Electrochemical analysis of proton and electron transfer equilibria of the reducible moieties in humic acids

Humic substances play a key role in biogeochemical and pollutant redox reactions. The objective of this work was to characterize the proton and electron transfer equilibria of the reducible moieties in different humic acids (HA). Cyclic voltammetry experiments demonstrated that diquat and ethylviologen mediated electron transfer between carbon working electrodes and HA. These compounds were used also to facilitate attainment of redox equilibria between redox electrodes and HA in potentiometric E(h) measurements. Bulk electrolysis of HA combined with pH-stat acid titration demonstrated that electron transfer to the reducible moieties in HA also resulted in proton uptake, suggesting decreasing reduction potentials E(h) of HA with increasing pH. This was confirmed by potentiometric E(h)-pH titrations of HA at different redox states. E(h) measurements of HA samples prereduced to different redox states by bulk electrolysis revealed reducible moieties in HA that cover a wide range of apparent standard reduction potentials at pH 7 from E(h)(0)* = +0.15 to -0.3 V. Modeling revealed an overall increase in the relative abundance of reducible moieties with decreasing E(h). The wide range of HA is consistent with its involvement in numerous environmental electron transfer reactions under various redox conditions.     

Pigments profile in monovarietal virgin olive oils from various Italian olive varieties

This paper presents the investigation of the chlorophyll and carotenoid pigments composition in monovarietal virgin olive oils produced from the five main olive varieties (Minuta, Ottobratica, Calabrese, Ogliarola, Baddarica) cultivated in Sicily (southern Italy), from four main olive varieties (DolceAgogia, Moraiolo, Leccino, Frantoio) cultivated in Umbria (central Italy), and from three main olive varieties (Leccino, Oliva Nera di Collecorto, Noccioluta) cultivated in Molise (central Italy). Reversed-phase high performance liquid chromatography using a C-30 column with photodiode array detection was used for pigments analyses. In all, 19 compounds were identified and quantified in 60 olive oils samples. The qualitative pigments pattern was similar among the varieties investigated, whereas quantitative differences were found among the different cultivars; among the varieties investigated in this work, the oils from Umbria showed the highest pigment content (34.19 ppm in average), followed by the oils from Molise (18.61 ppm in average) and the oils from Sicily which showed the lowest pigment contents (13.38 ppm in average). In general, pheophytin a was the major component (range 0.49–19.42 ppm), followed by β-carotene (range 1.27–9.30 ppm) and lutein (range 0.44–5.12 ppm). Those differences may be due to genetic factors and/or geographical differences. Moreover, auroxanthin was detected for the first time in olive oils and was detected only in olive oils from Umbria and Molise regions. The ratio between the two isochromic pigment fractions, namely the ratio between the chlorophyll and carotenoid fractions showed an average value close to unity. The lutein/β-carotene ratio was less than one in the majority of the cases. These parameters, along with other analytical parameters, could be used as indicators of typicality in olive oils. The presence of a specific pigment profile in olive oils could infact be used to guarantee the genuineness of the product, since the quality control of food requires a precise knowledge of the pigments composition of the original products.     

FT-NIR spectroscopy for the quality characterization of apricots (Prunus armeniaca L.)

Abstract: The nondestructive assessment of apricot fruit quality (Bora cultivar) was carried out by means of FT-NIR reflectance spectroscopy in the wavenumber range 12000 to 4000 cm⁻¹. Samples were harvested at four different ripening stages and scanned by a fiber optical probe immediately after harvesting and after a storage of 3 d (2 d at 4 °C and 1 d at 18 °C); the flesh firmness (FF), the soluble solids content (SSC), the acidity (A), and the titratable acidity (malic and citric acids) were then measured by destructive methods. Soft independent modeling of class analogy (SIMCA) analysis was used to classify spectra according to the ripening stage and the storage: partial least squares regression (PLS) models to predict FF, SSC, A, and the titratable acidity were also set-up for both just harvested and stored apricots. Spectral pretreatments and wavenumber selections were conducted on the basis of explorative principal component analysis (PCA). Apricot spectra were correctly classified in the right class with a mean classification rate of 87% (range: 80% to 100%). Test set validations of PLS models showed R² values up to 0.620, 0.863, 0.842, and 0.369 for FF, SSC, A, and the titratable acidity, respectively. The best models were obtained for the SSC and A and are suitable for rough screening; a lower power prediction emerged for the other maturity indices and the relative predictive models are not recommended. Practical Application : The results of the study could be used as a tool for the assessment of the ripening stage during the harvest and the quality during the postharvest storage of apricot fruits.     

Polycyclic aromatic hydrocarbon content in commercial Spanish fatty foods

The levels of polycyclic aromatic hydrocarbons (PAHs) were determined by reversed-phase high-performance liquid chromatography with fluorescence detection in different fatty foods from a Spanish market. The average concentration of the sum of total PAHs in edible vegetable oils was below 25 ng/g, whereas the sum of heavy PAHs did not surpass 5 ng/g. Olive pomace oils obtained before the summer of 2001 were an exception because they were highly contaminated. The effects of different technological processes, such as bleaching, deodorization, and hydrogenation, on PAH concentration in edible oils have been studied. The PAH profiles, as well as the influence of cooking procedures, of other fatty foods (margarine, mayonnaise, and oils from canned fishes) have been examined.     

Molecular Mechanisms and Physiological Changes behind Benign Tracheal and Subglottic Stenosis in Adults

Laryngotracheal stenosis (LTS) is a complex and heterogeneous disease whose pathogenesis remains unclear. LTS is considered to be the result of aberrant wound-healing process that leads to fibrotic scarring, originating from different aetiology. Although iatrogenic aetiology is the main cause of subglottic or tracheal stenosis, also autoimmune and infectious diseases may be involved in causing LTS. Furthermore, fibrotic obstruction in the anatomic region under the glottis can also be diagnosed without apparent aetiology after a comprehensive workup; in this case, the pathological process is called idiopathic subglottic stenosis (iSGS). So far, the laryngotracheal scar resulting from airway injury due to different diseases was considered as inert tissue requiring surgical removal to restore airway patency. However, this assumption has recently been revised by regarding the tracheal scarring process as a fibroinflammatory event due to immunological alteration, similar to other fibrotic diseases. Recent acquisitions suggest that different factors, such as growth factors, cytokines, altered fibroblast function and genetic susceptibility, can all interact in a complex way leading to aberrant and fibrotic wound healing after an insult that acts as a trigger. However, also physiological derangement due to LTS could play a role in promoting dysregulated response to laryngo-tracheal mucosal injury, through biomechanical stress and mechanotransduction activation. The aim of this narrative review is to present the state-of-the-art knowledge regarding molecular mechanisms, as well as mechanical and physio-pathological features behind LTS.     

Biological Effects of Cyclin-Dependent Kinase Inhibitors Ribociclib,Palbociclib and Abemaciclib on Breast Cancer Bone Microenvironment

The CDK4/6 inhibitors (CDKi) palbociclib, ribociclib, and abemaciclib are currently approved in combination with anti-estrogen therapy for the treatment of advanced and/or metastatic hormone receptor-positive/HER2-neu-negative breast cancer patients. Given the high incidence of bone metastases in this population, we investigated and compared the potential effects of palbociclib, ribociclib, and abemaciclib on the breast cancer bone microenvironment. Primary osteoclasts (OCs) and osteoblasts (OBs) were obtained from human monocyte and mesenchymal stem cells, respectively. OC function was evaluated by tartrate-resistant acid phosphatase assay and real-time PCR; OB activity was assessed by an alizarin red assay. OB/breast cancer co-culture models were generated via the seeding of MCF-7 cells on a layer of OBs, and tumor cell proliferation was analyzed using flow cytometry. Here, we showed that ribociclib, palbociclib, and abemaciclib exerted similar inhibitory effects on the OC differentiation and expression of bone resorption markers without affecting OC viability. On the other hand, the three CDKi did not affect the ability of OB to produce bone matrix, even if the higher doses of palbociclib and abemaciclib reduced the OB viability. In OB/MCF-7 co-culture models, palbociclib demonstrated a lower anti-tumor effect than ribociclib and abemaciclib. Overall, our results revealed the direct effects of CDKi on the tumor bone microenvironment, highlighting differences potentially relevant for clinical practice.     

Thin-film solar cells on commercial ceramic tiles

Amorphous silicon solar cells were deposited on porcelain stoneware tiles in order to develop a fully integrated PV building element. In a previous work we demonstrated the feasibility of adopting porcelain stoneware tiles as thin-film solar cell substrates and we fabricated solar cells on “industrial-level” ceramic substrates showing more than 4% efficiency. In this study we focus our attention on larger area devices deposited on tiles. As the active area increases additional problems arise from the surface of the substrate. In particular we find that short-circuit paths originate from the unfavorable properties of the substrate tiles (roughness, porosity, etc.) having dramatic consequences on the performance of larger area devices. With the assumption that spot-like regions, in which the back layer and the front layer are in electrical contact (local short-circuits), are present all over the device, we propose a new device structure to overcome the substrate drawbacks. A new contacts arrangement was designed in order to minimize the shunting effect of short-circuit paths. As a result an initial efficiency of 2.5% has been obtained using the new device structure for devices deposited on a PV mini-module tile.     

Low Sulfur Amino Acid,High Polyunsaturated Fatty Acid Diet Inhibits Breast Cancer Growth

Cancer cells may acquire resistance to stress signals and reprogram metabolism to meet the energetic demands to support their high proliferation rate and avoid death. Hence, targeting nutrient dependencies of cancer cells has been suggested as a promising anti-cancer strategy. We explored the possibility of killing breast cancer (BC) cells by modifying nutrient availability. We used in vitro models of BC (MCF7 and MDA-MB-231) that were maintained with a low amount of sulfur amino acids (SAAs) and a high amount of oxidizable polyunsatured fatty acids (PUFAs). Treatment with anti-apoptotic, anti-ferroptotic and antioxidant drugs were used to determine the modality of cell death. We reproduced these conditions in vivo by feeding BC-bearing mice with a diet poor in proteins and SAAs and rich in PUFAs (LSAA/HPUFA). Western blot analysis, qPCR and histological analyses were used to assess the anti-cancer effects and the molecular pathways involved. We found that BC cells underwent oxidative damage to DNA and proteins and both apoptosis and ferroptosis were induced. Along with caspases-mediated PARP1 cleavage, we found a lowering of the GSH-GPX4 system and an increase of lipid peroxides. A LSAA/HPUFA diet reduced tumor mass and its vascularization and immune cell infiltration, and induced apoptosis and ferroptotic hallmarks. Furthermore, mitochondrial mass was found to be increased, and the buffering of mitochondrial reactive oxygen species limited GPX4 reduction and DNA damage. Our results suggest that administration of custom diets, targeting the dependency of cancer cells on certain nutrients, can represent a promising complementary option for anti-cancer therapy.