter already included in the first series. The X-ray diffraction (XRD) patterns and scanning electron microscope (SEM) images of freshly prepared materials confirmed that all the materials were amorphous and homogeneous regardless of the content of PEG or CGA. The thermogravimetric (TG) analysis revealed a higher water content was adsorbed into the two component hybrids (SP50 and SC20) because of the availability of a larger number of H-bonds to be formed with water with respect to those of silica/PEG/CGA (SPC), where silica matrix was involved in these bonds with both organic components. Conversely, the PEG-rich materials (SP50C10 and SP50C20, both with 50 wt% of the polymer) retained a lower content of water. Decomposition of PEG and CGA occurred in almost the same temperature interval regardless of the content of each organic component. The antibacterial properties of the SiO2/PEG/CGA hybrid materials were studied in pellets using either Escherichia coli and Enterococcus faecalis, respectively. Excellent antibacterial activity was found against both bacteria regardless of the amount of polymer in the hybrids.

Valorization of the plastic residue from a WEEE treatment plant by pyrolysis.

The possibility of a pyrolysis process as a mean of recycling the residual plastic rich fraction (WEEE residue) derived from of a material recovery facility has been evaluated. The unknown product composition of WEEE residue has been supposed through coupled thermal - infrared analysis and ultimate analysis and resulted as PP 3 wt%, PBT 3 wt%, PVC 4 wt%, styrene-based polymers (principally ABS) 50 wt%, thermosetting resins (principally, epoxy/phenolic resins) 24 wt%, inorganic fraction (principally fiber glass) 16 wt%. DSC experiments showed that the overall energy, defined as the degradation heat, needed in order to completely degrade WEEE residue was about 4% of the exploitable energy of the input material. The effect of temperature and different zeolite catalysts were investigated, in particular in terms of yield and quality of the produced oils during the pyrolysis process. Produced oils were potentially exploitable as fuels and almost all catalysts improved their quality. The best performance was reached by NaUSY(5.7) with the second highest production of light oil and the greatest total monoaromatics yield, plus 12 wt% in comparison to thermal pyrolysis experiments. Furthermore, light oil produced by NaUSY(5.7) has one of the best LHV (36 MJ/kg) and no halogenated compounds were detected by GC-MS analysis. Char or pyrolytic gas combustion could supply the energy required for the thermal degradation of WEEE Residue.

Stabilizing lead halide perovskites with quaternary ammonium cations: the case of tetramethylammonium lead iodide.

Organoammonium lead halide perovskites, especially methylammonium lead iodide CH3NH3PbI3, are promising photovoltaic materials, but they are far from commercial applications due in particular to their thermal instability and moisture sensitivity. Here, we present a multitechnique study aimed at investigating the kinetic and thermodynamic stability of the simplest quaternary ammonium lead iodide, tetramethylammonium lead iodide N(CH3)4PbI3. The kinetics of thermal decomposition was studied by X-ray powder diffraction of samples treated in air at different temperatures combined with Rietveld quantitative phase analysis, and by the isoconversional analysis of differential thermal analysis measurements. Evidence for first order kinetics was obtained, with an activation energy of 280-290 kJ mol-1, suggesting that the breaking of the C-N bond is the rate determining step. The composition of the gas phase released under heating was investigated by Knudsen Effusion Mass Spectrometry, giving evidence for the occurrence of the process N(CH3)4PbI3(s) = PbI2(s) + N(CH3)3(g) + CH3I(g), consistent with the kinetic results. Decomposition pressures and thermodynamic properties were derived by Knudsen effusion mass loss experiments, obtaining values of 391.5 ± 2.0 kJ mol-1 and -577.4 ± 4.0 kJ mol-1 for the decomposition and formation enthalpies at 298 K, respectively. The reactivity towards water of N(CH3)4PbI3 was checked by XRD after total and prolonged immersion in water at room temperature. Overall, N(CH3)4PbI3 was found to be thermally much more stable than CH3NH3PbI3, both kinetically and thermodynamically, and much less prone to water-induced degradation, suggesting that the use of a quaternary ammonium cation may be an effective strategy in order to produce more stable materials.

Influence of the Heat Treatment on the Particles Size and on the Crystalline Phase of TiO2 Synthesized by the Sol-Gel Method.

Titanium biomaterials' response has been recognized to be affected by particles size, crystal structure, and surface properties. Chemical and structural properties of these nanoparticle materials are important, but their size is the key aspect. The aim of this study is the synthesis of TiO2 nanoparticles by the sol-gel method, which is an ideal technique to prepare nanomaterials at low temperature. The heat treatment can affect the structure of the final product and consequently its biological properties. For this reason, the chemical structure of the TiO2 nanoparticles synthesized was investigated after each heat treatment, in order to evaluate the presence of different phases formed among the nanoparticles. FTIR spectroscopy and XRD have been used to evaluate the different structures. The results of these analyses suggest that an increase of the calcination temperature induces the formation of mixed-crystalline-phases with different content of anatase and rutile phases. The results obtained by SEM measurements suggest that an increase in the particles size accompanied by a noticeable aggregation of TiO2 nanoparticles is due to high temperatures achieved during the thermal treatments and confirmed the presence of different content of the two crystalline phases of titanium dioxide.

Thermal Behavior and Structural Study of SiO2/Poly(ε-caprolactone) Hybrids Synthesized via Sol-Gel Method.

SiO2-based organic-inorganic hybrids (OIHs) are versatile materials whose properties may change significantly because of their thermal treatment. In fact, after their preparation at low temperature by the sol-gel method, they still have reactive silanol groups due to incomplete condensation reactions that can be removed by accelerating these processes upon heating them in controlled experimental conditions. In this study, the thermal behavior of pure SiO2 and four SiO2-based OIHs containing increasing amount (6, 12, 24 and 50 wt %) of poly(ε-caprolactone) (PCL) has been studied by simultaneous thermogravimetry (TG) and differential scanning calorimetry (DSC). The FTIR analysis of the gas mixture evolved at defined temperatures from the samples submitted to the TG experiments identified the mechanisms of thermally activated processes occurring upon heating. In particular, all samples already release ethanol at low temperature. Moreover, thermal degradation of PCL takes place in the richest-PCL sample, leading to 5-hexenoic acid, H2O, CO2, CO and ε-caprolactone. After the samples' treatment at 450, 600 and 1000 °C, the X-ray diffraction (XRD) spectra revealed that they were still amorphous, while the presence of cristobalite is found in the richest-PCL material.

Sol-Gel Synthesis, Spectroscopic and Thermal Behavior Study of SiO2/PEG Composites Containing Different Amount of Chlorogenic Acid.

In this work, new phenol-based materials have been synthesized by the sol-gel method, in which different amounts of the phenolic antioxidant chlorogenic acid (CGA) (from 5 wt % to 20 wt %) were embedded in two different silica matrices: pure silica and silica-based hybrids materials, containing 50 wt % of polyethylene glycol (PEG). The incorporation of CGA in different sol-gel matrices might protect them from degradation, which could cause the loss of their properties. The two series of materials were chemically characterized by Fourier transform infrared (FTIR) spectroscopy. In addition, the thermal behavior of both series of materials containing CGA was studied by thermogravimetry under both air and inert N2 flowing gas atmosphere. The bioactivity was evaluated by soaking the synthesized hybrids in a simulated body fluid, showing that the bioactivity of the silica matrix is not modified by the presence of PEG and CGA.

Synthesis, Characterization, and Electrochemical Behavior of LiMnxFe(1-x)PO4 Composites Obtained from Phenylphosphonate-Based Organic-Inorganic Hybrids.

The synthesis of organic-inorganic hybrid compounds based on phenylphosphonate and their use as precursors to form LiMnxFe(1-x)PO4 composites containing carbonaceous substances with sub-micrometric morphology are presented. The experimental procedure includes the preliminary synthesis of Fe2+ and/or Mn2+ phenylphosphonates with the general formula Fe(1-x)Mnx[(C6H5PO3)(H2O)] (with 0 < x < 1), which are then mixed at different molar ratios with lithium carbonate. In this way the carbon, obtained from in situ partial oxidation of the precursor organic part, coats the LiMnxFe(1-x)PO4 particles. After a structural and morphological characterization, the electrochemical behavior of lithium iron manganese phosphates has been compared to the one of pristine LiFePO4 and LiMnPO4, in order to evaluate the doping influence on the material.

Thermal and catalytic pyrolysis of a mixture of plastics from small waste electrical and electronic equipment (WEEE).

Pyrolysis seems a promising route for recycling of heterogeneous, contaminated and additives containing plastics from waste electrical and electronic equipment (WEEE). This study deals with the thermal and catalytic pyrolysis of a synthetic mixture containing real waste plastics, representative of polymers contained in small WEEE. Two zeolite-based catalysts were used at 400°C: HUSY and HZSM-5 with a high silica content, while three different temperatures were adopted for the thermal cracking: 400, 600 and 800°C. The mass balance showed that the oil produced by pyrolysis is always the main product regardless the process conditions selected, with yields ranging from 83% to 93%. A higher yield was obtained when pyrolysis was carried out with HZSM-5 at 400°C and without catalysts, but at 600 and 800°C. Formation of a significant amount of solid residue (about 13%) is observed using HUSY. The oily liquid product of pyrolysis, analysed by GC-MS and GC-FID, as well as by elemental analysis and for energy content, appeared lighter, less viscous and with a higher concentration of monoaromatics under catalytic condition, if compared to the liquid product derived from thermal degradation at the same temperature. HZSM-5 led to the production of a high yield of styrene (17.5%), while HUSY favoured the formation of ethylbenzene (15%). Energy released by combustion of the oil was around 39MJ/kg, thus suggesting the possibility to exploit it as a fuel, if the recovery of chemical compounds could not be realised. Elemental and proximate analysis of char and GC-TCD analysis of the gas were also performed. Finally, it was estimated to what extent these two products, showing a relevant ability to release energy, could fulfil the energy demand requested in pyrolysis.

Characterization of naproxen-polymer conjugates for drug-delivery.

The synthesis and the characterization of three new naproxen decorated polymers are described. A versatile and general approach is employed to link the drug to polymers, affording the derivatives with a very high degree of purity. The release of the drug from the conjugates proved to be exceptionally slow, even in acidic aqueous media, and the kinetic of the process seems to be triggered by their solubility in water. On the other hand, the interesting outcome of the first ex vivo drug release experiments on human blood samples makes this preliminary study valuable for future investigations on the use of these polymeric prodrugs in in vivo treatment of inflammatory states.

Vaporization of the prototypical ionic liquid BMImNTf2 under equilibrium conditions: a multitechnique study.

The vaporization behaviour and thermodynamics of the ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethyl)sulfonylimide (BMImNTf2) were studied by combining the Knudsen Effusion Mass Loss (KEML) and Knudsen Effusion Mass Spectrometry (KEMS) techniques. KEML studies were carried out in a large temperature range (398-567) K by using effusion orifices with 0.3, 1, and 3 mm diameters. The vapor pressures so measured revealed no kinetically hindered vaporization effects and provided second-law vaporization enthalpies at the mean experimental temperatures in close agreement with literature. By exploiting the large temperature range covered, the heat capacity change associated with vaporization was estimated, resulting in a value of -66.8 J K(-1) mol(-1), much lower than that predicted from calorimetric measurements on the liquid phase and theoretical calculations on the gas phase. The conversion of the high temperature vaporization enthalpy to 298 K was discussed and the value Δ(l)(g)H(m)(298 K) = (128.6 ± 1.3) kJ mol(-1) assessed on the basis of data from literature and present work. Vapor pressure data were also processed by the third-law procedure using different estimations for the auxiliary thermal functions, and a Δ(l)(g)H(m)(298 K) consistent with the assessed value was obtained, although the overall agreement is sensitive to the accuracy of heat capacity data. KEMS measurements were carried out in the lower temperature range (393-467) K and showed that the largely prevailing ion species is BMIm(+), supporting the common view of BMImNTf2 vaporizing as individual, neutral ion pairs also under equilibrium conditions. By monitoring the mass spectrometric signal of this ion as a function of temperature, a second-law Δ(l)(g)H(m)(298 K) of 129.4 ± 7.3 kJ mol(-1) was obtained, well consistent with KEML and literature results. Finally, by combining KEML and KEMS measurements, the electron impact ionization cross section of BMIm(+) was estimated.