Enzymes' Power for Plastics Degradation.

Plastics are everywhere in our modern way of living, and their production keeps increasing every year, causing major environmental concerns. Nowadays, the end-of-life management involves accumulation in landfills, incineration, and recycling to a lower extent. This ecological threat to the environment is inspiring alternative bio-based solutions for plastic waste treatment and recycling toward a circular economy. Over the past decade, considerable efforts have been made to degrade commodity plastics using biocatalytic approaches. Here, we provide a comprehensive review on the recent advances in enzyme-based biocatalysis and in the design of related biocatalytic processes to recycle or upcycle commodity plastics, including polyesters, polyamides, polyurethanes, and polyolefins. We also discuss scope and limitations, challenges, and opportunities of this field of research. An important message from this review is that polymer-assimilating enzymes are very likely part of the solution to reaching a circular plastic economy.

Bio-Based Poly(hydroxy urethane)s for Efficient Organic High-Power Energy Storage.

Fast, low-cost, and efficient energy storage technologies are urgently needed to balance the intermittence of sustainable energy sources. High-power capacitors using organic polymers offer a green and scalable answer. They require dielectrics with high permittivity (εr) and breakdown strength (EB), which bio-based poly(hydroxy urethane)s (PHUs) can provide. PHUs combine high concentrations of hydroxyl and carbamate groups, thus enhancing their εr, and a highly tunable glass transition (Tg), which dictates the regions of low dielectric losses. By reacting erythritol dicarbonate with bio-based diamines, fully bio-based PHUs were synthesized with Tg ∼ 50 °C, εr > 8, EB > 400 MV·m-1, and low losses (tan δ < 0.03). This results in energy storage performance comparable with the flagship petrochemical materials (discharge energy density, Ue > 6 J·cm-3) combined with a remarkably high discharge efficiency, with η = 85% at EB and up to 91% at 0.5 EB. These bio-based PHUs thus represent a highly promising route to green and sustainable energy storage.

Design and Self-Assembly of Sugar-Based Amphiphiles: Spherical to Cylindrical Micelles.

Sugar-based amphiphiles are a relevant natural alternative to synthetic ones due to their biodegradable properties. An understanding of their structure-assembly relationship is needed to allow the concrete synthesis of suitable derivatives. Here, four different mannose-derivative surfactants are characterized by pendant drop, dynamic light scattering, small-angle X-ray scattering, cryotransmission electron microscopy, and molecular dynamics techniques in aqueous media. Measurements denote how the polysaccharide average degree of polymerization (DP¯) and the addition of a hydroxyl group to the hydrophobic tail, and thus the presence of a second hydrophilic moiety, affect their self-assembly. A variation in the DP¯ of the amphiphile has no effect in the critical micelle concentration in contrast to a change in the hydrophobic molecular region. Moreover, high-DP¯ amphiphiles self-assemble into spherical micelles irrespective of the hydroxyl group presence. Low-DP¯ amphiphiles with only one hydrophilic moiety form cylindrical micelles, while the addition of a hydroxyl group to the tail leads to a spherical shape.

Synthesis and Characterization of Vanillin-Based π-Conjugated Polyazomethines and Their Oligomer Model Compounds.

The synthesis of π-conjugated polymers via an environmentally friendly procedure is generally challenging. Herein, we describe the synthesis of divanillin-based polyazomethines, which are derived from a potentially bio-based monomer. The polymerization is performed in 5 min under microwave irradiation without any metallic catalyst, with water as the only by-product. The vanillin-based polyazomethines were characterized by SEC, TGA, and UV-Vis spectroscopy. Model compounds were designed and characterized by X-ray diffraction and UV-Vis spectroscopy. The structure/properties study of vanillin-based azomethines used as models allowed us to unequivocally confirm the E configuration and to highlight the cross-conjugated nature of divanillin-based polymers.

Enantioselective Crystallization of Diglycerol Dicarbonate: Impact of the Microstructure on Polyhydroxyurethane Properties.

Bicylic carbonates are precursors employed in non-isocyanate polyurethane syntheses, namely polyhydroxyurethanes (PHUs) and, among them, ether-activated biobased diglycerol dicarbonate (DGDC) is widely investigated. Herein, the original separation of DGDC stereoisomers, thanks to a recrystallization procedure, leading to enantiomers having different crystal lattices, that is, square transparent crystals and needle-like structures, respectively, is reported. In this study, the separation and the characterization of the two crystal structures is first discussed and, second, the impact of the stereochemistry of DGDC on the corresponding PHUs properties is investigated.

Synthesis and Self-Assembly of Xylan-Based Amphiphiles: From Bio-Based Vesicles to Antifungal Properties.

This work aims at designing functional biomaterials through selective chemical modification of xylan from beechwood. Acidic hydrolysis of xylan led to well-defined oligomers with an average of six xylose units per chain and with an aldehyde group at the reductive end. Reductive amination was performed on this aldehyde end group to introduce an azide reactive group. "Click chemistry" was then applied to couple these hydrophilic xylans moieties with different hydrophobic fatty acid methyl esters that were previously functionalized with complementary alkyne functions. The resulting amphiphilic bio-based conjugates were then self-assembled using three different methods, namely, direct solubilization, thin-film rehydration/extrusion, and microfluidics. Well-defined micelles and vesicles were obtained, and their high loading capacity with propiconazole as an antifungal active molecule was shown. The resulting vesicles loaded with propiconazole in a microfluidic process proved to significantly improve the antifungal activity of propiconazole, demonstrating the high potential of such xylan-based amphiphiles.

Bio-Based Thermo-Reversible Aliphatic Polycarbonate Network.

Aliphatic polycarbonates represent an important class of materials with notable applications in the biomedical field. In this work, low Tg furan-functionalized bio-based aliphatic polycarbonates were cross-linked thanks to the Diels-Alder (DA) reaction with a bis-maleimide as the cross-linking agent. The thermo-reversible DA reaction allowed for the preparation of reversible cross-linked polycarbonate materials with tuneable properties as a function of the pendent furan content that was grafted on the polycarbonate backbone. The possibility to decrosslink the network around 70 °C could be an advantage for biomedical applications, despite the rather poor thermal stability of the furan-functionalized cross-linked polycarbonates.

From Lignin-derived Aromatic Compounds to Novel Biobased Polymers.

Nowadays, the synthesis of (semi)aromatic polymers from lignin derivatives is of major interest, as aromatic compounds are key intermediates in the manufacture of polymers and lignin is the main source of aromatic biobased substrates. Phenols with a variety of chemical structures can be obtained from lignin deconstruction; among them, vanillin and ferulic acid are the main ones. Depending on the phenol substrates, different chemical modifications and polymerization pathways are developed, leading to (semi)aromatic polymers covering a wide range of thermomechanical properties. This review discusses the synthesis and properties of thermosets (vinyl ester resins, cyanate ester, epoxy, and benzoxazine resins) and thermoplastic polymers (polyesters, polyanhydrides, Schiff base polymers, polyacetals, polyoxalates, polycarbonates, acrylate polymers) prepared from vanillin, ferulic acid, guaiacol, syringaldehyde, or 4-hydroxybenzoic acid.

Organocatalyzed step-growth polymerization through desymmetrization of cyclic anhydrides: synthesis of chiral polyesters.

The polymerization of prochiral bis-anhydrides with diols catalyzed by a cinchona alkaloid was shown to provide chiral polyesters in good yields and with high levels of stereocontrol. The structures of the polyesters were determined by (1) H and (13) C NMR analyses, whereas their size was estimated by both size-exclusion chromatography (SEC) and MALDI-TOF mass spectrometry, which indicated that moderate degrees of polymerization were attained through this step-growth polymerization. The enantioselectivity of the process was evaluated by using chiral HPLC analysis of the bis-lactones resulting from a controlled chemoselective degradation of the polyesters. The best stereocontrol was reached for oligomers formed from bis-anhydride and diol monomers bearing rigid aromatic spacers between the reactive functional groups. In this case, average enantioselectivities were comparable to those observed during ring-opening of simple anhydrides with similar alcohols. In contrast, the use of more flexible spacers between reactive entities generally led to lower levels of stereocontrol.

Preparation of water-free PEDOT dispersions in the presence of reactive polyisoprene stabilizers.

Poly(3,4-ethylenedioxythiophene) nanoparticles with narrow size distribution were prepared in organic dispersant media in the presence of both iron(III) dodecylbenzenesulfonate {Fe(DBS)3}-acting as both an oxidant and a stabilizer-and ω-functionalized polyisoprenes (ω-R-PI) as costabilizers. The effects of the solvent nature and concentration of Fe(DBS)3 on the size and morphology of the PEDOT particles were first studied in the absence of costabilizer. Second, the effects of the molar mass, concentration, and nature of the functional end group of the polyisoprene costabilizer were investigated. PEDOT nano-objects were characterized by transmission electron microscopy (TEM), atomic force microscopy (AFM), dynamic light scattering (DLS), and conductivity measurements.

Bio-based aliphatic polyurethanes through ADMET polymerization in bulk and green solvent.

A new route to α,ω-diene urethane monomer is proposed by converting 10-undecenoic acid into the corresponding acyl azide, followed by urethanization with 10-undecenol. ADMET polymerizations of this α,ω-diene urethane monomer as well as other bio-based α,ω-dienes bearing various organic functions (ester, carbonate, ether, amide) were carried out in bulk and solution conditions. A screening of the most commonly used metathesis catalysts allows to evaluate their tolerance toward the urethane function as well as toward Polarclean, a "green" and nontoxic high boiling point solvent. The influence of the nature of the central organic function in these α,ω-diene monomers on the thermomechanical properties is investigated.

Design of well-defined monofunctionalized poly(3-hexylthiophene)s: toward the synthesis of semiconducting graft copolymers.

The post-functionalization of poly(3-hexylthiophene) (P3HT) via various synthetic routes is reported. Well-defined and monofunctionalized ω-thiol-terminated P3HT, ω-carboxylic acid-terminated P3HT, ω-acrylate-terminated P3HT, and ω-methacrylate-terminated P3HT are obtained in high yields through a straightforward procedure. From those, different novel P3HT-based graft copolymers are synthesized following two routes: "grafting onto" and "grafting through" (macromonomer polymerization) methods. The synthesis of three types of graft copolymers is described. Each one has "rod" P3HT-grafted side chains on a "coil" main chain, which can be polyisoprene, poly(vinyl alcohol), or poly(butyl acrylate). Each copolymer is characterized by size-exclusion chromatography and NMR.

Mannose-based surfactant as biofunctional nanoemulsion stabilizer.

The development and implementation of new amphiphiles based on natural resources rather than petrochemical precursors is an essential requirement due to their feedstock depletion and adverse environmental impacts. In addition, the use of bio-based surfactants can provide unique characteristics and improve the properties and versatility of the colloidal systems in which they are applied, such as emulsions. Here, the emulsification properties of a synthesized biocompatible mannose-based surfactant were investigated. Its behavior was evaluated in the presence of four different natural oils (castor, sunflower, olive and soybean) as well as two different aqueous phases (pure water and phosphate-buffered saline). The results highlighted its interest as surfactant in O/W nanoemulsions for all tested oil and aqueous phases, using a low-energy preparation protocol and relatively low surfactant concentrations. Furthermore, the mannose groups present on the polar head of the surfactant and adsorbed on the surface of the emulsion droplets were shown to retain their native biological properties. The specific mannose-concanavalin A binding was observed in vitro by the designed nanoemulsions, revealing the biorecognition properties of the surfactant and its potential applicability as a nanocarrier.

Extraction and Characterization of Hemicelluloses from a Softwood Acid Sulfite Pulp.

Hemicelluloses were extracted from a softwood acid sulfite pulp in a three-step procedure. Further delignification step resulted in a holocellulose pulp containing only 1.7 wt.% of the lignin left. Cold caustic extraction (CCE) with 18 wt.% NaOH at 60 °C for 1 h was performed to solubilize hemicelluloses of the holocellulose. An unbleached cellulose pulp was then obtained 97% pure, which indicates that 89% of the hemicelluloses were removed. After purification, extraction yields between 1.1 wt.% and 9.5 wt.% were obtained from the delignified pulp and the hemicelluloses' chemical compositions and structures were investigated by 1H, 13C nuclear magnetic resonance spectroscopy (NMR) and two-dimensional NMR by correlation spectroscopy (2D-COSY) and proton-detected heteronuclear single-quantum correlation (2D-HSQC), high-performance anion-exchange chromatography coupled with a pulsed amperometry detector (HPAEC-PAD), size-exclusion chromatography coupled with a refractive index detector (SEC-RI) and thermogravimetric analyses (TGA). Hemicelluloses were obtained with a purity of 96%, with short cellulosic chains as the only residue. Sulfite pulping modified the hemicelluloses' structure, and it was found that two types of hemicelluloses were isolated, glucomannans, predominant at 67%, and methylglucuronoxylans. Finally, alkali-soluble hemicelluloses displayed relatively narrow size distributions and low molar masses, Mw varying between 18,900 and 30,000 g/mol after acid sulfite pulping.

Functional Polyethylenes by Organometallic-Mediated Radical Polymerization of Biobased Carbonates.

Partly or fully renewable (co)polymers are gaining interest in both academia and industry. Polyethylene is a widely used polymer, classically derived from fossil fuels, with a high versatility stemming from the introduction of comonomers altering the mechanical properties. The introduction of renewable functionalities into this polymer is highly attractive to obtain functional, tunable, and at least partially renewable polyethylenes. We herein report the introduction of biosourced cyclic carbonates into polyethylene using organometallic-mediated radical polymerization under mild conditions. Molecular weights of up to 14 600 g mol-1 with dispersities as low as 1.19 were obtained, and the cyclic carbonate content could be easily tuned by the ethylene pressure during the polymerization. As a proof of concept, the hydrolysis of the cyclic carbonates of a representative copolymer was explored, and it provided polyethylene-bearing vicinal diols, with a hydrolysis degree of 71%. Given the multitude of chemoselective modifications possible on cyclic carbonates as well as the fact that many allylic- and alkylidene-type cyclic carbonates are accessible from renewable resources, this work opens up an avenue for the design of functional and more sustainable polyethylenes.

Oxidative Depolymerization of Alkaline Lignin from Pinus Pinaster by Oxygen and Air for Value-Added Bio-Sourced Synthons.

In this work, an efficient 3-step process targeting the chemical modification and purification of lignin oligomers from industrial alkaline lignin is described. The oxidative depolymerization process of alkaline lignin with O2 or Air pressure, without use of metal catalyst, led to the production of two fractions of lignin oligomers named 'precipitated lignin' and 'hydrosoluble lignin' with 40% and 60% yield, respectively. These fractions were characterized with a wide range of methods including NMR spectroscopy (31P, 2D-HSQC), SEC (in basic media), FTIR. NMR analyses revealed the presence of carboxylic acid functions at a ratio of 1.80 mmol/g and 2.80 mmol/g for the precipitated and hydrosoluble lignin, respectively, values much higher than what is generally found in native lignin (between 0.2 and 0.5 mmol/g). SEC analyses revealed the formation of low molar masses for the precipitated (2200 g/mol) and hydrosoluble fractions (1500 g/mol) in contrast to the alkaline lignin (3900 g/mol). It is worth noting that the hydrosoluble fraction of lignin is soluble in water at any pH. Both processes (oxygen and air) were successfully scaled up and showed similar results in terms of yield and functionalization.

Synthesis of biobased polyurethane from oleic and ricinoleic acids as the renewable resources via the AB-type self-condensation approach.

Polyurethane (PU) from methyl oleate (derived from sunflower oil) and ricinoleic acid (derived from castor oil) was synthesized using the AB-type self-polycondensation approach for the first time. In the present work, three novel AB-type monomers, namely, a mixture of 10-hydroxy-9-methoxyoctadecanoyl azide/9-hydroxy-10-methoxyoctadecanoyl azide (HMODAz), 12-hydroxy-9-cis-octadecenoyl azide (HODEAz) and methyl-N-11-hydroxy-9-cis-heptadecen carbamate (MHHDC) were synthesized from methyl oleate and ricinoleic acid using simple reaction steps. Out of these, HMODAz and HODEAz monomers were polymerized by the acyl-azido and hydroxyl AB-type self-condensation approach, while MHHDC monomer was polymerized through AB-type self-condensation via transurethane reaction. The acyl-azido and hydroxyl self-condensations were carried out at various temperatures (50, 60, 80. and 110 degrees C) in bulk with and without catalyst. A FTIR study of the polymerization, using HMODAz at 80 degrees C without catalyst, indicates in situ formation of an intermediate isocyanate group in the first 15-30 min, and further onward, the molar mass increases as observed by SEC analysis. In the case of the MHHDC monomer, a transurethane reaction was used to obtain a similar PU (which was obtained by AB-type acyl-azido and hydroxyl self-condensation of HODEAz) in the presence of titanium tetrabutoxide as a catalyst at 130 degrees C. HMODAz, HODEAz, MHHDC, and corresponding polyurethanes were characterized by FTIR, (1)H NMR, (13)C NMR, and MALDI-TOF mass spectroscopy. Differential scanning calorimetric analysis of polyurethanes derived from HMODAz, HODEAz, and MHHDC showed two different glass transition temperatures for soft segments (at lower temperature) and hard segments (at higher temperature), indicating phase-separated morphology.

Fine tuning of emission through the engineering of colloidal crystals.

We describe the preparation and characterization of photonic colloidal crystals from silica spheres with incorporated luminescent [Mo(6)Br(14)](2-) cluster units. These structures exhibit strong angle-dependent luminescent properties. The incorporation of one or several planar defects in the periodic structures gives rise to the creation of a passband in the stopband. In the energy range of this passband, an increase of the emission intensity has been found.

Divanillin-Based Polyazomethines: Toward Biobased and Metal-Free π-Conjugated Polymers.

Divanillin was synthesized in high yield and purity using Laccase from Trametes versicolor. It was then polymerized with benzene-1,4-diamine and 2,7-diaminocarbazole to form polyazomethines. Polymerizations were performed under microwave irradiation and without transition-metal-based catalysts. These biobased conjugated polyazomethines present a broad fluorescence spectrum ranging from 400 to 600 nm. Depending on the co-monomer used, polyazomethines with molar masses of around 10 kg·mol-1 and with electronic gaps ranging from 2.66 to 2.85 eV were obtained. Furthermore, time-dependent density functional theory (TD-DFT) calculations were performed to corroborate the experimental results.