Green extraction of chitin from hard spider crab shells.

A green protocol to extract chitin from crab shells using water soluble ionic liquids (ILs) is here reported. Compared to conventional multistep acid-base extraction methods, this one-pot procedure achieves pulping of recalcitrant crustacean waste shells by employing ammonium acetate, ammonium formate and hydroxylammonium acetate as water-soluble, low-cost and easy to prepare ILs. An extensive parametric analysis of the pulping process has been carried out with different ILs, different ratios, temperature and time. The optimized protocol provides a high-quality chitin comparable, if not better, to commercial chitin. The best results were obtained at 150 °C with ammonium formate prepared in-situ from aqueous ammonia and formic acid: chitin was isolated in a 17 wt% yield (based on dried crab shells as starting biowaste), a degree of acetylation (DA) > 94 %, a crystallinity index of 39-46 %, a molecular weight up to 6.6 × 105 g/mol and a polydispersity of ca 2.0.

UPCYCLING OF CHITIN TO CROSS-COUPLING CATALYSTS: TAILORED SUPPORTS AND OPPORTUNITIES IN MECHANOCHEMISTRY.

In this study chitin derived from shrimp shells was used in the design of heterogeneous Pd-based catalysts for Heck and Suzuki-Miyaura cross-coupling reactions. The synthesis of Pd nanoparticles supported on N-doped carbons was performed through different approaches, including a sustainable mechanochemical approach, by using a twin-screw extruder. All catalytic systems were characterized by a multitechnique approach and the effect of nanoparticles size, N-doping on the support, and their synergistic interactions were elucidated. Specifically, Kelvin Probe Atomic Force Microscopy provided valuable insights on charge transfer and metal-support interactions. The catalytic behaviour of the samples was investigated in cross-coupling reactions under batch conditions and under semi-continuous flow solvent-free conditions, respectively obtaining a quantitative yield and a noteworthy productivity of 8.7 mol/(gPdh).

Selective Multiphase-Assisted Oxidation of Bio-Sourced Primary Alcohols over Ru- and Mo- Carbon Supported Catalysts.

The oxidation of representative bio-based benzyl-type alcohols has been successfully carried out in a multiphase (MP) system comprised of three mutually immiscible liquid components as water, isooctane, and a hydrophobic ionic liquid as methyltrioctylammonium chloride ([N8881][Cl]), a heterogeneous catalyst (either ad-hoc synthesized carbon-supported Mo or a commercial 5% Ru/C), and air as an oxidant. The MP-reaction proceeded as an interfacial process with Mo/C or Ru/C perfectly segregated in the ionic liquid phase and the reactant(s)/products(s) dissolved in the aqueous solution. This environment proved excellent to convert quantitatively benzyl alcohols into the corresponding aldehydes with a selectivity up to 99%, without overoxidation to carboxylic acids. The nature of the catalyst, however, affected the operating conditions with Ru/C active at a lower T and t (130 °C, 4-6 h) compared to Mo/C (150 °C, 24 h). The phase confinement was advantageous also to facilitate the products isolation and the recycle of the catalyst. Notably, in the Mo/C-catalyzed oxidation of benzyl alcohol, benzaldehyde was achieved with unaltered selectivity (>99%) at complete conversion, for 5 subsequent reactions through a semicontinuous procedure in which the catalyst was reused in-situ, without ever removing it from the reactor or treating it in any way.

Controllable deposition of dispersed Pd nanoparticles on ZnO for Suzuki-Miyaura cross-coupling reactions.

Palladium nanoparticles find extensive applications in catalysis in both homogeneously and heterogeneously catalyzed processes. Supporting metal nanoparticles enhances their stability as compared to their unsupported counterparts. The role of catalytic support is increasingly recognized as crucial in determining the behaviour of these materials. However, controlling the deposition and anchoring of palladium nanoparticles remains a significant challenge. This contribution discusses the preparation of straight lines of palladium particles on zinc oxide by wet impregnation. This phenomenon is attributed to the highly stepped morphology of the employed ZnO that created steric anchoring sites to stabilize the metal particles. Palladium-based catalysts were evaluated for the valuable Suzuki-Miyaura cross-coupling reaction. The dispersed Pd/ZnO catalyst achieved a conversion rate of 86% with 100% selectivity, remarkably superior to that of the Pd/Al2O3 and Pd/TiO2 counterparts.

Continuous Flow Hydrogenation of Lignin-model Aromatic Compounds over Carbon-supported Noble Metals.

An efficient continuous-flow (CF) protocol was designed for the hydrogenation of lignin-derived aromatics to the corresponding cycloalkanes derivatives. A parametric analysis of the reaction was carried out by tuning the temperature, the H2 pressure and the flow rate, and using diphenyl ether (DPE) as a model substrate, commercial Ru/C as a catalyst, and isopropanol as a solvent: at 25 °C, 50 bar H2 , and a flow rate of 0.1 mL min-1 , dicyclohexyl ether was achieved in an 86 % selectivity, at quantitative conversion. By-products from the competitive C-O bond cleavage of DPE, cyclohexanol and cyclohexane, did not exceed 14 % in total. Remarkably, prolonged experiments demonstrated an excellent stability of the catalyst whose performance was unaltered for up to 420 min of time-of-stream. A substrate scope evaluation proved that under the same conditions used for DPE, a variety of substrates including alkoxy-, allyl-, and carbonyl-functionalized phenols, biphenyl, aryl benzyl- and phenethyl ethers (10 examples) yielded the ring-hydrogenated products with selectivity up to 99 % at complete conversion.

Chitin-Derived Nanocatalysts for Reductive Amination Reactions.

Chitin, the second most abundant biopolymer in the planet after cellulose, represents a renewable carbon and nitrogen source. A thrilling opportunity for the valorization of chitin is focused on the preparation of biomass-derived N-doped carbonaceous materials. In this contribution, chitin-derived N-doped carbons were successfully prepared and functionalized with palladium metal nanoparticles. The physicochemical properties of these nanocomposites were investigated following a multi-technique strategy and their catalytic activity in reductive amination reactions was explored. In particular, a biomass-derived platform molecule, namely furfural, was upgraded to valuable bi-cyclic compounds under continuous flow conditions.

Fish-Waste-Derived Gelatin and Carbon Dots for Biobased UV-Blocking Films.

The fish industry produces every year huge amounts of waste that represent an underutilized source of chemical richness. In this contribution, type I collagen was extracted from the scales of Mugil cephalus and carbon dots (CDs) were synthesized from the scales of Dicentrarchus labrax. These materials were combined to make hybrid films with UV-blocking ability, by casting a mixture of gelatin, glycerol (15%), and CDs (0, 1, 3, and 5%). The films were fully characterized from the mechanical, morphological, and optical point of view. Here, 40 µm thick films were obtained, characterized by a high water solubility (70%); moreover, the presence of CDs improved the film mechanical properties, in particular increasing the tensile strength (TS) up to 17 MPa and elongation at break (EAB) up to 40%. The CDs also modulated water vapor permeability and the thermal stability of the films. From the optical point of view, with just 5% loading of CDs the films blocked almost 70% of the UV radiation with negligible change in transparency (88.6% for the nonloaded vs 84.4% for 5% CDs) and opacity (1.32 for nonloaded vs 1.61 for 5% CDs). These types of hybrid biobased films hold promise for the production of sustainable UV-shields both for human health and for prolonging the shelf life of food.

Tunable Multi-Phase System for Highly Chemo-Selective Oxidation of Hydroxymethyl-Furfural.

Three different multiphase systems (MP 1-3) comprised of two immiscible liquids, with or without an ionic liquid (IL: methyltrioctyl ammonium chloride), were investigated for the oxidation of 5-hydroxymethyl-furfural (HMF) over 5 % Ru/C as a catalyst and air (8 bar) as an oxidant. These conditions proved versatile for an excellent control of the reaction selectivity to 4 distinct products derived from full or partial oxidation of the carbonyl and alcohol functions of HMF, and each one achieved in 87-96 % isolated yield at complete conversion. MP1 based on water and isooctane, yielded 2,5-furandicarboxylic acid (FDCA, 91 % yield). In MP2, obtained by adding the IL to MP1, the oxidation proceeded towards the formation of 5-formyl-2-furancarboxylic acid (FFCA, 87-89 % yield). MP2 also proved successful in the design of a one pot-two step oxidation/reduction sequence to prepare 5-hydroxymethyl-2-furancarboxylic acid (HMFCA, 85 % yield). In MP3, the use of an acetonitrile/cyclooctane biphase yielded 2,5-diformylfuran (DFF, 96 % yield). All the multiphase systems MP 1-3 allowed a perfect segregation of the catalyst in a single phase (either the hydrocarbon or the IL) distinct from the one containing HMF and its oxidation products. This was crucial not only for the catalyst/product separation but also for the recycle of Ru/C that was possible under all the tested conditions. Accordingly, MP-reaction were run in a semicontinuous mode without removing the catalyst from the reactor nor resorting to conventional separation and activation techniques. Negligible Ru leaching, less than 0.96 ppb, was measured in all cases.

Tuning the Selectivity of the Hydrogenation/Hydrogenolysis of 5-Hydroxymethylfurfural under Batch Multiphase and Continuous-Flow Conditions.

The hydrogenation/hydrogenolysis of 5-hydroxymethylfurfural (HMF) has been carried out either under single (aqueous) phase or batch multiphase (MP) conditions using mutually immiscible aqueous/hydrocarbon phases, 5 % Ru/C as a catalyst, and both with and without the use of trioctylmethyl phosphonium bis-(trifluoro methane) sulfonimide ([P8881 ][NTf2 ]) as an ionic liquid (IL). Alternatively, the hydrogenation of HMF was explored in the continuous-flow (CF) mode with the same catalyst. By changing reaction parameters, experiments were optimized towards the formation of three products: 2,5-bis(hydroxy methyl)furan (BHMF), 2,5-bis(hydroxymethyl)tetrahydrofuran (BHMTHF), and 1-hydroxyhexane-2,5-dione (HHD), which were obtained in up to 92, 90, and 99 % selectivity, respectively, at quantitative conversion. In particular, the single (aqueous) phase reaction of HMF (0.2 m) carried out for 18 h at 60 °C under 30 bar of H2 , allowed the exclusive synthesis of BHMF from the partial (carbonyl) hydrogenation of HMF, while the MP reaction run at a higher T and p (100 °C and 50 bar) proved excellent to achieve only HHD derived from a sequence of hydrogenation/hydrogenolysis. It is worth noting that under MP conditions, the catalyst was perfectly segregated in the IL, where it could be recycled without any leaching in the aqueous/hydrocarbon phases. Finally, the hydrogenation of HMF was explored in a H-Cube® flow reactor in the presence of different solvents, such as ethyl acetate, tetrahydrofuran, and ethanol. At 100 °C, 50 bar H2 , and a flow rate of 0.1 mL min-1 , the process was optimized towards the formation of the full hydrogenation product BHMTHF. Ethyl acetate proved the best solvent.

Isopropenyl Esters (iPEs) in Green Organic Synthesis.

The need for greener compounds able to replace conventional ones with similar reactivity is crucial for the development of sustainable chemistry. Isopropenyl esters (iPEs) represent one eco-friendly alternative to acyl halides and anhydrides. This review provides a comprehensive overview of the preparation methodologies and reported synthetic applications of iPEs and, in particular, of isopropenyl acetate (iPAc). Intriguingly, the presence of a C=C double bond adjacent to the ester functionality makes iPEs appealing in different chemoselective organic synthesis transformations. For instance, the acyl moiety is suitable for transesterification reactions in presence of different heteroatom-based nucleophiles (C-, O-, N-, S-, Se-); these reactions are irreversible thanks to the formation of acetone, obtained upon keto-enol tautomerization of the prop-1-en-2-ol (isopropenyl) leaving group. Similarly, the unsaturation contained in the isopropenyl synthon could be selectively exploited in organic synthesis for electrophilic and/or radical additions as well as in metal-catalyzed cross-coupling reactions. To conclude, iPEs recently found major interest in the direct modification of biomass (i.e. lignin or cellulose) and in the implementation of tandem reactions of esterification-acetalization by exploiting the co-formation of acetone during the reaction.

A New Family of Renewable Thermosets: Kraft Lignin Poly-adipates.

Thermosetting polymeric materials have advantageous properties and are therefore used in numerous applications. In this study, it was hypothesized and ultimately shown that thermosets could be derived from comparably sustainable sub-components. A two-step procedure to produce a thermoset comprising of Kraft lignin (KL) and the cross-linker adipic acid (AdA) was developed. The cross-linking was activated by means of an acetylating agent comprising isopropenyl acetate (IPA) to form a cross-linking mixture (CLM). The cross-linking was confirmed by FTIR and solid-state NMR spectroscopy, and the esterification reactions were further studied using model compounds. When the KL lignin was mixed with the CLM, partial esterification occurred to yield a homogeneous viscous liquid that could easily be poured into a mold, as the first step in the procedure. Without any additions, the mold was heated and the material transformed into a thermoset by reaction of the two carboxylic acid-derivatives of AdA and KL in the second step.

N-Doped Carbon Dot Hydrogels from Brewing Waste for Photocatalytic Wastewater Treatment.

The brewery industry annually produces huge amounts of byproducts that represent an underutilized, yet valuable, source of biobased compounds. In this contribution, the two major beer wastes, that is, spent grains and spent yeasts, have been transformed into carbon dots (CDs) by a simple, scalable, and ecofriendly hydrothermal approach. The prepared CDs have been characterized from the chemical, morphological, and optical points of view, highlighting a high level of N-doping, because of the chemical composition of the starting material rich in proteins, photoluminescence emission centered at 420 nm, and lifetime in the range of 5.5-7.5 ns. With the aim of producing a reusable catalytic system for wastewater treatment, CDs have been entrapped into a polyvinyl alcohol matrix and tested for their dye removal ability. The results demonstrate that methylene blue can be efficiently adsorbed from water solutions into the composite hydrogel and subsequently fully degraded by UV irradiation.

Glycerol Valorization towards a Benzoxazine Derivative through a Milling and Microwave Sequential Strategy.

Glycerol and aminophenol intermolecular condensation has been investigated through a milling and microwave-assisted sequential strategy, towards the synthesis of a benzoxaxine derivative. Mechanochemical activation prior to the microwave-assisted process could improve the probability of contact between the reagents, and greatly favors the higher conversion of aminophenol. At the same time, following a mechanochemical-microwave sequential approach could tune the selectivity towards the formation of a benzoxazine derivative, which could find application in a wide range of biomedical areas.

Metal-Free N-Doped Carbons for Solvent-Less CO2 Fixation Reactions: A Shrimp Shell Valorization Opportunity.

High anthropogenic CO2 emissions are among the main causes of climate change. Herein, we investigate the use of CO2 for the synthesis of organic cyclic carbonates on metal-free nitrogen-doped carbon catalysts obtained from chitosan, chitin, and shrimp shell wastes, both in batch and in continuous flow (CF). The catalysts were characterized by N2 physisorption, CO2-temperature-programmed desorption, X-ray photoelectron spectroscopy, scanning electron microscopy, and CNHS elemental analysis, and all reactivity tests were run in the absence of solvents. Under batch conditions, the catalyst obtained by calcination of chitin exhibited excellent performance in the conversion of epichlorohydrin (selected as a model epoxide), resulting in the corresponding cyclic carbonate with 96% selectivity at complete conversion, at 150 °C and 30 bar CO2, for 4 h. On the other hand, in a CF regime, a quantitative conversion and a carbonate selectivity >99% were achieved at 150 °C, by using the catalyst obtained from shrimp waste. Remarkably, the material displayed an outstanding stability over a reaction run time of 180 min. The robustness of the synthetized catalysts was confirmed by their good operational stability and reusability: ca. (75 ± 3)% of the initial conversion was achieved/retained by all systems, after six recycles. Also, additional batch experiments proved that the catalysts were successful on different terminal and internal epoxides.

Biobased Carbon Dots: From Fish Scales to Photocatalysis.

The synthesis, characterization and photoreduction ability of a new class of carbon dots made from fish scales is here described. Fish scales are a waste material that contains mainly chitin, one of the most abundant natural biopolymers, and collagen. These components make the scales rich, not only in carbon, hydrogen and oxygen, but also in nitrogen. These self-nitrogen-doped carbonaceous nanostructured photocatalyst were synthesized from fish scales by a hydrothermal method in the absence of any other reagents. The morphology, structure and optical properties of these materials were investigated. Their photocatalytic activity was compared with the one of conventional nitrogen-doped carbon dots made from citric acid and diethylenetriamine in the photoreduction reaction of methyl viologen.

Advancements and Complexities in the Conversion of Lignocellulose Into Chemicals and Materials.

This Perspective describes the challenges and objectives associated to the development of new chemical technologies for the conversion of lignocellulose (non-food or waste) into chemicals and materials; it also provides an outlook on the sources, potential products, and issues to be addressed.

Upgrading of marine (fish and crustaceans) biowaste for high added-value molecules and bio(nano)-materials.

Currently, the Earth is subjected to environmental pressure of unprecedented proportions in the history of mankind. The inexorable growth of the global population and the establishment of large urban areas with increasingly higher expectations regarding the quality of life are issues demanding radically new strategies aimed to change the current model, which is still mostly based on linear economy approaches and fossil resources towards innovative standards, where both energy and daily use products and materials should be of renewable origin and 'made to be made again'. These concepts have inspired the circular economy vision, which redefines growth through the continuous valorisation of waste generated by any production or activity in a virtuous cycle. This not only has a positive impact on the environment, but builds long-term resilience, generating business, new technologies, livelihoods and jobs. In this scenario, among the discards of anthropogenic activities, biodegradable waste represents one of the largest and highly heterogeneous portions, which includes garden and park waste, food processing and kitchen waste from households, restaurants, caterers and retail premises, and food plants, domestic and sewage waste, manure, food waste, and residues from forestry, agriculture and fisheries. Thus, this review specifically aims to survey the processes and technologies for the recovery of fish waste and its sustainable conversion to high added-value molecules and bio(nano)materials.

Single-Step Methylation of Chitosan Using Dimethyl Carbonate as a Green Methylating Agent.

N,N,N-Trimethyl chitosan (TMC) is one chitosan derivative that, because of its improved solubility, has been studied for industrial and pharmaceutic applications. Conventional methods for the synthesis of TMC involve the use of highly toxic and harmful reagents, such as methyl iodide and dimethyl sulfate (DMS). Although the methylation of dimethylated chitosan to TMC by dimethyl carbonate (DMC, a green and benign methylating agent) was reported recently, it involved a formaldehyde-based procedure. In this paper we report the single-step synthesis of TMC from chitosan using DMC in an ionic liquid. The TMC synthesised was characterised by 1H NMR spectroscopy and a functionally meaningful degree of quaternisation of 9% was demonstrated after a 12-h reaction time.

Waste-to-wealth: biowaste valorization into valuable bio(nano)materials.

The waste-to-wealth concept aims to promote a future sustainable lifestyle where waste valorization is seen not only for its intrinsic benefits to the environment but also to develop new technologies, livelihoods and jobs. Based on the concept of waste valorization and circular economy, this review aims to provide an overview of present trends and future potential in the conversion of residues from different food sectors into valuable bio(nano)materials.

A Multiphase Protocol for Selective Hydrogenation and Reductive Amination of Levulinic Acid with Integrated Catalyst Recovery.

At 60-150 °C and 15-35 bar H2 , two model reactions of levulinic acid (LA), hydrogenation and reductive amination with cyclohexylamine, were explored in a multiphase system composed of an aqueous solution of reactants, a hydrocarbon, and commercial 5 % Ru/C as a heterogeneous catalyst. By tuning the relative volume of the immiscible water/hydrocarbon phases and the concentration of the aqueous solution, a quantitative conversion of LA was achieved with formation of γ-valerolactone or N-(cyclohexylmethyl)pyrrolidone in >95 and 88 % selectivity, respectively. Additionally, the catalyst could be segregated in the hydrocarbon phase and recycled in an effective semi-continuous protocol. Under such conditions, formic acid additive affected the reactivity of LA through a competitive adsorption on the catalyst surface. This effect was crucial to improve selectivity for the reductive amination process. The comparison of 5 % Ru/C with a series of carbon supports demonstrated that the segregation phenomenon in the hydrocarbon phase, never previously reported, was pH-dependent and effective for samples displaying a moderate surface acidity.