Unspecific peroxygenase enabled formation of azoxy compounds.

Enzymes are making a significant impact on chemical synthesis. However, the range of chemical products achievable through biocatalysis is still limited compared to the vast array of products possible with organic synthesis. For instance, azoxy products have rarely been synthesized using enzyme catalysts. In this study, we discovered that fungal unspecific peroxygenases are promising catalysts for synthesizing azoxy products from simple aniline starting materials. The catalytic features (up to 48,450 turnovers and a turnover frequency of 6.7 s-1) and substrate transformations (up to 99% conversion with 98% chemoselectivity) highlight the synthetic potential. We propose a mechanism where peroxygenase-derived hydroxylamine and nitroso compounds spontaneously (non-enzymatically) form the desired azoxy products. This work expands the reactivity repertoire of biocatalytic transformations in the underexplored field of azoxy compound formation reactions.

Preparation of Supercapacitor Carbon Electrode Materials by Low-Temperature Carbonization of High-Nitrogen-Doped Raw Materials from Food Waste.

To address the problem of the low nitrogen (N) content of carbon materials prepared through the direct carbonization of food waste, soybean meal and egg whites with high N contents were selected to carry out carbonization experiments on food waste. At 220 °C, the effects of hydrothermal carbonization and microwave carbonization on the properties of supercapacitor electrode materials were investigated. The results show that food waste doped with soybean meal and egg whites could achieve good N doping. At a current density of 1 A·g-1, the specific capacitance of the doped carbon prepared by hydrothermal doping is as high as 220.00 F·g-1, which is much greater than that of the raw material prepared through the hydrothermal carbonization of food waste alone, indicating that the hydrothermal carbonization reactions of soybean meal, egg white, and food waste promote the electrochemical properties of the prepared carbon materials well. However, when a variety of raw materials are mixed for pyrolysis carbonization, different raw materials cannot be fully mixed in the pyrolysis process, and under the etching action of potassium hydroxide, severe local etching and local nonetching occur, resulting in a severe increase in the pore size distribution and deterioration of the electrochemical performance of the prepared carbon materials. At a current density of 1 A·g-1, the specific capacitance of these prepared carbon materials is 157.70 F·g-1, whereas it is only 62.00 F·g-1 at a high current density of 20 A·g-1. Therefore, this study suggests that the hydrothermal carbonization process is superior to the microwave pyrolysis carbonization process for preparing supercapacitor electrode materials with multiple samples doped with each other.

A Photoenzymatic Pathway for Gram-Scale Synthesis of 25-Hydroxyvitamin D3.

Vitamin D and its analogues play a crucial role in promoting the well-being of both humans and animals. However, the current synthesis of this vital class of nutrients heavily relies on chemical transformations, which suffer from low step- and atom-efficiency due to lengthy synthetic pathways. To enhance sustainability in the chemical industry, it is necessary to develop alternative synthetic processes. Herein, we present a photoenzymatic approach for synthesizing 25-hydroxyvitamin D3 from 7-dehydrocholesterol. In this sequential synthesis, 7-dehydrocholesterol is initially hydroxylated at the C25 C-H bond, resulting in an 85 % conversion to 25-hydroxyl-7-dehydrocholesterol. Subsequently, by employing photo-irradiation using a monochromatic LED ultraviolet light source in a batch reactor and thermal isomerization, 25-hydroxyvitamin D3 is obtained in satisfactory yield. This photoenzymatic process significantly reduces the need for purification steps and allows for gram-scale synthesis of the target product. Our work offers a selective, efficient, and environmentally friendly method for synthesizing 25-OH-vitamin D3, addressing the limitations of current synthetic approaches.

Optimization and Deep Learning Modeling of the Yield and Properties of Baobab-Derived Biodiesel Catalyzed by Waste Banana Bunch Stalk Biochar.

The integration of optimization techniques and deep learning models, which offer a promising avenue for improving the efficiency and sustainability of biodiesel production processes from baobab seed oil (BSO), is rare. This study utilized a multi-input-multioutput (MIMO) deep learning technique and the most recent central composite design (CCD) optimization tool to model and optimize the yield and properties of biodiesel produced from BSO. First, the baobab seed oil was extracted using a solvent extraction method. BSO was subsequently analyzed and converted to biodiesel by reacting CH3OH catalyzed by waste banana bunch stalk biochar activated by KOH. Multiobjective optimization and prediction of the biodiesel yield (Y) and several key fuel properties, including the cetane number (CN), kinematic viscosity (VS), and purity (P), were achieved. With better correlation coefficients of 0.9709, 0.9464, and 0.9714 for response training, response testing, and response validation, respectively, and a root-mean-square error of 0.00755, the MIMO model on the logsig transfer function accurately predicted the biodiesel yield and properties more than did the MISO and response surface methodology models. The optimum Y (96 wt %), CN (48), VS (3.3 mm2/s), and P (98.3%) were concurrently accomplished at a reaction temperature of 56 °C, a reaction time of 115 min, a CH3OH/BSO molar ratio of 15:1, a catalyst dosage of 6 wt %, and a stirring speed of 400 rpm with 98% optimal validation accuracy. CCD sensitivity analysis revealed that the CH3OH/BSO ratio was the most sensitive (50.9%) input predictor among the other input variables studied.

Reaction engineering blocks ether cleavage for synthesizing chiral cyclic hemiacetals catalyzed by unspecific peroxygenase.

Hemiacetal compounds are valuable building blocks in synthetic chemistry, but their enzymatic synthesis is limited and often hindered by the instability of hemiacetals in aqueous environments. Here, we show that this challenge can be addressed through reaction engineering by using immobilized peroxygenase from Agrocybe aegerita (AaeUPO) under neat reaction conditions, which allows for the selective C-H bond oxyfunctionalization of environmentally significant cyclic ethers to cyclic hemiacetals. A wide range of chiral cyclic hemiacetal products are prepared in >99% enantiomeric excess and 95170 turnover numbers of AaeUPO. Furthermore, by changing the reaction medium from pure organic solvent to alkaline aqueous conditions, cyclic hemiacetals are in situ transformed into lactones. Lactams are obtained under the applied conditions, albeit with low enzyme activity. These findings showcase the synthetic potential of AaeUPO and offer a practical enzymatic approach to produce chiral cyclic hemiacetals through C-H oxyfunctionalization under mild conditions.

Distribution characteristics and migration pathways of metals during hydrothermal liquefaction of municipal sewage sludge in the presence of various catalysts.

A series of hydrothermal liquefaction (HTL) experiments with two different samples of municipal sewage sludge (MSS) were conducted at 350 °C for 30 min residence time in a high pressure batch reactor. The main aim of the study was to explore the distribution and migration pathways of a broad range of metals and metalloids in the HTL products (bio-oil, char and aqueous phase) obtained in the presence of various homogeneous and heterogeneous catalysts (Na2CO3, Li2CO3, K2CO3, Ba(OH)2, Fe2O3, CeO2, NiMo/MoO3, MoS2, Ni/NiO, SnO2, FeS). The elements under study included 16 environmentally significant metals and metalloids (As, B, Ba, Cd, Co, Cr, Cu, Mn, Mo, Ni, Pb, Sb, Se, Sn, Zn and Hg). The study showed that the quantitative migration of the tested metals and metalloids to the particular HTL products, relative to their initial content in the raw sludge, is different for the individual elements. Most metals exhibited a particularly strong affinity to the solid fraction (biochar). In the obtained HTL bio-oils, all tested elements were identified, except of Cd. It was also found that B and As have high affinity to the aqueous phase. A direct effect of catalysts on the contents of some elements in the products was also proved by the study, e.g. increased concentration of Cr in the biochar when Fe2O3 was used as a process catalyst. Due to the wide scope of the tested elements and broad range of catalyst used, the results obtained represent a unique and comprehensive set of environmental data compared to similar HTL studies previously conducted for MSS.

Peroxygenase-Catalysed Sulfoxidations in Non-Aqueous Media.

Chiral sulfoxides are valuable building blocks in asymmetric synthesis. However, the biocatalytic synthesis of chiral sulfoxides is still challenged by low product titres. Herein, we report the use of peroxygenase as a catalyst for asymmetric sulfoxidation under non-aqueous conditions. Upon covalent immobilisation, the peroxygenase showed stability and activity under neat reaction conditions. A large variety of sulfides was converted into chiral sulfoxides in very high product concentration with moderate to satisfactory optical purity (e. g. 626 mM of (R)-methyl phenyl sulfoxide in approx. 89 % ee in 48 h). Further polishing of the ee value via cascading methionine reductase A (MsrA) gave>99 % ee of the sulfoxide. The robustness of the enzymes and high product titer is superior to the state-of-the-art methodologies. Gram-scale synthesis has been demonstrated. Overall, we demonstrated a practical and facile catalytic method to synthesize chiral sulfoxides.

A Simple Access to γ- and ε-Keto Arenes via Enzymatic Divergent C─H Bond Oxyfunctionalization.

Performing divergent C─H bond functionalization on molecules with multiple reaction sites is a significant challenge in organic chemistry. Biocatalytic oxyfunctionalization reactions of these compounds to the corresponding ketones/aldehydes are typically hindered by selectivity issues. To address these challenges, the catalytic performance of oxidoreductases is explored. The results show that combining the peroxygenase-catalyzed propargylic C─H bond oxidation with the Old Yellow Enzyme-catalyzed reduction of conjugated C─C triple bonds in one-pot enables the regio- and chemoselective oxyfunctionalization of sp3 C─H bonds that are distant from benzylic sites. This enzymatic approach yielded a variety of γ-keto arenes with diverse structural and electronic properties in yields of up to 99% and regioselectivity of 100%, which are difficult to achieve using other chemocatalysis and enzymes. By adjusting the C─C triple bond, the carbonyl group's position can be further tuned to yield ε-keto arenes. This enzymatic approach can be combined with other biocatalysts to establish new synthetic pathways for accessing various challenging divergent C─H bond functionalization reactions.

H2O2-driven enzymatic oxyfunctionalization of tertiary C-H bonds.

Peroxygenase from Agrocybe aegerita catalyses the selective hydroxylation of tertiary C-H bonds, whereby tertiary alcohols, diols, ketols, etc., were obtained in good to high regioselectivity and turnover numbers. This method can also be expanded for late-stage functionalization of drug molecules, which represents a streamlined synthetic method to give access to useful compounds.

Catalytic hydrothermal carbonization of wet organic solid waste: A review.

Hydrothermal carbonization has gained attention in converting wet organic solid waste into hydrochar with many applications such as solid fuel, energy storage material precursor, fertilizer or soil conditioner. Recently, various catalysts such as organic and inorganic catalysts are employed to guide the properties of the hydrochar. This review presents a summarize and a critical discussion on types of catalysts, process parameters and catalytic mechanisms. The catalytic impact of carboxylic acids is related to their acidity level and the number of carboxylic groups. The catalysis level with strong mineral acids is likely related to the number of hydronium ions liberated from their hydrolysis. The impact of inorganic salts is determined by the Lewis acidity of the cation. The metallic ions in metallic salts may incorporate into the hydrochar and increase the ash of the hydrochar. The selection of catalysts for various applications of hydrochars and the environmental and the techno-economic aspects of the process are also presented. Although some catalysts might enhance the characteristics of hydrochar for various applications, these catalysts may also result in considerable carbon loss, particularly in the case of organic acid catalysts, which may potentially ruin the overall advantage of the process. Overall, depending on the expected application of the hydrochar, the type of catalyst and the amount of catalyst loading requires careful consideration. Some recommendations are made for future investigations to improve laboratory-scale process comprehension and understanding of pathways as well as to encourage widespread industrial adoption.

One-Pot Tandem Alcoholysis-Hydrogenation of Polylactic Acid to 1,2-Propanediol.

The chemical recycling of end-of-life polylactic acid (PLA) plays roles in mitigating environmental pressure and developing circular economy. In this regard, one-pot tandem alcoholysis and hydrogenation of PLA was carried out to produce 1,2-propanediol, which is a bulk chemical in polymer chemistry. In more detail, the commercially available Raney Co was employed as the catalyst, and transformation was conducted in ethanol, which acted as nucleophilic reagent and solvent. Single-factor analysis and Box-Behnken design were used to optimize the reaction conditions. Under the optimized condition, three kinds of PLA materials were subjected to degradation. Additionally, 74.8 ± 5.5%, 76.5 ± 6.2%, and 71.4 ± 5.7% of 1,2-propanediol was yielded from PLA powder, particle, and straws, respectively, which provided a recycle protocol to convert polylactic acid waste into value-added chemicals.

Hydrothermal Carbonization of Cellulose with Ammonium Sulfate and Thiourea for the Production of Supercapacitor Carbon.

Doping with heteroatoms is the main method used to enhance energy storage with carbon materials, and polyatomic doping is one of the main challenges. Hydrothermal carbonization of cellulose was performed at 240 °C for 1 h. Ammonium sulfate and thiourea dopants were selected as the sources of inorganic nitrogen and organic nitrogen in the preparation of supercapacitor carbon. The effects of boric acid on the properties of the resulting hydrochar after KOH activation were examined. The results showed that the proportion of functional groups and the specific surface area of the activated hydrochar were reduced by the addition of boric acid, and the formation of micropores was inhibited. The hydrochar obtained from the reaction of cellulose and organic nitrogen compounds had a better pore size distribution and electrochemical properties after activation. The largest specific surface area (952.27 m2/g) was obtained when thiourea was used as the sole dopant. In a three-electrode system, the specific capacitance of the activated hydrochar reached 235.8 F/g at a current density of 1 A/g. After 20,000 charging and discharging cycles at a current density of 10 A/g, the capacitance retention rate was 99.96%. Therefore, this study showed that supercapacitor carbon with good electrochemical properties was obtained by the direct reactions of cellulose with organic nitrogen compounds.

DES mediated synthesis of sewage sludge-derived B, N-doped carbons for electrochemical applications.

In order to effectively utilize organic matter in sewage sludge (SS), a new porous carbon material was successfully prepared from SS with deep eutectic solvents (DES) (boric acid and urea), in which DES was firstly used to solvent to separate organic matter, also playing the role as a B and N donor as well as acid activator to form porous B, N-carbons. As-synthesized B, N-carbon electrode materials possessed a high specific capacitance of 251.4 F/g at a current density of 1 A/g. It retained 84.28% of the capacitance at an ultrahigh current density of 5 A/g. The energy density was 9.502 Wh/Kg at a power density of 245.4 W/kg in 6 M KOH in symmetric supercapacitor.

Chemoenzymatic Hunsdiecker-Type Decarboxylative Bromination of Cinnamic Acids.

In this contribution, we report chemoenzymatic bromodecarboxylation (Hunsdiecker-type) of α,ß-unsaturated carboxylic acids. The extraordinarily robust chloroperoxidase from Curvularia inaequalis (CiVCPO) generated hypobromite from H2O2 and bromide, which then spontaneously reacted with a broad range of unsaturated carboxylic acids and yielded the corresponding vinyl bromide products. Selectivity issues arising from the (here undesired) addition of water to the intermediate bromonium ion could be solved by reaction medium engineering. The vinyl bromides so obtained could be used as starting materials for a range of cross-coupling and pericyclic reactions.

Enhanced catalytic activity of layered double hydroxides via in-situ reconstruction for conversion of glucose/food waste to methyl lactate in biorefinery.

Conversion of food waste into valuable chemicals under mild conditions has attracted increasing attention. Herein, a series of nano-sized MgAl layered double hydroxides (LDHs) were firstly developed as solid base catalyst for the methyl lactate (MLA) production directly from glucose/food waste. Glucose, which could be easily obtained from cellulose or starch-rich food waste via hydrolysis, was thus selected as the model compound. It is inspiring to find that the metal hydroxide layer in prepared LDHs was highly stable and suitable enlarged interlayer distance was reconstructed owing to in-situ intercalation of formed aromatics during the reaction, which was demonstrated by 27Al magic angle spinning nuclear magnetic resonance and time-of-flight secondary ion mass spectrometry analysis. As a result, in-situ activation of the catalysts along with gradually enhanced catalytic activity was obtained in the recycling runs and the highest MLA yield of 47.6% from glucose was achieved over LDHs (5:1) after 5 runs at 150 °C. Most importantly, the scope was further extended to other typical substrates (e.g. Chinese cabbage and rice) and the results demonstrated the effectiveness of present conversion system for real food waste.

From waste tire to high value-added chemicals: an analytical Py-GC/TOF-MS study.

A Pyroprobe 5000 pyrolyzer connected to a gas chromatography-time-of-flight mass spectrometry (Py-GC-TOF-MS) was used to analyze the decomposition behavior of waste tire (WT). Effects of several typical parameters such as heating rate, atmosphere, reaction temperature, retention time, and zeolites on molecular composition and relative contents of the liquid products were investigated. Without added zeolite, the pyrolysis products mainly consisted of limonene, 1,4-pentadiene, and monocyclic aromatic hydrocarbons (MAHs) such as benzene, toluene, ethylbenzene, and xylene (BTEX). L-limonene was the dominant fraction (> 85%) of the limonene. Temperature and time presented the most significant effect on the liquid products' molecular composition and relative content, and increasing temperature and time reduced the contents of alkenes and increased the concentration of MAHs. With added zeolite, the molecular composition of the liquid products was greatly affected. All the liquid products produced with zeolite had higher MAHs and lower alkenes compared with those without added zeolite. Among the zeolites tested, Hß was the most beneficial catalyst to the production of aromatic hydrocarbons as the MAHs reached the highest value of 53.09%. The N, S-compound mainly consisted of benzothiazole and 2-methyl-benzothiazoles-important rubber accelerators. The O, S-compound mainly consisted of sulfones or sulfoxides.

The study of hydrothermal liquefaction of corn straw with Nano ferrite + inorganic base catalyst system at low temperature.

Hydrothermal liquefaction of corn straw with different catalytic systems and temperatures were investigated in this study. Results showed dual catalytic system can effectively promote the degradation of corn straw at low temperature. With increase of temperature, aqueous phase increased and straw residue decreased for all catalytic systems. The heavy bio-oil yield increased with the increasing of temperature for single catalytic system, while the trend was opposite for dual catalytic system. In single catalytic system, ZnFe2O4 was more suitable for preparation of heavy bio-oil, and the maximum yield reached 34.02 wt% at 180 °C. The proportion of monophenyl compounds in heavy bio-oil for dual catalytic system reached the maximum of 84% at 220 °C with ZnFe2O4. At 180 °C, the contents of Benzofuran,2,3-dihydro and 2-Methoxy-4-vinylphenol reached the maximum of 31.42% and 17.64% in CoFe2O4 catalyst system, and the maximum yield of Vanillin was 10.82% with ZnFe2O4.

Progress in thermochemical conversion of duckweed and upgrading of the bio-oil: A critical review.

The processing of duckweed has been included in the list of promising pathways for biofuels production. This property is attributed to its simple manual harvesting method and its ability for high protein or starch content, depending on its species and growing environment. The biofuels production from duckweed, is not only a solution to energy and environmental problems, but also a reliable way to realize the utilization of duckweed. This critical review focuses on the bio-oil production from duckweed via pyrolysis and hydrothermal liquefaction processes. First, characteristics and eco-environmental benefits of duckweed are reviewed. Next, the impacts of different parameters on the properties and distribution of bio-oil from pyrolysis and hydrothermal liquefaction are discussed in detail. Subsequently, the effect of hydrogen donor solvents (as reaction media for upgrading) and catalysts on the upgrading of duckweed bio-oil are extensively discussed. This paper ends with the prospects for further development in thermochemical valorization of duckweed.

A new method for removal of nitrogen in sewage sludge-derived hydrochar with hydrotalcite as the catalyst.

The high content of nitrogen in hydrochar produced from hydrothermal carbonization (HTC) of sewage sludge (SS) leads to serious NOx pollution when the hydrochar is used as a solid fuel. Mg-Ga layered double hydroxides (LDHs), Mg-Al LDHs and their calcined samples (layered double oxides, LDO) were prepared. The LDHs and LDO all can notably promote the removal of nitrogen element, in which organic-N was transferred to NH4+-N to cause increasing pH value. Mg-Al LDO showed the highest efficiency for the removal of nitrogen among the catalysts. The thermal decomposition of the N-organic matter with acidic sites in catalyst was the key step to release NH3. The key role of basic sites in Mg-Al LDO was that it can effectively destroy the cell wall and extracellular polymeric substances structure. The lipid-like substance did not participate in the carbonization reaction, but they can be absorbed by the hydrochar. Partial SS floc directly transformed to hydrochar according to "solid-solid" reaction. The reaction pathways of remove nitrogen were proposed.

Effect of graphene oxide with different morphological characteristics on properties of immobilized enzyme in the covalent method.

Although graphene oxide (GO) has great potential in the field of immobilized enzyme catalysts, the detailed effects of GO with different morphological structures on immobilized enzyme are not well understood. GOs were prepared from 8000 mesh and nanoscale graphite at different reaction temperatures, and used as carriers to immobilize alpha-amylase by cross-linking method. The properties of GOs were characterized through Atomic force microscope, Fourier-transformed infrared, X-ray photoelectron spectroscopy, Raman and UV-Vis. Furthermore, the dosage of cross-linking agent, cross-linking time, optimum temperature/pH, thermal/pH/storage stability, reusability and kinetic parameters of immobilized enzymes were investigated. The results showed that the loading of alpha-amylase on GOs was 162.3-274.2 mg g-1. The reusability experiments revealed high activity maintenance of immobilized alpha-amylase even after seven reaction cycles. Moreover, the storage stability of immobilized enzyme improved via immobilization in comparison with free one and it maintained over 70% of their initial activity after 20 days storage at 4 °C.