Bio-based Building Block Research Articles

Recyclable Ir Nanoparticles for the Catalytic Hydrogenation of Biomass-Derived Carbonyl Compounds

The valorisation of biomass-derived platform chemicals via catalytic hydrogenation is an eco-friendly tool which allows us to recover bio-based building blocks and produce fine chemicals with high industrial appeal. In the present study, a novel surfactant-type triazolyl-thioether ligand was prepared, showing excellent catalytic activity in the presence of bis(1,5-cyclooctadiene)diiridium(I) dichloride [Ir(COD)Cl]2 for the hydrogenation of furfural, cinnamaldehyde, levulinic acid, 5-hydroxymethylfurfural, vanillin, and citral. Easy recovery by liquid/liquid extraction allowed us to recover the catalyst, which could then be efficiently recycled up to 11 times for the hydrogenation of furfural. In-depth analysis revealed the formation of spherical structures with metal nanoparticles as big as 2–6 nm surrounded by the anionic ligand, preventing iridium nanoparticle degradation.

The Green Approach to the Synthesis of Bio-Based Thermoplastic Polyurethane Elastomers with Partially Bio-Based Hard Blocks.

Bio-based polymeric materials and green routes for their preparation are current issues of many research works. In this work, we used the diisocyanate mixture based on partially bio-based diisocyanate origin and typical petrochemical diisocyanate for the preparation of novel bio-based thermoplastic polyurethane elastomers (bio-TPUs). We studied the influence of the diisocyanate mixture composition on the chemical structure, thermal, thermomechanical, and mechanical properties of obtained bio-TPUs. Diisocyanate mixture and bio-based 1,4-butanediol (as a low molecular chain extender) created bio-based hard blocks (HS). The diisocyanate mixture contained up to 75 wt % of partially bio-based diisocyanate. It is worth mentioning that the structure and amount of HS impact the phase separation, processing, thermal or mechanical properties of polyurethanes. The soft blocks (SS) in the bio-TPU’s materials were built from α,ω-oligo(ethylene-butylene adipate) diol. Hereby, bio-TPUs differed in hard segments content (c.a. 30; 34; 40, and 53%). We found that already increase of bio-based diisocyanate content of the bio-TPU impact the changes in their thermal stability which was measured by TGA. Based on DMTA results we observed changes in the viscoelastic behavior of bio-TPUs. The DSC analysis revealed decreasing in glass transition temperature and melting temperature of hard segments. In general, obtained materials were characterized by good mechanical properties. The results confirmed the validity of undertaken research problem related to obtaining bio-TPUs consist of bio-based hard building blocks. The application of partially bio-based diisocyanate mixtures and bio-based chain extender for bio-TPU synthesis leads to sustainable chemistry. Therefore the total level of “green carbons” increases with the increase of bio-based diisocyanate content in the bio-TPU structure. Obtained results constitute promising data for further works related to the preparation of fully bio-based thermoplastic polyurethane elastomers and development in the field of bio-based polymeric materials.

Preparation and Characterization of Biobased Lignin-Co-Polyester/Amide Thermoplastics.

More than 23 million tonnes of lignin are produced annually in the US from wood pulping and 98% of this lignin is burnt. Therefore, creating products from lignin, such as plastics, offers an approach for obtaining sustainable materials in a circular economy. Lignin-based copolymers were synthesized using a single pot, solvent free, melt condensation reaction. The synthesis occurred in two stages. In the first stage, a biobased prepolymer consisting of butanediol (BD, 0.8–1 molar content) and a diacid (succinic (SA), adipic (AA) and suberic acids (SuA), with varying amounts of diaminobutane (DAB, 0–0.2 molar content) was heated under vacuum and monitored by Fourier transform infra-red (FTIR) spectroscopy and electrospray ionization-mass spectrometry (ESI-MS). In the second stage, prepolymer was mixed with a softwood kraft lignin (0–50 wt.%) and further reacted under vacuum at elevated temperature. Progression of the polymerization reaction was monitored using FTIR spectroscopy. The lignin-copolyester/amide properties were characterized using tensile testing, X-ray diffraction (XRD), dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) techniques. Lignin co-polymer tensile (strength 0.1–2.1 MPa and modulus 2 to 338 MPa) properties were found to be influenced by the diacid chain length, lignin, and DAB contents. The lignin-copolymers were shown to be semi-crystalline polymer and have thermoplastic behavior. The SA based copolyesters/amides were relatively stiff and brittle materials while the AA based copolyesters/amides were flexible and the SuA based copolyesters/amides fell in-between. Additionally, > 30 wt.% lignin the lignin- copolyesters/amides did not exhibit melt behavior. Lignin-co-polyester/amides can be generated using green synthesis methods from biobased building blocks. The lignin- copolyesters/amides properties could be tuned based on the lignin content, DAB content and diacid chain length. This approach shows that undervalued lignin can be used in as a macromonomer in producing thermoplastic materials.

Proteins as Promising Biobased Building Blocks for Preparing Functional Hybrid Protein/Synthetic Polymer Nanoparticles

Fil: Cencha, Luisa Guadalupe. Consejo Nacional de Investigaciones Cientificas y Tecnicas. Centro Cientifico Tecnologico Conicet - Santa Fe. Instituto de Desarrollo Tecnologico para la Industria Quimica. Universidad Nacional del Litoral. Instituto de Desarrollo Tecnologico para la Industria Quimica; Argentina

Inventory review and environmental evaluation of first- and second-generation sugars through life cycle assessment.

In recent years, there has been a great movement towards the generation of knowledge related to the biorefinery concept. First-generation biorefineries bear the stigma of using arable land and edible crops for fuel instead of as sources of food and feed. However, second-generation biorefineries have not reached the level of full technical feasibility. Bearing in mind the objective of sugar production from sugar, starch, or lignocellulosic raw materials, the purpose of this study is to assess the environmental impact of first- and second-generation biorefineries, considering as an example for the comparative evaluation, the production of sugar fractions from crops (starch and sugar crops), and lignocellulosic biomass (hardwood and softwood). The characterization results were obtained using the ReCiPe 1.1 model, implemented through the SimaPro 9.0 software. Both production systems are inherently different and have strengths and weaknesses that must be carefully analyzed. The resulting environmental profile shows that the silviculture of wood contributes less to the environmental impact than cropping activities in most impact categories. In general, this study suggests that first-generation systems are burdened environmentally by the use of fertilizers, which havea significant impact on categories such as marine and freshwater eutrophication and terrestrial acidification, while second-generation systems are limited by the intensive processing steps needed for delignification, typically involving the use of chemicals and/or energy. LCA in early stages of the production of bio-based building blocks, rather than on the manufacture of biofuels or bioplastics, allows the precise identification of the environmental burdens that may be influencing the overall environmental profile of a biorefinery.

Synthesis and Characterization of Unsaturated Succinic Acid Biobased Polyester Resins

Polymers from renewable feedstocks are receiving increasing attention as the awareness about environmental issues derived from petroleum exploitation and waste accumulation is growing. With unsaturated polyester resins being one of the most used classes of polymers worldwide, the utilization of biobased monomers for manufacturing is more relevant than ever. In the present work, succinic acid, one of the most promising biobased building blocks, was incorporated in the structure of the resins in question to increase their biobased content. By reacting with ethylene glycol (EG) or poly(ethylene glycol) and maleic anhydride (MA) at several molar rations, unsaturated polyester resins (UPRs) were prepared. Their synthesis was evaluated by a variety of spectroscopical techniques, and their rheological properties made use of the reactive diluent mandatory for facilitating processing. Thus, in a second stage acrylic acid (AA) was used as cross-linking agent in the present of initiators and accelerators producing thermosetting resins. Differential scanning calorimetry (DSC) was employed to screen the cross-linking procedure, whereas with X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR) it was proven that thermosetting resins were prepared. The thermal stability of the cured materials was evaluated by thermogravimetric analysis (TGA).

Behavior characterization of lignosulfonate depolymerization products under acid-catalyzed conditions using gas chromatography–mass spectrometry

Depolymerized real lignin products are very complex mixtures. Comprehensive assessment of the decomposition efficiency and characterizing of depolymerized products still remain extremely challenging. In this study, based on depolymerization solution of commercially available sodium lignosulfonate under mild conditions, an improved method was well established for characterization of real lignin depolymerized products using GC–MS, which enabled the detection of main 37 lignin-based aromatic products. The effects of acid-catalyzed temperature, time and catalyst/lignin ratio on the depolymerization products were systematically investigated. The result revealed that ~ 25 wt% of lignosulfonate was depolymerized into lignin-derived aromatic products under optimized mild acid-catalyzed reaction conditions of 130 °C for 60 min with a catalyst/lignin ratio of 2.334. Most of the identified products were common commercial compounds, while the obtained bisphenols were potential compounds for new applications such as bio-based polymer building blocks. Preliminary studies also highlight that the depolymerization behavior seems to present selectivity to some extent during these specified acid-catalyzed reaction.

Selective formation of dihydrofuran fused [60] fullerene derivatives by TEMPO mediated [3 + 2] cycloaddition of medium chain β-keto esters to C60.

In this study, β-keto esters as readily available bio-based building blocks were used to decorate the C60 sphere. Generally, cyclopropanated fullerene derivatives are obtained by the standard Bingel–Hirsch procedure. Herein, omitting the iodine from the reaction mixture and adding TEMPO afforded dihydrofuran fused C60 fullerene derivatives. The mechanism of the reaction shifted from nucleophilic aliphatic substitution to oxidative [3 + 2] cycloaddition via fullerenyl cations as an intermediate. This mechanism is proposed based on a series of control experiments with radical scavengers. Therefore, dihydrofuran-fused C60 derivatives were selectively obtained in good yields and their structures were established based on UV-Vis, IR, NMR spectroscopy and mass spectrometry. The electrochemical properties of the synthesized compounds were investigated by cyclic voltammetry. DFT calculations were performed in order to investigate the difference in stability, electronic properties and π-electron delocalization between methano and furano fullerenes.

Synthetic lignin-like and degradable nanocarriers

Bio-based lignin-like building blocks were synthesized and transformed into polyurethane nanocarriers by interfacial polymerization in a miniemulsion. The nanocarriers were degradable by fungal enzymes and might be used for agrochemical delivery.

An Optimized Ustilago maydis for Itaconic Acid Production at Maximal Theoretical Yield.

Ustilago maydis, a member of the Ustilaginaceae family, is a promising host for the production of several metabolites including itaconic acid. This dicarboxylate has great potential as a bio-based building block in the polymer industry, and is of special interest for pharmaceutical applications. Several itaconate overproducing Ustilago strains have been generated by metabolic and morphology engineering. This yielded stabilized unicellular morphology through fuz7 deletion, reduction of by-product formation through deletion of genes responsible for itaconate oxidation and (glyco)lipid production, and the overexpression of the regulator of the itaconate cluster ria1 and the mitochondrial tricarboxylate transporter encoded by mttA from Aspergillus terreus. In this study, itaconate production was further optimized by consolidating these different optimizations into one strain. The combined modifications resulted in itaconic acid production at theoretical maximal yield, which was achieved under biotechnologically relevant fed-batch fermentations with continuous feed.

Chemically recyclable bio-based polyester composed of bifuran and glycerol acetal

Bio-based polymer alternatives to general-purpose polymers require new bio-based building blocks. The bifuran structure can be prepared from inedible biomass, and glycerol is manufactured as a byproduct. In this study, we constructed bifurylidene bis(glycerol acetal) (BFG)—composed of the bifuran and glycerol acetal structures—as a fully bio-based building block. Because the glycerol acetal formed five- and six-membered rings, with optical isomers and stereoisomers, BFG is a mixture of 22 isomers. BFG was polymerized with succinic anhydride to form poly[bifurylidene bis(glycerol acetal) succinate] (PBFGS). Td5% and Tg values for PBFGS were higher than those for poly(bifurfurylene succinate) (PBFS), in which the acetal structure is replaced with CH2, indicating that the acetal structure enhances the thermal properties of the polyester. Furthermore, the acetal-exchange reaction of PBFGS, to recover BFG, and the acid hydrolysis of poly[bifurylidene bis(glycerol acetal) dicarboxylate] (PBFGD), to recover bifurfural, a reactant of BFG, were successful, indicating that the introduction of the glycerol acetal structures endowed the bifuran-containing polymer with recyclability.

Biosourced All-Acrylic ABA Block Copolymers with Lactic Acid-Based Soft Phase.

Lactic acid is one of the key biobased chemical building blocks, given its readily availability from sugars through fermentation and facile conversion into a range of important chemical intermediates and polymers. Herein, well-defined rubbery polymers derived from butyl lactate solvent were successfully prepared by reversible addition–fragmentation chain transfer (RAFT) polymerization of the corresponding monomeric acrylic derivative. Good control over molecular weight and molecular weight distribution was achieved in bulk using either monofunctional or bifunctional trithiocarbonate-type chain transfer agents. Subsequently, poly(butyl lactate acrylate), with a relative low Tg (−20 °C), good thermal stability (5% wt. loss at 340 °C) and low toxicity was evaluated as a sustainable middle block in all-acrylic ABA copolymers using isosorbide and vanillin-derived glassy polyacrylates as representative end blocks. Thermal, morphological and mechanical properties of copolymers containing hard segment contents of <20 wt% were evaluated to demonstrate the suitability of rubbery poly(alkyl lactate) building blocks for developing functional sustainable materials. Noteworthy, 180° peel adhesion measurements showed that the synthesized biosourced all-acrylic ABA copolymers possess competitive performance when compared with commercial pressure-sensitive tapes.

Metabolic engineering of Aspergillus niger via ribonucleoprotein-based CRISPR\u2013Cas9 system for succinic acid production from renewable biomass

BackgroundSuccinic acid has great potential to be a new bio-based building block for deriving a number of value-added chemicals in industry. Bio-based succinic acid production from renewable biomass can provide a feasible approach to partially alleviate the dependence of global manufacturing on petroleum refinery. To improve the economics of biological processes, we attempted to explore possible solutions with a fungal cell platform. In this study, Aspergillus niger, a well-known industrial production organism for bio-based organic acids, was exploited for its potential for succinic acid production.ResultsWith a ribonucleoprotein (RNP)-based CRISPR–Cas9 system, consecutive genetic manipulations were realized in engineering of the citric acid-producing strain A. niger ATCC 1015. Two genes involved in production of two byproducts, gluconic acid and oxalic acid, were disrupted. In addition, an efficient C4-dicarboxylate transporter and a soluble NADH-dependent fumarate reductase were overexpressed. The resulting strain SAP-3 produced 17 g/L succinic acid while there was no succinic acid detected at a measurable level in the wild-type strain using a synthetic substrate. Furthermore, two cultivation parameters, temperature and pH, were investigated for their effects on succinic acid production. The highest amount of succinic acid was obtained at 35 °C after 3 days, and low culture pH had inhibitory effects on succinic acid production. Two types of renewable biomass were explored as substrates for succinic acid production. After 6 days, the SAP-3 strain was capable of producing 23 g/L and 9 g/L succinic acid from sugar beet molasses and wheat straw hydrolysate, respectively.ConclusionsIn this study, we have successfully applied the RNP-based CRISPR–Cas9 system in genetic engineering of A. niger and significantly improved the succinic acid production in the engineered strain. The studies on cultivation parameters revealed the impacts of pH and temperature on succinic acid production and the future challenges in strain development. The feasibility of using renewable biomass for succinic acid production by A. niger has been demonstrated with molasses and wheat straw hydrolysate.

Dual-Degradable Biohybrid Microgels by Direct Cross-Linking of Chitosan and Dextran Using Azide-Alkyne Cycloaddition.

In this work, biocompatible and degradable biohybrid microgels based on chitosan and dextran were synthesized for drug delivery applications. Two kinds of bio-based building blocks, alkyne-modified chitosan and azide-modified dextran, were used to fabricate microgels via single-step cross-linking in water-in-oil emulsions. The cross-linking was initiated in the presence of copper(II) without the use of any extra cross-linkers. A series of pH-responsive and degradable microgels were successfully synthesized by varying the degree of cross-links. The microgels were characterized using 1H NMR and FTIR spectroscopy which proved the successful cross-linking of alkyne-modified chitosan and azide-modified dextran by copper(II)-mediated click reaction. The obtained microgels exhibit polyampholyte character and can carry positive or negative charges in aqueous solutions at different pH values. Biodegradability of microgels was shown at pH 9 or in the presence of Dextranase due to the hydrolysis of carbonate esters in the microgels or 1,6-α-glucosidic linkages in dextran structure, respectively. Furthermore, the microgels could encapsulate vancomycin hydrochloride (VM), an antibiotic, with a high loading of approximately 93.67% via electrostatic interactions. The payload could be released in the presence of Dextranase or under an alkaline environment, making the microgels potential candidates for drug delivery, such as colon-specific drug release.

Preliminary evaluation of value—added bio-based building blocks

The global economic system is currently organised to exploit fossil fuel-based technologies. Resources are extracted from the earth and undergo a multitude of different processing steps to become a myriad of different and essential everyday products. Unfortunately, most of these products are disposed of soon after use and can cause huge waste disposal and environmental problems. In addition, the manufacturing process itself can cause further problems. This linear system has proven extremely effective at production; however, it is, ultimately, unsustainable. The dream future for both the environment and resource conservation is an economy that is capable to reusing used end-products – a circular economy. The path to a circular economy, however, is a winding and treacherous one. To make it work, it is necessary to consider the whole system and the wide variety of stakeholders therein. It is essential to work out the incentives for manufacturers, users and potential re-users, as well as those of governments and nations. Most importantly, the technology underpinning it has to be as good or better than those that are currently in use. Researchers at the Industrial Technology Research Institute (ITRI), Taiwan are working to develop one important section of the linear fossil fuel economy into a more circular form. The team, led by Dr Guang-Way Bill Jang, are working on producing polymers from biological sources. They are also working on developing new materials and chemicals from these sources.

Synthesize and introduce bio-based aromatic s-triazine in epoxy resin: Enabling extremely high thermal stability, mechanical properties, and flame retardancy to achieve high-performance sustainable polymers

Developing bio-based epoxy resins with high thermal stability and mechanical properties as well as satisfactory intrinsic flame retardancy is of increasing demand, though this has always been limited by the lack of bio-based polyaromatic building blocks. Herein, a simple and universal method was proposed to synthesize an aromatic s-triazine derivative from biomass feedstock, vanillin, and the obtained compound can be employed to construct a bio-based epoxy precursor (THMT-EP). With 4,4′-diaminodiphenyl sulfone (DDS) as curing agent, thanks to the unique structures of aromatic s-triazine, the resulting cured THMT-EP/DDS presented remarkable integrated properties outperforming than commercial petroleum-based bisphenol A epoxy resin (DGEBA), including a record glass transition temperature of 300 °C, as well as a high flexural modulus of 4137 MPa and a flexural strength of 134.2 MPa, which were 120 °C, 53.9% and 14.3% higher than those of DGEBA/DDS, respectively. Furthermore, the cured THMT-EP/DDS also showed excellent intrinsic flame retardancy, passing the V-0 rating in UL-94 test. This study opens an avenue for the synthesis of bio-based feedstocks with rigid aromatic and functional structure, and contributes to the development of bio-based high-performance polymers.

Co-Oligomers of Renewable and “Inert” 2-MeTHF and Propylene Oxide for Use in Bio-Based Adhesives

Commercial polyether polyols are usually obtained by the ring-opening polymerization of epoxides or tetrahydrofuran. 2-Methyl-tetrahydrofuran (2-MeTHF) could be an alternative bio-based building block for the synthesis of these polyols. Although 2-MeTHF cannot be polymerized, we did achieve the copolymerization of 2-MeTHF with propylene oxide (PO) using Lewis and Bronsted acids as catalysts and water or diols as initiators. The resulting polyether polyols have a molecular weight range, which allows their use as components for adhesives. The molar content of 2-MeTHF in the oligomers can be up to 48%. A 1:1 copolymer of 2-MeTHF and PO is produced when stoichiometric amounts of BF3·OEt2 are used. Here, the monomeric units in the chains alternate, but also cyclic or other nondiol products are formed that are detrimental to its further use in adhesives. Linear dihydroxyl-terminated polyether chains were formed when the heteropolyacid H3PW12O40·24H2O was used as a catalyst and a diol as an initiator. The formation of cyclic products can be drastically reduced when the accumulation of propylene oxide during the reaction is avoided. 1H NMR experiments indicate that the step of 2-MeTHF incorporation is the alkylation of 2-MeTHF by protonated PO. It was shown that the 2-MeTHF/PO copolymer had increased tensile strength compared to polypropylene glycol in a two-component adhesive formulation.

Synthesis of Polyoxygenated Heterocycles by Diastereoselective Functionalization of a Bio-Based Chiral Aldehyde Exploiting the Passerini Reaction.

A chiral bio-based building block, prepared by the lipase-mediated desymmetrization of an erythritol derivative, was further functionalized and then submitted to stereoselective Passerini reactions, allowing the synthesis of a small library of new molecules. Thanks to the presence of different functional groups, further cyclizations were performed providing bicyclic polyoxygenated heterocycles.

High-Level Production of Succinic Acid from Crude Glycerol by a Wild Type Organism

With the transition to the bio-based economy, it is becoming increasingly important for the chemical industry to obtain basic chemicals from renewable raw materials. Succinic acid, one of the most important bio-based building block chemicals, is used in the food and pharmaceutical industries, as well as in the field of bio-based plastics. An alternative process for the bio-based production of succinic acid was the main objective of this study, focusing on the biotechnological production of succinic acid using a newly isolated organism. Pure glycerol compared to crude glycerol, at the lowest purity, directly from a biodiesel plant side stream, was successfully converted. A maximum final titer of 117 g L−1 succinic acid and a yield of 1.3 g g−1 were achieved using pure glycerol and 86.9 g L−1 succinic acid and a yield of 0.9 g g−1 using crude glycerol. Finally, the succinic acid was crystallized, achieving maximum yield of 95% and a purity of up to 99%.

Sacrificial Substrate-Free Whole-Cell Biocatalysis for the Synthesis of 2,5-Furandicarboxylic Acid by Engineered Escherichia coli

2,5-Furandicarboxylic acid (FDCA) is a promising biobased building block for the synthesis of polymers. In this work, a novel whole-cell biocatalyst was constructed by coexpressing vanillin dehydrogenase (VDH1) and HMF/furfural oxidoreductase (HmfH) in Escherichia coli for cascade catalytic oxidation of 5-hydroxymethylfurfural (HMF) to FDCA under sacrificial substrate-free conditions. HMF was rapidly transformed to 5-hydroxymethyl-2-furancarboxylic acid (HMFCA) by VDH1, followed by subsequent oxidation to 5-formyl-2-furancarboxylic acid (FFCA) by HmfH, and finally, FFCA was converted to FDCA by VDH1 and/or HmfH. Under pH-controlled conditions, the biocatalyst enabled efficient synthesis of FDCA from 150 mM HMF in a 96% yield. Besides, FDCA was prepared in the gram scale with a productivity of around 0.4 g/L h.