Pd/IPrBIDEA-Catalyzed Hydrodefluorination of gem-Difluorocyclopropanes: Regioselective Synthesis of Terminal Fluoroalkenes.

Developing new strategies to enable chemo- and regioselective reductions is an important topic in chemical research. Herein, an efficient and regioselective Pd/IPrBIDEA-catalyzed ring-opening hydrodefluorination of gem-difluorocyclopropanes to access terminal fluoroalkenes is developed. The success of this transformation was attributed to the use of 3,3-dimethylallyl Bpin as a novel hydride donor. DFT calculations suggest that a direct 3,4'-hydride transfer via a 9-membered cyclic transition state is more favorable, which combined with the irreversibility of the reaction enables the unusual selectivity for the less thermodynamically stable terminal alkene isomer. This reaction mode is also applicable to a variety of regioselective allylic and propargyl reductions.

Advances in regulating vitamin K2 production through metabolic engineering strategies.

Vitamin K2 (menaquinone, VK2, MK) is an essential lipid-soluble vitamin that plays critical roles in inhibiting cell ferroptosis, improving blood clotting, and preventing osteoporosis. The increased global demand for VK2 has inspired interest in novel production strategies. In this review, various novel metabolic regulation strategies, including static and dynamic metabolic regulation, are summarized and discussed. Furthermore, the advantages and disadvantages of both strategies are analyzed in-depth to highlight the bottlenecks facing microbial VK2 production on an industrial scale. Finally, advanced metabolic engineering biotechnology for future microbial VK2 production will also be discussed. In summary, this review provides in-depth information and offers an outlook on metabolic engineering strategies for VK2 production.

Flavor Formation and Quality Maintenance in Meat Processing.

As an important source of nutrients, meat can supply protein, fat, vitamins and minerals, which are crucial in people's diet worldwide [...].

Enhanced vitamin K2 production by engineered Bacillus subtilis during leakage fermentation.

Menaquinone-7 (MK-7), a valuable member of the vitamin K2 series, is an essential nutrient for humans. It is used for treating coagulation disorders, and osteoporosis, promoting liver function recovery, and preventing cardiovascular diseases. In this study, to further improve the metabolic synthesis of MK-7 by the mutant strain, the effect of surfactants on the metabolic synthesis of MK-7 by the mutant strain Bacillus subtilis 168 KO-SinR (BS168 KO-SinR) was analyzed. The scanning electron microscopy and flow cytometry results showed that the addition of surfactants changed the permeability of the cell membrane of the mutant strain and the structural components of the biofilm. When 0.7% Tween-80 was added into the medium, the extracellular and intracellular synthesis of MK-7 reached 28.8 mg/L and 59.2 mg/L, respectively, increasing the total synthesis of MK-7 by 80.3%. Quantitative real-time PCR showed that the addition of surfactant significantly increased the expression level of MK-7 synthesis-related genes, and the electron microscopy results showed that the addition of surfactant changed the permeability of the cell membrane. The research results of this paper can serve as a reference for the industrial development of MK-7 prepared by fermentation.

The Regulatory Role of miR-107-Cdk6-Rb Pathway in Airway Smooth Muscle Cells in Asthma.

Purpose: Airway remodeling is a significant pathological change of asthma. This study aimed to detect differentially expressed microRNAs in the serum of asthma patients and airway smooth muscle cells (ASMCs) of asthmatic mice, exploring their role in the airway remodeling of asthma. Methods: The differentially expressed microRNAs in the serum of mild and moderate-severe asthma patients compared to healthy subjects were revealed using the "limma" package. Gene Ontology (GO) analysis was used to annotate the functions of microRNA target genes. The relative expressions of miR-107 (miR-107-3p in mice sharing the same sequence) in the primary airway smooth muscle cells (ASMCs) of the asthma mice model were tested by RT-qPCR. Cyclin-dependent kinases 6 (Cdk6), a target gene of miR-107, was predicted by algorithms and validated by dual-luciferase reporter assay and Western blot. The roles of miR-107, Cdk6, and protein Retinoblastoma (Rb) in ASMCs were examined by transwell assay and EDU KIT in vitro. Results: The expression of miR-107 was down-regulated in both mild and moderate-severe asthma patients. Intriguingly, the level of miR-107 was also decreased in ASMCs of the asthma mice model. Up-regulating miR-107 suppressed ASMCs' proliferation by targeting Cdk6 and the phosphorylation level of Rb. Increasing the expression of Cdk6 or suppressing Rb activity abrogated the proliferation inhibition effect of ASMCs induced by miR-107. In addition, miR-107 also inhibits ASMC migration by targeting Cdk6. Conclusion: The expression of miR-107 is down-regulated in serums of asthma patients and ASMCs of asthmatic mice. It plays a critical role in regulating the proliferation and migration of ASMCs via targeting Cdk6.

Selective photoelectrochemical oxidation of glucose to glucaric acid by single atom Pt decorated defective TiO2.

Photoelectrochemical reaction is emerging as a powerful approach for biomass conversion. However, it has been rarely explored for glucose conversion into value-added chemicals. Here we develop a photoelectrochemical approach for selective oxidation of glucose to high value-added glucaric acid by using single-atom Pt anchored on defective TiO2 nanorod arrays as photoanode. The defective structure induced by the oxygen vacancies can modulate the charge carrier dynamics and band structure, simultaneously. With optimized oxygen vacancies, the defective TiO2 photoanode shows greatly improved charge separation and significantly enhanced selectivity and yield of C6 products. By decorating single-atom Pt on the defective TiO2 photoanode, selective oxidation of glucose to glucaric acid can be achieved. In this work, defective TiO2 with single-atom Pt achieves a photocurrent density of 1.91 mA cm-2 for glucose oxidation at 0.6 V versus reversible hydrogen electrode, leading to an 84.3 % yield of glucaric acid under simulated sunlight irradiation.

Poly-γ-Glutamic Acid Production by Engineering a DegU Quorum-Sensing Circuit in Bacillus subtilis.

As a natural biological macromolecule, γ-polyglutamic acid (γ-PGA) plays a significant role in medicine, food, and cosmetic industries owing to its unique properties of biocompatibility, biodegradability, water solubility, and viscosity. Although many strategies have been adopted to increase the yield of γ-PGA in Bacillus subtilis, the effectiveness of these common approaches is not high because the strong viscosity affects cell growth. However, dynamic regulation based on quorum sensing (QS) has been extensively applied as a fundamental tool for fine-tuning gene expression in reaction to changes in cell density without adding expensive inducers. A modular PhrQ-RapQ-DegU QS system is developed based on promoter PD4, which is upregulated by phosphorylated DegU (DegU-P). In this study, first, we analyzed the DegU-based gene expression regulation system in B. subtilis 168. We constructed a promoter library of different abilities, selected suitable promoters from the library, and performed mutation screening on the selected promoters and degU region. Furthermore, we constructed a PhrQ-RapQ-DegU QS system to dynamically control the synthesis of γ-PGA in BS168. Cell growth and efficient synthesis of the target product can be dynamically balanced by the QS system. Our dynamic adjustment approach increased the yield of γ-PGA to 6.53-fold of that by static regulation in a 3 L bioreactor, which verified the effectiveness of this strategy. In summary, the PhrQ-RapQ-DegU QS system has been successfully integrated with biocatalytic functions to achieve dynamic metabolic pathway control in BS168, which can be stretched to a large number of microorganisms to fine-tune gene expression and enhance the production of metabolites.

Copper-Catalyzed Germyl-Azidation of Alkenes with Germanium Hydrides and Trimethylsilyl Azide.

The incorporation of a germyl group and another functional fragment across the C═C bond is a challenging task due to the prevailing hydrogermylation reaction. Herein, an efficient copper-catalyzed three-component reaction of alkenes, germanium hydrides, and trimethylsilyl azide has been disclosed. This transformation allows the concomitant introduction of germyl and azide groups across the double bonds in a highly regioselective manner with tert-butyl hydroperoxides as the bystanding oxidant. The resulting ß-germyl azides could be easily converted into ß-germyl amine and 1,2,3-triazoles of significant value.

Copper-Catalyzed Three-Component Germyl Peroxidation of Alkenes.

The concurrent incorporation of a germyl fragment and another functional group (beyond the hydrogen atom) across the C═C double bond is a highly appealing yet challenging task. Herein we demonstrate the efficient germyl peroxidation of alkenes with germanium hydrides and tert-butyl hydroperoxide via a copper-catalyzed three-component radical relay strategy. This protocol exhibits excellent functional group tolerance and exquisite chemo- and regioselectivity under mild conditions and represents a rare example of constructing synthetically challenging metal-embedded organic peroxides.

Three-Component Reactions of α-CF3 Carbonyls, NaN3, and Amines for the Synthesis of NH-1,2,3-Triazoles.

The development of methods for the assembly of 1,2,3-triazoles is an important topic due to the broad applications of this motif in various scientific fields. In this work, we demonstrate that the three-component assembly of α-CF3 carbonyls, NaN3, and amines was achieved for the selective construction of a variety of 5-amino NH-1,2,3-triazoles under transition-metal-free and open-air conditions. The method provides a general and operationally simple route to functionalized biologically important molecules including carbohydrates, nucleosides, and peptides and exhibits broad substrate scopes. We further demonstrate that the NH-1,2,3-triazoles can be smoothly converted to the regiospecific N-2 alkylated 1,2,3-triazole products. Mechanistic studies based on experiments and density functional theory calculations showed that this transformation proceeds via defluorination-initiated programmed substitution/cyclization/H-transfer to give the 4,5-difunctionalized captodative NH-1,2,3-triazole product.

Iron-catalysed radical cyclization to synthesize germanium-substituted indolo[2,1-a]isoquinolin-6(5H)-ones and indolin-2-ones.

A simple and efficient strategy for iron-catalysed cascade radical cyclization was developed, by which an array of germanium-substituted indolo[2,1-a]isoquinolin-6(5H)-ones and indolin-2-ones were obtained in one pot with germanium hydrides as radical precursors. A rapid intramolecular radical trapping mode enabled the selective arylgermylation of alkenes over the prevalent hydrogermylation reaction.

Monodispersed Ruthenium Nanoparticles on Nitrogen-Doped Reduced Graphene Oxide for an Efficient Lithium-Oxygen Battery.

Lithium-oxygen batteries with ultrahigh energy densities have drawn considerable attention as next-generation energy storage devices. However, their practical applications are challenged by sluggish reaction kinetics aimed at the formation/decomposition of discharge products on battery cathodes. Developing effective catalysts and understanding the fundamental catalytic mechanism are vital to improve the electrochemical performance of lithium-oxygen batteries. Here, uniformly dispersed ruthenium nanoparticles anchored on nitrogen-doped reduced graphene oxide are prepared by using an in situ pyrolysis procedure as a bifunctional catalyst for lithium-oxygen batteries. The abundance of ruthenium active sites and strong ruthenium-support interaction enable a feasible discharge product formation/decomposition route by modulating the surface adsorption of lithium superoxide intermediates and the nucleation and growth of lithium peroxide species. Benefiting from these merits, the electrode provides a drastically increased discharge capacity (17,074 mA h g-1), a decreased charge overpotential (0.51 V), and a long-term cyclability (100 cycles at 100 mA g-1). Our observations reveal the significance of the dispersion and coordination of metal catalysts, shedding light on the rational design of efficient catalysts for future lithium-oxygen batteries.

Application of functionalized graphene in Li-O2 batteries.

Li-O2 batteries (LOB) are considered as one of the most promising energy storage devices using renewable electricity to power electric vehicles because of its exceptionally high energy density. Carbon materials have been widely employed in LOB for its light weight and facile availability. In particular, graphene is a suitable candidate due to its unique two-dimensional structure, high conductivities, large specific surface areas, and good stability at high charge potential. However, the intrinsic catalytic activity of graphene is insufficient for the sluggish kinetics of oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in LOB. Therefore, various surface functionalization schemes for graphene have been developed to tailor the surface chemistry of graphene. In this review, the properties and performances of functionalized graphene cathodes are discussed from theoretical and experimental aspects, including heteroatomic doping, oxygen functional group modifications, and catalyst decoration. Heteroatomic doping breaks electric neutrality of sp2 carbon of graphene, which forms electron-deficient or electron-rich sites. Oxygen functional groups mainly create defective edges on graphene oxides with C-O, C=O, and -COO-. Catalyst decoration is widely attempted by various transition and precious metal and metal oxides. These induced reactive sites usually improve the ORR and/or OER in LOB by manipulating the adsorption energies of O2, LiO2, Li2O2, and promoting electron transportation of cathode. In addition, functionalized graphene is used in anode and separators to prevent shuttle effect of redox mediators and suppress growth of Li dendrite.

Simulated solar light driven Fe(III)/Fe(II) redox cycle for roxarsone degradation and simultaneous arsenate immobilization.

Organoarsenicals remediation requires degrading organoarsenicals and simultaneously immobilizing the resulted inorganic arsenic, and is thus a great challenge. In this study, a simulated solar light driven Fe(III)/Fe(II) cycle strategy was developed to degrade roxarsone and immobilize the generated inorganic arsenic via tuning the degree of Fe(III) hydrolysis. At pH values of 2.0 and 3.0, the hydrolysis of Fe(III) in the solution was suppressed to produce photoreactive Fe(III)-hydroxyl complexes, which could be excited by simulated solar light to generate OH for 85.3 % of roxarsone degradation into arsenate within 60 min. Density functional theory calculations suggested that Fe(OH)(H2O)52+ with lower energy separation gap was the most photoactive Fe(III)-hydroxyl complex for OH generation. With further increasing pH value to 6.0, the hydrolysis of Fe(III) was promoted to precipitate the arsenate for its immobilization, accompanying with the decrease of final iron ions and arsenate concentrations to 0.012 mmol L-1 and 58 µg L-1, respectively. Meanwhile, the undegraded roxarsone was also adsorbed by the precipitate, increasing the overall roxarsone removal efficiency to 99.0 %. This study offers a promising strategy for the efficient organoarsenicals treatment, and also sheds light on the dual effects of iron based materials in organic pollutants degradation and heavy metal ions immobilization.

Methylene-Bridged Tridentate Salicylaldiminato Binuclear Titanium Complexes as Copolymerization Catalysts for the Preparation of LLDPE through [Fe]/[Ti] Tandem Catalysis.

A novel tandem catalysis system consisted of salicylaldiminato binuclear/mononuclear titanium and 2,6-bis(imino)pyridyl iron complexes was developed to catalyze ethylene in-situ copolymerization. Linear low-density polyethylene (LLDPE) with varying molecular weight and branching degree was successfully prepared with ethylene as the sole monomer feed. The polymerization conditions, including the reaction temperature, the Fi/Ti molar ratio, and the structures of bi- or mononuclear Ti complexes were found to greatly influence the catalytic performances and the properties of obtained polymers. The polymers were characterized by differential scanning calorimetry (DSC), high temperature gel permeation chromatography (GPC) and high temperature 13C NMR spectroscopy, and found to contain ethyl, butyl, as well as some longer branches. The binuclear titanium complexes demonstrated excellent catalytic activity (up to 8.95 × 106 g/molTi·h·atm) and showed a strong positive comonomer effect when combined with the bisiminopyridyl Fe complex. The branching degree can be tuned from 2.53 to 22.89/1000C by changing the reaction conditions or using different copolymerization pre-catalysts. The melting points, crystallinity and molecular weights of the products can also be modified accordingly. The binuclear complex Ti2L1 with methylthio sidearm showed higher capability for comonomer incorporation and produced polymers with higher branching degree and much higher molecular weight compared with the mononuclear analogue.

Application of Polyaniline for Li-Ion Batteries, Lithium-Sulfur Batteries, and Supercapacitors.

Conducting polyaniline (PANI) exhibits interesting properties, such as high conductivity, reversible convertibility between redox states, and advantageous structural feature. It therefore receives ever-increasing attention for various applications. This Minireview evaluates recent studies on application of PANI for Li-ion batteries (LIBs), Li-S batteries (LSBs) and supercapacitors (SCPs). The flexible PANI is crucial for cyclability, especially for buffering the volumetric changes of electrode materials, in addition to enhancing the electron/ion transport. Furthermore, PANI can be directly used as an electroactive component in electrode materials for LIBs or SCPs and can be widely applied in LSBs due to its physically and chemically strong affinity for S and polysulfides. The evaluation of studies herein reveals significant improvements of electrochemical performance by physical/chemical modification and incorporation of PANI.