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The total mass of individual synthetic polymers present as microplastic (MP < 2 mm) pollutants in the sediments of interconnected aquatic environments was determined adopting the Polymer Identification and Specific Analysis (PISA) procedure. The investigated area includes a coastal lakebed (Massaciuccoli), a coastal seabed (Serchio River estuarine), and a sandy beach (Lecciona), all within a natural park area in Tuscany (Italy). Polyolefins, poly(styrene) (PS), poly(vinyl chloride) (PVC), polycarbonate (PC), poly(ethylene terephthalate) (PET), and the polyamides poly(caprolactame) (Nylon 6) and poly(hexamethylene adipamide) (Nylon 6,6) were fractionated and quantified through a sequence of selective solvent extractions followed by either analytical pyrolysis or reversed-phase HPLC analysis of the products of hydrolytic depolymerizations under acidic and alkaline conditions. The highest concentrations of polyolefins (highly degraded, up to 864 µg/kg of dry sediment) and PS (up to 1138 µg/kg) MPs were found in the beach dune sector, where larger plastic debris are not removed by the cyclic swash action and are thus prone to further aging and fragmentation. Surprisingly, low concentrations of less degraded polyolefins (around 30 µg/kg) were found throughout the transect zones of the beach. Positive correlation was found between polar polymers (PVC, PC) and phthalates, most likely absorbed from polluted environments. PET and nylons above their respective LOQ values were found in the lakebed and estuarine seabed hot spots. The pollution levels suggest a significant contribution from riverine and canalized surface waters collecting urban (treated) wastewaters and waters from Serchio River and the much larger Arno River aquifers, characterized by a high anthropogenic pressure. Graphical abstract

The current study uses a 2-level between-subjects design to explore how having aligned, or misaligned power may affect how a person responds when their attempts to influence are met with resistance. Initially, participants will be surveyed about their personal beliefs about power using ten Brinke and Keltner's survey - Hard and Soft Power in International relations, the workplace and at home (2020). They will then be randomly assigned to receive “feedback” on their response to the survey, denoting the condition they entered as either aligned or misaligned. Participants will receive the leadership role in all cases (high and low legitimacy). In half the cases, the leader will have legitimacy and, thus, a capacity for volitional influence. In the other half of the cases, the leader will have low legitimacy and, thus, a low capacity for volitional influence. They will take part in a scripted group interaction with four online chatbots. They will be required to achieve group unity by leading the group to agree on selecting a logo. They will be incentivised to achieve group unity by being offered a bonus of 50% to their prolific pay rate if they reach 100% group agreement and as long as they have a majority of members remaining at the end of the interaction (i.e. max 2 people can be kicked). During the group interaction, one member consistently disagrees with the leader's preference, three group members agree after persuasion, and one member always agrees. During the conversation, the leader can temporarily mute any other member or permanently kick them out of the group. These constitute punishment or exclusion responses. After the interaction ends, leaders will be asked to reward or punish each group member by increasing their automatic bonus by 25%, 50% (reward) or removing the bonus (punish).

Lake basins can behave as accumulators of microplastics released in wastewaters as such or resulting from degradation of larger items before and/or during their journey toward the marine environment as a final sink. A novel multianalytical approach was adopted for the detection and quantification of microplastics with size &lt, 2 mm in the sediments of the volcanic lake of Bracciano, Italy. Simple analytical techniques such as solvent extraction/fractionation (for polyolefins and polystyrene) or depolymerization (for polyethylene terephthalate, PET), along with chromatographic detection (SEC and HPLC), allowed quantitative and qualitative determination of the main synthetic polymer contaminants. In particular, PET microplastic concentrations of 0.8&ndash, 36 ppm were found, with variability related to the sampling site (exposure to incoming winds and wave action). Proton Nuclear Magnetic Resonance (1H-NMR) and Attenuated Total Reflectance Fourier Transformed InfraRed (ATR-FTIR spectroscopic investigations supported the identification and chemical characterization of plastic fragments and polymer extracts. The average molecular weight of solvent extractable polymers was evaluated from 2D 1H-NMR diffusion ordered spectroscopy (DOSY) experiments. The proposed, easily accessible multianalytical approach can be considered as a useful tool for improving our knowledge on the nature and the concentration of microplastics in sediments, giving insights on the impact of human activities on the health status of aquatic ecosystems.

“Composizione-Superficie Lunare” (1965) is an artwork of the Italian artist Giulio Turcato (Mantua, 1912- Rome, 1995). This painting, inspired by moon travels, was created on a polyurethane foam support, material experimentalized by some other contemporary artists in the late 1960′s. In the present paper the organic and inorganic materials used as binders, fillers and pigments, as well as the support itself, have been investigated by means of a multi-analytical approach based on the application of Environmental Scanning Electron Microscopy Energy-Dispersive X-ray spectroscopy (ESEM–EDX), Micro-Attenuated Total Reflection Fourier Transform Infrared spectroscopy (µ-ATR–FTIR), High Performance Liquid Chromatography coupled with Diode Array Dectector and tandem Mass Spectrometry (HPLC–DAD, LC–MS/MS), Pyrolysis-Gas Chromatography and Evolved Gas Analysis coupled with Mass Spectrometry (Py-GC/MS, multi-shot Py-GC/MS and EGA–MS). The plethora of analytical techniques available allowed to provide for the first time a full characterization of the different materials used in “Composizione-Superficie Lunare” and of a Turcato's painting. The polyurethane foam artwork was painted using synthetic inorganic and organic pigments, such as methyl violet and manganese violet, dispersed in polyvinyl acetate as medium. The study was fundamental for establishing the original materials and aesthetics of the artwork as well as assessing the degradation state of the painting materials and of the polyurethane foam support. The results collected, crucial for planning an effective restoration campaign, highlight the importance of the contribution of analytical chemistry to cultural heritage.

Sampling, separation, detection, and characterization of micro- and nanoplastics dispersed in natural water bodies and other ecosystems is a challenging and critical issue for a better understanding of the hazards for the environment posed by such ubiquitous and still poorly known form of pollution. There is still the need for cost-efficient, exhaustive, reliable and accurate analytical protocols allowing the quantification of these pollutants and of the toxic pollutants that they are known to act as concentrators for. The first results of broader research aiming at setting up new and effective methodologies and analytical protocols for the accurate determination of different polymeric pollutants in marine and freshwater sediments will be presented. Among them, preliminary results of a follow-up investigation on the low molecular weight volatile organic compounds released upon photo-oxidative degradation of microplastics will also be presented. Their significance for a better understanding of the fate of floating or stranded plastic debris will be discussed.

The isothermal crystallization kinetics of a set of bio-nanocomposites produced by in situ catalytic step growth polycondensation of adipic acid and 1,4-butanediol in the presence of Moroccan clay beidellite (BDT) organo-modified with hexadecyltrimethylammonium bromide (cetyltrimethylammonium bromide, CTA) was investigated and compared with that of the parent poly(butylene adipate) (PBA) matrices from which the clay had been extracted. In situ bio-nanocomposites had different contents (0-5 wt %) of CTA/BDT nanofillers characterized by different extents of organo-modification (CTA/BDT equivalent ratios from 0 to 5). The isothermal crystallization rates of the bio-nanocomposites and of the parent PBA matrices were investigated by differential scanning calorimetry (DSC) at 45, 40, and 37 °C and analyzed according to the Avrami model. The bionanocomposites with an intermediate (2 wt %) concentration of organoclays with a higher CTA/BDT ratio (3 and 5) showed the highest exfoliation degree, along with an increase in the crystallization rates, compared to those of the parent PBA matrices, which was larger than that in the other nanocomposites. The lack of a simple correlation between the nanoclay content/composition and crystallization kinetics was ascribed to the molecular mass, an additional variable for in situ bio-nanocomposites as compared to nanocomposites prepared by simple physical blending of nanoclays with a single polymer matrix. The specific contribution of the molecular mass to the crystallization kinetics was untangled from those of the organoclay content and CTA/BDT ratio by comparing each bio-nanocomposite with its parent polymer matrix. The crystallization rate of the nanocomposites was always found to reach a maximum within an intermediate range of molecular weights of the polymer matrix, a behavior previously reported only for pure polymers. Such differences in the crystallization rate of in situ bio-nanocomposites may affect the crystalline phase morphology and, in polymorphs such as in PBA, phase composition, with consequent effects on properties that may be of interest for specific applications.

Fish meal (FM) is an industrial product, mainly obtained from whole wild-caught fish, that is used as a high protein feedstuff component in aquaculture and intensive animal farming. Contamination of FM by microplastics (MPs), the synthetic polymer particles known to be nearly ubiquitous in the marine environment, is a likely consequence of their ingestion by zooplankton and other small marine animals that through the food chain end up in the fish commercialized not only for direct human consumption but also for the industrial production of FM. Unfortunately, analytical tools for quantifying contamination of FM by synthetic polymers are not available. A newly developed procedure described here allows quantification of the total amounts of polyolefins (including ethene and propene homo- and copolymers), polystyrene (PS), and poly(ethylene terephthalate) (PET), respectively, in FM. The multi-step procedure involves a sequence of solvent extractions, hydrolytic treatments to remove the biogenic matrix mainly consisting of proteins and some lipids, and selective depolymerization for PET. The gravimetric and SEC-UV techniques employed for the quantification of polyolefins and PS, respectively, only allowed to estimate their concentration in FM at around or below 100 mg/kg each, a more accurate quantification being prevented by the interference from the organic matrix and, in the case of polyolefins, by the limited sensitivity of the quantification by gravimetry. On the other hand, the contamination by PET MPs could accurately be quantified at 12.9 mg/kg based on the dry FM mass. Ways to overcome the sensitivity limitations for PS and polyolefins by using e.g. pyrolysis-GC/MS are highlighted.

A statistical design of experiments (DoE) was used to evaluate the effects of CF4 O2 plasma on Kapton films in which the duration of treatment, volume ratio of plasma gases, and microwave power were selected as effective experimental factors for systematic investigation of surface modification. Static water contact angle (θW), polar component of surface free energy (γSp) and surface O/C atomic ratio were analyzed as response variables. A significant enhancement in wettability and polarity of the treated films compared to untreated Kapton films was observed; depending on the experimental conditions, θW very significantly decreased, showing full wettability, and γSp rose dramatically, up to ten times. Within the DoE the conditions of plasma treatment were identified that resulted in selected optimal values of θW, γSp and O/C responses. Surface chemical changes were detected by XPS and ATR-IR investigations that evidenced both the introduction of fluorinated groups and the opening of the imide ring in the plasma-treated films.

Microplastics are ubiquitous pollutants in marine and freshwater bodies. Poly(ethylene terephthalate) microfibers (PMFs) are among the main primary microplastics (as-produced polymer microparticles). Released in large amounts in laundry wastewaters, PMFs end up in freshwater and marine sediments due to their high density. PMFs are potentially hazardous pollutants for ecosystems and human health, being a deceiving food source for animal organisms at the base of the food chain (e.g. sediment and water filtrators, including edible shellfish and small crustaceans). This study describes a simple, sensitive and versatile procedure for quantifying the total mass of PET micro- and nano-particles in sediments. The procedure involves aqueous alkaline PET depolymerization with phase transfer catalysis, oxidation and fractionations to remove interfering species and pre-concentrate the terephthalic acid (TPA) monomer, and TPA quantification by reversed-phase HPLC. Recovery of TPA from a model sediment spiked with 800 ppm PET micropowder was 98.2 %, with limits of detection/quantification LOD = 17.2 μg/kg and LOQ = 57.0 μg/kg. Analyses of sandy sediments from a marine beach in Tuscany, Italy, showed contamination in the 370–460 μg/kg range, suggesting that a not negligible fraction of PET microfibers released in surface waters ends up in shore sediments.

Poly(vinyl chloride) (PVC)/layered double hydroxide (LDH) composites and PVC/poly(methyl methacrylate) (PMMA)/LDH composites were prepared via solution intercalation into PVC using both unmodified and organo-modified LDHs and variable-molecular-weight PMMA as additional components. The LDH dispersion was investigated using X-ray diffraction analysis and electron microscopy in scanning and transmission modes. Spotlight fourier transform infrared (FTIR) chemical imaging analysis was also used to obtain a deeper insight into the dispersion of polymer phases and LDH segregation. Thermal properties were determined using thermogravimetric analysis and differential scanning calorimetry; moreover, a preliminary investigation of mechanical properties in tensile mode and evaluation of the Vicat softening temperature were carried out. The morphological analysis of PVC/LDH and PVC/PMMA/LDH composites evidenced in both cases the presence of disordered micro-aggregates with loss of the LDH crystallographic symmetry depending on the amount and molecular weight of PMMA. In particular, in the case of PVC/PMMA/LDH composites, the FTIR imaging analysis showed that PMMA mostly segregated in the LDH phase. However, even if the degree of LDH dispersion was not elevated (micro-aggregates with disordered structures and size ranging from 0.5 up to 11 µm were evidenced), thermal stability and mechanical properties of the composites were improved with a synergic effect of PMMA and LDH. © 2013 Society of Chemical Industry

Cardiac energy metabolism depends mainly on fatty acid (FA) oxidation; however, regulation of FA metabolism in acromegalic (Acro) heart is unknown. The aim of the study was to evaluate cardiac expression of key proteins of FA metabolism in young and elder transgenic mice overexpressing bovine GH Acro. Expression of proteins regulating FA entry into the cells, their uptake by mitochondria and beta-oxidation were evaluated by western blot, while FA content by Fourier transform infrared microspectrometry. Regulatory mechanisms of key steps of FA metabolism were also studied. The expression of plasma-membrane FA carriers (fatty acid-binding protein and fatty acid transport protein-1) and acylCoA synthetase was higher in young and lower in elder Acro than in corresponding controls; likewise, expression of cytoplasm to mitochondria-1 (CPT-1), the key enzyme of mitochondrial FA uptake, and that of medium-chain acyl-CoA dehydrogenase and long-chain acyl-CoA dehydrogenase, two regulatory beta-oxidation dehydrogenases, followed a similar pattern. FA content was lower in young and higher in elder Acro than in wild-type, suggesting an increased utilisation in young animals. GH regulated expression of key proteins of FA metabolism through changes in peroxisome proliferator-activated receptor alpha (PPARalpha) expression, which varied accordingly. GH effect was confirmed by treatment of Acro mice with a receptor antagonist, which abolished changes in key proteins of FA metabolism in young Acro. GH increased phosphorylation of AMP-activated protein kinase and anti-acetyl-CoA-carboxylase, two regulatory kinases, leading to lower CPT-1 inhibition by malonyl-CoA, and intervened in regulating PPARalpha expression through the ERK 1/2 pathway. In conclusion, chronic GH excess increased FA metabolism in the young age, whereas its action was overwhelmed in elder ages likely by GH-independent mechanisms, leading to reduced expression of key enzyme of FA metabolism.

The straightforward synthesis of polystyrene-supported Chinchona alkaloids and their application in the asymmetric dimerization of ketenes is reported. Six different immobilized derivatives, consisting of three dimeric and two monomeric 9-O ethers, were prepared by "click" anchoring of soluble alkaloid precursors on to azidomethyl resins. The resulting insoluble polymer-bound (IPB) organocatalysts were employed for promoting the dimerization of in-situ generated ketenes. After opening of the ketene dimer intermediates with N,O-dimethylhydroxylamine, valuable Weinreb amides were eventually obtained in good yield (up to 81 %) and excellent enantiomeric purity (up to 96 % ee). All of the IPB catalysts could be recycled effectively without significant loss of activity and enantioselectivity. The extension to other asymmetric transformations (meso-anhydride desymmetrization and α-amination of 2-oxindoles) is also briefly discussed.

The aim of this paper is to analyse the potential green practices that can be adopted onboard a cruise ship in order to enhance the environmental performance of the cruise with particular attention to paper input and output flows in a waste minimization perspective. A comparative life cycle assessment (LCA) of management scenarios of paper streams onboard a cruise ship is performed. The potential environmental impacts due to three strategic choices about paper and paper waste management onboard a case-study ship have been investigated through a so-called difference analysis, i.e. the digitalization of the daily information journal Today, the reduction of toilet paper and paper towels through the installation of auto-cut single extraction dispensers and the reduction of printing paper through dissemination of specific guidelines. In order to compare each scenario with the reference case in absence of the practice implementation, the functional unit in this study has been defined as 1 day of cruise. The implementation of the analysed green practices show comparable environmental benefits onboard a pilot ship, on the basis the set of assumptions and hypothesis identified in this simulation. In particular, when comparing the potential GHG emission reductions, it results that the two most realistically feasible scenarios in the communication area, i.e. digitalization of 25 and 50 % shares of Today journal, show environmental savings comparable to measures related to reduction of consumables and guidelines for personnel. Nevertheless, the addition of a reasonable number of touch-screen devices for this purpose would not significantly influence the environmental impacts. A set of reduction measures of paper items onboard a cruise ship is able to both avoid the impacts related to production and incineration stages. In the form of forecast scenarios, the results of such modelization may represent a set of indicators to be considered in a feasibility analysis prior to selection of the green practices to be introduced, as a support to decisions for cruise managers.

Coating materials characterised by intrinsic inhomogeneity or nanostructured morphology can display unique interfacial (e.g. surface and adhesion) and bulk (e.g. mechanical, thermal) properties, when heterophasic or self-segregating components are obtained by suitable design of the constitutive copolymers' structure. With the purpose of obtaining intrinsically photostable low-surface energy coating materials characterised by good penetration into porous substrates and variable response of the adhesive and polymer-air interface, fluorinated acrylic-based copolymers and water-borne acrylic-organosilane hybrids have been considered. For the latter, dispersed phase polymerisation procedures based on combined emulsion copolymerisation and hydrolysis-polycondensation of organosilane precursors have been adopted.

Poly(vinyl chloride) (PVC)/layered double hydroxide (LDH) composites and PVC/poly(methyl methacrylate) (PMMA)/LDH composites were prepared via solution intercalation into PVC using both unmodified and organo-modified LDHs and variable-molecular-weight PMMA as additional components. The LDH dispersion was investigated using X-ray diffraction analysis and electron microscopy in scanning and transmission modes. Spotlight fourier transform infrared (FTIR) chemical imaging analysis was also used to obtain a deeper insight into the dispersion of polymer phases and LDH segregation. Thermal properties were determined using thermogravimetric analysis and differential scanning calorimetry; moreover, a preliminary investigation of mechanical properties in tensile mode and evaluation of the Vicat softening temperature were carried out. The morphological analysis of PVC/LDH and PVC/PMMA/LDH composites evidenced in both cases the presence of disordered micro-aggregates with loss of the LDH crystallographic symmetry depending on the amount and molecular weight of PMMA. In particular, in the case of PVC/PMMA/LDH composites, the FTIR imaging analysis showed that PMMA mostly segregated in the LDH phase. However, even if the degree of LDH dispersion was not elevated (micro-aggregates with disordered structures and size ranging from 0.5 up to 11 mu m were evidenced), thermal stability and mechanical properties of the composites were improved with a synergic effect of PMMA and LDH. (c) 2013 Society of Chemical Industry