Two solvates of estetrol have been isolated and characterized by SCXRD and PXRD as well as by thermal analyses, morphology and spectroscopy. Estetrol monohydrate (Estetrol.H2O, S.G. P1, Z = 12) contains 12 molecules in its asymmetric unit with very subtle conformational differences with one another but reveals an intricate network made of intermolecular H-bonds established with the neighbour estetrol molecules and with crystallization water. Each molecule of estetrol methanol hemisolvate (Estetrol.0.5CH(3)OH, S.G. C2, Z = 4) establishes six O-H horizontal ellipsis O bonds with six different neighbours and additional H-bonds with methanol. In both structures, estetrol molecules are organized in a head-to-tail arrangement that favours the formation of O-H horizontal ellipsis O interactions. The increased thermal stability of Estetrol.0.5CH3OH crystals with respect to Estetrol.H2O can be correlated to the strengthened network of H-bonds.

Aerial drone technology is currently being investigated worldwide for the delivery of blood components. Although it has been demonstrated to be safe, the delivered medical substances still need to be analyzed at the end of the flight mission to assess the level of haemolysis and pH prior to the use in a patient. This process can last up to 30 min and prevent the time saved using drone delivery. Our study aims to integrating an innovative sensor for the haemolysis and pH detection into the Smart Capsule, an already demonstrated technology capable of managing transfusion transport through drones. In the proposed scenario, the haemolysis is evaluated optically by a minilysis device using LED-photodetector combination. The preliminary validation has been demonstrated for both the thermal stability of the Smart Capsule and the haemolysis detection of the minilysis device prototype. Firstly, the onboard temperature test has shown that the delivery system is capable of maintaining proper temperature, even though the samples have been manipulated to reach a higher temperature before inserting into the Smart Capsule. Then, in the laboratory haemolysis test, the trend of linear regression between the outputs from the spectrophotometer and the minilysis prototype confirmed the concept design of the minilysis device.

Optical characterization and thermal aging tests are performed on a sputter-deposited coating, consisting of SiO2/Cr2O3/Cr/Cr2O3 layers, designed and developed as a selective solar absorber to be used for unconcentrated solar thermal applications. Both measurements are performed by using a home-made apparatus, which mimics a flat plate collector under high vacuum. A Performance Criterion (PC?(T)), based on absorber efficiency is proposed, and a forecast of service lifetime is obtained. As a result of the thermal aging tests, the selective solar absorber under study appears to be highly efficient at mid temperatures (up to 573 K) and thermally stable at temperatures (up to 690 K). ? 2021 Elsevier B.V.

The commercialization of perovskite solar cells (PSCs) has seen an important limitation in the instability that afflicts the hole-transporting layer (HTL), namely, spiro-OMeTAD, used in high-efficiency devices. The latter is, in turn, relatively expensive, undermining the sustainability of the device. Its replacement with polymeric scaffolds, such as poly(3-hexylthiophene) (P3HT), will solve these issues. In this work, we adopted various sustainable synthetic methods to obtain four different homemade P3HTs with different molecular weights (MWs) and regioregularities (RRs), leading to different structural properties. They are implemented as HTLs in PSCs, and the effect of their properties on the efficiency and thermal stability of devices is thoroughly discussed. The highest efficiency is obtained with the highest MW and low-RR polymer (17.6%) owing to the more sustainable approach, but a very promising value is also reached with a lower-MW but fully regioregular polymer (15%). Finally, large-area devices with an efficiency of 16.7%, fabricated with a high-MW P3HT, show more than 1000 h (T80 = 1108 h) of stability under accelerated thermal stress tests (85 °C) out of glovebox while keeping over 85% of the initial efficiency of an unencapsulated device after more than 3000 min under continuous light soaking (AM 1.5G).

Phytic acid (PA), the main form of phosphorus storage present in seeds, is an antinutritional factor for its ability to chelate cations important for human nutrition. Plant breeders have spent many efforts to isolate and develop low phytic acid (lpa) mutants in different important crops. We isolated different common bean (Phaseolus vulgaris L.) lpa mutants with reduction of PA content at different extent. The consumption of common bean seeds harboring the lpa1 mutation, affecting the PvMRP1 transporter and causing a reduction of 90% in PA content, improved iron status of volunteers in human trials, but caused adverse gastrointestinal effects, presumably due to the increased stability of lectin phytohemagglutinin L (PHA-L) in these seeds, compared to the wild type (wt) ones. A hard-to-cook (HTC) defect observed in the lpa1 seeds intensified the problem. We confirmed and quantified the HTC phenotype of the lpa1 common bean seeds in three different genetic backgrounds, giving a genetic demonstration of the so-called "phytase-phytate- pectin" theory and found differences depending on the background. In one of them, we correlated the HTC defect to the redistribution of calcium, whose concentration in all parts of the seed and, particularly in the cell walls, was larger in the lpa1 compared to the wt. Furthermore, the lpa1 mutation, combined with the presence of different PHA alleles, affected the stability of the PHA-L lectin, due to an excess of free cations.

Monolayer tungsten disulfide (WS2) has recently attracted a great deal of interest as a promising material for advanced electronic and optoelectronic devices such as photodetectors, modulators, and sensors. Since these devices can be integrated in a silicon (Si) chip via back-end-of-line (BEOL) processes, the stability of monolayer WS2 in BEOL fabrication conditions should be studied. In this work, the thermal stability of monolayer single-crystal WS2 at typical BEOL conditions is investigated; namely (a) heating temperature of 300 oC, (b) pressures in the medium-(10-3 mbar) and high- (10-8 mbar) vacuum range; (c) heating times from 30 minutes to 20 hours. Structural, optical and chemical analyses of WS2 are performed via scanning electron microscopy, Raman spectroscopy, photoluminescence and X-ray photoelectron spectroscopy. It is found that monolayer single-crystal WS2 is intrinsically stable at these temperature and pressures, even after 20 h of thermal treatment. The thermal stability of WS2 is also preserved after exposure to low-current electron beam (12 pA) or low-fluence laser (0.9 mJ µm-2), while higher laser fluencies cause photo-activated degradation upon thermal treatment. These results are instrumental to define fabrication and inline monitoring procedures that allow the integration of WS2 in device fabrication flows without compromising the material quality.

The simultaneous optimization of device efficiency, stability and large area processing represents one of the biggest challenges to exploit the potential offered by polymer solar cells. In this context, detailed studies of the impact of different interlayers on the key device properties are of crucial importance. Herein, the thermal stability of inverted polymer solar cells containing two different metal oxides as an anode interlayer is compared: i) ?80 nm of solution-processed tungsten oxide (WOx) and, ii) 10 nm of (thermally evaporated) molybdenum oxide (MoOx) as a reference system. A detailed comparison focused on the evolution of device performances/properties before and after thermal stress (85?C for 140 h in dark) is reported, highlighting advantages arising from the use of WOx as an interlayer. Two sets of inverted solar cells, based on either HBG-1:PC61BM and P3HT:PC61BM as active layer, are fabricated and studied. Electrical, morphological and optical characterizations, performed both on freshly prepared and aged devices, are analyzed and correlated to explain the positive effect of the WOx interlayer on the resulting device thermal stability. Compared to fresh devices, thermally aged WOx (MoOx) based HBG-1:PC61BM and P3HT:PC61BM solar cells exhibit an efficiency decay of -16% (-24%) and -28% (-57%), respectively.

The performance of TiO2-based materials is highly dependent on the electronic structure and local defect configurations. Hence, a thorough understanding of defect interaction plays a key role. In this study, we report on the results from emission Fe-57 Mossbauer spectroscopy experiments, using dilute 57Mn implantation into pristine (TiO2) and hydrogenated anatase held at temperatures between 300 and 700 K. Results of the electronic structure and local environment are complemented with ab initio calculations. Upon implantation, both Fe2+ and Fe3+ are observed in pristine anatase, where the latter demonstrates the spin-lattice relaxation. The spectra recorded for hydrogenated anatase show no Fe3+ contribution, suggesting that hydrogen acts as a donor. Due to the low threshold, hydrogen diffuses out of the lattice, thus showing a dynamic behavior on the time scale of the Fe-57 14.4 keV state. The surrounding oxygen vacancies favor the high-spin Fe2+ state. The sample treated at room temperature shows two distinct processes of hydrogen motion. The motion commences with the interstitial hydrogen, followed by switching to the covalently bound state. Hydrogen out-diffusion is hindered by bulk defects, which could cause both processes to overlap. Supplementary UV-vis and electrical conductivity measurements show an improved electrical conductivity and higher optical absorption after the hydrogenation. X-ray photoelectron spectroscopy at room temperature reveals that the sample hydrogenated at 573 K shows the presence of both Ti3+ and Ti2+ states. This could imply that a significant amount of oxygen vacancies and -OH bonds is present in the samples. Theory suggests that, in the anatase sample implanted with Mn(Fe), probes were located near equatorial vacancies as next-nearest neighbors, while a metastable hydrogen configuration was responsible for the annealing behavior. The obtained information provides a deep insight into elusive hydrogen defects and their thermal stability.

Globally, lake surface water temperatures have warmed rapidly relative to air temperatures, but changes in deepwater temperatures and vertical thermal structure are still largely unknown. We have compiled the most comprehensive data set to date of long-term (1970-2009) summertime vertical temperature profiles in lakes across the world to examine trends and drivers of whole-lake vertical thermal structure. We found significant increases in surface water temperatures across lakes at an average rate of + 0.37 °C decade-1, comparable to changes reported previously for other lakes, and similarly consistent trends of increasing water column stability (+ 0.08 kg m-3 decade-1). In contrast, however, deepwater temperature trends showed little change on average (+ 0.06 °C decade-1), but had high variability across lakes, with trends in individual lakes ranging from - 0.68 °C decade-1 to + 0.65 °C decade-1. The variability in deepwater temperature trends was not explained by trends in either surface water temperatures or thermal stability within lakes, and only 8.4% was explained by lake thermal region or local lake characteristics in a random forest analysis. These findings suggest that external drivers beyond our tested lake characteristics are important in explaining long-term trends in thermal structure, such as local to regional climate patterns or additional external anthropogenic influences.

Organic-inorganic hybrid (ceramer) coatings were synthesized and deposited on the polyester nonwoven fabrics through the sol-gel process. This promoted the formation of an insulating barrier that was able to enhance the thermal stability and the hydrophobicity of fabrics. The hybrid phase is made of an organic network arising from different alkoxysilane precursors (trimethoxymethylalkoxysilane (TMEOS), 3-aminopropyl-trimethoxyalkoxysilane (APTMS), and tetraethylorthosilicate (TEOS)) and inorganic phase made of titanium dioxide TiO2 nanoparticles (NPs) and, in some cases, coated by P-based compound. The characterization of hybrid phase at liquid (size distribution and zeta potential of dispersed nanoparticles), dried state (crystalline phase, thermogravimetric (TGA), and Fourier transform infrared spectroscopic (FTIR) analyses), and on deposited coatings (contact angle, burn-out tests) aimed to find a correlation between the physicochemical properties of ceramer and functional performances of coated fabrics (thermal stability and hydrophobicity). The results showed that all ceramer formulations were able to improve the char formation after burn-out, in particular the highest thermal stability was obtained in the presence of TMEOS precursor and TiO2 NPs coated by P-based compound, which also provided the highest hydrophobicity. In conclusion, we presented an environmentally friendly and easily scalable process for the preparation of ceramer formulations capable of being formed into transparent, thermal-resistant, and hydrophobic fabric coatings, whose functions are extremely challenging for the textile market.

Non-specific lipid transfer proteins (nsLTPs) are characterized by an eight-cysteine motif backbone that is stabilized by four disulphide bonds. The strong interest towards this protein family is mainly due to the fact that nsLTPs are involved in many biological processes and have been identified as major human allergens. Since tomato (Solanum lycopersicum L.) is one of the most consumed and allergenic vegetables, a full characterization of this family is needed. In this study, hidden Markov model profiles were used to identify nsLTPs within the tomato protein complement. Following manual curation, 64 nsLTP genes were classified into six sub-families. Furthermore, nsLTP gene structure, distribution and arrangement along tomato chromosomes were investigated. Available RNA-seq expression profile data and Real-Time PCR analyses were used to derive expression patterns of tomato nsLTPs in different tissues/ organs. Non-specific LTP genes with high level of expression in tomato fruits were filtered out since they could play a key role in tomato allergenicity. Among these genes was Solyc10g075090 that encodes the allergen Sola l 3. Finally, cloning, heterologous expression, purification and biochemical characterization of the recombinant protein Sola l 3 was performed.

Plastics are perceived as modern and versatile materials, but their use is linked to numerous environmental issues as their production is based on finite raw materials (petroleum or natural gas). Additionally, their low biodegradability results in the accumulation of microplastics. As a result, there is extensive interest in the production of new, environmentally friendly, bio-based and biodegradable polymers. In this context, poly(ethylene vanillate) (PEV) has a great potential as a potentially bio-based alternative to poly(ethylene terephthalate); however, it has not yet been extensively studied. In the present work, the preparation of PEV is reported. The enthalpy and the entropy of fusion of the pure crystalline PEV have been estimated for the first time. Additionally, the equilibrium melting temperature has also been calculated. Furthermore, the isothermal and non-isothermal crystallization behavior are reported in detail, and new insights on the thermal stability and degradation mechanism of PEV are given.

?-Glucosidase (BG) was immobilized by adsorption on wrinkled silica nanoparticles (WSNs) and on tannic acid-templated mesoporous silica nanoparticles (TA-MSNPs). The effect induced by a different morphology of the pores of the sorbent on the catalytic performance of ?-glucosidase was investigated. A complete textural and morphological characterization of the two samples was performed by Brunauer-Emmett-Teller (BET) method, Fourier Transform Infrared (FT-IR) and transmission electron microscopy (TEM). The results demonstrated that the catalytic performance of the immobilized enzyme depends on the pores size of sorbent but a key factor is the pores morphology. In fact, the BG immobilized on WSNs and TA-MSNPs (BG/WSNs and BG/TA-MSNPs) shows in both cases good catalytic performances in cellobiose hydrolysis, but the catalyst with the best performance is BG/WSNs, in which the support exhibits a central-radial pore structure and a hierarchical trimodal micro-mesoporous pore size. This peculiar morphology allows the enzyme to settle in a place where the interactions with the walls are maximized, increasing its conformational rigidity. Furthermore, the enzyme is prevalently collocated in the interior of pore so that the pores are not completely capped.

Oxygen carrier materials based on La2O2SO4 and promoted by small amounts (1% wt.) of transition metals, namely Co, Mn and Cu, have been synthesized and characterized by means of X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET), Temperature-programmed reduction/oxidation (TPR/TPO) and thermogravimetry-mass-Fourier transform infrared spectrometry (TG-MS-FTIR) experiments under alternating feeds in order to investigate their potential use for the Chemical Looping Combustion process using either hydrogen or methane as the fuel. The chemical looping reactivity is based on the reversible redox cycle of sulfur from S6+ in La2O2SO4 to S2- in La2O2S and entails a large oxygen storage capacity, but it generally requires high temperatures to proceed, challenging material stability and durability. Herein we demonstrate a remarkable improvement of lattice oxygen availability and activity during the reduction step obtained by cost-effective metal doping in the order Co > Mn > Cu. Notably, the addition of Co or Mn has shown a significant beneficial effect to prevent the decomposition of the oxysulfate releasing SO2, which is identified as the main cause of progressive deactivation for the unpromoted La2O2SO4.

BACKGROUNDPea, lentil, faba bean, chickpea and bean proteins are potentially renewable raw materials for bioplastic production that can be obtained from agricultural waste. Plastics are usually processed under heating, and thus thermal stability is a mandatory requirement for the application. In this study, the thermal behavior of several legume protein isolates at different purity degrees was investigated.

The Mediterranean sponge Halichondria (Halichondria) panicea was explored as a novel matrix for the isolation of biosurfactant-producing bacteria. A total of 38 (out of 56) isolates gave a good response to the employed screening tests (e.g., stable emulsion detection, surface tension measurement, hemolytic activity, and blue agar plate assay) and were selected for further analyses. The thin layer chromatography revealed a possible glucidic composition of biosurfactants. Most promising strains, i.e., those able to produce stable emulsion with percentage higher than 30% and yellow spots on TLC plates, were affiliated to the genera Pseudovibrio, Acinetobacter, and Bacillus. The biosurfactant production by two isolates (i.e., Acinetobacter sp. SpN134 and Pseudovibrio sp. SpE85) was evaluated under different culture conditions, in terms of temperature, NaCl concentration, and pH. Surface tension reduction ability was more stable than the emulsification, and resulted differently influenced by salinity, temperature, and pH. Acinetobacter sp. SpN134 resulted particularly efficient and competitive if compared with other well-known biosurfactant producers. Data suggest that sponges may represent a promising matrix for the isolation of biosurfactant-producing bacteria, reinforcing the growing interest towards filter-feeding organisms as underexplored sources of specialized bacteria.

Heavy doping of Ge is crucial for several advanced micro- and optoelectronic applications, but, at the same time, it still remains extremely challenging. Ge heavily n-type doped at a concentration of 1 × 10cm by As ion implantation and melting laser thermal annealing (LTA) is shown here to be highly metastable. Upon post-LTA conventional thermal annealing As electrically deactivates already at 350 °C reaching an active concentration of ~4 × 10cm. No significant As diffusion is detected up to 450 °C, where the As activation decreases further to ~3 × 10cm. The reason for the observed detrimental deactivation was investigated by Atom Probe Tomography and in situ High Resolution X-Ray Diffraction measurements. In general, the thermal stability of heavily doped Ge layers needs to be carefully evaluated because, as shown here, deactivation might occur at very low temperatures, close to those required for low resistivity Ohmic contacting of n-type Ge.

The effects of global climate changes are progressively observable on the environment. Their direct correlation with the CO2 emission coming from the fossil fuel combustion and industrial processes elucidates the urgent need of renewable energies. In this context, organic photovoltaics (OPVs) attracts much attention because of the cost-competitiveness and the new device functionalities over existing solar cells. Indeed, the interesting properties of organic materials open the road to the economically sustainable production of flexible and light-weight devices, which also meet aesthetical requirements as semi-transparency and color-tunability. This Ph.D. thesis focuses on the performance, stability and environmental impact of solution-processed polymer solar cells (PSCs). In a preliminary part, the development of novel materials, the optimization of the processing conditions and a deeper understanding of the device physics elucidate the pathways towards the enhancement of the PSCs efficiency. However, PSCs still present some issues of stability under operation conditions, which slow down the widespread commercialization of this technology. To this end, part of the thesis discusses some specific aspects related to the stability of critical materials/layers of organic solar cells. In particular, the light stability of different active materials and ZnO layers is investigated in order to provide guidelines for the development of advanced materials for PSCs. Then, the impact of the processing conditions on the thermal stability of the resulting photovoltaic devices is studied. In particular, the effect of the replacement of common chlorinated solvents with a "greener" analogous is investigated both in terms of device efficiency and thermal stability. Finally, a contribution to the understanding of state-of-the-art tandem architectures is reported as a perspective for the large scale deployment of highly performing solar cells. The analysis of these crucial aspects of OPVs provides the basis for the development of improved devices heading to the widespread deployment of this technology.

The combination of mass-production compatible coating techniques and environmentally friendly solvents to process bulk heterojunction solar cells represents a key issue to scale up this technology. In this work we demonstrate that using a benchmark polymer HBG-1 blended with PC61BM, the replacement of a common chlorinated processing solvent (orthodichlorobenzene) with a non-chlorinated analogous (o-xylene) not only allows the fabrication of blade-coated bulk heterojunction devices with identical photovoltaic performance, but also determines a great enhancement of the resulting thermal stability. Thermal degradation tests were carried out in inert atmosphere, by keeping the solar cells onto a hot plate at 85 °C and monitoring their OPV performance. In parallel, the morphological changes of the active layers induced by thermal stress are investigated by combining two complementary light-based imaging techniques, laser scanning confocal and photocurrent microscopy, which offer the great advantage to simultaneously study on complete devices the blend morphology and the electrical properties, point-by-point, of the active layer even in regions unlikely accessible (e.g. the active area under the top electrode) using other techniques. As a result, we found that solar cells processed from a non-chlorinated based solvent, in comparison to an analogous reference system, exhibit a different evolution of the resulting BHJ morphology during thermal ageing, in perfect agreement with the corresponding photovoltaic responses.

A new semiconducting polymer based on two different electron deficient (quinoxaline and isoindigo) and electron rich (benzodithiophene) moieties is synthesized, characterized and used as donor material for photovoltaic devices. Blade-coated bulk heterojunction solar cells are fabricated in air by using chlorinated (o-dichlorobenzene) and non-chlorinated (o-xylene) solvents for the deposition of the active layer. The use of o-xylene allows a ~ 10% improvement of the device efficiency in comparison to the analogous system processed from o-dichlorobenzene. In addition, the evolution of the photovoltaic parameters of the resulting devices during thermal stress is monitored and compared, demonstrating a nearly identical resistance against temperature. The reported results not only highlight the promising properties of the new polymer in terms of environmental stability and compatibility with non-halogenated solvents, but also show an easy and ecofriendly way to further improve the device performance without altering the corresponding thermal stability.