Absolute configuration sensing of chiral aryl-and aryloxy-propionic acids by biphenyl chiroptical probes

The absolute configuration of chiral 2-aryl and 2-aryloxy propionic acids, which are among the most common chiral environmental pollutants, has been readily and reliably established by either electronic circular dichroism spectroscopy or optical rotation measurements employing suitably designed 4,4′-disubstituted biphenyl probes. In fact, the 4,4′-biphenyl substitution gives rise to a red shift of the diagnostic electronic circular dichroism signal of the biphenyl A band employed for the configuration assignment, removing its overlap with other interfering dichroic bands and allowing its clear sign identification. The largest A band red shift, and thus the most reliable results, are obtained by employing as a probe the 4,4′-dinitro substituted biphenylazepine 3c. The method was applied to the absolute configuration assignment of 2-arylpropionic acids ibuprofen (1a), naproxen (1b), ketoprofen (1c) and flurbiprofen (1d), as well as to the 2-aryloxypropionic acids 2-phenoxypropionic acid (2a) and 2-naphthoxypropionic acid (2b). This approach, allowing us to reveal the sample’s absolute configuration by simple optical rotation measurements, is potentially applicable to online analyses of both the enantiomeric composition and absolute configuration of these chiral pollutants

One-step synthesis of magnetic zeolites from waste materials

Magnetic zeolites can be successfully used for removing contaminants from polluted water, as they can be easily separated by the solution using an external magnetic field. In such a way, the wastewater treatment becomes simpler than conventional processes, which imply time and energy consuming centrifugation or filtration steps [1,2]. In this study, a low temperature environmentally friendly synthesis of magnetic zeolites by hydrothermal activation is presented [3]. The major novelty of the process is the use of a mixture of waste materials namely, fly ash (FA) and red mud (RM), as precursors to synthesize zeolites with good magnetic properties in a one step process, i.e. without passing through the additional synthesis of magnetic nanoparticles, which is commonly used for the preparation of the magnetic zeolites. The structural properties were investigated by SEM, XRD and TEM and showed that different types of zeolites (A, X and ZK-5) were obtained for different FA/RM percentages and incubation temperature. All of them possess sufficiently high magnetic moment to allow their easy separation by the solution using an external magnet (Fig. 1). The magnetic investigation was carried out by SQUID and VSM magnetometry. The global magnetic properties of the newly formed minerals were discussed on the basis of magnetic properties of precursors, where different magnetic behavior was observed (Fig.1). Good adsorbance properties of the final synthetic products were confirmed

Hydrothermal synthesis of zeolites from coal fly ash

The fly ash, from the combustion of coal to produce energy and heat, is an industrial waste, in which large accumulations represent a serious environmental threat. To reduce the environmental burden and improve the economic benefits of energy production, the science and industry focus on the transformation of coal combustion byproducts into new functional materials. The fly ash was studied by modern analytical methods. As a result of the hydrothermal reaction, several types of zeolites were synthesised from the fly ash: analcime, faujasite (zeolite X) and gismondine (zeolite P). It was shown that the experimental conditions (temperature, reaction time and alkali concentration) have a significant influence on the type of zeolite and its content in the reaction products. The series of experiments resulted in building approximate crystallisation field of zeolites and other phases as the first stage of the formation of ceramic membrane and other materials

Effect of hazelnut on serum lipid profile and fatty acid composition of erythrocyte phospholipids in children and adolescents with primary hyperlipidemia : a randomized controlled trial

Background & aim: Regular intake of nuts improves lipid profile and thus reduces the cardiovascular (CV) risk associated with hyperlipidemia. The aim of the study was to investigate the effect of a dietary intervention with hazelnuts (HZNs, 15-30 g/day, depending on patient weight) on serum lipid profile, anthropometric parameters and fatty acids (FAs) composition of erythrocyte phospholipids in children and adolescents with primary hyperlipidemia. Methods: Eight-week randomized, single blind, controlled, three-arm, parallel-group study. Sixty-six subjects were enrolled and randomized in 3 groups receiving: 1) hazelnuts with skin (HZN+S); 2) hazelnuts without skin (HZN-S); 3) dietary advices for hyperlipidemia only (controls). Before and after intervention, clinical parameters were measured and blood samples were collected for the evaluation of serum lipid levels and phospholipid FA composition of erythrocytes. Results: Two-way ANOVA showed a significant effect of time on serum low-density lipoprotein cholesterol (LDL-C), high-density lipoprotein cholesterol (HDL-C)/LDL-C ratio and non-HDL-C (p < 0.001), but not of treatment and time x treatment interaction. In particular, HZN+S and HZN-S significantly reduced the concentrations of LDL-C and increased HDL-C/LDL-C ratio. HZNs also had a favorable impact on FAs composition of erythrocyte phospholipids, as demonstrated by time x treatment interaction, with a significant increase of monounsaturated fatty acids (MUFAs) (p = 0.008) and MUFAs/saturated fatty acids (SFAs) ratio (p = 0.002) with respect to the control group. Conclusions: For the first time, we documented a positive effect of HZN consumption on lipid profile and FA composition of erythrocyte phospholipids in children with primary hyperlipidemia. Further studies are encouraged to better define HZN impact on the markers of CV risk in this population

Influence of tumor microenvironment and fibroblast population plasticity on melanoma growth, therapy resistance and immunoescape

Cutaneous melanoma (CM) tissue represents a network constituted by cancer cells and tumor microenvironment (TME). A key feature of CM is the high structural and cellular plasticity of TME, allowing its evolution with disease and adaptation to cancer cell and environmental alter-ations. In particular, during melanoma development and progression each component of TME by interacting with each other and with cancer cells is subjected to dramatic structural and cellular modifications. These alterations affect extracellular matrix (ECM) remodelling, phenotypic profile of stromal cells, cancer growth and therapeutic response. The stromal fibroblast populations of the TME include normal fibroblasts and melanoma‐associated fibroblasts (MAFs) that are highly abun-dant and flexible cell types interacting with melanoma and stromal cells and differently influencing CM outcomes. The shift from the normal microenvironment to TME and from normal fibroblasts to MAFs deeply sustains CM growth. Hence, in this article we review the features of the normal mi-croenvironment and TME and describe the phenotypic plasticity of normal dermal fibroblasts and MAFs, highlighting their roles in normal skin homeostasis and TME regulation. Moreover, we dis-cuss the influence of MAFs and their secretory profiles on TME remodelling, melanoma progres-sion, targeted therapy resistance and immunosurveillance, highlighting the cellular interactions, the signalling pathways and molecules involved in these processes

Spatial and temporal variability of the dimethylsulfide to chlorophyll ratio in the surface ocean: an assessment based on phytoplankton group dominance determined from space

Dimethylsulfoniopropionate (DMSP) is produced in surface seawater by phytoplankton. Phytoplankton culture experiments have shown that nanoeucaryotes (NANO) display much higher mean DMSP-to-Carbon or DMSP-to-Chlorophyll (Chl) ratios than Prochlorococcus (PRO), Synechococcus (SYN) or diatoms (DIAT). Moreover, the DMSP-lyase activity of algae which cleaves DMSP into dimethylsulfide (DMS) is even more group specific than DMSP itself. Ship-based observations have shown at limited spatial scales, that sea surface DMS-to-Chl ratios (DMS:Chl) are dependent on the composition of phytoplankton groups. Here we use satellite remote sensing of Chl (from SeaWiFS) and of Phytoplankton Group Dominance (PGD from PHYSAT) with ship-based sea surface DMS concentrations (8 cruises in total) to assess this dependence on an unprecedented spatial scale. PHYSAT provides PGD (either NANO, PRO, SYN, DIAT, Phaeocystis (PHAEO) or coccolithophores (COC)) in each satellite pixel (1/4° horizontal resolution). While there are identification errors in the PHYSAT method, it is important to note that these errors are lowest for NANO PGD which we typify by high DMSP:Chl. In summer, in the Indian sector of the Southern Ocean, we find that mean DMS:Chl associated with NANO + PHAEO and PRO + SYN + DIAT are 13.6±8.4 mmol g−1 (n=34) and 7.3±4.8 mmol g−1 (n=24), respectively. That is a statistically significant difference (P<0.001) that is consistent with NANO and PHAEO being relatively high DMSP producers. However, in the western North Atlantic between 40° N and 60° N, we find no significant difference between the same PGD. This is most likely because coccolithophores account for the non-dominant part of the summer phytoplankton assemblages. Meridional distributions at 22° W in the Atlantic, and 95° W and 110° W in the Pacific, both show a marked drop in DMS:Chl near the equator, down to few mmol g−1, yet the basins exhibit different PGD (NANO in the Atlantic, PRO and SYN in the Pacific). In tropical and subtropical Atlantic and Pacific waters away from the equatorial and coastal upwelling, mean DMS:Chl associated with high and low DMSP producers are statistically significantly different, but the difference is opposite of that expected from culture experiments. Hence, in a majority of cases PGD is not of primary importance in controlling DMS:Chl variations. We therefore conclude that water-leaving radiance spectra obtained simultaneously from ocean color sensor measurements of Chl concentrations and dominant phytoplankton groups can not be used to predict global fields of DMS

Groundwater flow process in the active volcanic system of Ischia Island (Italy)

The volcanic system of Ischia is characterized by an intense hydrothermal activity, documented since the early 16th century by the study of Iasolino (1588), which represents the first systematic analysis of the thermal springs of the island for therapeutic purposes. Later studies partially contributed to the enhancement of knowledge on the volcanic, hydrogeological and hydrothermal features of the island, highlighting the strong interaction between hydrothermal flowpaths and volcano- tectonic processes. The reconstruction of the interplay between hydrothermal and magmatic system becomes, therefore, a fundamental element for territorial planning, not only in terms of management of the huge water and geothermal resource, but also in a perspective of prevention and mitigation of volcanic risk. Thermal springs, fumaroles and mud deposits give beginning clues about deep hydrothermal conditions. Till now at Ischia, the local geochemical characterization of fluids and groundwater has been used for the definition of the origin and structure of the hydrothermal system as a whole, as the hydrogeological information is incomplete. However, volcanic hydrothermal systems, such as that characterizes the island of Ischia, are particularly difficult to analyze and outline, as the groundwater resources are the result of a complex and dynamic mixing among meteoric water, sea water and deep fluids. In such cases, the need for an interdisciplinary approach is evident, involving knowledge and research methods ranging from geology to volcanology, geophysics, geochemistry and hydrogeology. With particular reference to the functional and structural representation of the geothermal system of the Ischia island and the resulting correlations with the volcano-tectonic processes, the examination of previous information highlights the need to update and improve the knowledge on groundwater hydrodynamics and mineralization processes. Therefore, the present study aims at a strongly interdisciplinary action that, starting from the design and implementation of a database on the existing geological/volcanological and hydrogeological information, will contribute to highlight the critical issues, define an operating scheme of the hydro-geo-thermal system of the island of Ischia, and upgrade its hydrogeological, geochemical and volcanic monitoring system. The preliminary results improved the definition of the hydrogeological complexes and advanced knowledge of the groundwater flow conditions

Diversity of dermal fibroblasts as major determinant of variability in cell reprogramming

Induced pluripotent stem cells (iPSCs) are adult somatic cells genetically reprogrammed to an embryonic stem cell-like state. Notwithstanding their autologous origin and their potential to differentiate towards cells of all three germ layers, iPSC reprogramming is still affected by low efficiency. As dermal fibroblast is the most used human cell for reprogramming, we hypothesize that the variability in reprogramming is, at least partially, because of the skin fibroblasts used. Human dermal fibroblasts harvested from five different anatomical sites (neck, breast, arm, abdomen and thigh) were cultured and their morphology, proliferation, apoptotic rate, ability to migrate, expression of mesenchymal or epithelial markers, differentiation potential and production of growth factors were evaluated in vitro. Additionally, gene expression analysis was performed by real-time PCR including genes typically expressed by mesenchymal cells. Finally, fibroblasts isolated from different anatomic sites were reprogrammed to iPSCs by integration-free method. Intriguingly, while the morphology of fibroblasts derived from different anatomic sites differed only slightly, other features, known to affect cell reprogramming, varied greatly and in accordance with anatomic site of origin. Accordingly, difference also emerged in fibroblasts readiness to respond to reprogramming and ability to form colonies. Therefore, as fibroblasts derived from different anatomic sites preserve positional memory, it is of great importance to accurately evaluate and select dermal fibroblast population prior to induce reprogramming

Groundwater flow characterization and reconstruction of the hydrothermal system of Ischia as a tool for volcanic risk mitigation

The volcanic system of Ischia is characterized by an intense hydrothermal activity, documented since the early 16th century by the study of Iasolino [1588], which represents the first systematic analysis of the thermal springs of the island for therapeutic purposes. Later studies partially contributed to the enhancement of knowledge on the volcanic, hydrogeological and hydrothermal features of the island, highlighting the strong interaction between hydrothermal flowpaths and volcanotectonic processes. The reconstruction of the hydrothermal system becomes, therefore, a fundamental element for territorial planning, not only in terms of management of the huge water and geothermal resource, but also and above all in a perspective of prevention and mitigation of volcanic risk. Thermal springs, fumaroles and clay deposits due to the hydrothermal alteration of volcanic products testifies for the existence of an active deep hydrothermal system. However at Ischia the geochemical characterization of fluids and groundwater, performed through sampling and analysis of a discrete number of scattered springs, wells and fumaroles, has been used for the definition of the origin and structure of hydrothermal systems as a whole, as the hydrogeological information is incomplete. Moreover, volcanic hydrothermal systems, such as that characterizes the island of Ischia, are particularly difficult to analyze and outline, as the groundwater resources are the result of an articulated and dynamic interaction among meteoric water, sea water and fluids of deep origin. In such cases, the need for an interdisciplinary approach is evident, involving knowledge and research methods ranging from geology to volcanology, geophysics, geochemistry, mineralogy and hydrogeology. With particular reference to the functional and structural representation of the geothermal system of the island of Ischia and the resulting correlations with the volcanotectonic processes, the examination of previous information highlights the need to update and improve the knowledge on groundwater hydrodynamics and mineralization processes. Therefore, the present work represents a strong interdisciplinary action that, starting from the design and implementation of a database on the existing geological/volcanological and hydrogeological information, contributes to highlight the critical issues, define an operating scheme of the hydrogeothermal system of the island of Ischia, and upgrade its hydrogeological, geochemical and volcanic monitoring system, in order to contribute to the mitigation of volcanic and related risks. The knowledge of groundwater dynamics and pathways, in fact, is of fundamental importance for understanding the water/magma interaction processes in case of realimentation of the shallow magmatic system, and the assessment of the possibility of phreatic explosions occurrence. Moreover, the knowledge of the thermal fluids’ circulation and the related rock alteration processes is of paramount importance in the definition of the mechanic characteristics of rock masses and their proneness to failure