Bio-based Molecules Research Articles

Facilely Promoting the Concentration of Baicalin in Polylactic Acid Fiber for UV Shielding and Antibacterial Functions: A Customized and Sustainable Approach.

There is a significant trend towards the integration of natural substances with bio-polymers for fully bio-based functional composites. Polylactic acid is regarded as a promising biodegradable polymer for replacing synthetic polymers. Differing from the case of natural fiber, the incompatibility of polylactic acid with bio-based molecules prevents it from being used to fabricate high-quality sustainable composites. This work presents a simultaneous ultraviolet shielding and antibacterial finishing process of polylactic acid combined with bioactive baicalin and an eco-friendly ester, which is highlighted for (a) the lack of synthetic chemicals involved in such process, (b) adsorption enhancement achieved at a mild temperature, and (c) marginal color change on treated polylactic acid. A response surface methodology was adopted to analyze the impacts of various factors on the baicalin quantity in polylactic acid, and to optimize the treatment condition. The uptake ratio of baicalin in polylactic acid was drastically promoted from 8.5 mg/g to 21.1 mg/g using methyl cinnamate. The response surface methodology based on a central composite design experiment indicated that the usage of baicalin was the most significant factor followed by methyl cinnamate and temperature. After optimization, a very faint color depth of 1.2 was apparent, but UPF 50+ and 92% bacterial reduction could be achieved. In all, the success in strengthening of the functionalities of polylactic acid extends the applications of polylactic acid products.

Novel fluorescent sensor with 2,5-furandicarboxylic acid as the ligand for histamine detection

Using effective and sustainable technologies for food quality evaluation has become imperative due to the growing concerns regarding food safety and security. Fluorescent-based sensing is a rapid monitoring technique for food spoilage detection; however, the technique employs fossil-based compounds for sensor development. Here, a fluorescent sensor for histamine (biogenic amine) as an indicator for the detection of spoilage in the fish matrix was fabricated using 2,5-furandicarboxylic acid (FDCA) as the organic ligand. FDCA is a biobased molecule and serves as a replacement for petroleum-derived terephthalic acid, which is widely used in the synthesis of fluorescent metal-organic frameworks (MOF). Herein we report a MOF that was synthesized using two organic ligands: FDCA and adenine with Fe as the metal center, denoted as Fe-AD-FDCA. The fluorescent sensor was created by covalently bonding methyl red (MR) with an NH2-rich Fe-AD-FDCA framework by post-synthetic modification. When exposed to histamine, the sensor showed a fluorescent emissive response that increased MR emission and produced a distinctly visible color shift from dull pink to blue. By spreading and solidifying MR@Fe-AD-FDCA in the water-phase sodium salt of carboxy methyl cellulose (CMC-Na), portable sensory hydrogels were produced. This fluorescence sensor's ability could be utilized for real-time monitoring of the freshness of raw fish samples.

Iron-Catalyzed, Light-Driven Decarboxylative Alkoxyamination.

An iron-catalyzed visible-light driven decarboxylative alkoxyamination is disclosed. In the presence of FeBr2 and TEMPO, a large array of carboxylic acids including marketed drugs and biobased molecules is turned into the corresponding alkoxyamine derivatives. The versatility of the latter offers an entry towards molecular diversity generation from abundant starting materials and catalyst. Overall, this method proposes a unified and general approach for LMCT-based iron-catalyzed decarboxylative functionalization.

Assessing the feasibility and sustainability of a surfactin production process: a techno-economic and environmental analysis.

Biosurfactants have been profiled as a sustainable replacement for chemical-based surfactants since these bio-based molecules have higher biodegradability. Few research papers have focused on assessing biosurfactant production to elucidate potential bottlenecks. This research aims to assess the techno-economic and environmental performance of surfactin production in a potential scale of 65m3, considering different product yields and involving the European energy crisis of 2021-2022. The conceptual design, simulation, techno-economic, and environmental assessments were done by applying process engineering concepts and software tools such as Aspen Plus v.9.0 and SimaPro v.8.3.3. The results demonstrated the high economic potential of surfactin production since the higher values in the market offset the low fermentation yields, low recovery efficiency, and high capital investment. The sensitivity analysis of the economic assessment elucidated a minimum surfactin selling price between 29 and 31 USD/kg of surfactin, while a minimum processing scale for economic feasibility between 4 and 5kg/h is needed to reach an equilibrium point. The environmental performance must be improved since the carbon footprint was 43kg CO2eq/kg of surfactin. The downstream processing and energy demand are the main bottlenecks since these aspects contribute to 63 and 25% of the total emissions. The fermentation process and downstream process are key factors for future optimization and research.

Unlocking the Potential of Liquid Multiphase Systems for Metal‐Catalysed Reactions

AbstractLiquid multiphase systems (MPS) have gained attention in recent years due to their versatility for catalytic processes. This review article presents a critical discussion of the most recent advances on the utilization of MPS in both homogeneous and heterogeneous metal‐catalysed reactions. Pros and cons of some exemplificative multiphase configurations are highlighted and compared to conventional methods in single liquid solvents. The application of MPS for the implementation of strategies for the upgrading of biobased molecules is also examined with emphasis on process intensification and sustainability including the catalyst/products separation and the in‐situ recycle and reuse of the metal catalysts. These aspects are analyzed with a view on expanding MPS applications and whenever possible, explore scale‐up opportunities.

A Comparative Study on the Choice of the Support in the Elaboration of Photocatalysts for the Photooxidation of Benzyl Alcohol under Mild Conditions

In the quest to combat global warming, traditional thermal chemistry processes are giving way to selective photocatalysis, an eco-friendly approach that operates under milder conditions, using benign solvents like water. Benzaldehyde, a versatile compound with applications spanning agroindustry, pharmaceuticals, and cosmetics, serves as a fundamental building block for various fine chemicals. This study aims at enhancing benzaldehyde production sustainability by utilizing photooxidation of benzyl alcohol. Gold nanoparticle-based catalysts are renowned for their exceptional efficiency in oxidizing bio-based molecules. In this research, Au nanoparticles were anchored onto three distinct supports: TiO2, ZrO2, and graphitic carbon nitride (g-C3N4). The objective was to investigate the influence of the support material on the selective photocatalysis of benzyl alcohol. In the preparation of g-C3N4, three different precursors—melamine, urea, and a 50:50 mixture of both—were chosen to analyze their impact on catalyst performance. After 4 h of irradiation at 365 nm, operating under acidic conditions (pH = 2), the Au photocatalyst on graphitic carbon nitride support synthesized using urea precursor (Au@g-C3N4(urea)) displayed the optimal balance between conversion (75%) and selectivity (85%). This formulation outperformed the benchmark Au@TiO2, which achieved a similar conversion rate (80%) but exhibited lower selectivity (55%).

Radical scavenging and processing stability of novel biobased stabilizers in polypropylene

Bio-based molecules show great research potential to achieve alternatives to petrochemically produced products. Therefore, biogenic stabilizers (vanillates, syringates and gallates) were prepared, which were subsequently characterized by various analytical methods. Nuclear magnetic resonance spectroscopy was used for structural elucidation. Thermal stability and thus suitability for polymer processing were confirmed by thermogravimetric measurements. To assess the stabilizing effect, radical efficiency was determined using 2,2-diphenyl-1-picrylhydrazyl assays. Polymer compounds were processed in an extruder as well. In these prolonged extrusion experiments, the stabilizing effect in the melt was revealed.

Tannins as Biobased Molecules for Surface Treatments of Flax Wrapped Rovings for Epoxy/Flax Fabrics Biocomposites: Influence on Mechanical Properties through a Multi-Scale Approach

The present study examined the effect of biobased molecules grafted onto wrapped flax rovings on the mechanical properties of fabrics designed for epoxy-based biocomposites, aiming to optimize fiber/matrix adhesion. Biobased solutions, such as tannins from quebracho, were used to treat wrapped flax rovings in comparison to a non-biobased aminosilane solution used as a reference. The chemical treatment is performed using an innovative lab-scale impregnation line. The influence of the solution concentration has been investigated. SEM-EDX and FT-IR confirmed the grafting efficiency of molecules on wrapped rovings. Plain and 5-harness satin fabrics were then manufactured at lab scale with the resulting functionalized rovings. Tensile tests were carried out on rovings and on fabrics. A concentration of 1% silane is sufficient to improve the mechanical properties of rovings and fabrics. The addition of NaOH to tannins strengthens flax fiber rovings more than tannins alone, and the weave pattern influences mechanical performance.

A Bio-Based Molecule to Afford a Lithium-Metal Battery by Modification with the Electrode–Electrolyte Interphase

A Bio-Based Molecule to Afford a Lithium-Metal Battery by Modification with the Electrode–Electrolyte Interphase

First principles prediction of NRTL binary interaction parameters for furfural derivatives

AbstractBiobased molecules constitute sustainable alternatives for fossil‐based chemicals. However, to allow further valorization, the complex product mixtures resulting from biomass processing typically require downstream separation. Although many (semi)empirical thermodynamic models, like NRTL, are available for separation process design, their application for biobased molecules is hampered due to the lack of the necessary data to determine the binary interaction parameters used in these models. Therefore, in this work a case study comprising a set of furfural derivates has been used to showcase a methodology to efficiently determine these parameters. Based on first principles, COSMO‐RS is used to generate a dataset of thermodynamic activities, which is subsequently used to regress the NRTL model against. Comparison of NRTL‐HOC simulated vapor–liquid equilibria (VLE's) with experimental VLE's showed excellent agreement, confirming that COSMO‐RS can be used to extend the use of (semi)‐empirical models toward applications involving biobased molecules of which limited experimental data is available.

Sustainability: Advances and Applications. An Introduction to Manuscripts Based on the ACS Presidential–Agricultural & Food Chemistry Division Symposium Held during the 261st ACS National Meeting in April 2021

The symposium Sustainability: Advances and Applications was held during the virtual 261st ACS National Meeting, April 2021. The symposium was co-organized by 2021 ACS President H. N. Cheng and the Agricultural and Food Chemistry Division of ACS. Sixty (60) invited speakers presented their research on Biobased Polymers, Biobased Molecules, Byproduct Utilization, Waste-product Utilization, the Food-Energy-Water Nexus, Nanotech that Drives Sustainability, Food Safety and Security, and Sustainable Food Systems for Health. Contributions to this issue of ACS Food Science & Technology can be generally categorized as leveraging renewable resources for health and nutrition benefits, modifying renewable resources to extend their utility, and computational approaches to help enhance or increase the safety of renewable agricultural resources.

Optimizing the strain engineering process for industrial-scale production of bio-based molecules.

Biomanufacturing could contribute as much as ${\$}$30 trillion to the global economy by 2030. However, the success of the growing bioeconomy depends on our ability to manufacture high-performing strains in a time- and cost-effective manner. The Design-Build-Test-Learn (DBTL) framework has proven to be an effective strain engineering approach. Significant improvements have been made in genome engineering, genotyping, and phenotyping throughput over the last couple of decades that have greatly accelerated the DBTL cycles. However, to achieve a radical reduction in strain development time and cost, we need to look at the strain engineering process through a lens of optimizing the whole cycle, as opposed to simply increasing throughput at each stage. We propose an approach that integrates all 4 stages of the DBTL cycle and takes advantage of the advances in computational design, high-throughput genome engineering, and phenotyping methods, as well as machine learning tools for making predictions about strain scale-up performance. In this perspective, we discuss the challenges of industrial strain engineering, outline the best approaches to overcoming these challenges, and showcase examples of successful strain engineering projects for production of heterologous proteins, amino acids, and small molecules, as well as improving tolerance, fitness, and de-risking the scale-up of industrial strains.

Online Microfluidic Production of Sustainable Cyrene™-Derived Porous Microparticles

The use of sustainable raw materials is now a necessity in all industries, including the production of porous microparticles. Cyrene™ is a cellulose-derived compound that is readily prepared through the reduction of the α,β-unsaturation of levoglucosenone (LGO)—a wood-based platform molecule. In this work, the importance of Cyrene™ as a potential bio-based molecule to produce sustainable porous microparticles is demonstrated. First, a methacrylic derivative of Cyrene™ (m-Cyrene) was synthesized. A microfluidic co-flow device was then established to produce m-Cyrene-based oil-in-water (O/W) controlled-size emulsions and to polymerize them by ultraviolet (UV) radiation in a vial. The continuous phase was a sodium dodecyl sulfate aqueous solution, and the dispersed phase was a mixture of m-Cyrene with methacrylic anhydride (MAN) at two different mass concentrations (i.e., 1 wt.% MAN and 92 wt.% MAN) and 2,2-dimethoxy-2-phenylacetophenone (DMPA) as a photoinitiator. The process used the lowest possible quantity of raw materials and avoided excessive purifications to produce homogeneous porous m-Cyrene-MAN microparticles. The controlled size and homogeneous size distribution of the produced polymer microparticles were confirmed by scanning electron microscope (SEM) images. The 3D microstructure as well as the porosity were determined using X-ray microtomography. The high-resolution 3D images produced indicate that the pores of the microparticles are homogeneous and that their porosity is controllable through the concentration of MAN in the monomer mixture (porosity of 30% for a 1 wt.% MAN ratio and 2% for a 92 wt.% MAN ratio). Such porosity control is very important for future potential encapsulation processes that require precise release control.

Modified simultaneous saccharification and fermentation for the production of bioethanol from highly concentrated raw corn starch

Bioethanol is one of the main bio-based molecules produced mainly from sugar cane, molasses and corn. Its environmental advantages allow it to be considered as safe and the cleanest fuel alternative. Starch is a widespread renewable carbohydrate conventionally used for bioethanol production via energy demanding liquefaction and saccharification processes. Raw starch hydrolysis using enzymes capable of degrading it below the gelatinization temperature significantly simplifies the process and reduces the cost of starch processing. In this study, an innovative modified simultaneous saccharification and fermentation process is proposed for the production of bioethanol from highly concentrated raw corn starch (30 % w/v). A two-step synergistic hydrolysis and fermentation was carried out in a single bioreactor vessel. To ensure high process efficiency, factors influencing the hydrolysis of concentrated raw corn starch by raw starch degrading α-amylase from Bacillus paralicheniformis ATCC 9945a (BliAmy) and commercial glucoamylase were investigated. Box–Behnken experimental design was used to predict the effects of different ratios of added enzymes, glucoamylase addition time, incubation time, and pH on hydrolysis yield. Optimal conditions for the highest yield of hydrolysis of raw corn starch (90 %) were obtained after 8 h using 5.0 IU BliAmy per mg of starch and 0.5 % (v/v) glucoamylase at pH 4.5 and 60 °C. Obtained glucose was further fermented with Saccharomyces cerevisiae at 30 °C in the same vessel for bioethanol production. Bioethanol concentration at 129.2 g/L, with productivity of 2.94 g/L/h and ethanol yield (YP/S) at 0.50 g EtOH/g total sugar, equivalent to 87.8 % theoretical yield, was obtained by modified simultaneous saccharification and fermentation. This work enriches the information of bioethanol production and offers a novel strategy for raw starch hydrolysis under industrial conditions.

Straightforward sustainable synthesis of novel non-endocrine disruptive bio-based organic UV-B filters with antimicrobial activity

ABSTRACT With an increasing demand for safe and natural products from both industries and consumers, paired with the recent ban of decried molecules (i.e. octinoxate, avobenzone or octocrylene) due to their high negative impact on humans and the environment (i.e. endocrine disruption, coral bleaching), safe bio-based alternatives are a necessary and promising surrogate to substitute current commercialized petroleum-based UV filters. In this context, a class of bio-based molecules, displaying interesting UV-B filtering properties and great photostability were developed from furfural and 5-hydroxymethylfurfural (HMF), using the Knoevenagel condensation with a set of green conditions to minimize the impact on environment. Furthermore, those furfural- and HMF-based molecules demonstrated antimicrobial properties as secondary activity, highly sought by industries. Some furan derivatives being recognized to exhibit toxicological risks, in silico and in vitro assays were conducted and demonstrated the absence of endocrine disruption activity for these new molecules.

Itaconic Anhydride as a Green Compatibilizer in Composites Prepared by the Reinforcement of a Tung Oil-Based Thermosetting Resin with Miscanthus, Pine Wood, or Algae Biomass

Unsaturated vegetable oils with conjugated carbon–carbon double bonds, such as tung oil, can undergo free-radical polymerization, originating alternatives to petroleum-based materials. The introduction of fillers to vegetable oil-based polymer matrices results in composites with improved mechanical properties. In this work, thermosets were synthesized by the free-radical polymerization of a mixture of tung oil, divinylbenzene, and n-butyl methacrylate, and reinforced with bio-based fillers, namely Miscanthus, Pinus taeda (also known as southern pine), and algae (Microspora and Oedogonium) biomass. The effect of filler particle size on the composites’ properties was evaluated. Additionally, to develop a better interaction between the hydrophobic resin and the hydrophilic reinforcements, and improve the mechanical properties of the composites prepared, itaconic anhydride, a bio-based molecule derived from itaconic acid, was added to the resin. Thermogravimetric analysis (TGA) showed that the presence of itaconic anhydride improved the overall thermal stability of the composites. The storage modulus of the composites at room temperature, assessed by dynamic mechanical analysis (DMA), was increased by approximately 32% and 68%, for Miscanthus and southern pine composites, respectively, when itaconic acid was added to the resin. It was also observed that the glass transition temperatures were not significantly affected by the presence of itaconic acid. Scanning electron microscope (SEM) images indicated better matrix-reinforcement adhesion in the presence of itaconic anhydride.

Precursor prioritization for p-cymene production through synergistic integration of biology and chemistry

The strategy of synergistic application of biological and chemical catalysis is an important approach for efficiently converting renewable biomass into chemicals and fuels. In particular, the method of determining the appropriate intermediate between the two catalytic methods is critical. In this work, we demonstrate p-cymene production through the integration of biosynthesis and heterogenous catalysis and show how a preferred biologically derived precursor could be determined. On the biological side, we performed the limonene and 1,8-cineole production through the mevalonate pathway. Titers of 0.605 g/L and a 1.052 g/L were achieved, respectively. This difference is in agreement with the toxicity of these compounds toward the producing microorganisms, which has implications for subsequent development of the microbial platform. On the heterogeneous catalysis side, we performed the reaction with both biological precursors to allow for direct comparison. Using hydrogenation/dehydrogenation metals on supports with acid sites, both limonene and 1,8-cineole were converted to p-cymene with similar yields under equivalent reaction conditions. Thus, we could determine that the most promising strategy would be to target 1,8-cineole, the higher titer and lower toxicity bio-derived precursor with subsequent catalytic conversion to p-cymene. We further optimized the biological production of 1,8-cineole via fed-batch fermentation and reached the titer of 4.37 g/L which is the highest known 1,8-cineole titer from microbial production. This work provides a valuable paradigm for early stage considerations to determine the best route for the high-efficiency production of a target biobased molecule using an integration of biology and chemistry.

Organic-inorganic bi-functionalized hybrid KIT-5: A toolbox for catalytic dehydration of xylose to n-hexyl levulinate

Levulinate esters are bio-based molecules with wide industrial applications as solvents, flavorings, fragrances, diesel blend components, and plasticizers. The current study deals with the synthesis and characterization of a series of acidic mesoporous alumino-silicates (KIT-5, Al-KIT-5x (X = 20,10,5), and a hybrid organic-inorganic Al-KIT-5(20)-Pr-SO3H) and their application in the preparation of n-hexyl levulinate from xylose. The prepared catalysts were thoroughly characterized using various techniques, including FT-IR, XRD, N2 adsorption-desorption, ICP, and SEM. The best catalytic performance was achieved in the presence of Al-KIT-5(20)-Pr-SO3H, which is found to be a bi-functionalized Lewis/Bronsted acid catalyst. The yield of n-hexyl levulinate reached a maximum of 52% at 170 °C in only 7 h. Al-KIT-5(20)-Pr-SO3H represents not only excellent reusability over four successive runs but also shows simple separation from the reaction mixture.

The preparation technology and application of xylo-oligosaccharide as prebiotics in different fields: A review.

Xylo-oligosaccharide (XOS) is a class of functional oligosaccharides that have been demonstrated with prebiotic activity over several decades. XOS has several advantages relative to other oligosaccharide molecules, such as promoting root development as a plant regulator, a sugar supplement for people, and prebiotics to promote intestinal motility utilization health. Now, the preparation and extraction process of XOS is gradually mature, which can maximize the extraction and avoid waste. To fully understand the recent preparation and application of XOS in different areas, we summarized the various technologies for obtaining XOS (including acid hydrolysis, enzymatic hydrolysis, hydrothermal pretreatment, and alkaline extraction) and current applications of XOS, including in animal feed, human food additives, and medicine. It is hoped that this review will serve as an entry point for those looking into the prebiotic field of research, and perhaps begin to dedicate their work toward this exciting classification of bio-based molecules.

Oxidation of furfural to bio-based molecules with hydrogen peroxide via modified layered double hydroxides: the effect of gold nanoparticles on the selectivity

Oxidation of furfural to bio-based molecules with hydrogen peroxide via modified layered double hydroxides: the effect of gold nanoparticles on the selectivity