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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.

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.

Special issue Marine organic matter: from biological production in the ocean toorganic aerosol particles and marine clouds (ACP/OS inter-journalSI).-- 15 pages, 8 figures, 1 table, supplement https://doi.org/10.5194/acp-20-4193-2020, The concentrations of submicron aerosol particles in maritime regions around Antarctica are influenced by the extent of sea ice. This effect is two ways: on one side, sea ice regulates the production of particles by sea spray (primary aerosols); on the other side, it hosts complex communities of organisms emitting precursors for secondary particles. Past studies documenting the chemical composition of fine aerosols in Antarctica indicate various potential primary and secondary sources active in coastal areas, in offshore marine regions, and in the sea ice itself. In particular, beside the well-known sources of organic and sulfur material originating from the oxidation of dimethylsulfide (DMS) produced by microalgae, recent findings obtained during the 2015 PEGASO cruise suggest that nitrogen-containing organic compounds are also produced by the microbiota colonizing the marginal ice zone. To complement the aerosol source apportionment performed using online mass spectrometric techniques, here we discuss the outcomes of offline spectroscopic analysis performed by nuclear magnetic resonance (NMR) spectroscopy. In this study we (i) present the composition of ambient aerosols over open-ocean waters across bioregions, and compare it to the composition of (ii) seawater samples and (iii) bubble-bursting aerosols produced in a sea-spray chamber onboard the ship. Our results show that the process of aerosolization in the tank enriches primary marine particles with lipids and sugars while depleting them of free amino acids, providing an explanation for why amino acids occurred only at trace concentrations in the marine aerosol samples analyzed. The analysis of water-soluble organic carbon (WSOC) in ambient submicron aerosol samples shows distinct NMR fingerprints for three bioregions: (1) the open Southern Ocean pelagic environments, in which aerosols are enriched with primary marine particles containing lipids and sugars; (2) sympagic areas in the Weddell Sea, where secondary organic compounds, including methanesulfonic acid and semivolatile amines abound in the aerosol composition; and (3) terrestrial coastal areas, traced by sugars such as sucrose, emitted by land vegetation. Finally, a new biogenic chemical marker, creatinine, was identified in the samples from the Weddell Sea, providing another confirmation of the importance of nitrogen-containing metabolites in Antarctic polar aerosols, The cruise was funded by the Spanish Ministry of Economy through projects PEGASO (CTM2012-37615) and Bio-Nuc (CGL2013-49020-R). The research leading to these results has received funding from the European Union's Seventh Framework Programme (FP7/2007–2013) Project BACCHUS under grant agreement no. 603445. The research activities of CNR were also supported by the project AirSEaLab: Progetto Laboratori Congiunti, With the funding support of the ‘Severo Ochoa Centre of Excellence’ accreditation (CEX2019-000928-S), of the Spanish Research Agency (AEI)

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.

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.

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.

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.

Atmospheric organic aerosols are generally classified as primary and secondary (POA and SOA) according to their formation processes. An actual separation, however, is challenging when the timescales of emission and gas-to-particle formation overlap. The presence of SOA formation in biomass burning plumes leads to scientific questions about whether the oxidized fraction of biomass burning aerosol is rather of secondary or primary origin, as some studies would suggest, and about the chemical compositions of oxidized biomass burning POA and SOA. In this study, we apply nuclear magnetic resonance (NMR) spectroscopy to investigate the functional group composition of fresh and aged biomass burning aerosols during an intensive field campaign in the Po Valley, Italy. The campaign was part of the EUCAARI project and was held at the rural station of San Pietro Capofiume in spring 2008. Factor analysis applied to the set of NMR spectra was used to apportion the wood burning contribution and other organic carbon (OC) source contributions, including aliphatic amines. Our NMR results, referred to the polar, water-soluble fraction of OC, show that fresh wood burning particles are composed of polyols and aromatic compounds, with a sharp resemblance to wood burning POA produced in wood stoves, while aged samples are clearly depleted of alcohols and are enriched in aliphatic acids with a smaller contribution of aromatic compounds. The comparison with biomass burning organic aerosols (BBOA) determined by high-resolution aerosol mass spectrometry (HR-TOF-AMS) at the site shows only a partial overlap between NMR BB-POA and AMS BBOA, which can be explained by either the inability of BBOA to capture all BB-POA composition, especially the alcohol fraction, or the fact that BBOA account for insoluble organic compounds unmeasured by the NMR. Therefore, an unambiguous composition for biomass burning POA could not be derived from this study, with NMR analysis indicating a higher O / C ratio compared to that measured for AMS BBOA. The comparison between the two techniques substantially improves when adding factors tracing possible contributions from biomass burning SOA, showing that the operational definitions of biomass burning organic aerosols are more consistent between techniques when including more factors tracing chemical classes over a range of oxidation levels. Overall, the non-fossil total carbon fraction was 50–57%, depending on the assumptions about the 14C content of non-fossil carbon, and the fraction of organic carbon estimated to be oxidized organic aerosol (OOA) from HR-TOF-AMS measurements was 73–100% modern.

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.

This article describes the toxic effects of imidazolium ionic liquids bearing alkyl (BMIM), monoethoxy (MOEMIM), and diethoxy (M(OE)(2)MIM) side chains toward two marine diatoms, Skeletonema marinoi and Phaeodactylum tricornutum. MOEMIM and M(OE)(2)MIM cations showed a lower inhibition of growth and photosynthetic efficiency with respect to their alkyl counter part, with both algal Species. However, a large difference in sensitivity was found between S. marinoi and P. tricornutum, the first being much more Sensitive to the action of ionic liquids than the second one. The effects of salinity on BMIM Cl toxicity toward S. marinoi revealed that a decrease from salinity 35 to salinity 15 does not influence the biological effects toward the alga. Finally, Fourier transform infrared (FT-IR) microscopy of alga cells after ionic liquids exposure allowed us to detect an alteration of the organic cellular components related. to silica uptake and organization. On the basis of these results, the different behavior of the two diatom species can be tentatively ascribed to different silica uptake and organization in outer cell walls

Since the 1990s red-tide blooms of Fibrocapsa japonica have frequently been observed in European waters; despite their recurrence also in the Adriatic coastal areas, they have never been conclusively linked to ichthyotoxic events. Since the toxicity of F. japonica is still under debate and its effects differ among the strains, in this study all the compounds previously postulated as involved in the toxic mechanism, such as brevetoxins, fatty acids and ROS, were screened for Adriatic strains. Whole algal extracts were analyzed for brevetoxin PbTx-2, which was not found, and for a qualitative and quantitative analysis of fatty acids. The fatty acid profile evidenced the presence of PUFAs, with considerable amounts of 18:4n-3, 20:4n-6, and 20:5n-3, as already found in different strains, but with a lower amount of arachidonic acid (20:4n-6). None of the PUFAs was released in the extracellular medium. Different toxicological assays (Vibrio fischeri, Artemia sp., haemolysis of fish erythrocytes) were performed using algal cellular, extracellular or subcellular samples as well as fractions of the algal extract, in order to identify the toxic compounds. The tested cultures were found to inhibit V. fischeri bioluminescence, to affect Artemia nauplii viability and to have haemolytic effects comparable to those previously observed in different strains. The solid phase extraction (SPE) of the Adriatic F. japonica extracts resulted in a high concentration of PUFAs in two main fractions, which caused mortality in Artemia nauplii and inhibition of V. fischeri bioluminescence. Fish (Dicentrarchus labrax) assays were also performed, reporting mortality after long exposure times and the cause of fish death was investigated. A significant increase of H2O2 in the tanks where sea basses were exposed to F. japonica was obtained, indicating that the presence of fish stimulates H2O2 production by algal cells and leading to the hypothesis of H2O2 involvement in F. japonica toxicity. The presence of oxidative stress in the exposed fish was confirmed by the increased malondialdehyde concentration in their gills. Overall these results indicate that since F. japonica cells can easily cling to fish gills, due to their high polysaccharide production, it is presumable that high PUFA amounts are released in loco, as a result of cell breakage, and that exert their toxicity together with ROS. This study shows that the Adriatic strains of F. japonica can be harmful to higher level organisms. Nevertheless a high cell density and a long lasting bloom are necessary to cause severe damage to fish gills or death for crustaceans.

Lipid extraction is a critical step in the development of biofuels from microalgae. Here a new procedure was proposed to extract hydrocarbons from dried and water-suspended samples of the microalga Botryococcus braunii by using switchable-polarity solvents (SPS) based on 1,8-diazabicyclo-[5.4.0]-undec-7-ene (DBU) and an alcohol. The high affinity of the non-ionic form of DBU/alcohol SPS towards non-polar compounds was exploited to extract hydrocarbons from algae, while the ionic character of the DBU-alkyl carbonate form, obtained by the addition of CO(2), was used to recover hydrocarbons from the SPS. DBU/octanol and DBU/ethanol SPS were tested for the extraction efficiency of lipids from freeze-dried B. braunii samples and compared with n-hexane and chloroform/methanol. The DBU/octanol system was further evaluated for the extraction of hydrocarbons directly from algal culture samples. DBU/octanol exhibited the highest yields of extracted hydrocarbons from both freeze-dried and liquid algal samples (16% and 8.2% respectively against 7.8% and 5.6% with n-hexane).

Oil wastes and slops are complex mixtures of hydrocarbons, which may contain a variety of contaminants including tetrachloroethylene (perchloroethylene, PCE) and other volatile halogenated organic compounds (VHOCs). The analytical determination of PCE at trace levels in petroleum-derived matrices is difficult to carry out in the presence of large amounts of hydrocarbon matrix components. In the following study, we demonstrate that headspace solid-phase microextraction (HS-SPME) combined with GC–MS analysis can be applied for the rapid measurement of PCE concentration in oil samples. The HS-SPME method was developed using liquid paraffin as matrix matching reference material for external and internal calibration and optimisation of experimental parameters. The limit of quantitation was 0.05 mg kg−1, and linearity was established up to 25 mg kg−1. The HS-SPME method was extended to several VHOCs, including trichloroethylene (TCE) in different matrices and was applied to the quantitative analysis of PCE and TCE in real samples.

Comb polyelectrolytes (CPs) having neutral hydrophilic teeth, similar to double hydrophilic block copolymers, are a powerful tool to modify the chemical-physical properties of inorganic crystalline materials. One of their main applications is in concrete technology, where they work as superplasticizers, particle-dispersing agents. Here, CPs, having the same poly(acrylic acid) (PAA) backbone chain and differing in the grafting with methoxy poly(ethylene glycol) chains (MPEG) of two molecular weights, were used to investigate the influence of tooth chains in polymer aggregation and in control on morphology and aggregation of calcite particles. These polymers aggregate, forming interpolymer hydrogen bonds between carboxylic groups and ether oxygen functionalities. The presence of calcium ions in solution further enhances aggregation. Crystallization experiments of calcite in the presence of CPs show that the specificity of interactions between polymers and crystal planes and control on aggregation and size of particles is a function of the content and chain length of the MPEG in the PAA backbone. These parameters limit and can make specific the electrostatic interactions with ionic crystalline planes. Moreover, the mechanism of crystallization, classical or nonclassical, is addressed by the CP structure and concentration. These findings have implications in the understanding of the complex chemical processes associated to concrete superplasticizers action and in the study of the biomineralization processes, where biological comb polyelectrolytes, the acidic glycoproteins, govern formation of calcitic structures.

EDDHSA/Fe is a promising substitute of EDDHA/Fe to fight iron chlorosis. o,o-EDDHSA structure contains two chiral carbons giving the racemic and meso couples of stereoisomers. Ion-pair HPLC and UHPLC–UV/Vis–ESI-MS/MS methods were developed for the determination of racemic and meso-o,o-EDDHSA/Fe in commercial samples of chelates. The lack of a commercial EDDHSA standard was overcome by sulfonation of a commercial available o,o-EDDHA standard and subsequent quantification by 1H-NMR. Assignment of configurations was carried out starting from racemic and meso-o,o-EDDHA/Fe by direct sulfonation to give the corresponding o,o-EDDHSA/Fe isomers. The performances of these methods were assessed in terms of intra and inter-day precision, linearity and selectivity. The high selectivity and lower detection limit (nanomolar) of the UHPLC–ESI-MS/MS method could allow to deepen the knowledge relative to meso and rac-o,o-EDDHSA/Fe interactions with plants, its fate in different soil conditions, its mobility and other environmental aspects.

The design, construction and evaluation of hybrid organic–organometallic and inorganic–organometallic crystalline materials held together by charge assisted hydrogen bonding interactions are described. It is shown that the convolution of the properties typical of coordination complexes (topology, oxidation and charge states etc.) with the extramolecular bonding capacity of ligands carrying hydrogen bonding groups allows one to prepare molecular and materials with desired architectures. The ionic or neutral nature of the building blocks can be utilized not only to control the strength of intermolecular bonding, but also to attain structure–function relationships and desired properties. In the case of organometallic species it is possible to vary in a controlled way both the redox properties of the metal centers and/or the acid/base behavior of the ligands. The possibility of utilizing the same building blocks in different neutral and ionic conditions can be exploited to construct complex structures for a variety of supramolecular applications.

The bidentate ferrocenyl sandwich [Fe(η5-C5H4-1-C5H4N)2] (1) has been used as a coordination ligand in reactions with AgNO3, Cd(NO3)2, Cu(CH3COO)2, Zn(CH3COO)2, and ZnCl2 to obtain the heterobimetallic metallamacrocyclic derivatives [Fe(η5-C5H4-1-C5H4N)2]2Ag2(NO3)2·1.5H2O, [Fe(η5-C5H4-1-C5H4N)2]2 Cu2(CH3COO)4·3H2O, [Fe(η5-C5H4-1-C5H4N)2]2Cd2(NO3)4·CH3OH·0.5C6H6, [Fe(η5-C5H4-1-C5H4N)2]2Zn2(CH3COO)4, and [Fe(η5-C5H4-1-C5H4N)2]2Zn2Cl4 (abbreviated in the following as (1AgI)22+, (1CdII)24+, (1CuII)24+, (1ZnIIacetate)24+, and (1ZnIIchloride)24+). The reaction with the ferrocenedicarboxylic acid complex [Fe(η5-C5H4COOH)2] has led to the supramolecular adduct [Fe(η5-C5H4-1-C5H4N)2][Fe(η5-C5H4COOH)2] (1[Fe(η5-C5H4COOH)2]). All compounds have been structurally characterized by single-crystal X-ray diffraction.

The synthesis and structural characterization of the ferrocenyl diboronic acid complex [Fe(η5-C5H4-B(OH)2)2] (1) and of its products of monosubstitution, [Fe(η5-C5H4-4-C5H4N)(η5-C5H4-B(OH)2)] (2 in three polymorphic modifications, 2a−c), and of disubstitution, [Fe(η5-C5H4-4-C5H4N)2] (4), [Fe(η5-C5H4-C6H4-4-C5H4N)2] (6), and [Fe(η5-C5H4-5-C4H3N2)2] (7), are reported together with an investigation of the mode of supramolecular bonding in the solid state. The competition between the hydrogen-bonding interactions of the (B)O−H···O(B) and (B)O−H···N types in the cases of crystalline 1 and 2 has been investigated. The B(OH)2 group provides two hydrogen bonding donor groups and two acceptors, forming mainly cyclic hydrogen-bonded systems in topological analogy with a primary amido group. Compounds 4, 6, and 7 are examples of neutral disubstituted pyridyl and pyrimidyl ferrocenyl complexes with potentials as supramolecular ligands. The compounds [Fe(η5-C5H4-4-C5H4NH)(η5-C5H4-B(OH)2)][NO3] (3a), [Fe(η5-C5H4-4-C5H4...

Polyhydroxyalkanoates (PHAs) can be extracted from mixed microbial cultures (MMCs) by means of dimethyl carbonate (DMC) or combination of DMC and sodium hypochlorite (NaClO). The protocol based on DMC, a green solvent never used before for the extraction of PHAs from MMC, allows an overall polymer recovery of 63%; also the purity and the molecular weight of the recovered polymers are good (98% and 1.2 MDa, respectively). The use of NaClO pretreatment before DMC extraction increases the overall PHA recovery (82%) but lowers the mean molecular weight to 0.6–0.2 MDa. A double extraction with DMC results to be the method of choice for the recovery of high quality PHAs from attractive but challenging MMCs.

Decesari, S. ... et. al.-- 24 pages, 15 figures, 4 tables, the supplement related to this article is available online https://doi.org/10.5194/acp-14-12109-2014-supplement, The use of co-located multiple spectroscopic techniques can provide detailed information on the atmospheric processes regulating aerosol chemical composition and mixing state. So far, field campaigns heavily equipped with aerosol mass spectrometers have been carried out mainly in large conurbations and in areas directly affected by their outflow, whereas lesser efforts have been dedicated to continental areas characterised by a less dense urbanisation. We present here the results obtained at a background site in the Po Valley, Italy, in summer 2009. For the first time in Europe, six state-of-the-art spectrometric techniques were used in parallel: aerosol time-of-flight mass spectrometer (ATOFMS), two aerosol mass spectrometers (high-resolution time-of-flight aerosol mass spectrometer - HR-ToF-AMS and soot particle aerosol mass spectrometer - SP-AMS), thermal desorption aerosol gas chromatography (TAG), chemical ionisation mass spectrometry (CIMS) and (offline) proton nuclear magnetic resonance (1H-NMR) spectroscopy. The results indicate that, under high-pressure conditions, atmospheric stratification at night and early morning hours led to the accumulation of aerosols produced by anthropogenic sources distributed over the Po Valley plain. Such aerosols include primary components such as black carbon (BC), secondary semivolatile compounds such as ammonium nitrate and amines and a class of monocarboxylic acids which correspond to the AMS cooking organic aerosol (COA) already identified in urban areas. In daytime, the entrainment of aged air masses in the mixing layer is responsible for the accumulation of low-volatility oxygenated organic aerosol (LV-OOA) and also for the recycling of non-volatile primary species such as black carbon. According to organic aerosol source apportionment, anthropogenic aerosols accumulating in the lower layers overnight accounted for 38% of organic aerosol mass on average, another 21% was accounted for by aerosols recirculated in residual layers but still originating in northern Italy, while a substantial fraction (41 %) was due to the most aged aerosols imported from transalpine areas. The different meteorological regimes also affected the BC mixing state: in periods of enhanced stagnation and recirculation of pollutants, the number fraction of the BC-containing particles determined by ATOFMS was 75% of the total, while in the days of enhanced ventilation of the planetary boundary layer (PBL), such fraction was significantly lower (50 %) because of the relative greater influence of non-BC-containing aerosol local sources in the Po Valley. Overall, a full internal mixing between BC and the nonrefractory aerosol chemical components was not observed during the experiment in this environment. © Author(s) 2014, This work was funded by European integrated project on aerosol cloud climate and air quality interactions (no. 036833-2, EUCAARI). The ERA-Interim data were kindly provided by Silvio Davolio (CNR-ISAC). Data analysis was co-funded by the project PEGASOS (EC FP7-ENV-2010-265148) and by the project SUPERSITO of Region Emilia-Romagna. ACCENTC is also gratefully acknowledged. Finally, Emanuela Finessi (CNR-ISAC, now at University of York) is also gratefully acknowledged for the precious work in aerosol filter collection in the field. Manuel Dall’Osto and Roy M. Harrison thank the UK National Centre for Atmospheric Science for financial support

The novel ferrocene-based compounds [Fe(η5-C5H4CH(CH3)OH)2] (1), [Fe(η5-C5H3(CH3)COOH)2] (2), [Fe(η5-C5H4CH(CH3)NH(η5-C5H4CH(CH3))] (3) and the diaminecyclohexane salt [Fe(η5-C5H4COO)2]2−[1S,2S-(NH3)2C6H10]2+·2[H2O] (4) have been synthesised and their molecular and supramolecular structures determined by single-crystal X-ray diffraction. The hydrogen bonding networks established by the COOH, CH(CH3)OH, and COO(−) groups have been studied and the structural parameters compared with those available for the prototypical dicarboxylic acid [Fe(η5-C5H4COOH)2].

The properties of atmospheric aerosol organic compounds are often simulated in models by arbitrarily choosing model compounds which have, in most cases, little contact with the physical reality. We propose here a procedure with which to derive a simplified model of the water soluble organic fraction of the atmospheric aerosol. Quantitative measurements of organic carbon concentration and proton concentration of the main functional groups contained in the aerosol water soluble organic compounds (WSOC) mixture are used to formulate a set of a few model compounds, representative of the whole WSOC mass, which can simulate in models the chemical and physical properties of aerosol WSOC.

We have carried out a combined theoretical-experimental study of the structures and energies of ZrCl(4)-aldehyde complexes using (13)C NMR spectroscopy and a DFT (B3LYP) computational approach. The computational investigation has demonstrated the existence of different types of complexes: a 1:1 complex (H(2)CO-ZrCl(4)), various 2:1 complexes ((H(2)CO)(2)-ZrCl(4)), and several dimeric species. The analysis of the energies involved in the formation of the various complexes has indicated that the dimeric species should correspond to the only adduct observed in the (13)C NMR spectra (carbonyl resonance at 226.96 ppm) when a 1:1 ZrCl(4)/aldehyde molar ratio is used, while the 2:1 complex should be responsible for the signal at 224.30 ppm that is recorded when this molar ratio is 1:2.

As an extension of our interest in developing new enantioselective reactions based on the binaphthol privileged ligand, we report a simple approach to the synthesis of 7,7′-disubstituted binaphthols. The commercially available 1,7-dihydroxynaphthalene (1) was used as starting material for the preparation of the bromoderivatives 2, which were oxidatively coupled to afford 3, a key intermediate for the preparation of a variety of enantiopure substituted binaphthols (8, 10). The absolute configuration of the new compounds was established by chiroptical analysis and by cholesteric induction. The optically active catalysts derived from the ligands 3, 8, 10, 16 and 17, complexed with Ti(OiPr)2Cl2, Zr(OiPr)4 and ZrCl4(THF)2, were employed for the enantioselective addition of allyltributyltin to aldehydes. Finally, the influence of the substituents of the binaphthyl core on the transmission of the chiral information was also investigated.

A new methodological approach is proposed to characterize aerosol water-soluble organic compounds (WSOC). Real aerosol and fog water samples were subjected to a procedure based on a combination of Chromatographic separations, functional group investigation by proton nuclear magnetic resonance (HNMR), and total organic carbon determination. The complex mixture of aerosol/fog WSOC was separated by a Chromatographic procedure into three main classes of compounds: (1) neutral/basic compounds; (2) mono- and di-carboxylic acids; (3) polyacidic compounds. Characterization by HNMR spectroscopy showed that fraction 1 is mainly composed of polyols or polyethers, fraction 2 is mainly composed of hydroxylated aliphatic acidic compounds, while fraction 3 is composed of highly unsaturated polyacidic compounds of predominantly aliphatic character, with a minor content of hydroxyl- groups. Quantitative data on the three classes of compounds were then derived from total organic carbon analysis, showing that the three separated fractions together account for 77% (in terms of C) of the total WSOC concentration of a fog water sample. Further quantitative information on the functional groups present in the three separated fractions can be obtained from HNMR spectra. This newly proposed approach to aerosol WSOC characterization provides comprehensive and synthetic information on aerosol organic composition which can be helpful for modeling purposes and is also particularly useful when aerosol chemical mass closure is pursued.

The crystal architecture, stability, and behavior with temperature of bis(formyl)ferrocene, [Fe(η5-C5H4CHO)2], have been investigated by variable-temperature X-ray diffraction experiments, differential scanning calorimetry, and thermogravimetry experiments. [Fe(η5-C5H4CHO)2] is present with two independent molecules with cisoid and transoid relative orientations of the two formyl groups in the crystals obtained from the reaction sequence (phase RT-1). The role of C−H- - -O interactions involving the formyl groups has been examined. When RT-1 is heated, the first irreversible phase transition to a plastic phase (phase HT) is observed at ca. 38 °C (311 K). When it is cooled, phase HT transforms into a new room-temperature phase (RT-2). Once RT-2 has been formed, the system switches reversibly between HT and RT-2 (transition temperature in the heating cycles ca. 35 °C), while RT-1 can no longer be obtained. Further heating of phase HT shows the occurrence of an exothermic reaction at ca. 150 °C (423 K) leadi...

The polycarboxylic acids C6H3(CO2H)3-1,3,5 (trimesic acid, H3tma) and O 2,O 3-dibenzoyl-L-tartaric acid (L-H2bta) reacted in water or thf with [Co(η5-C5H5)2][OH] prepared in situ by oxidation of [Co(η5-C5H5)2] to generate organic superanions self-assembled via negatively charged O–H· · ·O– and neutral O–H· · ·O hydrogen bonds. The resulting organic host accommodates the cations via charge assisted C–Hδ+· · ·Oδ– hydrogen bonds between organometallic and organic components. Crystalline [Co(η5-C5H5)2]+[(H3tma)(H2tma)]–·2H2O 1 was obtained as the major product from acid and base in a 1∶2 stoichiometric ratio. Compound 1 contains a complex hydrogen bonded honeycomb-type structure formed by superanions [(H3tma)(H2tma)]– and water molecules. The mixed salt [Co(η5-C5H5)2]+[Co(H2O)6]2+[tma]3– 2 was obtained as a minor product from the same reaction. In crystalline 2 the water molecules of the aqua complex form hydrogen bonds with the three carboxylic groups of the organic anion resulting in a caged structure that encapsulates the [Co(η5-C5H5)2]+ cation. When dibenzoyl-L-tartaric acid was used the chiral crystal [Co(η5-C5H5)2]+[L-Hbta]– 3 is obtained. The crystal contains chains of O–H· · ·O– hydrogen bonded anions. These results are used to discuss a design strategy for the engineering of organometallic crystals with predesigned structures. Though on a limited data set, the structure of the elusive crystalline hydrate [Co(η5-C5H5)2]+[OH]–·4H2O 4, which is liquid at ambient temperature, is discussed.

Reaction of aldehydes with allyltrimethylsilane promoted by BF3 (Sakurai reaction) affords fluorotrimethylsilane and a borylated homoallylic alcohol in a noncatalytic fashion. These reaction products have been identified through 13C NMR and 29Si NMR. A model system formed by acetaldehyde, allylsilane, and BH2F has been used to investigate the mechanism of this reaction at the DFT computational level. Four transition states, quite close in energy, have been found for the model reaction. These transition states, which explain the stereochemical features of the Sakurai reaction, correspond to eight-membered cyclic structures deriving from C−C (tight) and Si−F (loosen) bond formation and synclynal (gauche) disposition of the reacting double bonds. No antiperiplanar or six-membered cyclic transition structures have been located.

The engineering of organic−organometallic crystals based on strong O−H---O and charge-assisted C−H---O hydrogen bonds is discussed. The organic acids d,l- and l-tartaric acid (d,l-H2TA and l-H2TA) can be utilized to generate honeycomb-type organic frameworks around the organometallic cation [(η5-C5H5)2Co]+. The crystalline products of chemical formulae [(η5-C5H5)2Co]+[(d,l-HTA)(d,l-H2TA)]- (1) and [(η5-C5H5)2Co]+[l-HTA]- (3) are, respectively, constituted of hexagonal and tetragonal superanions molded around the cobalticinium cations. On changing the stoichiometric ratio [(η5-C5H5)2Co]/(d,l-H2TA) from 1:2 to 1:1, the crystalline material [(η5-C5H5)2Co]+[d,l-HTA]-·H2O (2) is produced while the undecahydrate crystalline material {[(η5-C5H5)2Co]+}2[l-BTA]2-·11H2O (4) is obtained when the organic partner is dibenzoyl-l-tartaric acid (l-H2BTA). The use of chiral acids in the preparation of 2 and 4 provides a simple route to chiral crystals. The participation of water molecules in interactions of the C−H---O ty...

The engineering of organic−organometallic crystals based on hydrogen bonding and on shape complementarity is discussed. The crystalline salts [(η6-C6H6)2Cr][(CHD)4] (1) and [(η6-C6H5Me)2Cr][(CHD)2]...

In this paper we introduce a simple, new system for promoting enantioselective catalytic allylation of aldehydes. Chiral bis(oxazalinyl) zinc complexes have been shown to catalyze the allylation of aldehydes in good yield when allyl tributyltin is used as the nucleophile. The values of e.e. obtained for this reaction are in the range of 40–46%. A number of different reaction conditions were screened and the results obtained with other metal systems are also reported.

A new chiral Lewis acid catalyst, [BINOL-Zr(O i Pr) 2 ], is prepared from ( R ) or ( S )-BINOL and commercially available Zr(O i Pr) 4 · i PrOH; it efficently promotes the enantioselective allylation of aldehydes by allyltributyltin in shorter times and at lower temperatures with respect to related catalysts.

New polyethoxylated tertiary amines were synthesised and applied as Switchable Hydrophilicity Solvents (SHS) in the extraction and recovery of lipids from algal cultures, bypassing harvesting and de-watering steps. The eco-toxicological profile of the new amines was explored by evaluating their potential in inhibiting algal growth, and deepened by measuring the acute toxicity towards the crustacean Daphnia magna and the ready biodegradability in water. Among the synthesised amines, the one bearing two ethoxy units, named amine 2, showed the best combination in terms of lipids' extractive performances and toxicity; therefore it could be considered as a good alternative to N,N-dimethylcyclohexylamine (DMCHA), at the moment the most studied and effective SHS. © 2014 The Royal Society of Chemistry.

(Z)-Vinyloxy boranes are obtained via 1,4-hydroboration of acyclic disubstituted (E)-α,β-unsaturated ketones with dicyclohexylborane or diisopinocampheylborane in tetrahydrofuran, CH2Cl2 or CHCl3 at 20 °C; treatment of the hydroboration mixture with an aldehyde allows pure syn aldols to be synthesized in good yields, and in excellent enantiomeric excesses, using the latter borane.

The stereoselectivity of the Lewis acid induced acylation of open-chain silyl enoi ethers by chiral orthoesters is strongly affected by the CC bond configuration: both Z and E silyl enol ethers are acylated in good isolated yields, but the Z isomers give rise to a 1 : 1 ratio of diastereoisomeric monoprotected 1,3-diketones, while excellent stereoselectivities are obtained with E enols.