Industrial Synthesis Research Articles

A fungal CYP from Beauveria bassiana with promiscuous steroid hydroxylation capabilities

Hydroxylation of steroid core is critical to the synthesis of steroid drugs. Direct sp3 C–H hydroxylation is challenging through chemical catalysis, alternatively, fungal biotransformation offers a possible solution to this problem. However, mining and metabolic engineering of cytochrome P450 monooxygenases (CYPs) is usually regarded as a more eco-friendly and efficient strategy. Herein, we report the mining and identification of a new steroid CYP (CYP68BE1) from Beauveria bassiana by transcriptomics, heterologous expression, in vivo and in vitro functional characterization. The catalytic promiscuity of CYP68BE1 was explored, and CYP68BE1 showed promiscuously and catalytically versatile, which is qualified for monohydroxylation on C11α, C1α, C6β and dihydroxylation on C1β,11α and C6β,11α of six steroids, leading to the production of key steroid intermediates required in the industrial synthesis of some indispensable steroid drugs. Molecular dynamics simulations were performed, revealing the molecular basis of different binding orientations of CYP68BE1 with different substrates. The discovery of CYP68BE1 offers a promising biocatalyst for enriching the steroid structural and functional diversity, which also can be applied to biosynthesize valuable steroid drug intermediates.

Computation of stagnation coating flow of electro-conductive ternary Williamson hybrid mathrm{GO}-mathrm{AU}-{mathrm{Co}}_{3}{mathrm{O}}_{4}/mathrm{EO} nanofluid with a Cattaneo–Christov heat flux model and magnetic induction

Modern smart coating systems are increasingly exploiting functional materials which combine multiple features including rheology, electromagnetic properties and nanotechnological capabilities and provide a range of advantages in diverse operations including medical, energy and transport designs (aerospace, marine, automotive). The simulation of the industrial synthesis of these multi-faceted coatings (including stagnation flow deposition processes) requires advanced mathematical models which can address multiple effects simultaneously. Inspired by these requests, this study investigates the interconnected magnetohydrodynamic non-Newtonian movement and thermal transfer in the Hiemenz plane's stagnation flow. Additionally, it explores the application of a transverse static magnetic field to a ternary hybrid nanofluid coating through theoretical and numerical analysis. The base fluid (polymeric) considered is engine-oil (EO) doped with graphene left(GOright), gold left(Auright) and Cobalt oxide left(C{o}_{3}{O}_{4}right) nanoparticles. The model includes the integration of non-linear radiation, heat source, convective wall heating, and magnetic induction effects. For non-Newtonian characteristics, the Williamson model is utilized, while the Rosseland diffusion flux model is used for radiative transfer. Additionally, a non-Fourier Cattaneo–Christov heat flux model is utilized to include thermal relaxation effects. The governing partial differential conservation equations for mass, momentum, energy and magnetic induction are rendered into a system of coupled self-similar and non-linear ordinary differential equations (ODEs) with boundary restrictions using appropriate scaling transformations. The dimensionless boundary value problem that arises is solved using the bvp4c built-in function in MATLAB software, which employs the fourth-order Runge–Kutta (RK-4) method. An extensive examination is conducted to evaluate the impact of essential control parameters on the velocity f{^{prime}}left(zeta right), induced magnetic field stream function gradient g{^{prime}}left(zeta right) and temperature theta left(zeta right) is conducted. The relative performance of ternary, hybrid binary and unitary nanofluids for all transport characteristics is evaluated. The inclusion of verification of the MATLAB solutions with prior studies is incorporated. Fluid velocity is observed to be minimized for the ternary mathrm{GO}–mathrm{Au}–{mathrm{Co}}_{3}{mathrm{O}}_{4} nanofluid whereas the velocity is maximized for the unitary cobalt oxide left({mathrm{Co}}_{3}{mathrm{O}}_{4}right) nanofluid with increasing magnetic parameter (beta ). Temperatures are elevated with increment in thermal radiation parameter (Rd). Streamlines are strongly modified in local regions with greater viscoelasticity i.e. higher Weissenberg number (We). Dimensionless skin friction is significantly greater for the ternary hybrid GO–Au–C{o}_{3}{O}_{4}/EO nanofluid compared with binary hybrid or unitary nanofluid cases.

In Ukrainian

The goal of the research work was the pyrolytic synthesis of straight and spiral carbon nanotubes of approximately the same diameter, as well as their comprehensive analysis. To solve the given problem, a new installation for the pyrolytic synthesis of carbon nanostructures (CNS) with a fusion reactor, which for each fusion process can have its own angle relative to the classical horizontal position of the reactor axis. This reactor made it possible to develop a method for obtaining conglomerates of spiral-shaped multi-walled carbon nanotubes with a diameter of 15–60 nm and to synthesize straight multi-walled carbon nanotubes with a diameter of 5 to 60 nm. The research of pyrolytic synthesis of carbon nanostructures in a vertical reactor allows to work out the technology of purposeful synthesis of nanotubes that have a spiral shape with a certain diameter and pitch of the turn. As part of the work, a new mechanism for the formation of spiral multi-walled carbon nanotubes is also considered and proposed, which is important for their further industrial synthesis and their use in related composites. A scheme is proposed of conditions for the synthesis of carbon nanostructures by the pyrolytic method. Thermal analysis was carried out in the work, which recorded the presence of two different structures with low thermal stability (probably amorphous carbon and higher hydrocarbons). When using scanning and transmission electron microscopy, the formation of spiral nanofibers with a diameter of 15–60 nm in the vertical position of the reactor was recorded, and in the horizontal position of the reactor, the formation of straight and slightly curved MWCTs with a diameter of nanofibers from 5 to 60 nm was found. Raman spectroscopy confirms the presence of multi-layered carbon tubular formation, i.e. MWCT, in both synthesis products.

Research Advances on the Bioactivity of 1,2,3-Triazolium Salts

1,2,3-Triazolium salts have demonstrated significant potential in the fields of medicine and agriculture, exhibiting exceptional antibacterial, antifungal, anticancer, and antileishmanial properties. Moreover, these salts can be utilized as additives or components to produce nano- and fiber-based materials with antibacterial properties. In this review, we summarize several synthetic strategies to obtain 1,2,3-triazolium salts and the structures of 1,2,3-triazolium derivatives with biological activities in the domains of pharmaceuticals, pesticides, and functional materials. Additionally, the structure–activity relationship (SAR) of 1,2,3-triazolium salts with different biological activities has been analyzed. Finally, this review presents the potential applications and prospects of 1,2,3-triazolium salts in the fields of agriculture, medicine, and industrial synthesis.

Additive‐Free Transfer Hydrogenative Direct Asymmetric Reductive Amination Using a Chiral Pyridine‐Derived Half‐Sandwich Catalyst

AbstractChiral amines are broadly used compounds in pharmaceutical industry and organic synthesis, and reductive amination reactions have been the most appreciated methods for their syntheses. However, one‐step transfer hydrogenative direct asymmetric reductive amination (THDARA) that could expand the scope, simplify the operation and eliminate the use of additives has been challenging. In this work, based on the Xiao's racemic transfer hydrogenative reductive amination in 2010 and our recent work in novel chiral pyridine ligands, chiral half‐sandwich iridium catalysts were rationally designed and synthesized. Using the optimized catalyst and azeotropic mixture of formic acid and triethylamine as the hydrogen source, a broad range of α‐chiral (hetero)aryl amines, including various polar functional groups and heterocycles, were prepared in generally high yield and enantioselectivity under mild and operationally simple conditions. Density functional theory (DFT) calculation of the catalytically active Ir−H species and the key hydride transfer step supported the chiral pyridine‐induced stereospecific generation of the iridium center, and the enantioselection by taming the highly flexible key transition structure with multiple attractive non‐covalent interactions. This work introduced a type of effective chiral catalysts for simplified approach to medicinally important chiral amines, as well as a rare example of robust enantioselective transition‐metal catalysis.

Additive-Free Transfer Hydrogenative Direct Asymmetric Reductive Amination Using a Chiral Pyridine-Derived Half-Sandwich Catalyst.

Chiral amines are broadly used compounds in pharmaceutical industry and organic synthesis, and reductive amination reactions have been the most appreciated methods for their syntheses. However, one-step transfer hydrogenative direct asymmetric reductive amination (THDARA) that could expand the scope, simplify the operation and eliminate the use of additives has been challenging. In this work, based on the Xiao's racemic transfer hydrogenative reductive amination in 2010 and our recent work in novel chiral pyridine ligands, chiral half-sandwich iridium catalysts were rationally designed and synthesized. Using the optimized catalyst and azeotropic mixture of formic acid and triethylamine as the hydrogen source, a broad range of α-chiral (hetero)aryl amines, including various polar functional groups and heterocycles, were prepared in generally high yield and enantioselectivity under mild and operationally simple conditions. Density functional theory (DFT) calculation of the catalytically active Ir-H species and the key hydride transfer step supported the chiral pyridine-induced stereospecific generation of the iridium center, and the enantioselection by taming the highly flexible key transition structure with multiple attractive non-covalent interactions. This work introduced a type of effective chiral catalysts for simplified approach to medicinally important chiral amines, as well as a rare example of robust enantioselective transition-metal catalysis.

Glycerol Carbonate Solventless Synthesis Using Ethylene Carbonate, Glycerol and a Tunisian Smectite Clay: Activity, Stability and Kinetic Studies

Biodiesel is nowadays added in 5–10% v/v to diesel, and its production involves the parallel creation of a vast glycerol amount as a by-product. Despite its many applications, there is a surplus of glycerol (Gly) that has boosted the search for new applications of this compound, now transformed into an industrial synthesis intermediate or platform chemical. Its transcarbonation is a type of reaction that occurs under mild conditions, using weak or moderate basic catalysts, and allows the parallel production of glycols of industrial interest with high selectivity, such as ethylene glycol. In this research, we have studied the activity of a Tunisian clay rich in inorganic carbonates that give it a weak basic character. The raw clay (RC) has been fully characterized by XRD, FTIR, SEM-EDS and nitrogen porosimetry. Subsequently, it has been employed as a catalyst to react glycerol (G) with ethylene carbonate (EC) to obtain glycerol carbonate (GC) and ethylene glycol (EG). The main operating variables and their effects on glycerol conversion and initial reaction rate were analyzed: catalyst concentration (2–6% w/w glycerol), reagent molar ratio (EC:G 1.5:1 to 3:1), and temperature (80–110 °C). Then, an appropriate kinetic model was selected from the results obtained under various reaction conditions, including the total deactivation of order 1 of the catalyst. The kinetic constant activation energy in this reaction using Tunisian smectite was found to be around 183.3 kJ·mol−1. In the second phase of the investigation, we explored the reuse of smectite using the kinetic model to appreciate the effect of cycle-to-cycle deactivation. It can be seen that the kinetic constant of the main reaction generally decreases with the number of cycles at low temperature and goes through a maximum at high operating temperature, while the deactivation constant increases with the number of catalytic cycles. The catalyst shows more stability, in general, at higher temperatures.

Intelligent Prediction of Nitrous Oxide Capture in Designable Ionic Liquids

As a greenhouse gas, nitrous oxide (N2O) is increasingly damaging the atmosphere and environment, and the capture of N2O using ionic liquids (ILs) has recently attracted wide attention. Machine learning can be utilized to rapidly screen ILs suitable for N2O removal. In this study, intelligent predictions of nitrous oxide capture in designable ionic liquids are proposed based on a series of machine learning methods, including linear regression, voting, and a two-layer feed-forward neural network (TLFFNN). The voting model can utilize various algorithms and is highly generalizable to various systems. The TLFFNN model produced the most accurate prediction, with an MSE of 0.00002 and R2 of 0.9981 on test sets. The acceptable performance of the TLFFNN model demonstrates its utility as an accurate and promising candidate model for the prediction of N2O solubility in ILs over other intelligent models. Based on the analysis of the thermodynamic and molecular properties of ionic liquids, in the low-pressure zone, components of [(OH)2IM] and [AC] perform best in capturing N2O, while in the high-pressure zone, components of [(ETO)2IM] and [SCN] are best. This finding will provide new chemical insights for the industrial synthesis of ionic liquids in capturing N2O.

Catalytic conversion of biomass-derived compounds to high added value products using an acid treated natural mordenite

Herein, the mordenite catalyst TECHΝOSA-H2 that originates from volcanic soils in Greek islands is utilized for the synthesis of ethers and acetals from renewable raw materials. Di-furfuryl ether and furfuryl ethyl ether are used in perfumery and fuels, respectively, and are usually produced by employing either homogeneous catalysts or heterogeneous catalysts which however may lead to undesirable polymer products. Using TECHNOSA H2 we achieved yields in di-furfuryl ether and furfuryl ethyl ether 30% and 60%, respectively, in 3 h and 150 °C. We also report the synthesis of citral propylene glycol acetal and citral diethyl acetal, two important compounds in perfumery industry whose industrial synthesis often requires homogeneous catalysts while with TECHNOSA-H2 50% yields are achieved in 20 min and mild temperatures. The nature of the active sites of TECHNOSA-H2 was inspected by its application to relevant test reactions revealing that Brønsted acidity dominates in this catalyst. To that end, the one-step isomerization of a-pinene oxide to campholenic aldehyde and the one-step cyclization of citronellal to isopulegol in 10min were achieved. Finally, the shape selectivity of the catalyst was examined, proving TECHNOSA-H2 to be selective between the (E)- and (Z)- isomers of Citral. Based on our findings, TECHNOSA-H2 applications vary and include acetalization, isomerization and etherification reactions, as well as reactions where shape selectivity between reactants is desired.

Стрес-протекторні та регуляторні властивості саліцилової кислоти і перспективи її використання в рослинництві

Salicylic acid (SA), as a secondary phenolic metabolite with phytohormonal activity, is an important component of the plant defense system against biotic and abiotic stresses. The scale of industrial synthesis of SA in the world is constantly growing, it is used as an intermediate for the synthesis of drugs and dyes, it is also used in cosmetology, food industry, plant biotechnology, etc. Recently, it has been considered as a promising growth-regulating agent in crop production for decreasing harmful effects of biotic and abiotic stresses in plants. Over the past two decades, numerous data have been published concerning the metabolic pathways of SA synthesis and its signaling in plant immunity. It regulates and affects various stages of plant ontogenesis and metabolism: seed germination, flowering, stomatal movements, pigment synthesis, photosynthesis and respiration, ethylene biosynthesis, thermoregulation, the activity of antioxidant enzymes, nutrient absorption, membrane integrity and functioning, nodulation in legumes, synthesis of secondary metabolites, general growth and development of plants. Numerous studies have confirmed that endogenous SA and/or its derivatives are involved in stress responses to heavy metals (HMs), hyper- and hypothermia, salinity, water deficiency, and, primarily, pathogenic infections. In parallel with fundamental studies of regulatory functions of SA and/or its derivatives, new ways of their exogenous application are constantly discovered. The use of low concentrations of exogenous SA (0.1–0.5 mM) for seed priming or foliar treatment is reported as an economically viable alternative approach for increasing plant tolerance from both economic and environmental points of view. Exogenous SA leads to an increase in endogenous SA levels that induces plant adaptive responses by changing phytohormonal status, increased synthesis of a number of secondary metabolites (alkaloids, cyanogenic glycosides, phenolics, terpenes), by increasing activity of antioxidant enzymes. One of the main advantages of using SA in crop production is the ability to reduce the dosage of pesticides and fertilizers that are potentially harmful to the environment and human health. It is also reported that the use of SA in some cases may lead to negative results – growth retardation, sterility, and yield decrease; the causes of this phenomenon are actively investigated. Further studies are necessary to clarify the mechanisms of exogenic SA action and its use on various crops in different growing conditions. This review aims to analyze the recent data on SA, crop production, and biotechnology areas where it is possible to effectively apply the SA and/or its derivatives.

Push-pull intramolecular charge transfer solvatofluorochromic fluorophore for the selective and real-time detection of hydrazine

Hydrazine (N2H4) is a chemical molecule having a wide range of applications starting from its use in chemical reactions for the synthesis of pesticides, pharma and dye industry, rocket fuel etc. Along with its wide range of applications, it is also becoming a reason for environmental and health concerns, as a result wide ranging detection tools have been developed for the detection of hydrazine. Amongst various sensing tools fluorescence-based molecular probes that can be used for sensing chemical toxics are seeking attention due to their easy operability, high selectivity, sensitivity and their biocompatibility. In this work, we have synthesized and evaluated a solvatochromic fluorescent probe (MQM) that is capable for the rapid and selective detection of hydrazine in water samples with a limit of detection (0.58 µM). The most important application is the probe can be transformed into a portable analytical tool that can be used for the rapid on-site detection of hydrazine without the use of any sophisticated analytical instruments. The probe can be used for real-time detection of hydrazine in water, vapour phase, soil, and biological samples.

Copper-Based Electrocatalysts for Nitrate Reduction to Ammonia.

Ammonia (NH3) is a highly important industrial chemical used as fuel and fertilizer. The industrial synthesis of NH3 relies heavily on the Haber-Bosch route, which accounts for roughly 1.2% of global annual CO2 emissions. As an alternative route, the electrosynthesis of NH3 from nitrate anion (NO3-) reduction (NO3-RR) has drawn increasing attention, since NO3-RR from wastewater to produce NH3 can not only recycle waste into treasure but also alleviate the adverse effects of excessive NO3- contamination in the environment. This review presents contemporary views on the state of the art in electrocatalytic NO3- reduction over Cu-based nanostructured materials, discusses the merits of electrocatalytic performance, and summarizes current advances in the exploration of this technology using different strategies for nanostructured-material modification. The electrocatalytic mechanism of nitrate reduction is also reviewed here, especially with regard to copper-based catalysts.

Salzabfall‐freie Carboxylierung von Acetylen: Grüne Synthese von C4‐Chemikalien durch einen CO2‐Druck‐induzierten Aciditätsswitch

AbstractDie Vermeidung der Bildung equimolarer Mengen an Salzabfällen ist eine der größten Herausforderungen zur Nutzung von CO2 als C1 Baustein in C‐H‐Carboxylierungsreaktionen. Zur Lösung dieses Problems wurde ein zyklischer Prozess entwickelt, in welchem die industrielle Basischemikalie Dimethylsuccinat aus CO2 und Acetylen synthetisiert wird. Bei moderatem CO2‐Druck kann Acetylen mit Cäsiumcarbonat zweifach carboxyliert und das intermediäre Salz durch Hydrierung der C‐C‐Dreifachbindung stabilisiert werden. Bei 70 bar CO2 wird das Reaktionsmedium reversibel angesäuert, was die Veresterung des Carboxylatsalzes mit dem Lösemittel Methanol ermöglicht. Die Cäsiumbase und der Hydrierkatalysator können regeneriert und wiederverwendet werden. Dieses Reaktionskonzept eröffnet einen neuen Weg zur Umsetzung von Biogas (CH4/CO2) zu industriell relevanten C4 Basischemikalien. Der reversible Aziditätsswitch, die Rolle der Cäsiumbase so wie die des Lösungsmittelgemisches wurden durch thermodynamische Modellierung aufgeklärt.

Carboxylation of Acetylene without Salt Waste: Green Synthesis of C4 Chemicals Enabled by a CO2-Pressure Induced Acidity Switch.

The inherent formation of salt waste in C-H carboxylations is a key obstacle precluding the utilization of CO2 as C1 building block in the industrial synthesis of base chemicals. This challenge is addressed in a circular process for the production of the C4 base chemical dimethyl succinate from CO2 and acetylene. At moderate CO2 pressures, acetylene is doubly carboxylated in the presence of cesium carbonate. Hydrogenation of the C-C triple bond stabilizes the product against decarboxylation. By increasing the CO2 pressure to 70 bar, the medium is reversibly acidified, allowing an esterification of the succinate salt with methanol. The cesium base and the hydrogenation catalyst are regenerated and can be reused. This provides the proof of concept for a salt-free route to C4 chemicals from biogas (CH4/CO2). The origin of this reversible acidity switch and the critical roles of the cesium base and the NMP/MeOH solvents were elucidated by thermodynamic modeling.

Pd Atomic Engineering of Nanoporous Ni/NiO for Efficient Nitrophenol Hydrogenation Reaction.

The catalytic hydrogenation of nitrophenols is widely utilized for both industrial synthesis and environmental protection, thus efficient and cost-effective catalysts are in urgent need. Still, the cost and scarcity of the materials still inhibit their application and the active sites are not well specified, especially in the complex catalysts. Herein, we developed an atomic Pd-doped nanoporous Ni/NiO (Pd1@np-Ni/NiO) catalyst via facial dealloying for efficient nitrophenol hydrogenation reaction under mild conditions. Pd1@np-Ni/NiO achieves an excellent specific activity (1301 min-1 mgPd-1, 35.2 times that of commercial Pd/C), nearly 100% selectivity, and continuous reproducibility. The catalytic performance is highly relevant to the Ni sites on the catalysts regarding the exposure sites and the intrinsic property. The metal/metal oxide interfacial structure could cooperatively accelerate the catalytic reaction kinetics. The atomic dopants could effectively modulate the electronic structure, facilitate the absorption of molecules, and reduce the energy barrier of catalytic hydrogenation reaction. Based on the efficient catalyst, the protype nitrophenol//NaBH4 battery is designed for efficient material conversion and power output, which is very attractive for green energy systems.

A review of hydrogen chloride removal from calcium- and sodium-based sorbents.

With the steady progress of ultra-low emissions in various industries, the management of unconventional pollutants is gradually attracting attention. A such unconventional pollutant that negatively affects many different processes and pieces of equipment is hydrogen chloride (HCl). Although it has strong advantages and potential in the treatment of industrial waste gas and synthesis gas, the process technology of removing HCl by calcium- and sodium-based alkaline powder has not yet been thoroughly studied. The impact of reaction factors on the dechlorination of calcium- and sodium-based sorbents is reviewed, including temperature, particle size, and water form. The most recent developments in sodium- and calcium-based sorbents for capturing hydrogen chloride were presented, and the dechlorination capabilities of various sorbents were contrasted. In the low-temperature range, sodium-based sorbents had a stronger dechlorination impact than calcium-based sorbents. Surface chemical reactions and product layer diffusion between solid sorbents and gases are crucial mechanisms. Meanwhile, the effect of the competitive behavior of SO2 and CO2 with HCl on the dechlorination performance has been taken into account. The mechanism and necessity of selective hydrogen chloride removal are also provided and discussed, and future research directions are pointed out to provide the theoretical basis and technical reference for future industrial practical applications.

Facile synthesis and characterization of peroxy-initiated monomers

ABSTRACT Novel peroxide-initiating monomer with the peroxide group and the polymerizable vinyl double bond was designed and prepared through cheap industrial chemical reactants and facile synthesis. Here, one kind of the peroxide-initiating monomer 2-(tert-butylperoxy)ethyl methacrylate (BPEMA) prepared through three-step simple chemical reactions, using tert-butyl hydroperoxide and 2-bromoethanol as the raw ingredients, which reacted at low temperature and obtained the 2-tert-butyl peroxy ethanol, then esterified with methacryloyl chloride or isobutyryl chloride to obtain the peroxide-initiating monomer 2-(tert-butylperoxy)ethyl methacrylate(BPEMA). The analogue peroxide-initiating compound 2-(tert-butylperoxy)ethyl isobutyrate (BPEIB) was designed and obtained using the same reactions as those employed with BPEMA. The other kind of the peroxide-initiating monomer 2-hydroperoxide ethyl methacrylate (HPEMA). The purity of the three products was determined to be above 95%. Here, develop convenient and effective methods in using peroxide-initiating monomer for the in-depth study on the preparation of branched polymers.

Discovery and Engineering of the l-Threonine Aldolase from Neptunomonas marine for the Efficient Synthesis of β-Hydroxy-α-amino Acids via C–C Formation

l-Threonine aldolases (LTAs) are attractive biocatalysts for synthesizing β-hydroxy-α-amino acids (HAAs) via C–C bond formation in pharmaceuticals, although their industrial applications suffer from low activity and diastereoselectivity. Herein, we describe the discovery of an LTA from Neptunomonas marine (NmLTA) that displays both ideal enzymatic activity (64.8 U mg–1) and diastereoselectivity (89.5% diastereomeric excess, de) for the desired product l-threo-4-methylsulfonylphenylserine (l-threo-MTPS). Using X-ray crystallography, site-directed mutagenesis, and computational modeling, we propose a “dual-conformation” mechanism for the diastereoselectivity control of NmLTA, whereby the incoming 4-methylsulfonylbenzaldehyde (4-MTB) could potentially bind at the NmLTA active site in two distinct orientations, potentially forming two diastereoisomers (threo- or erythro-form products). Importantly, two key NmLTA residues H140 and Y319 play critical roles in fine-tuning the binding mode of 4-MTB, supported by our site-mutagenesis assays. Uncovering of the catalytic mechanism in NmLTA guides us to further improve the diastereoselectivity of this enzyme. A triple variant of NmLTA (N18S/Q39R/Y319L, SRL) exhibited both improved diastereoselectivity (de value > 99%) and enzymatic activity (95.7 U mg–1) for the synthesis of l-threo-MTPS compared with that of the wild type. The preparative gram-scale synthesis for l-threo-MTPS with the SRL variant produced a space-time yield of up to 9.0 g L–1 h–1, suggesting a potential role as a robust C–C bond synthetic tool for the industrial synthesis of HAAs at a preparative scale. Finally, the SRL variant accepted a wider range of aromatic aldehyde derivatives as substrates and exhibited improved diastereoselectivity toward para-site substituents. This work provides deep structural insights into the molecular mechanism underlying the catalysis in NmLTA and pinpoints the key structural motifs responsible for regulating the diastereoselectivity control, thereby guiding future attempts for protein engineering of various LTAs from different sources.

The Functional Characterization of DzCYP72A12-4 Related to Diosgenin Biosynthesis and Drought Adaptability in Dioscorea zingiberensis.

Dioscorea zingiberensis is a perennial herb famous for the production of diosgenin, which is a valuable initial material for the industrial synthesis of steroid drugs. Sterol C26-hydroxylases, such as TfCYP72A616 and PpCYP72A613, play an important role in the diosgenin biosynthesis pathway. In the present study, a novel gene, DzCYP72A12-4, was identified as C26-hydroxylase and was found to be involved in diosgenin biosynthesis, for the first time in D. zingiberensis, using comprehensive methods. Then, the diosgenin heterogenous biosynthesis pathway starting from cholesterol was created in stable transgenic tobacco (Nicotiana tabacum L.) harboring DzCYP90B71(QPZ88854), DzCYP90G6(QPZ88855) and DzCYP72A12-4. Meanwhile, diosgenin was detected in the transgenic tobacco using an ultra-performance liquid chromatography system (Vanquish UPLC 689, Thermo Fisher Scientific, Bremen, Germany) tandem MS (Q Exactive Hybrid Quadrupole-Orbitrap Mass Spectrometer, Thermo Fisher Scientific, Bremen, Germany). Further RT-qPCR analysis showed that DzCYP72A12-4 was highly expressed in both rhizomes and leaves and was upregulated under 15% polyethylene glycol (PEG) treatment, indicating that DzCYP72A12-4 may be related to drought resistance. In addition, the germination rate of the diosgenin-producing tobacco seeds was higher than that of the negative controls under 15% PEG pressure. In addition, the concentration of malonaldehyde (MDA) was lower in the diosgenin-producing tobacco seedlings than those of the control, indicating higher drought adaptability. The results of this study provide valuable information for further research on diosgenin biosynthesis in D. zingiberensis and its functions related to drought adaptability.

Unique Tubular BiOBr/g-C3 N4 Heterojunction with Efficient Separation of Charge Carriers for Photocatalytic Nitrogen Fixation.

The industrial ammonia synthesis process consumes a lot of energy and causes serious environmental pollution. As a sustainable approach for ammonia synthesis, photocatalytic nitrogen reduction employing water as the reducing agent has a lot of potential. A simple surfactant-assisted solvothermal method is used to synthesize g-C3 N4 nanotubes with flower-like spherical BiOBr grown inside and outside (BiOBr/g-C3 N4 , BC). The hollow tubular structure realizes the full use of visible light by the multi-scattering effect of light. Large surface areas and more active sites for N2 adsorption and activation are present in the distinctive spatially dispersed hierarchical structures. Particularly, the quick separation and transfer of electrons and holes are facilitated by the sandwich tubular heterojunctions and tight contact interface of BiOBr and g-C3 N4 . The maximal NH3 generation rate of the BiOBr/g-C3 N4 composite catalysts can reach 255.04 μmol⋅ g-1 ⋅ h-1 , and it is 13.9 and 5.8 times that of pure BiOBr and g-C3 N4 . This work provides a novel method for designing and constructing unique heterojunctions for efficient photocatalytic nitrogen fixation.