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The aim of the present study was to investigate starch-based materials, prepared in an environmentally friendly way and from renewable resources, suitable for the development of biodegradable active food packaging. For this purpose, a bioactive compound (thymol) was incorporated into thermoplastic starch (TPS) and a TPS blend with poly (ε-caprolactone) (TPS-PCL) by the supercritical CO

Restrictions about the use of chemicals have limited the availability of control measures against plant-parasitic nematodes. The search for more sustainable approaches has focused the attention on biological control agents, such as Trichoderma species. In recent years, there has been a growing interest in the use of biopolymers for a wide range of applications. These polysaccharide-based compounds may be 20 good carriers of microbial agents or act as barriers against pathogens or pests for their ability to form coating films. In this study, we evaluated the combination of a biopolymer obtained from the leguminous plant Ceratonia siliqua and T. harzianum M10, T. atroviride P1 or T. longibrachiatum MK1, as root protector or adjuvant agents, for the management of the root-knot nematode Meloidogyne incognita. Coating tomato roots with the carob galactomannan biopolymer followed by soil application of selected Trichoderma strains reduced the root galling index caused by M. incognita and soil nematode population in comparison to untreated control under greenhouse conditions. 25 Scanning electron microscopy revealed that coated tomato roots were embedded within a polymeric material. The sedimentation test showed that the addition of this biopolymer retarded the tendency of Trichoderma spores to settle in the bottom of aqueous suspension. In conclusion, beneficial fungi combined or formulated with a biopolymer could represent a promising strategy to increase their activity in plant protection and enhance their proliferation or distribution into rhizosphere.

In this study, a novel extraction method has been employed to obtain highly efficient cellulose nanocrystals (CNCs) and cellulose nanofibers (CNFs) from waste hemp fibers with maximum potential. By...

Introduction The demand for Gallium-68 (68Ga) for labelling PET radiopharmaceuticals has increased over the past few years. 68Ga is obtained through the decayed parent radionuclide 68Ge using commercial 68Ge/68Ga generators. The principal limitation of commercial 68Ge/68Ga generators is that only a limited and finite quantity of 68Ga ( Methods Enriched ZnCl2 was electrodeposited on a platinum backing using a NH4Cl (pH 2–4) buffer. The Zn target was irradiated with GE PETtrace 880 at 35 μA and 14.5 and 12.0 MeV beam energy. The irradiated Zn target was purified using octanol resin on an automated system. Results Following the described procedure, 68Ga was obtained in 6.30 ± 0.42 GBq after 8.5 min bombardment and with low radionuclidic impurities (66Ga ( 70%. Conclusions A straightforward procedure for producing 68Ga on a low energy medical cyclotron was described. Current efforts are focus on high activity production and radiolabelling using solid target produced 68Ga.

Background Weed control represents a major issue in plant cultivation in containers. Manual weed control is very expensive and the use of chemical herbicide or plastic mulch films has a large environmental impact. The aim of this study was to test the efficacy of an experimental biodegradable chitosan-based mulching spray in controlling weed growth in containers. This research also studied the effect of this mulch on the growth of Viburnum lucidum Mill. plants to test for possible phytotoxic effects. Results The study compared a total of six treatments derived from three types of weed control (no weed control; herbicide, oxadiazon; mulching spray) applied in containers either filled only with the sterile substrate or filled with the sterile substrate and then artificially inoculated with seeds of the weed species [Sonchus asper (L.) Hill subsp. asper and Epilobium montanum L.]. The mulch controlled the weeds effectively for more than 2 months after its application even under severe weed infestation. The mulching spray controlled the emergence of S. asper more efficiently than E. montanum plants, probably because the latter has a stronger capacity to penetrate the mulch film during emergence. Conclusions Three months after its application, the mulch started to degrade and this allowed some weeds to emerge in the containers, but, in general, the mulch performed better than the herbicide. The chitosan-based mulch did not have any negative effective on the growth of V. lucidum plants.

The hitherto known polyamidoamines (PAAs) are not suitable as structural materials because they are usually water-soluble or swellable in water. This paper deals with the synthesis and characterization of semi-crystalline hydrophobic PAAs (H-PAAs) by combining different bis-sec-amines with bis-acrylamides obtained from C6–C12 bis-prim-amines. H-PAAs were initially obtained in a solution of benzyl alcohol, a solvent suitable for both monomers and polymers. Their number average molecular weights, M¯n, which were determined with 1H-NMR by evaluating the percentage of their terminal units, varied from 6000 to &gt, 10,000. The solubility, thermal properties, ignitability and water resistance of H-PAAs were determined. They were soluble in organic solvents, semi-crystalline and thermally stable. The most promising ones were also prepared using a bulk process, which has never been previously reported for PAA synthesis. In the form of films, these H-PAAs were apparently unaffected by water. The films underwent tensile and wettability tests. They showed similar Young moduli (260–263 MPa), whereas the maximum stress and the stress at break depended on the number of methylene groups of the starting bis-acrylamides. Their wettability was somewhat higher than that of common Nylons. Interestingly, none of the H-PAAs considered, either as films or powders, ignited after prolonged exposure to a methane flame.

Renewable bio-based polymers are one of the effective answers that the bioeconomy offers to solve the environmental emergency connected to plastics and more specifically fossil-based plastics. Previous studies have shown that more than 70 % of the natural capital cost associated with plastic derives from the extraction and processing of fossil raw materials and that the price of fossil plastic would be on average 44 % higher if such impact was fully paid by businesses. The disclosure of the hidden costs of plastics will contribute to dispelling the myth of the expensiveness of renewable polymers. Nevertheless, the adoption of bio-based plastics in the market must be motivated by their functional properties and not merely by their green credentials. This article highlights some successful examples of synergies between chemistry and biotechnology in achieving a new generation of bio-based monomers and polymers. Their success is justified by the combination of scientific advances with positive environmental and social fallouts.

Ulomoides dermestoides (UL) are macroinvertebrates insects belonging to Tenebrionidae Coleopteran family. They were used to hasten, in five days, the biodegradation-mineralization of thermoplastic starch (TPS)-poly(lactic acid) (PLA) films, otherwise biodegradable under composting conditions. After the contact of TPS-PLA film with UL for five days, TPS was metabolized and PLA was hydrolysed, as evidenced by decreasing of hydroxyl and carbonyl group peaks intensity by FTIR spectra, increasing of 13% of PLA crystallinity by DSC thermograms, reduction of PLA and TPS thermal stability by TGA analysis; faecal residues evidenced two glass transition temperature T

In the present study, chitosan-based wound dressings loaded with the extract of Opuntia ficus-indica (OPU) were prepared. OPU is known for its capability to accelerate skin injury repair. Chitosan (Ch) was crosslinked with a low molecular weight diepoxy-poly(ethylene glycol) (diePEG), and hydrogel films with different Ch/PEG composition and OPU content were prepared by casting. The occurrence of crosslinking reaction was confirmed by FTIR spectroscopy. FTIR and DSC analysis suggested that ionic interactions occur between chitosan and OPU. Tensile tests evidenced that the crosslinking caused a decrease of Young’s modulus, which approaches the value of the human skin modulus. Swelling characteristics, water vapor transmission rate, and release kinetics demonstrated that these films are adequate for the proposed application. Finally, a scratch test on a keratinocytes monolayer showed that the rate of cell migration in the presence of OPU-loaded samples is about 3-fold higher compared to unloaded films, confirming the repairing activity of OPU.

In this work, α−costic acid (α-CA), a metabolite coming from a perennial autochthon shrub Dittrichia viscose, was used as natural additive of polylactic acid (PLA), a biodegradable thermoplastic polymer, in order to modulate its chemico-physical properties, for the achievement of a wholly biobased packaging system. It’s the first time that α−costic acid is exploited for this appealing and novel application. The investigations performed on PLA/α-CA films, evidenced strong physical interaction occurring between the polymer and α-CA, as confirmed by NMR and FTIR-ATR analyses; SEM micrographs showed a good embedding of α-CA particles inside PLA polymer matrix; GPC analysis highlighted a slight hydrolysis of polymer matrix clearly evidenced in mechanical properties. DSC analysis underlined the significant decreasing of Tg, associated with the increase of PLA chain mobility. TGA thermograms evidenced one broad degradation profile of PLA/α-CA system, accounting for the weighty physical interaction occurring between the polar groups of both polymer and plasticizer. Finally, PLA surface wettability notably enhanced by the inclusion of α-CA polar groups. In conclusion, α-CA can be considered as a promising plasticizer of PLA and a worthy modifier of its overall properties.

In this study, chitosan (C) tripolyphosphate (T) sub-micro particles containing ungeremine (CTUn), an alkaloid particularly active against Penicillium roqueforti, a fungus responsible of the bakery products deterioration, were prepared through external gelation crosslinking process. The particles were included in a thermoplastic starch based polymer Mater-Bi (MBi), and MBi/CTUn bioactive biocomposites were obtained. The films showed bioactivity against P. roqueforti. In particular, the bioassays were performed on films with different concentration of CTUn and at different pH values. CTUn particles influenced MBi crystallization (DSC analysis) and promoted thermal degradation of MBi starch component (TGA). Morphological analysis confirmed even distribution of sub-micro particles into the polymeric matrix. Water permeability slightly increased, as expected, whereas oxygen permeability decreased. Tensile tests showed CTUN sub-microparticles improved rigidity and tensile strength of the films at the expense of ductility. Finally, MBi/CTUn biocomposites evidenced interesting performances potentially exploitable in bioactive bakery based food packaging materials.

Background The organic extracts (OEs) of Dittrichia viscosa, a ruderal plant common in the Mediterranean regions, proved to have herbicidal properties. In order to improve OE effectiveness and to develop novel eco-friendly bioherbicidal products, different amounts of OE were included in poly(butylene succinate)- and polycaprolactone-based films (PBS and PCL, respectively). Particular attention was given to the study of interactions between the polymers and OEs, with a deep spotlight concerning the influence of OEs on structural, morphological and thermal properties of both polymers, in order to assess the OE releasing kinetics from the matrices and its tuned herbicidal action against seeds. Results The bioassays carried out on Lepidium sativum and Phelipanche ramosa seeds evidenced a more controlled and effective OE release by PBS than PCL, and a longer lasting efficacy by the polymers with a higher OE content. The chemical-physical analyses were performed on films before and after biological assays. The thermogravimetric analysis confirmed that OE was a thermal stabilizer of the polymer; the presence of OE and polymer separated degradative kinetics suggested that only a partial and functional miscibility between polymers and OE occurred. The morphological analysis confirmed the good OE dispersion between PBS and PCL molecular chains. Infrared spectroscopy highlighted the enhanced hydrolysed structure of the doped polymers after the bioassays. These outcomes well matched the quantitative information outlined by release kinetics. Discussion The use of biodegradable polymers allows the effectiveness and tuning of the release of the formulated bioactive compounds to be improved. The easy-to-obtain and easy-to-formulate OE could become a suitable and environmentally friendly instrument in weed management programmes.

In this study, chitosan based microbeads containing Ungeremine, an antimicrobial alkaloid particularly active against Penicillium roqueforti, a filamentous fungus responsible of the bakery products deterioration, were prepared by external gelation by using sodium tripolyphosphate (TPP) as crosslinking agent. The stability of the beads, as well as the loading efficiency of the bioactive molecule, were assessed at different pH and TPP concentrations resulting particularly enhanced at low pH. All the microbeads evidenced antimicrobial activity against Penicillium roqueforti. The release kinetics of Ungeremine was tailored by opportunely modulating pH and TPP concentrations. Morphological analysis evidenced the improvement of the structural crosslinking density of microbeads including Ungeremine and spectroscopic analysis emphasized the active participation of Ungeremine to the crosslinking process occurring between chitosan and TPP. Finally, thermogravimetric analysis confirmed the increasing of free volume in three-dimensional networks and their liability to thermal degradation.

Lignocellulose from agro-food biowaste represents a valuable source of cost-effective structural fillers for wholly renewable polymer composites. In this work, pecan (Carya illinoinensis) nutshell (NS) fiber and its structural components, holocellulose (HC) and acid insoluble lignin (AIL), were isolated, characterized and used as reinforcing fillers to manufacture poly(lactic acid) (PLA) based biocomposites. Thermal, morphological and mechanical properties of the prepared materials were analyzed. NS and HC acted as heterogeneous nucleating agents, potentially able to control PLA physical aging. Moreover, they significantly enhanced the viscoelastic response of PLA, mainly restricting the melt molecular mobility due to hydrodynamic effects and the formation of a three-dimensional particulate network. Flexural tests demonstrated that HC induced a 25% increase in modulus compared to the plain polymer. AIL, conversely, conferred higher ductility to the PLA matrix producing an increase in stress and strain at break of 55% and 65%, respectively. Finally, all the biocomposites showed lower resilience with respect to plain PLA due to the lack of chemical adhesion between filler and matrix. These results emphasize the potential of NS as a source of reinforcing filler in polymer-based biocomposites.

Wound healing can lead to complex clinical problems, hence finding an efficient approach to enhance the healing process is necessary. An ideal wound dressing should treat wounds at reasonable costs, with minimal inconveniences for the patient. Chitosan is one of the most investigated biopolymers for wound healing applications due to its biocompatibility, biodegradability, non-toxicity, and antimicrobial activity. Moreover, chitosan and its derivative have attracted numerous attentions because of the accelerating wound healing, and easy processability into different forms (gels, foams, membranes, and beads). All these properties make chitosan-based materials particularly versatile and promising for wound dressings. Besides, secondary natural metabolites could potentially act like the antimicrobial and anti-inflammatory agents and accelerate the healing process. This review collected almost all studies regarding natural compounds applications in wound healing by focusing on the chitosan-based bioactive wound dressing systems. An accurate analysis of different chitosan formulations and the influence of bioactive compounds on their wound healing properties are reported.

Polymeric nanoparticles (NPs) of poly(e-caprolactone) (PCL) covered with a hydrophilic poly(ethylene glycol) (PEG) shell are usually prepared from diblock PEG-PCL copolymers through different techniques. Furthermore PEG, NPs can be decorated with targeting ligands to accumulate in specific cell lines. However, the density and conformation of PEG on the surface and its impact on the exposition of small targeting ligands has been poorly considered so far although this has a huge impact on biological behaviour. Here, we focus on PEG-PCL NPs and their folate-targeted version to encourage accumulation in cancer cells overexpressing folate receptor α. NPs were prepared with mixtures of PEG-PCL with different PEG length (short 1.0 kDa, long 2.0 kDa,) and a folate-functionalized PEG-PCL (PEG 1.5 kDa) by the widely employed solvent displacement method. In depth characterization of NPs surface by 1H NMR, fluorescence and photon correlation spectroscopy evidenced a PEGylation extent below 7% with PEG in a mushroom conformation and the presence of folate more exposed to water pool in the case of copolymer with short PEG. NPs with short PEG adsorbed HSA forming a soft corona without aggregating. Although limited, PEGylation overall reduced NPs uptake in human macrophages. Uptake of NPs exposing folate prepared with short PEG was higher in KB cells (FR +) than in A549 (FR −), occurred via FR-receptor and involved lipid rafts-dependent endocytosis. In conclusion, the present results demonstrate that PEG length critically affects protein interaction and folate exposition with a logical impact on receptor-mediated cell uptake. Our study highlights that the too simplistic view suggesting that PEG-PCL gives PEG-coated NPs needs to be re-examined in the light of actual surface properties, which should always be considered case-by-case.

Two field trials in integrated cultivation (2014 and 2016) were carried out with the aim to evaluate the efficacy and the persistence of copper oxychloride to control downy mildew of grapevine in mixture with a new natural adjuvant (PSS®) derived from locust bean (Ceratonia siliqua L.) gum. Copper amount applied in vineyards is the subject of interest for its use in organic farming due to the concern about its ecotoxicological profile in the soil that need to modify its use in rates, strategy and total amount per season. Copper oxychloride was applied every 7 and 14 days mixed or not with locust bean gum. Locust bean gum was also applied alone. To evaluate the distribution of copper on grapevine leaves, observations by scanning electron microscope were made. Locust bean gum alone did not influence the development of disease, while significantly increased efficacy and persistence of copper oxychloride both on leaves and bunches. On bunches, at 14 days interval, efficacy on incidence of copper oxychloride plus locust bean gum was about 60% while efficacy on severity was 60.1 and 65.6% for the year 2014 and 2016, respectively. With no locust bean gum, at the same interval, efficacy was significantly lower. Scanning electron microscopy demonstrated that copper fungicide particles when mixed with locust bean gum were still uniformly distributed on leaves after 14 days from application, but if applied alone already after 7 days became scattered with a lower concentration. To our knowledge, it is the first time that galactomannans-derived compounds have been used as adjuvant in pesticides. The use of locust bean gum reduced the annual amount of copper in integrated cultivation from 7.9 kg ha−1 applying copper oxychloride every 7 days to 4.5 kg ha−1 when applied every 14 days mixed with the new locust bean gum sticker.

Il percorso formativo “ESPERTO NELLA GESTIONE DI BIORAFFINERIE: ALLESTIMENTO DI SISTEMI COLTURALI SOSTENIBILI, BIOCONVERSIONE DI BIOMASSE IN BIOCHEMICALS, LORO POLIMERIZZAZIONE E SUCCESSIVA TRASFORMAZIONE DEI POLIMERI IN MATERIALI PER L’INDUSTRIA”

Cynara Cardunculus plant was used as source of seed oil. The epoxidized oil (ECO) and presscake waste fibers (CP) recovered from post-oil extraction, were recombined for developing PLA functional biocomposites, according to “zero waste” circular economy approach. Different compositions of PLA/CP and PLA/CP/ECO were prepared in form of platelets and investigated by thermal, morphological, structural and mechanical analyses. The poor interfacial adhesion between the hydrophobic PLA matrix and short, hydrophilic and randomly dispersed presscake fibers, well evidenced by morphological analysis, was responsible of PLA thermal degradation hastening, Tg decreasing and tensile properties dropping down, since no mechanical stress transfer occurred from the polymer to the dispersed phase. The inclusion of ECO slightly improved the above properties due to its mild compatibilizing action inducing a fairly tightening of the macromolecular structure. The recycling of CP waste fibers was effective in hastening the polymer biodegradation in common soil under environmental conditions. Indeed, biocomposites recovered after 90 days of soil burial tests evidenced morphological features typical of late stage PLA biodegradation, a drastic dropping down of molecular weights and a decreasing of PLA thermal stability. These experimental evidences, not detected in soil buried neat PLA, assessed that the inclusion of CP waste fibers inside PLA matrix, represented a valid route to promote a fast and easy PLA biodegradation if compared to the composting method commonly used, for which severe atmosphere conditions and specific microbial population are necessary.

This work details the first example of enhancement of crystallization rate of poly ( l -lactic acid) (PLLA) by introducing optically pure short chain branches. A biobased PLLA copolymer was prepared by initial radical functionalization of commercial PLLA with itaconic anhydride (IAH) in a Brabender mixer, then by reaction with a tailor-made hydroxyl-terminated, optically pure PLLA with molar mass Mn = 4 kDa, the latter prepared via ring opening polymerization. Gel permeation chromatography and infrared spectroscopy proved the efficiency of grafting reaction, with the amount of grafted IAH quantified via UV–Vis. The synthesized graft copolymer displays faster crystallization rate with respect not only to the commercial grade, but also to a binary blend with the same nominal composition. The role played by the short branches in favoring both crystal nucleation and growth was discussed in terms of molecular nucleation. The results detailed in this manuscript demonstrate that synthesis of a graft copolymer with optically pure short branches is an efficient way to improve the poor crystallization kinetics of PLLA, which is one of the major drawbacks of this polymer.

This manuscript describes antifungal, structural, thermal and morphological properties of a novel, eco-friendly bioplastic film, based on poly(butylenesuccinate) and cavoxin, a chalcone phytopathogenic metabolite, isolated from cultures by the fungus Phoma cava and included inside the biodegradable polymeric matrix. The antagonistic activity of the film explored against two fungal food contaminants Penicilliumroqueforti and Aspergillusniger, highlighted that cavoxin was fungicide at MIC concentrations. The chemico-physical analysis were performed on films before and after antifungal activity. Thermal analysis evidenced both the higher thermal stability of poly(butylenesuccinate) and cavoxin blend and the sharp nucleating action of cavoxin on the polymer. Infrared spectroscopy highlighted the presence of physical interaction between the polar groups of the blend components, whereas gel permeation chromatography highlighted that the hydrolytic effect of cavoxin on poly(butylenesuccinate) was responsible for the diffusion and releasing of the biomolecule from the matrix and UV–Vis spectroscopy provided quantitative information of release kinetics. Finally, morphological analysis confirmed both the polymeric surface hydrolysis exerted by cavoxin, and the adhesion of fungal spores on films after contact occurred during the antifungal assay.

A one-pot route to extract and chemically modify lignin from a pre-treated Phragmites australis lignocellulosic biomass is proposed herein. The lignocellulosic biomass was first pre-treated through steam explosion at two different severity factors. Lignin was then extracted from the steam-exploded biomasses through a microwave-assisted organosolv extraction method, solely using γ-valerolactone as solvent. The most severe steam explosion condition yielded a delignification of 78%. Morphological analysis, spectroscopic investigation and thermal characterization showed that essentially pure lignin was extracted through this process. Lignin was then chemically modified in the γ-valerolactone extraction solution, through acetylation and Mannich condensation. This work provides proof-of-evidence that pure lignin can be solvent-extracted in high yields from a pre-treated biomass without the addition of any further chemicals and successfully modified in a one-pot route through a cleaner process. The modified lignin could be used as building block for the development of novel bio-based polymer materials.

One of the greatest problems in food packaging system is prevention of food from the mold contamination. In particular, in the bakery products Penicillium roqueforti (PR) is the main contaminator associated to the food deterioration. Food packaging systems are responsible to protect food substrate from physical damage, chemical and biological contaminations. In addition, packages are designed to preserve the food quality and safety, extending their shelf-life. However, finalized to enhance the food packaging performances recently, the attention of research and industrial partnerships is increasingly focused on bioactive packaging. Antimicrobial food packaging is based on the incorporation of natural bioactive metabolites into polymer or biopolymer matrices, acts to reduce, inhibit or hinder the growth of microorganisms able to develop not only in the food but also in the packaging material itself. In particular, some plants material showed antifungal activity with potential application in food packaging. In this respect, ungeremine (Un) is one of the most active plant metabolites against P.roqueforti. Ungeremine is a betaine type alkaloids isolated from Pancratium maritimim L., a well knows species of Amaryllidaceae collected on Egypt northern coasts. Ungeremine was also obtained from SeO2 oxidation of lycorine, the main Amaryllideacea alkaloids. In this study, chitosan (Ch) based sub-micro particles containing ungeremine were prepared by using sodium tripolyphosphate (TPP) and formulated into Mater-Bi (MBi) polymer matrix. The Ch_TPP_Un/MBi composites were obtained by compression molding. The bioassay result of the films evidenced their activity against P.roqueforti. In addition, determination of residual ungeremine into films after 72h inhibition showed that, depending on the different food substrate pH, the diverse releasing pattern of fungicide from the package system could be expected. The morphological analysis confirmed a homogeneous distribution of sub-micro particles into MaterBi polymer matrix. The tensile test analysis showed that sub-micro particles could significantly decrease the ductility and slight increase in the elastic modulus of the films. Finally, thermogravimetric analysis confirmed specific physical interaction between chitosan based sub-microparticles and the starch fraction of MBi which, in turn, resulted in a decrease of thermal stability of MBi starch segments.

One of the greatest problems in food packaging system is the prevention of food from the mold contamination. Indeed, food mold infestation is very dangerous for human health and also can considerably increase the financial cost. In particular, in the bakery products, Penicillium roqueforti and Aspergillus niger are the main contaminators. On the other hand, food packaging systems are responsible to protect food substrate from physical damage, chemical and biological contaminations. In addition, packages are designed to preserve the food quality and safety, extending their shelf-life. However, due to environmental impact of the conventional polymers recently, the attention of researchers and industrial sectors are mainly on bioactive packaging by using bio polymer based package system. Antimicrobial food packaging known as active packing is based on the incorporation of natural bioactive metabolites into the polymer or biopolymer matrices to reduce, inhibit or hinder the growth of microorganisms on the packaged food. In particular, some plants material showed antifungal activity with potential application in food packaging. This project assayed the inhibitory activity of 13 bacterial, fungal and plant metabolites against P.roqueforti and A.niger and selected the most active ones which were cavoxin, ungeremine and ?-costic acid. The potential application of those natural metabolites into bio packaging system was investigated by the formulation of those metabolites into the biopolymer matrix in order to obtain active packaging system to increase the quality of food packaging, the food shelf-life, and microbiological safety.

This study spotlighted a successful synthesis of a novel series of biobased poly(decamethylene-co-isosorbide 2,5-furandicarboxylate)s (PDIsFs) copolyesters from dimethylfuran-2,5-dicarboxylate (DMFD), isosorbide (Is), and 1,10-decanediol (1,10-DD) by melt polycondensation, using titanium(IV) isopropoxide (TTIP). The chemical structure and composition of prepared polymers were confirmed in detail by H NMR and FTIR spectroscopies. Satisfactory weight-average molecular weights (M ) in the 55,300-84,500 g/mol range and random microstructures were obtained for PDIsFs. It was shown that Is unit incorporation into the copolyesters molecular chains was dramatically effective in increasing the glass transition temperatures (T ) and in delaying the onset decomposition temperatures of PDIsFs. Hence, an excellent improvement of the thermal stability exceeding 405 °C for all copolymers was obtained. In addition, the degradation behavior in soil as well as the mechanical properties of PDIsFs were duly investigated in detail. The biodegradation rate of the copolyesters depended on the comonomer ratio. Rotational rheometry characterization of polymer melts revealed prevailing viscous properties for all formulations, whereas the presence of isosorbide favored a Newtonian behavior. Oxygen induction time (OIT) measurements by chemiluminescence (CL) demonstrated that isosorbide incorporation also dramatically increases polymer thermo-oxidative stability. Taking advantage of their features, PDIsFs have the potential to serve as promising and innovative biobased polymers for practical applications such as ecofriendly and sustainable plastic packaging.

Polymeric nanoparticles (NPs) play an important role in drug delivery as nanocarriers for small hydrophobic molecule drugs and as non-viral vectors for gene delivery [1] (plasmid DNA or siRNA). Combination of both properties in a single nanoparticle formulation can be useful in cancer treatment. In this topic, amphiphilic autoassembling block copolymers for realization of NPs offer a wide range of opportunities, due to the possibility of fine tuning the structure (nature, length and ratio of blocks) and surface properties of final NPs. In this work, synthesis and characterization of amphiphilic triblock copolymers based on polyethyleneglycol (PEG)-poly(dimethylaminoethyl-methacrylate) (pDMAEMA)-polycaprolactone (PCL) with different blocks length are described, with the aim to realize NPs for a combined anticancer therapy. The structure of triblock copolymers is shown in Figure 1. Figure 1 PEG was chosen as hydrophilic block for its stealth properties; pDMAEMA cationic block, intended for siRNA complexation, was synthesized via atom transfer radical polymerization (ATRP)[2]; finally, PCL was conjugated via "click" reaction through copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) as biodegradable hydrophobic block. Copolymers were characterized through 1H-NMR, FTIR, GPC and DSC. NPs were obtained by nanoprecipitation and characterized for size, polydispersity index, surface charge and stability. Critical micellar concentrations (CMC) were determined. NPs were loaded with docetaxel (DTX), and a non-targeting pool siRNA was adsorbed by gentle stirring on DTX-loaded NPs. The complexes were characterized by electrophoresis on agarose gel. The final NPs showed narrow size distribution and good loading efficiency and release profiles.

Cardoon seed oil (CO), derived from the nonedible Cynara cardunculus plant, growing in marginal and contaminated soils of Mediterranean regions, was successfully epoxidized (ECO) in a fed-batch modality. The cost-effective and environmentally friendly oils have been used as bioplasticizers of poly(lactic acid) (PLA), to improve the overall properties and broaden its industrial applications as a biodegradable packaging material. Hence, physical blends and films of PLA, containing 3% by weight of CO and ECO, were prepared by melt extrusion and compression molding, and the effect of the both bioplasticizers on structural, thermal, and mechanical properties of the obtained films was investigated. Cardoon oils induced the decreasing of glass transition temperature due to PLA free volume enhancement. This effect was particularly marked in PLA–ECO film. Thermal stability of PLA was meaningfully improved upon addition of the oils, and the mechanical properties made evident the increase of PLA ductility, particularly enhanced in the PLA–ECO system, where the polymeric matrix and the oil showed stronger physical interaction and improved phase compatibility, as also revealed by spectroscopic and morphological analyses. Therefore, the plasticization action exerted by very low concentrations of epoxidized cardoon oil efficiently overcomes PLA drawbacks, thus encouraging the feasibility of its use as a bioplastic for packaging material.

The demand for Gallium-68 (Enriched ZnClFollowing the described procedure,A straightforward procedure for producing

Poly(3-hydroxybutyrate) (PHB) is a biodegradable polymer, whose applicability is limited by its relatively poor mechanical properties and narrow processing window. In this paper, a natural polyphenolic additive, tannic acid (TA) was used as thermal and processing stabilizer for PHB. The thermal stability of both neat and TA-doped PHB samples was studied by rheology and calorimetry. The experimental results show that the neat PHB massively degrades and that the addition of tannic acid enhances the thermal stability of PHB, thus widening the processing window of the polymer. Physical and chemical interactions between the polymer and the additive were considered as key factors to interpret the experimental data. The described results are of interest for the development of sustainable alternatives to synthetic polymer additives, by increasing the applicability of bio-based materials. (C) 2014 Elsevier Ltd. All rights reserved.

Carbon fibers reinforced epoxy resins are used in a wide range of applications, such as automotive and aerospace industry. Because of their thermosetting nature, recycling at the end of the life cycle is a difficult issue. However, lack of recyclability poses environmental concerns to the use of these composite materials. In this article, a sustainable, cost-effective technological approach aiming at recycling postconsumer carbon fibers reinforced thermosets (CFRT) is proposed. Composites containing 50 and 70 wt% of CFRT particles were prepared by incorporating the filler fraction into a fluidified postconsumer expanded polystyrene matrix. A cold mixing approach consisting in the use of a low boiling solvent as a binder to guarantee the dispersion homogeneity on micro- and macroscopic level was set up. For comparison, analog composites were also prepared through melt mixing process. Morphological, mechanical, and thermal analyses allowed to prove the effectiveness of the cold mixing approach and to evaluate the influence of particle size on the performance of new recycled composites. Thermogravimetric analysis and thermal conductivity tests of samples highlighted further peculiarities of the cold mixing process. The approach proposed is an effective recycling technology for CFRT and could be extended to other postconsumer materials. POLYM. COMPOS., 35:1621–1628, 2014. © 2013 Society of Plastics Engineers

Aim This work describes a small-scale production of iodine-124 using a 16.5 MeV cyclotron, and a subsequent validation of the formulated sodium [124I]iodide solution for routinely clinical applications. Methods Iodine-124 (124I) was produced via the 124Te(p, n)124I reaction using a 16.5 MeV GE PETtrace® cyclotron. Irradiation was performed with a pre-prepared solid target consisting of [124Te]TeO2 (99.93%) and Al2O3. Different layer thicknesses, irradiation and extraction parameters were tested. After irradiation at the cyclotron, the shuttle with irradiated material was transferred fully automatically via a tube system to the Comecer ALCEO® Halogen 2.0 extraction unit. Iodine-124 was subsequently extracted in form of sodium [124I]iodide ([124I]NaI) in 0.05 N aqueous NaOH solution, followed by reconstitution and validation for preclinical and clinical uses. Results Good result was achieved using a beam degradation foil of 500 µm thickness in combination with beam currents between 10 and 15 µA. Under these conditions, up to 150 MBq no-carrier-added [124I]NaI was obtained after a 2 h irradiation time in less than 500 µl 0.05 N NaOH. Isolation of [124I]NaI, including evaporation and extraction at the ALCEO® Halogen EVP unit was accomplished in 90 min 24 h after production (irradiation), the amount of iodine-123 as assessed by gamma-ray spectroscopy was less than 1.5%. The undesirable iodine-125 was not detectable by gamma spectroscopy. The extracted [124I]NaI could be used directly for radiolabeling purposes, and after buffering with phosphate buffered saline (PBS) and sterile filtration for clinical applications. Conclusions Through the optimized conditions for irradiation and extraction, iodine-124 was produced in good radiochemical yields and high radionuclide purity. The generated injectable [124I]NaI solution was sterile, non-pyrogenic and ready for preclinical and clinical applications after a sterile filtration through a 0.22 µm membrane filter.

The present paper reports on pectin based films modified with carboxymethyl cellulose intended for food packaging. The films are prepared by solvent-casting method with different carboxymethyl cellulose content and cross-linker concentration (Ca2+ ions) in the presence of glycerol as a plasticizer. FT-IR spectra of the prepared films propose that carboxyl group from pectin are mainly involved in interactions with CMC, whereas −OH groups are mainly involved in self-associated hydrogen bonding of neat polymers. Further, an addition of carboxymethyl cellulose improved mechanical properties compared to pure pectin films, while TGA analysis confirmed satisfying thermal stability regarding their potential application as packaging material. Finally, water vapor permeability values are in the range of 1.32 × 10−7 up to 2.03 × 10−7 g/m h Pa. The 24th Annual World Forum on Advanced Materials, Poznan, Poland, May 9–13, 2016

The aim of this study was the development of novel polysaccharide based films intended to be used as edible food packaging material. The films were prepared by solution casting method using highly methoxylated pectin (PEC) and poly(ethylene glycol) (PEG) of various molecular weights (400, 600 and 1000 gmol(-1)) in different ratios (5:1, 3:1 and 1:1). The film formation was supported by hydrogen bonding between PEC and PEG, which was evidenced by means of ATR-FTIR and NMR analysis. TGA revealed that generally PEG behaves like a pro-degrading agent for pectin, except in the case of PEC/PEG film with a ratio of 1:1. Furthermore, DSC thermograms indicated that PEG1000 exists as a separate phase in the pectin matrix while the formulations with PEG400 and PEG600 showed mainly amorphous morphology. The addition of PEG enhanced the plasticization of PEC films, as evidenced by progressive decreasing of the glass transition temperature values (T-g). The tensile test measurements showed that increasing concentration of PEG produced weaker and more flexibile films. Due to the increased molecular mobility, the pectin phase became more permeable to water vapor as the PEG concentration increased. The obtained results showed that the combination of both polymers resulted in interesting bio -inspired edible films with the potential to compete with commercially used synthetic package materials. This is the peer-reviewed version of the article: Šešlija, S., Nešić, A., Ružić, J., Kalagasidis Krušić, M., Veličković, S. J., Avolio, R., Santagata, G.,& Malinconico, M. (2018). Edible blend films of pectin and poly(ethylene glycol): Preparation and physico-chemical evaluation. Food HydrocolloidsElsevier Sci Ltd, Oxford., 77, 494-501. [https://doi.org/10.1016/j.foodhyd.2017.10.027] The published version: [https://cer.ihtm.bg.ac.rs/handle/123456789/2473]

The use of oil-derived polymers has been of great benefit to mankind, but it is evident that it causes considerable damage to the ecosystem. Public concern about the environmental impact of wastes is growing day by day and waste management methods are limited as are petroleum resources, so it is very important to find substitutes, particularly in those applications where a relatively short lifetime can be forecast, such as packaging and agriculture. This has led to research work to find new biodegradable polymers as an alternative to conventional non-degradable ones. Among bio-based totally biodegradable polymers, poly(lactic acid) (PLA) has been studied for use in different fields because of its compostability and renewability. In this chapter, information on the present situation and trends regarding the applications of PLA is offered. The use of life cycle assessment principles helps to quantify the environmental benefits of PLA polymers. Most recent developments with PLA in the field of packaging show how this plastic material is moving from commodity to specialty applications, facing competition from polyolefins, particularly as barrier polymers for shelf-life enhancement.

Active packaging refers to packaging systems with active functions beyond the inert passive containment and protection of the product. It is commonly used with foods, as it helps extend shelf life, improve safety or sensory properties and maintain food quality [1]. Most diffused active packaging systems include the use of oxygen scavengers, carbon dioxide or ethylene emitters and scavengers, ethanol releaser, as well as antimicrobial and antioxidant agents. The active agent may be placed in the package with the food, within a small sachet or pad of permeable material, able to release volatile antimicrobial agents without allowing a direct contact with the food product. Incorporation of volatile active agents into polymers is a technological challenge, due to the need to avoid evaporation of the additive during melt processing of the polymer. Such challenge can be solved by incorporation of the volatile molecules within cyclodextrins (CD), as detailed in this contribution. Cyclodextrins are biocompatible, biodegradable cyclic oligosaccharides produced from a renewable natural material, starch [2]. Cyclodextrins can form inclusion complexes with various non-polar, aliphatic and aromatic compounds, including antibacterial molecules, whose release could enhance the quality of the packaged product and extend its shelf life [3]. In the research detailed below, b-CD was used as cage to include D-limonene (4-isopropenyl-1-methylcyclohexene), the major constituent in several citrus-derived essential oils, which is also a natural antimicrobial agent [4-6]. D-limonene is listed in the Code of Federal Regulations and generally recognized as safe flavoring agent and food preservative [7]. Its outstanding antimicrobial activities have already been tested with different species of food-related microorganisms, such as staphylococcus aureus, Listeria monocytogenes, Salmonella enterica, Saccharomyces bayanus [8, 9]. Unfortunately, D-limonene is susceptible to oxidative degradation, which directly results in its loss of activity [7, 10]. Moreover, similar to other volatile essential oils, limonene aroma could be easily released to the packaged food, thus contaminating it. In order to overcome to these drawbacks, D-limonene was included into CDs, and the inclusion complex CD-Lim thus obtained was dispersed into a biodegradable and bio-based polymer matrix, namely poly(butylene succinate) (PBS). PBS is a biodegradable and bio-based polyester, currently used for food packaging, and its use in this market area is expected to largely increase in the coming years [11]. The aim of this paper is to prepare a novel biodegradable polymeric-based system, as potential bioactive food packaging material, by dispersing CD-Lim inclusion complex into PBS polymeric matrix and to investigate the chemical-physical properties of the obtained blends.

Biodegradable polymer films based on polybutylene succinate (PBS) and polybutylene adipate terephthalate (PBAT) blends with varying weight ratios were prepared by extrusion and chill roll calendering. The films were characterized by infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), mechanical tensile tests, scanning electron microscopy (SEM), and rheology. In the blends with higher content of PBAT, PBS crystallization was inhibited. As for mechanical performance, increasing the PBS content in PBAT an increase in the stiffness and a decrease in the ductility of the blends is detected. Finally, rheological measurements evidence an increase in the viscosity of the blends with increasing the PBAT content.

Ungeremine is a betaine type alkaloid isolated from Pancratium maritimim L., 1 and thus could be synthesized by SeO2 oxidation of lycorine, which is the main Amaryllideacea alkaloid obtained in high yield from Sterbergia lutea Ker Gawl. a wild species coollected on the coasts Apulia region in South Italy. 2 Ungeremine have shown a very significant antifungal activity against Penicillium roqueforti,3 a filamentous fungus responsible of the bakery products deterioration. In this study, chitosan based microbeads containing ungeremine, were prepared by external gelation by using sodium tripolyphosphate (TPP) as crosslinking agent. The stability of the microbeads, as well as the loading efficiency of the antifungal metabolite were assessed at different pH and TPP concentrations and resulted particularly enhanced at low pH. All the microbeads evidenced antimicrobial activity against Penicillium roqueforti. The release kinetics of ungeremine was tailored by opportunely modulating pH and TPP concentrations. Morphological analysis evidenced the improvement of the structural cross linking density of microbeads including ungeremine and spectroscopic analysis emphasized the active participation of ungeremine to the crosslinking process occurring between chitosan and TPP. Finally, thermogravimetric analysis confirmed the increasing of free volume in threedimensional networks and their liability to thermal degradation.

The application of the circular economy to the fashion supply chain is one of the objectives which is gaining interest among corporate stakeholders of the sector. In particular, the development of technologies able to reuse by-products instead of raw materials can be a solution both to reduce waste generation and to improve the use of resources over the long term. In the examined case, the company Orange FiberTM, through a chemical process, extracts cellulose from citrus peels to produce a textile fiber. This fiber can be compared to traditional ones such as silk, cotton and viscose. Nowadays citrus peels constitute a by-product of the fruit industry and its traditional disposal represents a low-value recovery as waste or animal feed. The presentation aims to determine the environmental impacts of this process. The consequential LCA identifies the environmental benefits of implementing the process for a real application case in Italy. System boundaries include the fruit growing stage, the harvesting phase, the use of citruses in the food chain, the expected end-of-life of the waste, transports, the cellulose extraction, the textile fiber production as well as the production of the substituted fibers. The parameters responsible for the highest shares of the scenario uncertainty are the economic allocation of the food industry waste, the type of citrus cultivation, the yield of the fiber production process and the compared citrus peels end-of-life. Results suggest that the assessed process can potentially be beneficial from an environmental point of view while providing a high added value product.

In this paper, a novel and sustainable process for the fruit dehydration was described. Specifically, edible coatings based on pectin and honey were prepared and used as dehydrating and antimicrobial agents of cut fruit samples, in this way promoting the fruit preservation from irreversible deteriorative processes. Pectin-honey coating was tested on apple, cantaloupe melon, mango and pineapple. The analysis were performed also on uncoated dehydrated fruits (control). The coated fruit evidenced enhanced dehydration percentage, enriched polyphenol and vitamin C contents, improved antioxidant activity and volatile molecules profile. Moreover, the antimicrobial activity against Pseudomonas and Escherichia coli was assessed. Finally, morphological analysis performed on fruit fractured surface, highlighted the formation of a non-sticky and homogeneous thin layer. These outcomes suggested that the novel fruit dehydration process, performed by using pectin-honey coating, was able to both preserve the safety and quality of dehydrated fruits, and enhance their authenticity and naturalness.

Nowadays, the need of novel strategies to repair and regenerate bone defects in the field of biomedical applications has increased. Novel approaches include the design of natural bioactive scaffolds mimicking bone tissue. These bioactive scaffolds have to possess biophysical properties suitable to address biological response towards newly bone tissue formation. In particular, scaffold porosity and pore size play a pivotal role in cell migration, adhesion and proliferation, thus increasing cell-material surface interaction and osteogenic signals transmission. Here we propose the development of macroporous alginate foams (MAFs) with porous and well interconnected structure, useful to enhance growth and osteogenic differentiation of human Mesenchymal Stem Cells (hMSCs). Moreover, in this study we report a new method for MAFs fabrication based on the combination of internal gelation technique with gas foaming. Strontium was employed in combination with calcium as cross-linking agent for the alginate chains and as enhancer of the osteogenic differentiation. The influence of strontium ions on the gelation kinetics, physical properties and degradation in physiological medium of MAFs was investigated. Our results suggest that the combination of internal gelation technique with gas foaming followed by freeze-drying is an easy and straightforward procedure to prepare alginate foams with high porosity and interconnectivity, able to support cell infiltration. Finally, biological assays showed how scaffolds with high strontium content are able to support cell growth and differentiation in long times by promoting osteogenic marker expression.