Upgrade of Acetone-Butanol-Ethanol Mixture to High-Value Biofuels over Ca-Doped Ni-CaO-SiO2 catalyst.

The selective conversion of biomass fermentation derived from an acetone-butanol-ethanol (ABE) mixture into high-value biofuels is of paramount importance for industrial applications. However, challenges persist in effectively controlling the selectivity of long carbon chain ketones in elevated ABE conversion. In this research, a Ca-doped Ni-CaO-SiO2 catalyst was designed and employed to achieve a remarkable conversion of 89.9% into ketone products from the extracted ABE mixture. The selectivity for C8+ ketones reaches 41.8%, demonstrating exceptional performance. The reversible phase transition between Ca2SiO4 and CaCO3 enhances the recyclability, thereby improving the sustainability of the process. Additionally, the trace intermediate 3-hepten-2-one was successfully detected using two-dimensional GC×GC-MS, elucidating the conversion pathway in the catalytic upgrading of the ABE mixture. This finding offers a potential route for the efficient utilization of biomass and the highly selective production of value-added chemicals.

Revealing the Mechanisms of Enhanced ß-Farnesene Production in Yarrowia lipolytica through Metabolomics Analysis.

ß-Farnesene is an advanced molecule with promising applications in agriculture, the cosmetics industry, pharmaceuticals, and bioenergy. To supplement the shortcomings of rational design in the development of high-producing ß-farnesene strains, a Metabolic Pathway Design-Fermentation Test-Metabolomic Analysis-Target Mining experimental cycle was designed. In this study, by over-adding 20 different amino acids/nucleobases to induce fluctuations in the production of ß-farnesene, the changes in intracellular metabolites in the ß-farnesene titer-increased group were analyzed using non-targeted metabolomics. Differential metabolites that were detected in each experimental group were selected, and their metabolic pathways were located. Based on these differential metabolites, targeted strain gene editing and culture medium optimization were performed. The overexpression of the coenzyme A synthesis-related gene pantothenate kinase (PanK) and the addition of four mixed water-soluble vitamins in the culture medium increased the ß-farnesene titer in the shake flask to 1054.8 mg/L, a 48.5% increase from the initial strain. In the subsequent fed-batch fermentation, the ß-farnesene titer further reached 24.6 g/L. This work demonstrates the tremendous application value of metabolomics analysis for the development of industrial recombinant strains and the optimization of fermentation conditions.

Enhancing precursor supply and modulating metabolism to achieve high-level production of ß-farnesene in Yarrowia lipolytica.

ß-Farnesene is a sesquiterpene commonly found in essential oils of plants, with applications spanning from agricultural pest control and biofuels to industrial chemicals. The use of renewable substrates in microbial cell factories offers a sustainable approach to ß-farnesene biosynthesis. In this study, malic enzyme from Mucor circinelloides was examined for NADPH regeneration, concomitant with the augmentation of cytosolic acetyl-CoA supply by expressing ATP-citrate lyase from Mus musculus and manipulating the citrate pathway via AMP deaminase and isocitrate dehydrogenase. Carbon flux was modulated through the elimination of native 6-phosphofructokinase, while the incorporation of an exogenous non-oxidative glycolysis pathway served to bridge the pentose phosphate pathway with the mevalonate pathway. The resulting orthogonal precursor supply pathway facilitated ß-farnesene production, reaching 810 mg/L in shake-flask fermentation. Employing optimal fermentation conditions and feeding strategy, a titer of 28.9 g/L of ß-farnesene was attained in a 2 L bioreactor.

The role of oxygen-vacancy in bifunctional indium oxyhydroxide catalysts for electrochemical coupling of biomass valorization with CO2 conversion.

Electrochemical coupling of biomass valorization with carbon dioxide (CO2) conversion provides a promising approach to generate value-added chemicals on both sides of the electrolyzer. Herein, oxygen-vacancy-rich indium oxyhydroxide (InOOH-OV) is developed as a bifunctional catalyst for CO2 reduction to formate and 5-hydroxymethylfurfural electrooxidation to 2,5-furandicarboxylic acid with faradaic efficiencies for both over 90.0% at optimized potentials. Atomic-scale electron microscopy images and density functional theory calculations reveal that the introduction of oxygen vacancy sites causes lattice distortion and charge redistribution. Operando Raman spectra indicate oxygen vacancies could protect the InOOH-OV from being further reduced during CO2 conversion and increase the adsorption competitiveness for 5-hydroxymethylfurfural over hydroxide ions in alkaline electrolytes, making InOOH-OV a main-group p-block metal oxide electrocatalyst with bifunctional activities. Based on the catalytic performance of InOOH-OV, a pH-asymmetric integrated cell is fabricated by combining the CO2 reduction and 5-hydroxymethylfurfural oxidation together in a single electrochemical cell to produce 2,5-furandicarboxylic acid and formate with high yields (both around 90.0%), providing a promising approach to generate valuable commodity chemicals simultaneously on both electrodes.

Organizing Enzymes on Self-Assembled Protein Cages for Cascade Reactions.

Cells use self-assembled biomaterials such as lipid membranes or proteinaceous shells to coordinate thousands of reactions that simultaneously take place within crowded spaces. However, mimicking such spatial organization for synthetic applications in engineered systems remains a challenge, resulting in inferior catalytic efficiency. In this work, we show that protein cages as an ideal scaffold to organize enzymes to enhance cascade reactions both in vitro and in living cells. We demonstrate that not only enzyme-enzyme distance but also the improved Km value contribute to the enhanced reaction rate of cascade reactions. Three sequential enzymes for lycopene biosynthesis have been co-localized on the exterior of the engineered protein cages in Escherichia coli, leading to an 8.5-fold increase of lycopene production by streamlining metabolic flux towards its biosynthesis. This versatile system offers a powerful tool to achieve enzyme spatial organization for broad applications in biocatalysis.

Rational highly dispersed ruthenium for reductive catalytic fractionation of lignocellulose.

Producing monomeric phenols from lignin biopolymer depolymerization in a detachable and efficient manner comes under the spotlight on the fullest utilization of sustainable lignocellulosic biomass. Here, we report a low-loaded and highly dispersed Ru anchored on a chitosan-derived N-doped carbon catalyst (RuN/ZnO/C), which exhibits outstanding performance in the reductive catalytic fractionation of lignocellulose. Nearly theoretical maximum yields of phenolic monomers from lignin are achieved, corresponding to TON as 431 molphenols molRu-1, 20 times higher than that from commercial Ru/C catalyst; high selectivity toward propyl end-chained guaiacol and syringol allow them to be readily purified. The RCF leave high retention of (hemi)cellulose amenable to enzymatic hydrolysis due to the successful breakdown of biomass recalcitrance. The RuN/ZnO/C catalyst shows good stability in recycling experiments as well as after a harsh hydrothermal treatment, benefiting from the coordination of Ru species with N atoms. Characterizations of the RuN/ZnO/C imply a transformation from Ru single atoms to nanoclusters under current reaction conditions. Time-course experiment, as well as reactivity screening of a series of lignin model compounds, offer insight into the mechanism of current RCF over RuN/ZnO/C. This work opens a new opportunity for achieving the valuable aromatic products from lignin and promoting the industrial economic feasibility of lignocellulosic biomass.

Hydro-deoxygenation at atmospheric pressure converts the phenolic-rich pyrolysis liquid fraction into aromatics.

Ambient pressure hydro-deoxygenation (HDO) of the phenolic-rich pyrolysis liquid fraction is a complex task due to the presence multiple phenolic compounds and light oxygenates. The phenolic-rich fraction differs from the overall pyrolysis liquid, known to be prone to re-polymerization and coking in the reactor or of the catalyst. In the present research, hydro-deoxygenation of oxygen-containing compounds in the phenolic fraction over Mo-based catalysts was carried out for the first time. It was found that Mo-based catalysts can successfully upgrade the phenolics into aromatics, the conversion rate was nearly 100%. The small amount of light oxygenates in the phenolic-rich fraction had no obvious effect on the hydro-deoxygenation reaction, the phenolic conversion was more than 95%. After assessing the performance for a representative phenolic model compound, the reaction was also successfully carried out on the phenolic fraction of the real pyrolysis liquid. It can be concluded that the catalysts can also be used for the HDO of the real pyrolysis liquid fraction at atmospheric pressure.

Engineering the oleaginous yeast Yarrowia lipolytica for ß-farnesene overproduction.

ß-farnesene is a sesquiterpenoid with various industrial applications which is now commercially produced by a Saccharomyces cerevisiae strain obtained by random mutagenesis and genetic engineering. We rationally designed a genetically defined Yarrowia lipolytica through recovery of L-leucine biosynthetic route, gene dosage optimization of ß-farnesene synthase and disruption of the competition pathway. The resulting ß-farnesene titer was improved from 8 to 345 mg L-1 . Finally, the strategy for decreasing the lipid accumulation by individually and iteratively knocking out four acyltransferases encoding genes was adopted. The result displayed that ß-farnesene titer in the engineered strain CIBT6304 in which acyltransferases (DGA1 and DGA2) were deleted increased by 45% and reached 539 mg L-1 (88 mg g-1 DCW). Using fed-batch fermentation, CIBT6304 could produce the highest ß-farnesene titer (22.8 g L-1 ) among the genetically defined strains. This study will provide the foundation of engineering Y. lipolytica to produce other terpenoids more cost-efficiently.

Prospects and perspectives foster enhanced research on bio-aviation fuels.

Bio-aviation fuels are a major research and development topic, with strong interests from the aviation sector, the public, lawmakers and potential producers. Yet the development and market penetration in the air-transportation sector is slow, despite proven environmental benefits. Bio-fuels can indeed mitigate the environmental impact of the aviation sector mostly due to their low carbon intensity and favourable chemical structure. Such bio-aviation fuels must have "drop-in" characteristics with specifications and compatibility with the combustion behaviour of kerosene. The ASTM approval procedures are an important guarantee in this respect. Additional emission reductions rely on the production pathways, while optimum flight-related strategies are an additional benefit. An analysis of both the production pathways, and the environmental and Life Cycle Assessment findings delineates important research directions to enhance the production and use of bio-aviation fuels. Towards specific environmental issues, target research topics should include various topics. A better quantification of particulate and soot emissions, condensation contrails and NOx are of primary concern. The impact of geographic parameters on the bio-aviation fuel benefits should be investigated towards using bio-aviation fuels primarily in specific climate zones. Emission prediction models should be further developed. LCA approaches should be extended. More on-flight emission patterns should be measured to provide relevant data for the above considerations; Towards bio-aviation fuel characterization, safety and reliability are major criteria of the ASTM approval. Towards production pathways, the technical viability studies of synthesis pathways should be combined with economic assessments. Towards fuel costs, the reason for the high production cost of bio-aviation fuel is at least partly due to the oxygen-rich bio-polymer nature of biomass with unsuitable carbon chain length. In order to reduce the cost of bio-aviation fuel, several research directions are encouraged and discussed in the paper.

Task-Specific Catalyst Development for Lignin-First Biorefinery toward Hemicellulose Retention or Feedstock Extension.

A catalytic reductive fractionation method for lignocellulosic biomass, termed lignin-first biorefinery, has emerged, which emphasises preferential depolymerization of the protolignin. However, in most studies, the lignin-first biorefinery is only effective for hardwood that has a high syringyl/guaiacol (S/G) ratio of lignin building blocks, and the degradation of hemicellulose also takes place simultaneously to a certain degree. In this study, two task-specific catalysts were developed to realize hemicellulose retention and feedstock extension through the development of an objective performance-structure relationship. It is found that Mox C/carbon nanotube (CNT) is highly selective in the cleavage of bonds between carbohydrates and lignin and ether bonds in lignin during the catalytic reductive fractionation of hardwood, leading to a carbohydrate (both cellulose and hemicellulose) retention degree in the solid product close to the theoretical maximum and a delignification degree as high as 98.1 %. Ru/CMK-3 is demonstrated to be effective in the catalytic reductive fractionation of softwood and grass, resulting from its weak acidity and high mesoporosity.

Highly efficient conversion of plant oil to bio-aviation fuel and valuable chemicals by combination of enzymatic transesterification, olefin cross-metathesis, and hydrotreating.

BACKGROUND: The production of fuels and chemicals from renewable resources is increasingly important due to the environmental concern and depletion of fossil fuel. Despite the fast technical development in the production of aviation fuels, there are still several shortcomings such as a high cost of raw materials, a low yield of aviation fuels, and poor process techno-economic consideration. In recent years, olefin metathesis has become a powerful and versatile tool for generating new carbon-carbon bonds. The cross-metathesis reaction, one kind of metathesis reaction, has a high potential to efficiently convert plant oil into valuable chemicals, such as α-olefin and bio-aviation fuel by combining with a hydrotreatment process. RESULTS: In this research, an efficient, four-step conversion of plant oil into bio-aviation fuel and valuable chemicals was developed by the combination of enzymatic transesterification, olefin cross-metathesis, and hydrotreating. Firstly, plant oil including oil with poor properties was esterified to fatty acid methyl esters by an enzyme-catalyzed process. Secondly, the fatty acid methyl esters were partially hydrotreated catalytically to transform poly-unsaturated fatty acid such as linoleic acid into oleic acid. The olefin cross-metathesis then transformed the oleic acid methyl ester (OAME) into 1-decene and 1-decenoic acid methyl ester (DAME). The catalysts used in this process were prepared/selected in function of the catalytic reaction and the reaction conditions were optimized. The carbon efficiency analysis of the new process illustrated that it was more economically feasible than the traditional hydrotreatment process. CONCLUSIONS: A highly efficient conversion process of plant oil into bio-aviation fuel and valuable chemicals by the combination of enzymatic transesterification, olefin cross-metathesis, and hydrotreatment with prepared and selected catalysts was designed. The reaction conditions were optimized. Plant oil was transformed into bio-aviation fuel and a high value α-olefin product with high carbon utilization.

Cofactor engineering for more efficient production of chemicals and biofuels.

Cofactors are involved in numerous intracellular reactions and critically influence redox balance and cellular metabolism. Cofactor engineering can support and promote the biocatalysis process, even help driving thermodynamically unfavorable reactions forwards. To achieve efficient production of chemicals and biofuels, cofactor engineering strategies such as altering cofactor supply or modifying reactants' cofactor preference have been developed to maintain redox balance. This review focuses primarily on the effects of cofactor engineering on carbon and energy metabolism. Coupling carbon metabolism with cofactor engineering can promote large-scale production, and even offer possibilities for producing new products or converting new materials.

Biosynthesis of medium chain length alkanes for bio-aviation fuel by metabolic engineered Escherichia coli.

The aim of this work was to study the synthesis of medium-chain length alkanes (MCLA), as bio-aviation product. To control the chain length of alkanes and increase the production of MCLA, Escherichia coli cells were engineered by incorporating (i) a chain length specific thioesterase from Umbellularia californica (UC), (ii) a plant origin acyl carrier protein (ACP) gene and (iii) the whole fatty acid synthesis system (FASs) from Jatropha curcas (JC). The genetic combination was designed to control the product spectrum towards optimum MCLA. Decanoic, lauric and myristic acid were produced at concentrations of 0.011, 0.093 and 1.657mg/g, respectively. The concentration of final products nonane, undecane and tridecane were 0.00062mg/g, 0.0052mg/g, and 0.249mg/g respectively. Thioesterase from UC controlled the fatty acid chain length in a range of 10-14 carbons and the ACP gene with whole FASs from JC significantly increased the production of MCLA.

From biomass to advanced bio-fuel by catalytic pyrolysis/hydro-processing: hydrodeoxygenation of bio-oil derived from biomass catalytic pyrolysis.

Compared hydrodeoxygenation experimental studies of both model compounds and real bio-oil derived from biomass fast pyrolysis and catalytic pyrolysis was carried out over two different supported Pt catalysts. For the model compounds, the deoxygenation degree of dibenzofuran was higher than that of cresol and guaiacol over both Pt/Al(2)O(3) and the newly developed Pt supported on mesoporous zeolite (Pt/MZ-5) catalyst, and the deoxygenation degree of cresol over Pt/MZ-5 was higher than that over Pt/Al(2)O(3). The results indicated that hydrodeoxygenation become much easier upon oxygen reduction. Similar to model compounds study, the hydrodeoxygenation of the real bio-oil derived from catalytic pyrolysis was much easier than that from fast pyrolysis over both Pt catalysts, and the Pt/MZ-5 again shows much higher deoxygenation ability than Pt/Al(2)O(3). Clearly synergy between catalytic pyrolysis and bio-oil hydro-processing was found in this paper and this finding will lead an advanced biofuel production pathway in the future.

An ordered mesoporous aluminosilicate with completely crystalline zeolite wall structure.

An ordered mesoporous aluminosilicate with completely crystalline zeolite pore wall structure, denoted as OMZ-1, was successfully synthesized by recrystallization of SBA-15 using in situ formed CMK-5 as the hard template. The role of carbon material not only serves as a hard template to preserve ordered mesoporous structure but also kinetically controls the crystallization process to form large crystals.