Molecular catalysts for ammonia oxidation to dinitrogen represent enabling components to utilize ammonia as a fuel and/or source of hydrogen. Ammonia oxidation requires not only the breaking of multiple strong N-H bonds but also controlled N-N bond formation. We report a novel β-diketiminato copper complex [iPr2NNF6]CuI-NH3 ([CuI]-NH3 (2)) as a robust electrocatalyst for NH3 oxidation in acetonitrile under homogeneous conditions. Complex 2 operates at a moderate overpotential (η = 700 mV) with a TOFmax = 940 h-1 as determined from CV data in 1.3 M NH3-MeCN solvent. Prolonged (>5 h) controlled potential electrolysis (CPE) reveals the stability and robustness of the catalyst under electrocatalytic conditions. Detailed mechanistic investigations indicate that electrochemical oxidation of [CuI]-NH3 forms {[CuII]-NH3}+ (4), which undergoes deprotonation by excess NH3 to form reactive copper(II)-amide ([CuII]-NH2, 6) unstable toward N-N bond formation to give the dinuclear hydrazine complex [CuI]2(μ-N2H4). Electrochemical studies reveal that the diammine complex [CuI](NH3)2 (7) forms at high ammonia concentration as part of the {[CuII](NH3)2}+/[CuI](NH3)2 redox couple that is electrocatalytically inactive. DFT analysis reveals a much higher thermodynamic barrier for deprotonation of the four-coordinate {[CuII](NH3)2}+ (8) by NH3 to give the copper(II) amide [CuII](NH2)(NH3) (9) (ΔG = 31.7 kcal/mol) as compared to deprotonation of the three-coordinate {[CuII]-NH3}+ by NH3 to provide the reactive three-coordinate parent amide [CuII]-NH2 (ΔG = 18.1 kcal/mol) susceptible to N-N coupling to form [CuI]2(μ-N2H4) (ΔG = -11.8 kcal/mol).

/pdf/electrocatalytic-ammonia-oxidation-by-a-low-coordinate-15h3vvwy.pdf

Electrocatalytic Ammonia Oxidation by a Low-Coordinate Copper Complex.

Light‐driven microrobots with different propulsion mechanisms have attracted great attention in microrobot synthesis and applications. However, current systems rely heavily on precious metals, using a complex synthesis process and limited working wavelength. It is therefore of great interest to fabricate microrobots that can be driven by multi‐wavelength irradiation and with simple components. Here, metal–phenolic network (MPN)‐based microrobots are synthesized using a sacrificial polystyrene bead template and an extra capping is added to regulate their symmetry. The hollow MPN microrobots with different layers of capping are capable of moving under both near‐infrared (NIR) irradiation and ultraviolet (UV) irradiation, without fuel. The velocity of the microrobots under irradiation is altered by the thickness of the asymmetric capping and their motion could be manipulated remotely by switching the NIR or UV irradiation on and off. With light‐driven mobility, the reactive oxygen and nitrogen species (RONS) scavenging activity of the microrobots is significantly increased. Therefore, this proposed microrobot system provides a synthesis strategy to develop asymmetric light‐navigated microrobots for future medical treatment with tunable structure, multi‐wavelength light‐responsive mobility, and great RONS scavenging capacity.

Multi‐Wavelength Light‐Responsive Metal–Phenolic Network‐Based Microrobots for Reactive Species Scavenging

Microalgae are microscopic algae in sizes ranging from a few micrometers to several hundred micrometers. On average, half of the oxygen in the atmosphere is produced by the photosynthetic process of microalgae, so the role of these microorganisms in the life cycle of the planet is very significant. Pharmaceutical products derived from microalgae and commercial developments of a variety of supplements extracted from them originate from a variety of their specific secondary metabolites. Many of these microalgae are a reservoir of unique biological compounds including carotenoids, antioxidants, fatty acids, polysaccharides, enzymes, polymers, peptides, pigments, toxins and sterols with antimicrobial, antiviral, antifungal, antiparasitic, anticoagulant, and anticancer properties. The present work begins with an introduction of the importance of microalgae in renewable fuels and biodiesel production, the development of healthy food industry, and the creation of optimal conditions for efficient biomass yield. This paper provides the latest research related to microalgae-derived substances in the field of improving drug delivery, immunomodulatory, and anticancer attributes. Also, the latest advances in algal biocompounds to combat the COVID-19 pandemic are presented. In the subject of cultivation and growth of microalgae, the characteristics of different types of photobioreactors, especially their latest forms, are fully discussed along with their advantages and obstacles. Finally, the potential of microalgae biomass in biotechnological applications, biofuel production, as well as various biomass harvesting methods are described. 

/pdf/recent-advances-in-the-bio-application-of-microalgae-derived-23eb7t9a.pdf

Recent advances in the bio-application of microalgae-derived biochemical metabolites and development trends of photobioreactor-based culture systems

Food poisoning caused by eating contaminated food remains a threat to global public health. Making the situation even worse is the aggravated global environmental pollution, which poses a major threat to the safety of agricultural resources. Food adulteration has been rampant owing to negligent national food safety regulations. The speed at which contaminated food is detected and disposed of determines the extent to which consumers' lives are safeguarded and agricultural economic losses are prevented. Micro/nanomotors offer a high-speed mobile loading platform that substantially increases the chemical reaction rates and, accordingly, exhibit great potential as alternatives to conventional detection and degradation techniques. This review summarizes the propulsion modes applicable to micro/nanomotors in food systems and the advantages of using micro/nanomotors, highlighting examples of their potential use in recent years for the detection and removal of food contaminants. Micro/nanomotors are an emerging technology for food applications that is moving toward mass production, simple preparation, and important functions.

Micro/nanomotor technology: the new era for food safety control.

A Pd-catalyzed three-component syn-1,2-arylmethylation of internal alkynes (ynamides/yne-acetates/alkynes) is described. The readily available and bench stable coupling partners iodo-arenes, and methyl boronic acid are successfully used in this coupling strategy to access the methyl-containing tetra-substituted olefins; the scope is broad showing excellent functional-group tolerance. Notably, the transformation is regio as well as stereoselective. The biologically relevant motifs (BRM) bearing iodo-arenes and ynamides are also used for the late-stage syn-1,2-arylmethylation of alkynes. Aryl-alkylation, aryl-trideuteriomethylation, alkynyl-methylation, and alkenyl-methylation of ynamides are also presented. The Me-substituted alkenes are further transformed into synthetically important β-amino-indenones and α-fluoro-α'-methyl ketones.

Three Component syn-1,2-Arylmethylation of Internal Alkynes.

Copper-Catalyzed C(sp3)–H Methylation via Radical Relay

Bifunctional Biohybrid Magnetically Propelled Microswimmer

A rhombic metallocycle [CoII6Cl6(L)2(HL)2]·5.5DMF·3.5H2O (1) (H2L = tris(2-naphthimidazolylmethyl) amine) composed of two CoIICl(HL) moieties and two CoIICl(L) moieties alternately bridged by two μ3-CoII ions has been synthesized under solvothermal condition. Each metallocycle associate with its six neighbors through intermolecular π···π interactions between naphthimidazolylmethyl arms forming a supramolecular framework with a pcu network. Magnetic measurements on the metallocycle reveal dominant antiferromagnetic couplings between CoII centers. 

Synthesis, Structure, and Magnetism of a Rhombic Metallocycle

Precisely Modeling the Potential of a Surface Electrode Ion Trap

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Copper-Catalyzed C(sp3)–H Methylation via Radical Relay

Bifunctional Biohybrid Magnetically Propelled Microswimmer

Synthesis, Structure, and Magnetism of a Rhombic Metallocycle

Precisely Modeling the Potential of a Surface Electrode Ion Trap