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In this paper the technological areas related to packaging end of life involved in MERLIN are resumed: (1) development of technology based on packaging identification and characterization for the sorting of multilayer packaging, (2) separation and recovery of the constituent multilayer packaging by delamination, (3) recovery and reprocessing for recycling of the delaminated fractions, and (4) production and validation of upcycled packaging with the materials developed in the project.

Two novel protocols for the chemical valorization of polyhydroxybutyrate (PHB) were developed, aiming at the production of two bio-based molecules: methyl 3-hydroxybutyrate (MHB) and methyl 3-methoxybutyrate (MMB). Optimized reaction conditions were applied to pure PHB and PHB inclusions inside bacterial cells as starting materials. MHB was synthesized through a single-step catalytic methanolysis, while MMB was synthesized through a three-step process: thermolytic distillation to give crotonic acid (CA), esterification to give methyl crotonate (MC), and oxa-Michael addition of MeOH. The obtained MHB and MMB were tested as solvents for the recovery of PHB itself both from freeze-dried single strain cultures (SSC) and mixed microbial cultures (MMC) with low to medium contents of PHB (22-57 wt %). High PHB recovery was achieved: up to 96 ± 1% through MHB and up to 98 ± 1% through MMB. Extraction from MMC slurry (with a PHB content of 39% on dry weight) was also performed, recovering 77 ± 2% using MHB and 92 ± 2% using MMB. High purities and excellent molecular weights and polydispersity indexes of extracted PHB were obtained with both MHB and MMB. Solubility in water, octanol/water partition coefficients (log Kow), and aerobic ready biodegradability of both solvents were also evaluated.

A novel thermolytic distillation process was developed to depolymerize polyhydroxybutyrate (PHB) for the selective production of crotonic acid. The conditions adopted (170 °C, 150 mbar) were applied to pure PHB and PHB-enriched bacteria containing 60 and 30% of PHB, giving a recovery of crotonic acid of 92, 78 and 58%, respectively. The high efficiency of the developed process poses the basis for a drop-in production of bio-based crotonic acid, whose versatility as a platform chemical has been investigated through a photochemical approach. The photocatalytic addition (promoted by tetrabutylammonium decatungstate – TBADT) of aliphatic and aromatic aldehydes to crotonic acid took place under solar-simulated light irradiation. TBADT triggered the in situ formation of valuable acyl radicals from the corresponding aldehydes, thus inducing the desired hydroacylation via radical conjugate addition. Notably, the functionalization took place in a satisfactory yield quite independently of the adopted sample of crotonic acid (whether commercial or bio-based).

L’invenzione consente la gestione fine vita di plastiche a base di amido tramite processi termochimici come alternativa al compostaggio e alla digestione anaerobica. Il procedimento permette di recuperare e riciclare gli atomi e le funzionalità presenti nelle plastiche a base di amido mediante depolimerizzazione e riarrangiamento, producendo nuovi composti chimici e materiali, in un’ottica di economia circolare.

Food waste is a global problem due to its environmental and economic impact, so there is great demand for the exploitation of new functional applications. The winemaking process leads to an incomplete extraction of high-value compounds, leaving the pomace still rich in polyphenols. This study was aimed at optimising and validating sustainable routes toward the extraction and further valorisation of these polyphenols, particularly for cosmeceutical applications. New formulations based on red grape pomace polyphenols and natural deep eutectic solvents (NaDESs) were here investigated, namely betaine combined with citric acid (BET-CA), urea (BET-U) and ethylene glycol (BET-EG), in which DESs were used both as extracting and carrying agents for polyphenols. The flavonoid profile determined by HPLC-MS/MS analysis showed similar malvidin content (51–56 μg mL−1) in the DES combinations, while BET-CA gave the best permeation performance in Franz cells, so it was further investigated in 3D human keratinocytes (HaCat spheroids) injured with the pro-oxidant agent menadione. BET-CA treatment showed good intracellular antioxidant activity (IC50 0.15 ± 0.02 μg mL−1 in malvidin content) and significantly decreased (p &lt, 0.001) the release of the pro-inflammatory cytokine IL-8, improving cell viability. Thus, BET-CA formulation is worthy of investigation for potential use as a cosmetic ingredient to reduce oxidative stress and inflammation, which are causes of skin aging.

Gels have been recently introduced in conservation to better control the cleaning action. The slow solvent release is of utmost importance to selectively remove varnish layers of a few microns in thickness, applied on paint layers which may have similar chemical properties. To evaluate the interactions of the underlying paint with solvents, diagnostic methods should study the physical and chemical changes that occur during and after the treatment. In this paper, we propose an innovative analytical protocol based on the combination of solid phase microextraction (SPME) and nuclear magnetic resonance (NMR) relaxometry to evaluate solvent entry and retention in the paint layer, as well as the induced microscopic and macroscopic changes to the elasticity of the binder. Moreover, FTIR and optical microscopy are used to evaluate the cleaning efficacy. The proposed analytical protocol can be used to identify solvents or gels which show minimal interaction with the paint. In particular, we have tested the protocol to evaluate the performance of non-toxic and biodegradable green gels on mock-ups and on a painting dated 19th century showing that they perform better than solvents applied with swabs. Five-minute gel treatments were found to be as effective at varnish removal as thirty-second swab treatments following traditional cleaning methods. Cleaning with gels limits the mechanical stress, solvent entry and retention in the paint layer, and reduces the embrittlement due to lower mass transfer. An unusual “sandwich” system was used to avoid the retention of gel residues on the surface with the gels contained in two sheets of Japanese papers – one on top and the other at the bottom.

Chemoenzymatic oxidations involving the CAL-B/H2O2 system was developed in a sugar derived Natural Deep Eutectic Solvent (NaDES) composed by a mixture of glucose, fructose and sucrose. Good to excellent conversions of substrates like cyclooctene, limonene, oleic acid and stilbene to their corresponding epoxides, cyclohexanone to its corresponding lactone and 2-phenylacetophenone to its corresponding ester, demonstrate the viability of the sugar NaDES as a reaction medium for epoxidation and Baeyer-Villiger oxidation.

Three novel hydrophobic deep eutectic solvents (DESs) based on oleic acid and terpenes (thymol, DL-menthol, and geraniol) were prepared, characterized, and used to extract astaxanthin from the microalga Haematococcus pluvialis without any pre-treatment of the cells. The three DES were composed of Generally Recognized As Safe (GRAS) and edible ingredients. All the tested DESs gave astaxanthin recovery values of about 60 and 30% in 6 h if applied on freeze-dried biomass or directly on algae culture, respectively. The carotenoid profile was qualitatively identical to what was obtained by using traditional organic solvents, regardless of the DES used; the monoesters of astaxanthin with C18-fatty acids were the main compounds found in all the carotenoid extracts. The thymol:oleic acid DES (TAO) could preserve astaxanthin content after prolonged oxidative stress (40% of the astaxanthin initially extracted was still present after 13.5 h of light exposure), thanks to the superior antioxidant properties of thymol. The capacity of improving astaxanthin stability combined with the intrinsic safety and edibility of the DES components makes the formulation astaxanthin-TAO appealing for the food ingredients/additives industry.

This work aims to develop methodologies and tools to support the design and management of sustainable processes for the production of biodegradable polyhydroxyalcanoates (PHAs) biopolymers. PHAs are linear polyesters produced in nature by bacteria through aerobic fermentation of many carbon sources, completely biodegradable and biocompatible. We carried out a study inherent to the advancement of an innovative, cost-effective and environmentally sustainable technology for isolating PHAs from bacteria mixed cultures by combining: (a) innovative cells’ pre-treatments and polymer purification’s strategy by means of TiO2/UV or Ag0 nanostructured materials; (b) polymer extraction through a green and safe system directly applicable to bacterial cultures, which combines the advantages of solvent extraction and these of dissolution of the non-PHAs cellular matrix through surfactants; (c) monitoring and control tools for process energy and efficiency management. The outcomes put the basis for the design and subsequent building of a working pilot system for the production of completely biodegradable and biocompatible PHAs. The efficiency can be improved and the investments and operating costs can be decreased thanks to the optimization of the production process with the introduction of safe and cheap PHAs extraction route without use of toxic and harmful chemicals and the integration of monitoring and automation tools. The engineering and integration of nano-TiO2 phase within textile fibres and their use as photocatalytic active media for bacteria pre- and post-treatment of waste water added a new opportunity for improving process efficiency and sustainability.

The recycling of polyhydroxybutyrate (PHB) via depolymerization-polymerization is here proposed and assessed for the first time. Effective depolymerization of PHB to crotonic acid through a thermolytic distillation at mild conditions (170 °C and 150 mbar), and without the need of any catalyst, gives a crotonic acid-enriched condensate (94% yield and 98% selectivity towards trans-crotonic acid) that was used without any further purification as a substrate for producing renewed PHB with a culture of Cupriavidus necator. The yield of PHB (0.6 g PHB per g of crotonic acid), final PHB content (63%), and PHB-molecular weight (1.5 MDa) confirmed the technical feasibility of this tandem approach, with a 55% overall yield. A preliminary evaluation of the energy consumption of various depolymerization approaches indicated that the thermolytic distillation consumes 20–25% less energy than previously reported methods; the energy requirement for producing crotonic acid from PHBwaste with 50% moisture has a still acceptable energy demand (4 MJ/kgcrotonic acid), comparable to the energy required for obtaining fermentable sugars (4.4 MJ/kgsugar) to be used for feeding bacteria that accumulate PHB.

Viene descritto un procedimento per il trasferimento di acidi organici da una soluzione acquosa di alimentazione proveniente da un reattore di fermentazione anaerobica ad una soluzione acquosa tramite l’ausilio di una membrana liquida a base organica immiscibile con tali fasi acquose, preferibilmente in cui tale soluzione acquosa di alimentazione presenta un pH inferiore rispetto al pH della soluzione acquosa ricevente; viene descritto altresì un sistema per l’esecuzione di tale procedimento.

Organo- and hydrogels have been proposed in the restoration field to treat different types of surfaces. The possibility to retain solvents and to have a controlled and superficial action allowed to use these materials for the removal of very thin layers applied on ancient historical objects, when the under paint layers are particularly delicate and water sensitive. In the last years, an increased attention has been devoted to the proposal of more healthy products to guarantee the safeguard of the operators. Few attention has been devoted to the development of green methods which foresee the use of renewable and biodegradable materials. The aim of this paper is to test a green organo-gel for the cleaning of water sensitive surfaces like varnished egg tempera paintings. The gel has been tested experimented on mock ups varnished with natural and synthetic materials and has been validated on a small portion of a Cimabue painting for the removal of two varnishes applied on two different test areas of the painting.

One of the most widely used approaches for improving drug permeation across the stratum corneum barrier of the skin is the use of chemical penetration enhancers, such as surfactants. In this study, two anionic surfactants, named C12-OPK and C18-OPK, were synthesized via condensation of itaconic acid and fatty amines, with C12 and C18 alkyl chains, respectively. Assessment of impacts on HaCaT keratinocyte cell viability was used as indicator of their potential to cause skin irritation 24 h post exposure (Alamar Blue assay). The LC50 values of C12-OPK and C18-OPK (144 and 85 mg/L, respectively) were lower than LC50 values of the most used commercial surfactants (e.g. SDS). The effect of different surfactant concentrations (up to ten times the critical micellar concentration, CMC) on hydrocortisone (HC) solubility and permeation through porcine skin was also evaluated. Results showed that drug solubility increased linearly with increasing concentrations of both surfactants, as a consequence of the association between drug and micelles. In vitro permeation results showed that the permeability coefficient increased at surfactant concentrations lower than the CMC. In particular, a higher enhancement effect on drug permeation was obtained with C18-OPK, due to its hydrophobic properties that ensured a more effective HC permeation in comparison to C12-OPK.

New formulations based on red grape pomace polyphenols and deep eutectic solvents (DES) have been here evaluated as inhibitors of urease of agricultural interest (jack bean urease, JBU). DES based on choline chloride (CHO) and betaine (BET), combined with ethylene glycol (EG), citric acid (CA), and urea (U), were used both as extracting and carrying agents for polyphenols, becoming active components of the formulations here obtained. Among the various DES combinations, U- and CA-based ones gave the best polyphenol extraction performances, 1.2-1.4-times higher than those of the hydroalcoholic mixture. Among the various DES-polyphenols formulations, the one composed by CHO-EG showed the best antioxidant potential and urease inhibition: 60-90% inhibition of the total JBU activity was achieved with a CHO concentration of 5-20 mM. Good results were also achieved with the BET-EG polyphenol formulation, which was able to inhibit ca. 50% of urease activity at 20 mM concentration of BET. Low phytotoxicity of DES and their polyphenol formulations tested at a concentration of 34 mM of CHO or BET was here observed on cress seedlings and the early growth of oat, in particular, for EG-based DES. On the other hand, tests performed on earthworms showed that CHO-based DES could impair the reproduction, and U-based DES caused severe mortality.

Volatile fatty acids (VFAs) are ideal substrates for mixed microbial cultures to synthesize polyhydroxyalkanoates. Therefore, VFA pertraction from anaerobic diluted fermentation broths to slightly alkaline aerobic medium becomes a crucial step to develop a closed loop concept in which VFAs are used for polyhydroxyalkanoate production. New liquid membranes (LMs) based on lipophilic amines and biodiesel were proposed for this purpose. The performance of each LM was tested through a VFA distribution coefficient test and pertraction kinetic experiments. The transfer of VFAs from LM to receiving solution was the main limiting step of the process, with flux rates of 0.001–0.04 cm3 cm−2 h−1 (best LM with 10 wt% of trioctylamine). The biocompatibility of trioctylamine -biodiesel LM towards anaerobic bacteria was confirmed through a 15-d acidogenic fermentation test. Trioctylamine-biodiesel LM was finally tested in a specifically designed continuous pertraction module, where VFA transfer rates of 1–3 h−1 were achieved.

In this research, we propose an advanced system for the cleaning of wax-based coatings applied on indoor bronzes. To this aim we developed a new kind of eco-friendly gel based on PHB (poly-3-hydroxybutyrate) used as thickening agent, biodiesel (BD) and dimethyl carbonate (DMC). BD is a mixture of methyl esters obtained from palm oil, which acts as cleaning agent while DMC was added as additional solvent to partially solubilize PHB and forming a gelly phase. For the first time a PHB-based gel obtained by mixing two solvents with different proprieties was proposed, expanding the range of possible formulations, that can be used according to the specific restoration purpose. After the preliminary characterization of chemical and physical properties of the gel, an ad hoc analytical protocol was implemented to evaluate both the cleaning efficiency and the release of residues on the treated surfaces. Standard samples were prepared following ancient recipes and submitted to spectroscopic and chromatographic analysis before and after the cleaning procedures. Finally, the performances of PHB-DMC/BD gel were assessed on a real case of study presenting a wax-based coating: the Pulpito della passione attributed to Donatello and dated back to 1460. In situ analysis demonstrated the high cleaning efficiency of the proposed systems also for the removal of aged coatings.

A transdisciplinary approach that integrates thermochemical conversions and biological transformations for valorizing C-content and chemical energy of anaerobically digested sewage sludge and producing biopolymers (polyhydroxyalkanoates, PHA) and drop-in chemicals (crotonic acid) has been presented here. Hydrothermal carbonization has increased by 10-times the soluble COD of sewage sludge, allowing it to split 44-54% of its COD into an aqueous phase (HTCap) enriched in small fermentable organic molecules; the coupling of acidogenic fermentation and aerobic fermentation converted these substrates first into volatile fatty acids (20% of CODHTCap) and then into PHA (about 20% of CODVFA). The extraction of microbial biomass with dimethyl carbonate (DMC) allowed high quality PHA to be produced, with a high molecular weight (0.9 MDa) and a percentage of medium chain monomers (hydroxyvalerate and hydrohexanoate) close to 12%. The postextraction microbial biomass, still containing a relevant portion of "unextractable" PHA, was last treated at 300 °C to selectively convert the PHA-backbone into crotonic acid with a 42% yield on PHA content basis.

We thank the University of Bologna (RFO program) for funding. The microalga Haematococcus pluvialis is capable of accumulating natural astaxanthin when subjected to external stress and shifted towards a red-cyst phase, characterized by a robust and multilayered cell wall. In the present study, still-unexplored solvents were applied for extracting astaxanthin from H. pluvialis, directly from algae culture and without any pre-treatment of the cells. Among the tested solvents, some of them (e.g. ethyl acetate and 2-methyltehydrofuran) gave excellent astaxanthin recovery (>80%) in a short time (30 min) and others (e.g. isoamyl acetate, well known as a human-compatible solvent and already in use as a food additive) gave an astaxanthin recovery close to 90% in 1 hour and thus they are exploitable in the natural astaxanthin market. Almond oil is proved to be able to extract astaxanthin and keep H. pluvialis alive, without affecting the algal photosynthetic activity, providing the possibility to milk and regeneratively cultivate H. pluvialis and avoid an uneconomical loss of biomass.

By dissecting the structure of β-lactam-based ligands, a new series of compounds was designed, synthesized, and evaluated toward integrins αvβ3, α5β1, and α4β1. New selective ligands with antagonist or agonist activities of cell adhesion in the nanomolar range were obtained. The best agonist molecules induced significant adhesion of SK-MEL-24 cells and Saos-2 cells as a valuable model for osteoblast adhesion. These data could lead to the development of new agents to improve cellular osseointegration and bone regeneration. Molecular modeling studies on prototypic compounds and αvβ3 or α5β1 integrin supported the notion that ligand carboxylate fixing to the metal ion-dependent adhesion site in the β-subunit can be sufficient for binding the receptors, while the aryl side chains play a role in determining the selectivity as well as agonism versus antagonism.

Pyrolysis was explored as a technology for depolymerizing and charring starch-based plastic bags in a novel valorization perspective based on a chemical recycling strategy, alternative to anaerobic digestion or composting. The char obtained from the thermal treatment (420°C for 15 h) was sulfonated to give a highly active and recyclable heterogeneous acid catalyst (10 wt% yield based on starch-based plastic bags subjected to pyrolysis), comparable in terms of catalytic activity and reusability to the analog catalyst prepared from potato starch and tested on a model esterification reaction. From pyrolysis liquid of starch-based plastic bags, highly pure terephthalic acid (4 wt% yield) was isolated through self-precipitation, whereas the remaining pyrolysis liquid produced (21 wt%) was solvent-fractionated to give a polar fraction (7 wt% yield) enriched in levoglucosan, and a less polar fraction (14 wt% yield) enriched in monobutenyl adipate and terephthalate.

A novel series of β-lactam derivatives that was designed and synthesized to target RGD-binding and leukocyte integrins is reported. The compound library was evaluated by investigating the effects on integrin-mediated cell adhesion and cell signaling in cell lines expressing αvβ3, αvβ5, αvβ6, α5β1, αIIbβ3, α4β1, and αLβ2 integrins. SAR analysis of the new series of azetidinones enabled the recognition of structural elements associated with integrin selectivity. We obtained selective and potent agonists that could induce cell adhesion and promote cell signaling mediated by αvβ3, αvβ5, α5β1, or α4β1 integrin, and antagonists for the integrins αvβ3 and α5β1, as well as α4β1 and αLβ2, preventing the effects elicited by the respective endogenous agonists.

In view of the potential use of pyrolysis-based technologies, it is crucial to understand the environmental hazards of pyrolysis-derived products, in particular bio-oils. Here, three bio-oils were produced from fast pyrolysis of pine wood and intermediate pyrolysis of corn stalk and poultry litter. They were fully characterized by chemical analysis and tested for their biodegradability and their ecotoxicity on the crustacean Daphnia magna and the green alga Raphidocelis subcapitata. These tests were chosen as required by the European REACH regulation. These three bio-oils were biodegradable, with 40-60% of biodegradation after 28 days, and had EC50 values above 100mgL(-1) for the crustacean and above 10mgL(-1) for the alga, showing low toxicity to the aquatic life. The toxic unit approach was applied to verify whether the observed toxicity could be predicted from the data available for the substances detected in the bio-oils. The predicted values largely underestimated the experimental values.

none 9 no Fully biodegradable novel bio-based organogels were developed for removing aged protective films from the surfaces of paintings, aiming at providing effective cleaning tools, easily controllable by reducing the solvent permeation into underlying paint layers and not dangerous for human health and the environment. The gels were based on poly-3-hydroxybutyrate (PHB) as gelling agent, γ-valerolactone (GVL) as solvent and triethyl citrate (TEC) as plasticizer. PHB-gels were able to completely remove protective varnishes on real oil paintings, without affecting the pictorial layer and leaving negligible residues after the application. Moreover, the gels showed good mechanical and handling properties, they were fully composed by non-toxic ingredients and resulted readily biodegradable in water, therefore easily disposable after the use. mixed Samorì, Chiara; Galletti, Paola; Giorgini, Loris; Mazzeo, Rocco; Mazzocchetti, Laura; Prati, Silvia; Sciutto, Giorgia; Volpi, Francesca; Tagliavini, Emilio Samorì, Chiara; Galletti, Paola; Giorgini, Loris; Mazzeo, Rocco; Mazzocchetti, Laura; Prati, Silvia; Sciutto, Giorgia; Volpi, Francesca; Tagliavini, Emilio

The challenging multicomponent cascade synthesis of biaryl-based chalcones was carried out in pure water and in an aqueous micellar system. The first step of the protocol was a simple Pd-catalysed, ligand-free, and aerobic Suzuki–Miyaura reaction in aqueous medium. This proved to be extremely efficient for the coupling of aryl and heteroaryl bromides with different arylboronic acids. Subsequently, the resulting intermediates underwent an in-situ aldol condensation reaction to give biaryl(hetero)chalcones in good to excellent yields. When the protocol was applied to highly lipophilic or less reactive reagents, micellar catalysis was required for good results. To achieve this, we successfully used a new surfactant obtained from renewable resources that we recently designed. Furthermore, using this additive, the catalytic system can be repeatedly recycled without significant loss of activity.

CO2 is a renewable, abundant and cheap C1-feedstock and its conversion to cyclic carbonates starting from epoxides has been widely explored in the last years. Nevertheless, conducting this reaction under mild and sustainable conditions is still a challenging task. Herein we present the use of choline-salt based eutectic mixtures as catalysts for the reaction of CO2 with epoxides to give cyclic carbonates. Choline chloride and choline iodide have been coupled with various hydrogen bond donors (HBDs), mainly cheap and bio-based carboxylic acids and polyols, to form two classes of eutectic mixtures. Very good yields were achieved under mild conditions (80 °C in 7–22 h) for various terminal epoxides, with both classes of catalysts. While a pressure of 0.4 MPa of CO2 is required to obtain appreciable conversions using choline chloride-based mixture, atmospheric pressure of CO2 (balloon) has been successfully used with choline iodide-based mixtures. Furthermore, the catalysts could be recycled without appreciable loss of the catalytic activity. The improved catalytic performance of both choline-based eutectic mixtures is attributed to the synergistic activity of the halide, responsible for the opening of the epoxy-ring, and the HBD that has a role in the stabilization of the alkoxide intermediate.

A “cradle-to-grave” life cycle assessment is performed to identify the environmental issues of polyhydroxyalkanoates (PHAs) produced through a hybrid thermochemical-biological process using anaerobically digested sewage sludge (ADSS) as feedstock. The assessment includes a measure of the energy performance of the process. The system boundary includes: (i) Sludge pyrolysis followed by volatile fatty acids (VFAs) production; (ii) PHAs-enriched biomass production using a mixed microbial culture (MMC); (iii) PHAs extraction with dimethyl carbonate; and iv) PHAs end-of-life. Three scenarios differing in the use of the syngas produced by both pyrolysis and biochar gasification, and two more scenarios differing only in the external energy sources were evaluated. Results show a trade-off between environmental impacts at global scale, such as climate change and resources depletion, and those having an effect at the local/regional scale, such as acidification, eutrophication, and toxicity. Process configurations based only on the sludge-to-PHAs route require an external energy supply, which determines the highest impacts with respect to climate change, resources depletion, and water depletion. On the contrary, process configurations also integrating the sludge-to-energy route for self-sustainment imply more onsite sludge processing and combustion; this results in the highest values of eutrophication, ecotoxicity, and human toxicity. There is not a categorical winner among the investigated configurations; however, the use of a selected mix of external renewable sources while using sludge to produce PHAs only seems the best compromise. The results are comparable to those of both other PHAs production processes found in the literature and various fossil-based and bio-based polymers, in terms of both non-biogenic GHG emissions and energy demand. Further process advancements and technology improvement in high impact stages are required to make this PHAs production process a competitive candidate for the production of biopolymers on a wide scale.

none 5 no A new metal-free protocol for promoting oxidation of amines in aqueous-organic medium was developed. NaIO4and TEMPO as the catalyst emerged as the most efficient and selective system for oxidation of differently substituted benzyl amines to the corresponding benzaldehydes without overoxidation. Unsymmetrical secondary amines underwent selective oxidation only at the benzylic position thus realising an oxidative deprotection of a benzylic group with an easy amine recovery. open Galletti, P.*; Martelli, G.; Prandini, G.; Colucci, C.; Giacomini, D. Galletti, P.*; Martelli, G.; Prandini, G.; Colucci, C.; Giacomini, D.

Gorgonian corals play a structural role in temperate and tropical biogenic reefs, forming animal forests and creating biodiversity hot spots. In the Mediterranean Sea, slow-growing and long-lived gorgonian species are threatened by human disturbances and global environmental changes and concern about their conservation is rising. Alkaloid metabolites have proven to be essential in protecting these species from environmental stressors. Traditional profiling methodologies to detect these metabolites require a large quantity of living tissue. Here, the chemodiversity of gorgonian alkaloids was investigated by applying a fast and effective protocol combining extraction and derivatization using small-scale tissue samples and GC/MS analysis. The method was effective in identifying and quantifying alkaloids and guanine-based compounds. Eight N-heterocyclic compounds were found in six Mediterranean gorgonians differing for types and quantity. The metabolomic profile was conservative in species of the Eunicella genus, with three species sharing the same pattern. Conversely, Paramuricea clavata displayed a noticeable spatial pattern of variation among colonies collected in different locations. The analytical approach presented here proved to be effective, allowing rare, endangered, and small-sized species to be screened rapidly for detection of new compounds in order to explore their biological and ecological functions.

Ionic liquids (ILs) are promising materials exploited as solvents and media in many innovative applications, some already used at the industrial scale. The chemical structure and physicochemical properties of ILs can differ significantly according to the specific applications for which they have been synthesized. As a consequence, their interaction with biological entities and toxicity can vary substantially. To select highly effective and minimally harmful ILs, these properties need to be investigated. Here we use the so called chromatophores - protein-phospholipid membrane vesicles obtained from the photosynthetic bacterium Rhodobacter sphaeroides- to assess the effects of imidazolinium and pyrrolidinium ILs, with chloride or dicyanamide as counter anions, on the ionic permeability of a native biological membrane. The extent and modalities by which these ILs affect the ionic conductivity can be studied in chromatophores by analyzing the electrochromic response of endogenous carotenoids, acting as an intramembrane voltmeter at the molecular level. We show that chromatophores represent an in vitro experimental model suitable to probe permeability changes induced in cell membranes by ILs differing in chemical nature, degree of oxygenation of the cationic moiety and counter anion. (C) 2015 Elsevier B.V. All rights reserved.

none 5 no Surfactants are a wide class of compounds used in a broad spectrum of industrial and everyday applications. In this paper, we present the synthesis of a new family of surfactants having C12 and C18 alkyl chains obtained from itaconic acid and fatty amines, molecules industrially obtained from renewable resources. Main physicochemical properties of synthesized surfactants have been measured and their rheological behaviors have been evaluated at the air-water interface using the pendant drop technique. Some of the synthesized surfactants are stimuli responsive compounds, switchable to a polar form in the presence of CO2. The synthetic strategies have been optimized aiming at the sustainability of the process employing a complete set of green metrics and the software EATOS. none Malferrari, Danilo; Armenise, Nicola; Decesari, Stefano; Galletti, Paola; Tagliavini, Emilio Malferrari, Danilo; Armenise, Nicola; Decesari, Stefano; Galletti, Paola; Tagliavini, Emilio

The availability of green and cheap technologies to recover polyhydroxyalkanoates (PHAs) from microbial biomass is crucial for the development of a reliable and sustainable production chain. Here, two novel protocols are proposed to extract PHAs from Cupriavidus necator. The first method is based on PHA-extraction with dimethyl carbonate (DMC), a green solvent that is completely biodegradable and less harmful to humans and the environment than most solvents. The procedure can be applied directly to concentrated microbial slurries or to dry biomass, affording very high polymer recovery (>85%) and excellent purity (>95%). No degradation/decomposition of the polymer is observed in both cases. The second protocol uses fatty acid carboxylates as surfactants, which disrupt cell membranes, providing excellent polymer recovery (>99%) and high purity (>90%). Ammonium laurate can be successfully used and easily recycled (98%) by lowering the pH through CO2 addition. Therefore, both protocols reported here are effective and sustainable: the recovery and purity of the obtained PHAs are very high, the use of toxic chemicals is avoided, and the recycling of various solvents/surfactants used in the processes is optimal.

Plastic materials have wide commercial applicability. However, they are made from non-renewable resources and are characterised by resistance to degradation. Poly-hydroxyalkanoates (PHAs) provides one example of a polymer biodegradable, biocompatible and produced from renewable raw materials. With respect to other bioplastics the share of PHAs in the market is very limited because of their commercial costs. To develop more cost effective processes for PHAs production, a multilevel approach is usually undertaken combining innovative, cheaper and more effective cultivation with safe and cheap extraction and purification methodologies. This study assesses the potential environmental impacts related to a production processes based on the novel protocol to extract PHAs comparing them to the impacts of extraction process based on the use of halogenated hydrocarbons.

A new procedure based on switchable hydrophilicity solvents (SHS) was proposed for polyethylene and aluminium recovery from food aseptic packaging. Treatment with N,N-dimethylcyclohexylamine (DMCHA) allowed very high material recovery (>99% for aluminium and >80% for polyethylene), without compromising the quality in terms of oxidation or polymer degradation. Moreover, the results from a simplified and preliminary life cycle analysis confirm the potential environmental benefits of a SHS approach compared with other treatment and disposal scenarios. A new procedure based on switchable hydrophilicity solvents (SHS) was proposed for polyethylene and aluminium recovery from food aseptic packaging. Treatment with N,N-dimethylcyclohexylamine (DMCHA) allowed very high material recovery (>99% for aluminium and >80% for polyethylene), without compromising the quality in terms of oxidation or polymer degradation. Moreover, the results from a simplified and preliminary life cycle analysis confirm the potential environmental benefits of a SHS approach compared with other treatment and disposal scenarios.

Poly-hydroxyalkanoates are an example of biodegradable and biocompatible polymers, produced from renewable raw materials. With respect to other bioplastics the market share of poly-hydroxyalkanoates is still limited because of their commercial costs. To develop more cost-effective processes, a multilevel approach is usually undertaken combining innovative, cheaper and more effective microbial cultivation with safe and cheap extraction and purification methodologies. This study assesses the potential life cycle environmental impacts related to a novel protocol poly-hydroxyalkanoates extraction based on dimethyl carbonate in comparison to the use of halogenated hydrocarbons (in particular 1,2 dicholoroethane). Four scenarios are analysed for the dimethyl carbonate protocol considering: extraction from microbial slurry or from dried biomass, and recovery by solvent evaporation or polymer precipitation. The life cycle assessment demonstrates that the environmental performances of dimethyl carbonate-based protocols are far better than those of the most comparative process using the halogenated hydrocarbons. The scenario that foresees the extraction of dried biomass and recovers solvent by evaporation appears to be the most promising in terms of environmental sustainability performance.

Microalgae are promising alternative sources of several bioactive compounds that are useful for human applications. However, lipids are traditionally extracted with toxic organic solvents (e.g., mixtures of chloroform and methanol or hexane). In this work, we develop a new lipid extraction protocol for obtaining a fatty-acids-rich extract from the diatom Phaeodactylum tricornutum. Deep eutectic solvents (DESs) and microwaves (MWs) were investigated as pretreatments for environmentally friendly solvent extractions using dimethyl carbonate (DMC) and supercritical CO2 (scCO2). Pretreatments with various DESs formed by choline chloride (ChCl) and different hydrogen-bond donors (oxalic acid, levulinic acid, urea, ethylene glycol, and sorbitol) were tested in combination with DMC extraction. DESs formed by ChCl and carboxylic acids gave the best results, increasing both the selectivity and the total fatty acid (TFA) extraction yield of DMC (by 16% and 80%, respectively). DESs combined with MW heating followed by DMC extraction allowed a TFA yield and fatty acid profile comparable to those of the traditional Bligh and Dyer extraction method to be reached, along with a much better selectivity (88% vs 35%). This pretreatment was also demonstrated to significantly improve the extraction efficiency of scCO2, increasing the TFA yield by a factor of 20 and providing highly purified triglyceride extracts.

Antimicrobial resistance is one of the major and growing concerns in hospital- and community acquired infections, and new antimicrobial agents are therefore urgently required. It was reported that oxidative stress could contribute to the selection of resistant bacterial strains, since reactive oxygen species (ROS) revealed to be an essential driving force. In the present work 4-alkylidene-azetidinones, a new class of antibacterial agents, were functionalized with phytochemical polyphenolic acids such as protocatechuic, piperonyl, caffeic, ferulic, or sinapic acids and investigated as dual target antibacterial-antioxidant compounds. The best candidates showed good activities against multidrug resistant clinical isolates of MRSA (MICs 2–8 μg/mL). Among the new compounds, two revealed the best antioxidant capacity with TEAC-DPPH and TEAC-ABTS being significantly more active than Trolox®.

We describe a new synthesis of the 5-(aminomethyl)oxazolidin-3-one core of linezolid in enantiomerically pure form. The expedient cyclization of the α-hydroxy amide derived from isoserine and 3-fluoro-4-morpholinoaniline to give the corresponding (aminomethyl)oxazolidine-2,4-dione, followed by its mild selective reduction at the C(4)-position, gave linezolid in almost quantitative overall yield.

Obtainment and testing of pure enantiomers are of great importance for bioactive compounds, because of the assessed implications of enantioselectivity in receptor-mediated responses. Herein we evaluated the use of biocatalysis to obtain enantiomerically pure β-lactam intermediates further exploited in the synthesis of novel integrin ligands as single enantiomers. From a preliminary screening on a set of commercially available hydrolases, Burkholderia Cepacia Lipase (BCL)emerged as a suitable and highly performing enzyme for the kinetic resolution of a racemic azetidinone, key intermediate for the synthesis of novel agonists of integrins. Upon optimization of the biocatalytic protocol in terms of enzymes, acylating agents and procedures, the two β-lactam enantiomers were obtained in excellent enantiomeric excesses (94% and 98% ee). Synthetic elaborations on the separated enantiomers allowed the synthesis of four chiral β-lactams which were evaluated in cell adhesion assays on Jurkat cell line expressing α 4 β 1 integrin, and K562 cell line expressing α 5 β 1 integrin. Biological tests revealed that only (S)-enantiomers maintained the agonist activity of racemates with a nanomolar potency, and a specific enantio-recognition by integrin receptors was demonstrated.

An efficient and practical chemo-enzymatic aerobic oxidation in water of benzylamines to obtain aldehydes or imines is described. Laccase from Trametes versicolor was chosen as biocatalyst, and TEMPO (radical 2,2,6,6-tetramethylpiperidine 1-oxyl) as mediator. A study on the pH dependence of the aqueous medium allowed us to realise a fine tuning on product selectivity. Under our optimized reaction conditions, the bio-oxidation of a series of primary, secondary and cyclic amines has been achieved

The synthesis of a series of new chiral α-aminonitriles was achieved in a diastereoselective Strecker reaction in a one-pot procedure with aldehydes, enantiopure amines, and acetone cyanohydrin in water. Primary and secondary amines derived from L-α-amino acids were used as sources of chirality. The reactions proceeded efficiently without any catalyst at room temperature. The diastereoselectivity of the process, and the configurational stability of new chiral α-aminonitriles were investigated. The identification of labile intermediates by NMR analysis, and a proposed mechanism and a model for the asymmetric induction are reported. The chemical transformation of proline-derived chiral α-amino-nitriles into chiral amino-diacids, aminols, and amides is reported.

A new procedure based on switchable polarity solvents (SPS) was proposed for lipid extraction of wet algal samples or cultures, thereby circumventing the need for an energy intensive drying step and facilitating easy recovery of the lipids from the extraction liquid. Lipids were extracted by using N,N-dimethylcyclohexylamine (DMCHA) and recovered by adding CO2, thereby switching DMCHA into a hydrogen carbonate ammonium salt and resulting in the formation of a separate liquid lipid phase.

In this study we have explored the effects of different groups of ionic liquids (ILs) on membrane fusion. The ILs used contain different head groups: N-methylimidazolium, 3-methylpyridinium and N-methylpyrrolidinium; short alkyl or ether functionalized side chains (with one or two ethoxy functionalities), paired with chloride anion. These ILs have been compared with 1-dodecyl-3-methylimidazolium bromide as example of a highly lipophilic IL. The effect of ILs on membrane fusion was investigated through pyrene steady state fluorescence probing, using the IE factor and excimer/monomer ratio (IE/IM) as parameters. The ratio between the vibronic bands of pyrene ( I 1 / I 3 ratio) has been used to monitor the effect of ILs on the aggregation properties of egg-PC liposomes. The effect of different ILs’ families was evident; the pyridinium ILs induced a greater extent of fusion than pyrrolidinium and imidazolium ILs having the same side chain. Marginal effect could be attributed to different anions. ILs with short alkyl chains were usually more effective than ether functionalized ones. The aggregation behaviors of ILs having dioxygenated chains have been measured in buffer solution.

The challenging multicomponent cascade synthesis of biaryl-based chalcones was carried out in pure water and in an aqueous micellar system. The first step of the protocol was a simple Pd-catalysed, ligand-free, and aerobic Suzuki–Miyaura reaction in aqueous medium. This proved to be extremely efficient for the coupling of aryl and heteroaryl bromides with different arylboronic acids. Subsequently, the resulting intermediates underwent an in-situ aldol condensation reaction to give biaryl(hetero)chalcones in good to excellent yields. When the protocol was applied to highly lipophilic or less reactive reagents, micellar catalysis was required for good results. To achieve this, we successfully used a new surfactant obtained from renewable resources that we recently designed. Furthermore, using this additive, the catalytic system can be repeatedly recycled without significant loss of activity.

By combining two green and efficient catalysts, such as the commercially available enzyme laccase from Trametes versicolor and the stable free radical 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO), the oxidation in water of some primary alcohols to the corresponding carboxylic acids or aldehydes and of selected secondary alcohols to ketones can be accomplished. The range of applicability of bio-oxidation is widened by applying the optimized protocol to the oxidation of enantiomerically pure 2-arylpropanols (profenols) into the corresponding 2-arylpropionic acids (profens), in high yields and with complete retention of configuration.

Polydiacetylenes (PDAs) constitute a family of conjugated polymers exhibiting unique colorimetric and fluorescence transitions, and have attracted significant interest as chemo- and biosensing materials. We spin-coated PDA films upon poly(methyl methacrylate) (PMMA), and investigated the photophysical properties and sensing applications of the new PDA configuration. Specifically, the as-polymerized blue PDA layer underwent distinct transformations to purple, red, and yellow phases, which could be quantified through conventional color scanning combined with application of image analysis algorithms. Furthermore, we recorded a reversible red-purple PDA transition that was induced by ultraviolet irradiation, a phenomenon that had not been reported previously in PDA film systems. We show that distinct color and fluorescence transitions were induced in the PMMA-supported PDA films by amphiphilic substances-surfactants and ionic liquids-and that the chromatic transformations were correlated to the analyte structures and properties. Overall, this study presents a new chromatic PDA film system in which noncovalent interactions between the PMMA substrate and spin-coated PDA give rise to distinct chromatic properties and molecular sensing capabilities. © 2014 American Chemical Society.