Novel terephthalamide diol monomers synthesis from PET waste to Poly(Urethane acrylates).

Due to its excellent properties, poly(ethylene terephthalate) (PET) is one of the most produced and consumed polymers. Among plastics, it represents the main contributor to environmental pollution. Following the circular economy model, the chemical upcycling of PET reduces the amount of waste generated and transforms it into high-value products. The depolymerization of poly(ethylene terephthalate) into oligomers or monomers leads to forming a library of reactive molecules involved in different polymerization processes to obtain compounds with improved properties. Herein, several ß-hydroxy amines were synthesized and used for the chemical recycling of water bottle waste by an environmental benefit aminolysis process to get very useful new terephthalamide diol monomers. The recycled diol monomers were subsequently exploited to synthesize poly(urethane acrylates) (PUAs) UV-curable coatings, and their chemical, thermal and mechanical characterizations were performed. The results show the great potential of the developed synthesis protocols to obtain PUAs with final properties that can be modulated to meet the requirements of different applications.

Recent Developments in Chemical Derivatization of Microcrystalline Cellulose (MCC): Pre-Treatments, Functionalization, and Applications.

Microcrystalline Cellulose (MCC) is an isolated, colloidal crystalline portion of cellulose fibers, and it is a valuable alternative to non-renewable fossil-based materials. It is used for a large plethora of different fields, such as composites, food applications, pharmaceutical and medical developments, and cosmetic and material industries. The interest of MCC has also been driven by its economic value. In the last decade, particular attention has been driven to the functionalization of its hydroxyl groups to expand the field of applications of such biopolymer. Herein, we report and describe several pre-treatment methods that have been developed to increase the accessibility of MCC by breaking its dense structure allowing further functionalization. This review also collects the results that have appeared in the literature during the last two decades on the utilization of functionalized MCC as adsorbents (dyes, heavy metals, and carbon dioxide), flame retardants, reinforcing agents, energetic materials, such as azide- and azidodeoxy-modified, and nitrate-based cellulose and biomedical applications.

Chemical, Thermal and Mechanical Characterization of Licorice Root, Willow, Holm Oak, and Palm Leaf Waste Incorporated into Maleated Polypropylene (MAPP).

The effect of four lignocellulosic waste fillers on the thermal and mechanical properties of biocomposites was investigated. Powdered licorice root, palm leaf, holm oak and willow fillers were melt compounded with polypropylene at two different weight contents, i.e., 10 and 30, and then injection molded. A commercially available maleated coupling agent was used to improve the filler/matrix interfacial adhesion at 5 wt.%. Composites were subjected to chemical (FTIR-ATR), thermal (TGA, DSC, DMA) and mechanical (tensile, bending and Charpy impact) analyses coupled with a morphological investigation by scanning electron microscopy. Although similarities among the different formulations were noted, holm oak fillers provided the best combination of thermal and mechanical performance. In particular, at 30 wt.% content with coupling agent, this composite formulation displayed remarkable increases in tensile strength and modulus, flexural strength and modulus, of 28% and 110%, 58% and 111%, compared to neat PP, respectively. The results imply that all these lignocellulosic waste fillers can be used successfully as raw materials for biocomposites, with properties comparable to those featured by other natural fillers.

Microplastics accumulation in gastrointestinal tracts of Mullus barbatus and Merluccius merluccius is associated with increased cytokine production and signaling.

There is clear evidence that different marine species can be impacted by microplastic (MP) ingestion accumulating such MPs mainly in the gastrointestinal tract. However, there is still limited knowledge on the consequences of MPs' accumulation in the gut. The present study aims to assess MPs and their potential immunotoxic effects in the digestive tract of two species showing different ecological traits: the red mullet (Mullus barbatus) and the European hake (Merluccius merluccius). Infrared spectroscopy (FTIR-ATR), micro-Raman and electron scanning microscope (SEM) were used to accurately identify the main plastic polymers detected in gut contents. In addition, we investigated the association between MP uptake and intestinal inflammation by evaluating expression and secretion of proinflammatory cytokines. MP abundance ranged from 1 to 20 items/individual in red mullet and from 2 to 15 items/individual in European hake. The majority of ingested MPs were fibers, while the dominant colors were black and blue in both species. Chemical characterization indicated polyethylene and polypropylene as the most common polymer types. Moreover, it was observed that MP abundance was highly positive correlated to cytokines (i.e. interleukin-1ß, 10, and interferon) and antioxidant enzyme (i.e. catalase and superoxide dismutase) transcript levels suggesting ROS generation and an infiltration of immune cells in the gut. Our findings provide evidence that the induction of cytokine-dependent signaling pathways is one aspect of the complex mechanism by which MPs affect the gut system in fish.

A novel treatment and derivatization for quantification of residual aromatic diisocyanates in polyamide resins.

In the scientific context, the environmental and healthy impact of polymers is more related to the residual monomer content rather than their macromolecular structure, due to the monomer capability to interact with membrane cells. For this a novel method to stabilize and quantify residual monomeric isocyanates in high thermal resistance polyamide resins (PAs) has been developed. This new analytical method resulted in an improvement concerning the quantification of residual aromatic diisocyanates in viscous polymeric matrices by using a simple and cheap technique like HPLC-VWD. Diisocyanate monomers were derivatized with dibutylamine, resulting in stable urea derivatives that were simultaneously analysed and quantified. The method was applied to solvent-based polyamide resins, used as primary electrical insulation, for avoiding additional step of solvent removing before the analysis. The quantification of residual monomers answers to the provisions imposed by European Regulation N. 1907/2006 (REACH) for polymer registration, and the necessity of an early evaluation of the occupational risk associated with the use of diisocyanates, due to their toxicity and high reactivity towards moisture.

Chemical and Mechanical Characterization of Licorice Root and Palm Leaf Waste Incorporated into Poly(urethane-acrylate) (PUA).

A poly(urethane-acrylate) polymer (PUA) was synthesized, and a sufficiently high molecular weight starting from urethane-acrylate oligomer (UAO) was obtained. PUA was then loaded with two types of powdered ligno-cellulosic waste, namely from licorice root and palm leaf, in amounts of 1, 5 and 10%, and the obtained composites were chemically and mechanically characterized. FTIR analysis of final PUA synthesized used for the composite production confirmed the new bonds formed during the polymerization process. The degradation temperatures of the two types of waste used were in line with what observed in most common natural fibers with an onset at 270 °C for licorice waste, and at 290 °C for palm leaf one. The former was more abundant in cellulose (44% vs. 12% lignin), whilst the latter was richer in lignin (30% vs. 26% cellulose). In the composites, only a limited reduction of degradation temperature was observed for palm leaf waste addition and some dispersion issues are observed for licorice root, leading to fluctuating results. Tensile performance of the composites indicates some reduction with respect to the pure polymer in terms of tensile strength, though stabilizing between data with 5 and 10% filler. In contrast, Shore A hardness of both composites slightly increases with higher filler content, while in stiffness-driven applications licorice-based composites showed potential due to an increase up to 50% compared to neat PUA. In general terms, the fracture surfaces tend to become rougher with filler introduction, which indicates the need for optimizing interfacial adhesion.

A New Dimeric Copper(II) Complex of Hexyl Bis(pyrazolyl)acetate Ligand as an Efficient Catalyst for Allylic Oxidations.

A new dimeric copper(II) bromide complex, [Cu(LOHex)Br(µ-Br)]2 (1), was prepared by a reaction of CuBr2 with the hexyl bis(pyrazol-1-yl)acetate ligand (LOHex) in acetonitrile solution and fully characterized in the solid state and in solution. The crystal structure of 1 was also determined: the complex is interlinked by two bridging bromide ligands and possesses terminal bromide ligands on each copper atom. The two pyrazolyl ligands in 1 coordinate with the nitrogen atoms to complete the Cu coordination sphere, resulting in a five-coordinated geometry-away from idealized trigonal bipyramidal and square pyramidal geometries-which can better be described as distorted square pyramidal, as measured by the τ and χ structural parameters. The pendant hexyloxy chain is disordered over two arrangements, with final site occupancies refined to 0.705 and 0.295. The newly synthesized complex was evaluated as a catalyst in copper-catalyzed C-H oxidation for allylic functionalization through a Kharasch-Sosnovsky reaction without any external reducing agent. Using 0.5 mol% of this catalyst, and tert-butyl peroxybenzoate (Luperox) as an oxidant, allylic benzoates were obtained with up to 90% yield. The general reaction time was only slightly decreased to 24 h but a very significant decrease in the alkene:Luperox ratio to 3:1 was achieved. These factors show relevant improvements with respect to classical Kharasch-Sosnovsky reactions in terms of rate and amount of reagents. The present study highlights the potential of copper(II) complexes containing functionalized bis(pyrazol-1-yl)acetate ligands as efficient catalysts for allylic oxidations.

Fe3O4/Graphene Composite Anode Material for Fast-Charging Li-Ion Batteries.

Composite anode material based on Fe3O4 and reduced graphene oxide is prepared by base-catalysed co-precipitation and sonochemical dispersion. Structural and morphological characterizations demonstrate an effective and homogeneous embedding of Fe3O4 nanoparticles in the carbonaceous matrix. Electrochemical characterization highlights specific capacities higher than 1000 mAh g-1 at 1C, while a capacity of 980 mAhg-1 is retained at 4C, with outstanding cycling stability. These results demonstrate a synergistic effect by nanosize morphology of Fe3O4 and inter-particle conductivity of graphene nanosheets, which also contribute to enhancing the mechanical and cycling stability of the electrode. The outstanding capacity delivered at high rates suggests a possible application of the anode material for high-power systems.

A new and efficient lactic acid polymerization by multimetallic cerium complexes: a poly(lactic acid) suitable for biomedical applications.

Among many, poly(lactic acid) (PLA) has received significant consideration. The striking price and accessibility of l-lactic acid, as a naturally occurring organic acid, are important reasons for poly-(l)-lactic acid (PLLA) improvement. PLLA is a compostable and biocompatible/bioresorbable polymer used for disposable products, for biomedical applications, for packaging film, in the automotive industry, for electronic device components, and for many other applications. Formerly, titanium and other metals have been used in different orthopaedic screws and plates, but they are not degradable and therefore remain in the body. So, the development of innovative and eco compatible catalysts for polyester synthesis is of great interest. In this study, an innovative and eco sustainable catalyst was employed for PLLA synthesis. The combined CeCl3·7H2O-NaI system has been demonstrated to be a very valuable and nontoxic catalyst toward PLLA synthesis, and it represents a further example of how to exploit the antibacterial properties of cerium ions in biomaterials engineering. A novel synthesis of poly-(l)-lactic acid was developed in high yields up to 95% conversion and with a truly valuable molecular weight ranging from 9000 to 145 000 g mol-1, testing different synthetic routes.

Development of new and efficient copper(II) complexes of hexyl bis(pyrazolyl)acetate ligands as catalysts for allylic oxidation.

In this study, two new hexyl bis(pyrazol-1-yl)acetate ligands and related copper(ii) complexes were prepared and fully characterized in the solid state and in solution. Their electronic and molecular structures were investigated by X-ray photoelectron spectroscopy and near edge X-ray absorption; their ligand molecular structural stability upon coordination to copper was also investigated. The Cu(ii) complexes were studied as new catalysts in copper-catalyzed C-H oxidation for allylic functionalization (the Kharasch-Sosnovsky reaction) avoiding the use of any external reducing agents. Using 5 mol% of these catalysts and tert-butylperoxybenzoate as the oxidant, allylic benzoates were obtained in up to 90% yield: the general reaction time was decreased to 6 h and a 5 to 1 ratio of the alkene and tert-butylperoxybenzoate was used to overcome the two most important limitations on their use in chemistry.

Development and application of a solid-phase microextraction gas cromatography mass spectrometry method for analysing volatile organic compounds produced during cooking.

In the last decades, there is more awareness on the impact on human health of pollutants emitted during cooking processes, both from commercial and from domestic activities. In this study, a new method exploiting solid-phase microextraction and gas chromatography coupled to mass spectrometry (SPME-GC-MS) was developed to analyse the volatile organic compounds (VOCs) emitted during cooking. The air above the cooking plate was sampled using a polyethylene terephthalate olfactometric bag that allows to transport the sample to the instrument location and to perform the SPME extraction of the sampled air. The efficiency of different extraction systems and different extraction times (1, 8, 16, and 24 h) was evaluated in order to obtain sufficient sensitivity. Thus, the proposed system, combining the use of olfactometric bags and SPME-GC-MS, was applied for the first time to study VOCs emitted during cooking allowing to perform the analysis, even on samples produced in sites far from the instrument location, in an easy way and with instrumentations available in most of laboratories. Then, the method was applied to assess the efficiency of odour filters used in common kitchen hoods, using deep frying of potatoes in sunflower oil as cooking model system. VOCs were analysed in the air before and after passage through the filter, calculating then percentages of dejection for the different classes of VOCs that resulted to be in the range 31-77%.

A New Valuable Synthesis of Polyfunctionalized Furans Starting from ß-Nitroenones and Active Methylene Compounds.

Highly functionalized furans are the key scaffolds of many pharmaceuticals and bioactive natural products. Herein, we disclose a new fruitful synthesis of polyfunctionalized furans starting from ß-nitroenones and α-functionalized ketones. The protocol involves two steps promoted by solid supported species, and it provides the title targets from satisfactory to very good overall yields and in an excellent diastereomeric ratios.

Novel MIPs-Parabens based SPE Stationary Phases Characterization and Application.

In this work, the synthesis, characterization, and application of novel parabens imprinted polymers as highly selective solid-phase extraction (SPE) sorbents have been reported. The imprinted polymers were created using sol-gel molecular imprinting process. All the seven parabens were considered herein in order to check the phase selectivity. By means of a validated HPLC-photodiode array detector (PDA) method all seven parabens were resolved in a single chromatographic run of 25 min. These SPE sorbents, in-house packed in SPE empty cartridges, were first characterized in terms of extraction capability, breakthrough volume, retention volume, hold-up volume, number of theoretical plates, and retention factor. Finally, the device was applied to a real urine sample to check the method feasibility on a very complex matrix. The new paraben imprinted SPE sorbents, not yet present in the literature, potentially encourage the development of novel molecularly imprinted polymers (MIPs) to enhance the extraction efficiency, and consequently the overall analytical performances, when the trace quantification is required.

Depolymerization of waste poly(methyl methacrylate) scraps and purification of depolymerized products.

A big challenge for the civilization in energy saving/waste management can be "the regeneration of monomers from the waste plastics followed by their re-polymerization" using an ideal recycling method. Herein, we investigate the thermal depolymerization of poly(methyl methacrylate) (PMMA) using thermogravimetric analysis coupled with mass spectrometry (TGA-MS). In this process, the polymer chains were decomposed to methyl methacrylate (MMA) in high yield and the degradation species were thoroughly characterized. The obtained MMA contained traces of byproducts. Firstly, the byproducts were found to be nonpolymerizable, secondly, their presence interrupt the polymerization reaction, and thirdly, they reduce the quality of re-polymerized PMMA (r-PMMA). This study reclaims that besides the main byproduct (methyl isobutyrate), traces of methyl pyruvate and 2,3-butanedione were also formed during the thermal depolymerization of PMMA. The formed 2,3-butanedione was found to be responsible for the unpleasant smell in the recovered MMA that also found itself in the r-PMMA. Further, the generated byproducts were eliminated from the r-PMMA by a dissolution/re-precipitation method. The structural characterizations of the recycled and purified PMMA were carried out by Fourier-transform-infrared spectroscopy (FT-IR), Hydrogen-1 (1H)- and Carbon-13 (13C)-nuclear magnetic resonance (NMR), differential scanning calorimetry (DSC) and gel permeation chromatography (GPC). The chemical properties of the r-PMMA and purified PMMA proved to be similar to that of the virgin commercial PMMA. This study can provide an effective and practical prototype for the recycling of waste PMMA scraps and thus reduction in pollution caused by the landfilling of waste PMMA scraps.

Synthetic Approach to the Preparation of (2-Acetoxy)allyl Nitro Compounds.

A synthetic approach to a new class of allyl nitro derivatives is reported. (2-Acetoxy)allyl nitro compounds have been prepared for the first time in a four-step procedure by a preliminary reaction of nitroalkanes with 2-(phenylselenyl)acetaldehyde. After the acetylation of the obtained nitro alcohols, the unsaturation is installed by an oxidation reaction involving the phenylselenyl group followed by a thermal elimination. The oxidation process is accomplished under flow conditions ensuring a notable lowering of overoxidation by products observed in batch.

A New One-Pot Synthesis of Quinoline-2-carboxylates under Heterogeneous Conditions.

Quinoline-2-carboxylates are an important subclass of quinoline derivatives largely present in a variety of biologically active molecules, as well as useful ligands in metal-catalyzed reactions. Herein, we present a new one-pot protocol for synthesizing this class of derivatives starting from ß-nitroacrylates and 2-aminobenzaldehydes. In order to optimize the protocol, we investigated several reaction conditions, obtaining the best results using the 2-tert-Butylimino-2-diethylamino-1,3-dimethylperhydro-1,3,2-diazaphosphorine (BEMP) as solid base, in acetonitrile. Finally, we demonstrated the generality of our approach over several substrates which led to synthesize a plethora of functionalized quinolines-2-carboxylate derivatives in good overall yields.

A salting out system for improving the efficiency of the headspace solid-phase microextraction of short and medium chain free fatty acids.

Given the importance of short and medium chain free fatty acids (FFAs) in several fields, this study sought to improve the extraction efficiency of the solid-phase microextraction (SPME) of FFAs by evaluating salting out agents that appear promising for this application. The salts ammonium sulfate ((NH4)2SO4) and sodium dihydrogen phosphate (NaH2PO4) were tried on their own and in combination (3.7/1), in four different total amounts, as salting out agents in the headspace-SPME-gas chromatographic (HS-SPME-GC) analysis of the FFAs from acetic acid (C2) to decanoic acid (C10). Their performance in a model system of an aqueous standard mixture of FFAs at a pH of 3.5 was compared to that of the more commonly used sodium chloride (NaCl) and sodium sulfate (Na2SO4). All of the salts and salt systems evaluated, in proper amount, gave improved results compared to NaCl (saturated), which instead gave interesting results only for the least volatile FFAs C8 and C10. For C2-C6, the salt system that gave the best results compared to NaCl was (NH4)2SO4/NaH2PO4, in the highest of the four amounts evaluated, with factor increases between 1.2 and 4.1-fold, and NaH2PO4, between 1.0 and 4.3-fold. The SPME extraction efficiency given by the mixture (NH4)2SO4/NaH2PO4 was also assessed on biological and food samples, confirming that overall it performed better than NaCl.

Easy and direct conversion of tosylates and mesylates into nitroalkanes.

Tosylates and mesylates were directly converted into the corresponding nitroalkanes, by their treatment with tetrabutylammonium nitrite (TBAN) under mild conditions.

Alkoxyamine-cyanoborane adducts: efficient cyanoborane transfer agents.

We report the synthesis of the hitherto unknown zwitterionic alkoxyamino cyanoboranes by reduction of O-alkyloximes with sodium cyanoborohydride; unprecedented cyanoboronated N-alkoxyformamidines were also isolated as by-products. Boronated alkoxyamines were found to be efficient cyanoborane transfer agents towards more basic amines, including aminosugars; they were also successfully transformed into neoglycoconjugates by the neoglycorandomization reaction with reducing sugars.

Efficient two-step sequence for the synthesis of 2,5-disubstituted furan derivatives from functionalized nitroalkanes: successive Amberlyst A21- and Amberlyst 15-catalyzed processes.

The nitroaldol reaction of ketal-functionalized nitroalkanes with alpha-oxoaldehydes, promoted by Amberlyst A21, followed by acidic treatment (Amberlyst 15) of the obtained nitroalkanol, leads to the formation of 2,5-disubstituted furans in good yields. The procedure was successfully applied to the total synthesis of 1-benzyl-3-(5'-hydroxymethyl-2'-furyl)-indazole (YC-1), an important pharmaceutical target.