Renewable Fatty Acids Research Articles

Hydrophobic enzymatic cellulose nanocrystals via a novel, one-pot green method

Cellulose nanocrystals (CNCs) are a rapidly growing bionanomaterial with remarkable properties that have been harnessed in various applications, including mechanical reinforcement, biomedical materials, and coatings. However, for non-water-based applications, hydrophobization of CNCs while preserving their integrity is crucial. In this study, we propose a new eco-friendly, one-pot surface esterification method for hydrophobizing enzymatic CNCs in aqueous suspension without solvent exchange. By establishing an appropriate set of reaction conditions, it was possible to create a miscibility gradient that enabled a low-cost, and renewable fatty acid to be utilized as an acyl donor and solvent, allowing direct hydrophobic modification of the as-produced aqueous suspension of enzymatic CNC. FT-IR and AFM-IR analyses confirmed the formation of ester groups, while 13C NMR confirmed the emergence of carboxyl groups. XPS revealed a high degree of surface substitution (0.39) in the modified CNC, while a substantial increase in contact angle (from 40 to approximately 90°) quantitatively confirmed the high efficiency of the enzymatic CNC's hydrophobic modification. Additionally, important properties such as morphology remained practically unchanged, except for a slight increase in thermal stability and crystallinity of the CNCs. Therefore, hydrophobic enzymatic CNCs were successfully produced via a simple, scalable, and environmentally friendly approach without compromising their properties. These hydrophobic CNCs have the potential to enhance nanocomposite compatibility, improve packaging performance for electronics and foods, optimize adhesion in coatings, and offer advancements in cosmetics and drug delivery. However, comprehensive studies are needed to confirm their applicability across these sectors.

Steric modulation of CAACs controls orientation and ethenolysis performance

In this issue of Chem Catalysis, Sytniczuk, Kajetanowicz, and Grela report sterically tuned Cyclic(Alkyl)(Amino)Carbene (CAAC) ligands to protect the requisite Ru-methylidene ([Ru]=CH2) intermediate present during ethenolysis of renewable fatty acid methyl esters (FAME). Surprising structural characteristics of the Ru-CAAC complexes resulted in TON up to 740,000 and sub-ppm catalyst loadings.

Immobilization of fatty acid photodecarboxylase in magnetic nickel ferrite nanoparticle

Fatty acid photodecarboxylase in Chlorella variabilis NC64A (CvFAP) performed excellent ability to exclusively decarboxylate renewable fatty acids for C1-shortened hydrocarbons fuel production under visible light. However, the large-scale application by such an approach is limited by the free state of CvFAP catalyst, which is unstable for efficient biofuel production. In this study, CvFAP was immobilized in magnetic nickel ferrite (NiFe2O4) nanoparticles for facile recovery by a simple procedure. The shift of Ni 2p in electron binding energy was detected to clarify the interaction between Ni2+ and histidine of CvFAP. The coordination of NiFe2O4 and CvFAP contributed to an efficient affinity binding with an immobilization capacity of 98 mg/g carrier. Hydrocarbon fuel concentration of 3.7 mM was obtained by NiFe2O4@CvFAP-induced photoenzymatic decarboxylation. The high stability of CvFAP in terms of residual enzyme activity of 79.7% at pH 9.0 and that of 68% at organic solvent ratio of 60%, respectively, were observed.

Regio- and stereo-selective amination of fatty acids tod-amino acids by a three-step one-pot cascade

A novel multienzyme cascade was designed for the regio- and stereo-selective amination of renewable fatty acids to value-addedd-amino acids.

Reducing particle emissions of heavy-duty diesel vehicles in India: Combined effects of diesel, biodiesel and lubricating oil

Diesel engines contribute significantly to deteriorating air quality. Tightening legislation has led to various technological advances, but developments differ between countries. In India, air quality has not improved and fine particle (PM2.5) related premature deaths are predicted to increase. In this study, we characterized the particle emissions of an Indian-manufactured BS IV (Bharat Stage, comparable to Euro emission standards) heavy-duty diesel vehicle and studied the effects of different fuels, fuel blends and lubricating oils. The main aims of the study were to investigate the particle emission dependency on fuel types and fuel blends used in India and to produce useful data for further use (e.g. legislative parties and modeling): emission factors (PN, PM, BC, other chemical compounds), size distributions and volatility of particles. Additionally, the sensitivity of the emissions to the lubricating oil choice was studied. Two lubricating oils, two fossil fuels conforming to BS IV and BS VI emission standards and two biofuel – BS IV fossil fuel blends were tested, one containing Renewable Paraffinic Diesel (RPD) and the other renewable Fatty Acid Methyl Ester (r-FAME). The tests were conducted on a chassis dynamometer (Delhi Bus Driving Cycle, DBDC). Our results show that the emitted particles were in ultrafine particle size range, and both the soot mode particles and smaller nanoparticles were affected by fuels and lubricating oils. The transition from BS IV grade diesel to BSVI was shown to have potential in reducing particle emissions (PN and eBC) of heavy-duty diesel vehicles in India. Blending fossil fuel with biofuel strongly affected particle number emissions, chemical composition, and eBC emissions and the emissions were highly sensitive to biofuel type. Changing the lubricating oil had a comparable magnitude of effect as changing the fuel and the results indicate that in order to reduce particle emissions, a combination of fuel and lubricating oil should be chosen, instead of choosing them separately.

Photobiocatalytic Decarboxylation for the Synthesis of Fatty Epoxides from Renewable Fatty Acids.

Fatty epoxides are unique building blocks in organic transformations and materials production; however, their synthetic methodologies are currently not accessible from renewable fatty acids. Herein, a photoenzymatic decarboxylation of epoxy fatty acids into fatty epoxides was demonstrated using fatty acid photodecarboxylase (FAP) from Chlorella variabilis NC64A (CvFAP). Various fatty epoxides were synthesized in excellent selectivity by wild-type CvFAP. The decarboxylation reaction was also achieved with four new FAP homologues, potentially suggesting a broad availability of the biocatalysts for this challenging decarboxylation reaction. By combining CvFAP with lipase and peroxygenase, a multienzymatic cascade to transform oleic acid and its triglyceride into the corresponding fatty epoxides was established. The obtained fatty epoxides were further converted into rather unusual fatty compounds including diol, alcohol, ether, and chain-shortened carboxylic acids. The present photobiocatalytic synthesis of fatty epoxides from natural starting materials excels by its intrinsic selectivity, mild conditions, and independence of nicotinamide cofactors.

Synthesis and Evaluation of Thermoresponsive Renewable Lipid-Based Block Copolymers for Drug Delivery.

Polymeric micelle forming from self-assembly of amphiphilic macromolecules is one of the most potent drug delivery systems. Fatty acids, naturally occurring hydrophobic lipid components, can be considered as potential candidates for the fabrication of block copolymer micelles. However, examples of synthesis of responsive block copolymers using renewable fatty acids are scarce. Herein, we report the synthesis, characterization and testing of block copolymer micelles composed of a renewable fatty-acid-based hydrophobic block and thermoresponsive hydrophilic block for controlled drug delivery. The block copolymers of functionalized fatty acid and poly(N-isopropylacrylamide) (PNIPAM) were prepared via consecutive microwave-assisted reversible addition fragmentation chain transfer (RAFT) polymerization. The block copolymers with variable hydrophobic block length self-assembled in aqueous media and formed spherical nanoparticles of ~30 nm with low critical micelle concentration (CMC). To demonstrate the proof-of-concept, carbamazepine (CBZ) was used as a hydrophobic model drug to evaluate the performance of these micelles as nanocarriers. The in vitro drug release tests were carried out below (25 °C) and above (37 °C) the lower critical solution temperature (LCST) of the block copolymer. The drug release showed obvious temperature-triggered response and an accelerated drug release at 37 °C.

Renewable fatty acid ester production in Clostridium

Bioproduction of renewable chemicals is considered as an urgent solution for fossil energy crisis. However, despite tremendous efforts, it is still challenging to generate microbial strains that can produce target biochemical to high levels. Here, we report an example of biosynthesis of high-value and easy-recoverable derivatives built upon natural microbial pathways, leading to improvement in bioproduction efficiency. By leveraging pathways in solventogenic clostridia for co-producing acyl-CoAs, acids and alcohols as precursors, through rational screening for host strains and enzymes, systematic metabolic engineering-including elimination of putative prophages, we develop strains that can produce 20.3 g/L butyl acetate and 1.6 g/L butyl butyrate. Techno-economic analysis results suggest the economic competitiveness of our developed bioprocess. Our principles of selecting the most appropriate host for specific bioproduction and engineering microbial chassis to produce high-value and easy-separable end products may be applicable to other bioprocesses.

Thermal and Mechanical Properties of Esterified Lignin in Various Polymer Blends.

Lignin is an abundant polymeric renewable material and thus a promising candidate for incorporation in various commercial thermoplastic polymers. One challenge is to increase the dispersibility of amphiphilic lignin in lipophilic thermoplastic polymers We altered Kraft lignin using widely available and renewable fatty acids, such as oleic acid, yielding more than 8 kg of lignin ester as a light brown powder. SEC showed a molecular weight of 5.8 kDa with a PDI = 3.80, while the Tg of the lignin ester was concluded to 70 °C. Furthermore, the lignin ester was incorporated (20%) into PLA, HDPE, and PP to establish the thermal and mechanical behavior of the blends. DSC and rheological measurements suggest that the lignin ester blends consist of a phase-separated system. The results demonstrate how esterification of lignin allows dispersion in all the evaluated thermoplastic polymers maintaining, to a large extent, the tensile properties of the original material. The impact strength of HDPE and PLA blends show substantial loss upon the addition of the lignin ester. Reconverting the acetic acid side stream into acetic anhydride and reusing the catalyst, the presented methodology can be scaled up to produce a lignin-based substitute to fossil materials.

Heterogeneous Ni and MoOx co-loaded CeO2 catalyst for the hydrogenation of fatty acids to fatty alcohols under mild reaction conditions

To develop an efficient Ni-based catalyst for converting renewable fatty acids into high value-added fatty alcohols under mild reaction conditions, the scope of metal oxide modified nickel catalysts was scrutinized. The results show that MoOx modified Ni/CeO2 catalyst exhibits the excellent catalytic performance in the conversion of fatty acids to form corresponding alcohols at mild reaction conditions (235 °C, 3.0 MPa H2). Using stearic acid as a model substrate, Ni-MoOx/CeO2 catalyst shows the 98.0% conversion and 96.2% selectivity to stearyl alcohol, which is significantly higher than that of Ni/CeO2 catalyst and of a physical mixture of both Ni/CeO2 and MoOx/CeO2. Detailed characterization (XRD, Raman, XPS, in situ CO-FTIR, HRTEM, and EPR) indicates that NiMoO4 is the mainly active phase in the pre-reduced bimetallic catalysts. After reduction at 500 °C in a H2 flow, the surface of Ni metal is decorated by the MoOx species, the phenomenon is similar to the strong metal-support interaction (SMSI) previously observed on reducible oxides. The presence of MoOx species in the bimetallic Ni-MoOx/CeO2 catalyst not only improves the dispersion of metallic Ni, but also promotes the charge transfer from Ni to Mo. The electronic interaction at the interface of Ni and MoOx provides synergistic catalysis sites of electron-deficient Ni and MoOx species, which is primarily responsible for the excellent catalytic performance of the bimetallic Ni-MoOx catalyst. Additionally, the introduction of Mo species provides much oxygen vacancy sites for the adsorption of fatty acids, which results in high activity for the conversion of fatty acids. The insights into the synergistic catalysis between Ni and MoOx will provide new possibilities in the design of efficient Ni-based catalysts for selective hydrogenation of other biomass-derived compounds containing carboxylic group.

Epoxidized soybean oil modified using fatty acids as tougheners for thermosetting epoxy resins: Part 2—Effect of curing agent and epoxy molecular weight

AbstractA series of bio‐rubber (BR) tougheners for thermosetting epoxy resins was prepared by grafting renewable fatty acids with different chain lengths onto epoxidized soybean oil at varying molar ratios. BR‐toughened samples were prepared by blending BRs with diglycidyl ether of bisphenol A resins, Epon 828 and Epon 1001F, at different weight fractions and stoichiometrically cured using an amine curing agent, 4, 4′‐methylene biscyclohexanamine (PACM). Fracture toughness properties of the unmodified and BR toughened polymer samples—including critical strain energy release rate (GIc), and critical stress intensity factor (KIc)—were measured to investigate the toughening effect of prepared BRs. It was found that the degree of phase separation and toughening were more controllable relative to similar polymers cured using the aromatic curing agent Epikure W, and the use of higher molecular epoxy resins produces a synergistic effect increasing the toughness much more than similar polymers made with lower molecular weight epoxy resins. Average BR domain sizes ranging from 200 to 900 nm were observed, and formulations with GIc, values KIc as high as 1.0 kJ/m2 and 1.4 MPa m1/2 were attained respectively for epoxy systems with Tg greater than 130°C.

Intensification of Photobiocatalytic Decarboxylation of Fatty Acids for the Production of Biodiesel.

Light‐driven biocatalytic processes are notoriously hampered by poor penetration of light into the turbid reaction media. In this study, wirelessly powered light‐emitting diodes are found to represent an efficient and scalable approach for process intensification of the photobiosynthetic production of diesel alkanes from renewable fatty acids.

Secretion of Pseudomonas aeruginosa Lipoxygenase by Pichia pastoris upon Glycerol Feed.

Pseudomonas aeruginosa lipoxygenase (PaLOX) catalyzes the peroxidation of unsaturated fatty acids. Not only linoleic acid, but also linolenic acid and oleic acid are oxidized. The natural host secretes PaLOX into the periplasmic space. Herein, the aim is to secrete PaLOX to the culture supernatant of Pichia pastoris. Since protein background in the culture supernatant is typically rather low, this strategy allows for almost pure production of PaLOX applicable for the valorization of renewable fatty acids, for example for the production of green leaf volatiles. Using the CAT1 promoter system and the well-established α-factor signal sequence for secretion, methanol- and glycerol-induced secretion are compared and the latter shows four times more LOX activity in the culture supernatant under methanol-free conditions. In addition, secreted PaLOX is purified and the specific activity with enzyme in culture supernatant is compared. Notably, the predominant specific activity is achieved for enzyme in culture supernatant - 11.6 U mg-1 - reaching five times higher specific activity than purified PaLOX.

Metabolic Engineering of Oleaginous Yeast Yarrowia lipolytica for Overproduction of Fatty Acids.

The oleaginous yeast Yarrowia lipolytica has attracted much attention due to its ability to utilize a wide range of substrates to accumulate high lipid content and its flexibility for genetic manipulation. In this study, intracellular lipid metabolism in Y. lipolytica was tailored to produce fatty acid, a renewable oleochemical and precursor for production of advanced biofuels. Two main strategies, including blocking activation and peroxisomal uptake of fatty acids and elimination of biosynthesis of lipids, were employed to reduce fatty acid consumption by the native pathways in Y. lipolytica. Both genetic modifications improved fatty acid production. However, disruption of the genes responsible for assembly of nonpolar lipid molecules including triacylglycerols (TAGs) and steryl esters resulted in the deleterious effects on the cell growth. The gene tesA encoding thioesterase from Escherichia coli was expressed in the strain with disrupted faa genes encoding fatty acyl-CoA synthetases and pxa1 encoding peroxisomal acyl-CoA transporter, and the titer of fatty acids resulted in 2.3 g/L in shake flask culture, representing 11-fold improvement compared with the parent strain. Expressing the native genes encoding acetyl-CoA carboxylase (ACC) and hexokinase also increased fatty acid production, although the improvement was not as significant as that with tesA expression. Saturated fatty acids including palmitic acid (C16:0) and stearic acid (C18:0) increased remarkably in the fatty acid composition of the recombinant bearing tesA compared with the parent strain. The recombinant expressing tesA gene resulted in high lipid content, indicating the great fatty acid producing potential of Y. lipolytica. The results highlight the achievement of fatty acid overproduction without adverse effect on growth of the strain. Results of this study provided insight into the relationship between fatty acid and lipid metabolism in Y. lipolytica, confirming the avenue to reprogram lipid metabolism of this host for overproduction of renewable fatty acids.

Transfer Hydrogenation of Fatty Acids on Cu/ZrO2: Demystifying the Role of Carrier Structure and Metal–Support Interface

Catalytic transformation of renewable fatty acids into value-added fatty alcohols without the use of gaseous hydrogen is a versatile technique for the utilization of waste cooking oil, where Cu-bas...

Deoxygenation of heptanoic acid to hexene over cobalt-based catalysts: A model study for α-olefin production from renewable fatty acid

Deoxygenation of heptanoic acid, a model compound, over bimetallic cobalt (Co-Pt, Co-Au, Co-Pd, Co-Ru) supported silica catalysts, was examined for α-olefin production. The catalysts were prepared by conventional impregnation of the metal precursors on silica and characterized by XRF, TEM, H2-TPR, acetic acid-TPD, and XANES. Catalytic testing was performed in a fixed-bed flow reactor under atmospheric H2 pressure. Monometallic cobalt catalysts yielded mainly 1-hexene, but rapid deactivation was observed. Incorporation of 0.5%wt secondary metal, particularly Pt, increases activity and stability under H2. A relatively higher olefin/paraffin ratio can be obtained from the reaction over 5%Co+0.5%Pt/SiO2 when compared to that with higher Pt loading. The co-impregnation method offers Co-Pt catalysts with stability higher than that prepared by the sequential impregnation method. Over cobalt-based catalysts, the deoxygenation is proposed to proceed via reduction of heptanoic acid to heptanal that is an intermediate for decarbonylation to hexene; while other side reactions are suppressed.

A simple approach with scale-up potential towards intrinsically flame-retardant bio-based co-plasticizer for PVC artificial materials

As an imitation of genuine leather, polyvinyl chloride (PVC) artificial materials are versatile, but suffers from being flammable due to the presence of large amounts of combustible plasticizers. Under such circumstance, intrinsically flame-retardant plasticizers displaying dual functions have been a subject of intensive research interest. However, previous strategies attempting to covalently attach flame-retardant moiety to plasticizers invariably required either expensive starting materials or laborious and tedious procedures, ultimately limiting their scale-up application in industry. In addition, driven by escalating demand of halogen-free flame retardants worldwide from an environmental health perspective, previously reported intrinsically flame-retardant plasticizers were mainly halogen-free, less attractive in PVC artificial material industry simply because PVC itself is a halogen-containing polymer. Here, we report an approach to introduce chlorine moieties into unsaturated fatty acid methyl ester by a simple addition reaction occurring on carbon-carbon double bonds, yielding a chlorine-containing, intrinsically flame-retardant bio-plasticizer. When combined with di-(2-ethylhexyl) phthalate (DOP) in PVC formulations, the chlorinated fatty acid methyl ester is qualified as a co-plasticizer while conferring flame retardancy upon the PVC coatings. This approach involves only a one-step procedure that employs renewable fatty acid methyl esters and cheap chlorine gas as raw materials, thus being of great potential to enable intrinsically flame-retardant bio-plasticizers on a large scale to manufacture functional PVC artificial materials for application in fire-prone scenarios.Graphical abstract

Multilayer Engineering of Enzyme Cascade Catalysis for One-Pot Preparation of Nylon Monomers from Renewable Fatty Acids

Enzyme cascade catalysis has critical problems in obtaining the high concentrations of products, such as the low stabilities and activities of biocatalysts and the inhibition by hydrophobic reactan...

Whole‐Cell Photoenzymatic Cascades to Synthesize Long‐Chain Aliphatic Amines and Esters from Renewable Fatty Acids

AbstractLong‐chain aliphatic amines such as (S,Z)‐heptadec‐9‐en‐7‐amine and 9‐aminoheptadecane were synthesized from ricinoleic acid and oleic acid, respectively, by whole‐cell cascade reactions using the combination of an alcohol dehydrogenase (ADH) from Micrococcus luteus, an engineered amine transaminase from Vibrio fluvialis (Vf‐ATA), and a photoactivated decarboxylase from Chlorella variabilis NC64A (Cv‐FAP) in a one‐pot process. In addition, long chain aliphatic esters such as 10‐(heptanoyloxy)dec‐8‐ene and octylnonanoate were prepared from ricinoleic acid and oleic acid, respectively, by using the combination of the ADH, a Baeyer–Villiger monooxygenase variant from Pseudomonas putida KT2440, and the Cv‐FAP. The target compounds were produced at rates of up to 37 U g−1 dry cells with conversions up to 90 %. Therefore, this study contributes to the preparation of industrially relevant long‐chain aliphatic chiral amines and esters from renewable fatty acid resources.

Whole-Cell Photoenzymatic Cascades to Synthesize Long-Chain Aliphatic Amines and Esters from Renewable Fatty Acids.

Long-chain aliphatic amines such as (S,Z)-heptadec-9-en-7-amine and 9-aminoheptadecane were synthesized from ricinoleic acid and oleic acid, respectively, by whole-cell cascade reactions using the combination of an alcohol dehydrogenase (ADH) from Micrococcus luteus, an engineered amine transaminase from Vibrio fluvialis (Vf-ATA), and a photoactivated decarboxylase from Chlorella variabilis NC64A (Cv-FAP) in a one-pot process. In addition, long chain aliphatic esters such as 10-(heptanoyloxy)dec-8-ene and octylnonanoate were prepared from ricinoleic acid and oleic acid, respectively, by using the combination of the ADH, a Baeyer-Villiger monooxygenase variant from Pseudomonas putida KT2440, and the Cv-FAP. The target compounds were produced at rates of up to 37 U g-1 dry cells with conversions up to 90 %. Therefore, this study contributes to the preparation of industrially relevant long-chain aliphatic chiral amines and esters from renewable fatty acid resources.