Activated Mn-MACHO Complexes Form Stable CO Adducts.

Manganese(I) carbonyl complexes bearing a MACHO-type ligand (HN(CH CH PR ) ) readily react in their amido form with CO to generate 4-membered {Mn-N-C-O} metallacycles. The stability of the adducts decreases with the steric demand of the R groups at phosphorous (R=isopropyl>adamantyl). The CO -adducts display generally a lower reactivity as compared to the parent amido complexes.

Dehydrogenative Electrochemical Synthesis of N-Aryl-3,4-Dihydroquinolin-2-ones by Iodine(III)-Mediated Coupling Reaction.

Electrochemically generated hypervalent iodine(III) species are powerful reagents for oxidative C-N coupling reactions, providing access to valuable N-heterocycles. A new electrocatalytic hypervalent iodine(III)-mediated in-cell synthesis of 1H-N-aryl-3,4-dihydroquinolin-2-ones by dehydrogenative C-N bond formation is presented. Catalytic amounts of the redox mediator, a low supporting electrolyte concentration and recycling of the solvent used make this method a sustainable alternative to electrochemical ex-cell or conventional approaches.

Reactive high-spin iron(IV)-oxo sites through dioxygen activation in a metal-organic framework.

In nature, nonheme iron enzymes use dioxygen to generate high-spin iron(IV)=O species for a variety of oxygenation reactions. Although synthetic chemists have long sought to mimic this reactivity, the enzyme-like activation of O to form high-spin iron(IV) = O species remains an unrealized goal. Here, we report a metal-organic framework featuring iron(II) sites with a local structure similar to that in α-ketoglutarate-dependent dioxygenases.

Mössbauer and Nuclear Resonance Vibrational Spectroscopy Studies of Iron Species Involved in N-N Bond Cleavage.

Diketiminate-supported iron complexes are capable of cleaving the strong triple bond of N to give a tetra-iron complex with two nitrides (Rodriguez et al., , 334, 780-783). The mechanism of this reaction has been difficult to determine, but a transient green species was observed during the reaction that corresponds to a potential intermediate.

Outstanding women scientists who have broadened the knowledge on biological photoreceptors.

Short biographical sketches are given of women born before 1955 who have contributed to our knowledge on the function, structure, and molecular basis of biological photoreceptors, both energy converters and photosensors.

Stability Investigations on a Pt@HGS Catalyst as a Model Material for Fuel Cell Applications: The Role of the Local pH.

Increasing the resistance of catalysts against electrochemical degradation is one of the key requirements for the wider use of Proton Exchange Membrane Fuel Cells (PEMFCs). Here, we study the degradation of one entity of a highly stable catalyst, Pt@HGS, on a nanoelectrode under accelerated mass transport conditions. We find that the catalyst degrades more rapidly than expected based on previous ensemble measurements.

Tailoring C─N Containing Compounds into Carbon Nanomaterials with Tunable Morphologies for Electrocatalytic Applications.

Carbon materials with unique sp -hybridization are extensively researched for catalytic applications due to their excellent conductivity and tunable physicochemical properties. However, the development of economic approaches to tailoring carbon materials into desired morphologies remains a challenge. Herein, a convenient "bottom-up" strategy by pyrolysis of graphitic carbon nitride (g-C N ) (or other carbon/nitrogen (C, N)-enriched compounds) together with selected metal salts and molecules is reported for the construction of different carbon-based catalysts with tunable morphologies, including carbon nano-balls, carbon nanotubes, nitrogen/sulfur (S, N) doped-carbon nanosheets, and single-atom catalysts, supported by carbon layers.

Decarboxylation and Tandem Reduction/Decarboxylation Pathways to Substituted Phenols from Aromatic Carboxylic Acids Using Bimetallic Nanoparticles on Supported Ionic Liquid Phases as Multifunctional Catalysts.

Valuable substituted phenols are accessible via the selective decarboxylation of hydroxybenzoic acid derivatives using multifunctional catalysts composed of bimetallic iron-ruthenium nanoparticles immobilized on an amine-functionalized supported ionic liquid phase (FeRu@SILP+IL-NEt). The individual components of the catalytic system are assembled using a molecular approach to bring metal and amine sites into close contact on the support material, providing high stability and high decarboxylation activity. Operating under a hydrogen atmosphere was found to be essential to achieve high selectivity and yields.

A high-purity gas-solid photoreactor for reliable and reproducible photocatalytic CO reduction measurements.

Reactions between a gas phase and a solid material are of high importance in the study of alternative ways for energy conversion utilizing otherwise useless carbon dioxide (CO). The photocatalytic CO reduction to hydrocarbon fuels like e.g.

An Analysis of Nucleotide-Amyloid Interactions Reveals Selective Binding to Codon-Sized RNA.

Interactions between RNA and proteins are the cornerstone of many important biological processes from transcription and translation to gene regulation, yet little is known about the ancient origin of said interactions. We hypothesized that peptide amyloids played a role in the origin of life and that their repetitive structure lends itself to building interfaces with other polymers through avidity. Here, we report that short RNA with a minimum length of three nucleotides binds in a sequence-dependent manner to peptide amyloids.

A Simple and Versatile Approach for the Low-Temperature Synthesis of Transition Metal Phosphide Nanoparticles from Metal Chloride Complexes and P(SiMe ).

Metal chloride complexes react with tris(trimethylsilyl)phosphine under mild condition to produce metal phosphide (TMP) nanoparticles (NPs), and chlorotrimethylsilane as a byproduct. The formation of Si-Cl bonds that are stronger than the starting M-Cl bonds acts as a driving force for the reaction. The potential of this strategy is illustrated through the preparation of ruthenium phosphide NPs using [RuCl (cymene)] and tris(trimethylsilyl)phosphine at 35 °C.

Conformational coupling of redox-driven Na-translocation in Vibrio cholerae NADH:quinone oxidoreductase.

In the respiratory chain, NADH oxidation is coupled to ion translocation across the membrane to build up an electrochemical gradient. In the human pathogen Vibrio cholerae, the sodium-pumping NADH:quinone oxidoreductase (Na-NQR) generates a sodium gradient by a so far unknown mechanism. Here we show that ion pumping in Na-NQR is driven by large conformational changes coupling electron transfer to ion translocation.

Well-Defined Iron Sites in Crystalline Carbon Nitride.

Carbon nitride materials can be hosts for transition metal sites, but Mössbauer studies on iron complexes in carbon nitrides have always shown a mixture of environments and oxidation states. Here we describe the synthesis and characterization of a crystalline carbon nitride with stoichiometric iron sites that all have the same environment. The material (formula CNHFeLiCl, abbreviated PTI/FeCl) is derived from reacting poly(triazine imide)·LiCl (PTI/LiCl) with a low-melting FeCl/KCl flux, followed by anaerobic rinsing with methanol.

Adaptive Catalysts for the Selective Hydrogenation of Bicyclic Heteroaromatics using Ruthenium Nanoparticles on a CO -Responsive Support.

Ruthenium nanoparticles (NPs) immobilized on an amine-functionalized polymer-grafted silica support act as adaptive catalysts for the hydrogenation of bicyclic heteroaromatics. Whereas full hydrogenation of benzofuran and quinoline derivatives is achieved under pure H , introducing CO into the H gas phase leads to an effective shutdown of the arene hydrogenation while preserving the activity for the hydrogenation of the heteroaromatic part. The selectivity switch originates from the generation of ammonium formate species on the surface of the materials by catalytic hydrogenation of CO .

Toward Understanding the Formation Mechanism and OER Catalytic Mechanism of Hydroxides by In Situ and Operando Techniques.

Developing efficient and affordable electrocatalysts for the sluggish oxygen evolution reaction (OER) remains a significant barrier that needs to be overcome for the practical applications of hydrogen production via water electrolysis, transforming CO to value-added chemicals, and metal-air batteries. Recently, hydroxides have shown promise as electrocatalysts for OER. In situ or operando techniques are particularly indispensable for monitoring the key intermediates together with understanding the reaction process, which is extremely important for revealing the formation/OER catalytic mechanism of hydroxides and preparing cost-effective electrocatalysts for OER.

Structural Identification and Observation of Dose Rate-Dependent Beam-Induced Structural Changes of Micro- and Nanoplastic Particles by Pair Distribution Function Analysis in the Transmission Electron Microscope (ePDF).

Micro- and nanoplastics (MNPs) are considered a possible threat to microorganisms in the aquatic environment. Here, we show that total scattering intensity analysis of electron diffraction (ED) data measured by transmission electron microscopy, which yields the electron pair distribution function (ePDF), is a feasible method for the characterization and identification of MNPs down to 100 nm. To demonstrate the applicability, cryo ball-milled powders of the most common polymers [i.

Photon Energy-Dependent Ultrafast Exciton Transfer in Chlorosomes of and the Role of Supramolecular Dynamics.

The antenna complex of green sulfur bacteria, the chlorosome, is one of the most efficient supramolecular systems for efficient long-range exciton transfer in nature. Femtosecond transient absorption experiments provide new insight into how vibrationally induced quantum overlap between exciton states supports highly efficient long-range exciton transfer in the chlorosome of . Our work shows that excitation energy is delocalized over the chlorosome in <1 ps at room temperature.

Oxidative Addition of Aryl Electrophiles into a Red-Light-Active Bismuthinidene.

The oxidative addition of aryl electrophiles is a fundamental organometallic reaction widely applied in the field of transition metal chemistry and catalysis. However, the analogous version based on main group elements still remains largely underexplored. Here, we report the ability of a well-defined organobismuth(I) complex to undergo formal oxidative addition with a wide range of aryl electrophiles.

Ultrafast Anisotropy Decay Reveals Structure and Energy Transfer in Supramolecular Aggregates.

Chlorosomes from green bacteria perform the most efficient light capture and energy transfer, as observed among natural light-harvesting antennae. Hence, their unique functional properties inspire developments in artificial light-harvesting and molecular optoelectronics. We examine two distinct organizations of the molecular building blocks as proposed in the literature, demonstrating how these organizations alter light capture and energy transfer, which can serve as a mechanism that the bacteria utilize to adapt to changes in light conditions.

Comprehensive structural, infrared spectroscopic and kinetic investigations of the roles of the active-site arginine in bidirectional hydrogen activation by the [NiFe]-hydrogenase 'Hyd-2' from .

The active site of [NiFe]-hydrogenases contains a strictly-conserved pendant arginine, the guanidine head group of which is suspended immediately above the Ni and Fe atoms. Replacement of this arginine (R479) in hydrogenase-2 from results in an enzyme that is isolated with a very tightly-bound diatomic ligand attached end-on to the Ni and stabilised by hydrogen bonding to the Nζ atom of the pendant lysine and one of the three additional water molecules located in the active site of the variant. The diatomic ligand is bound under oxidising conditions and is removed only after a prolonged period of reduction with H and reduced methyl viologen.

studies of Mn oxide based electrocatalysts for the oxygen evolution reaction.

Inspired by photosystem II (PS II), Mn oxide based electrocatalysts have been repeatedly investigated as catalysts for the electrochemical oxygen evolution reaction (OER), the anodic reaction in water electrolysis. However, a comparison of the conditions in biological OER catalysed by the water splitting complex CaMnO with the requirements for an electrocatalyst for industrially relevant applications reveals fundamental differences. Thus, a systematic development of artificial Mn-based OER catalysts requires both a fundamental understanding of the catalytic mechanisms as well as an evaluation of the practicality of the system for industrial scale applications.

A Conserved Second Sphere Residue Tunes Copper Site Reactivity in Lytic Polysaccharide Monooxygenases.

Lytic polysaccharide monooxygenases (LPMOs) are powerful monocopper enzymes that can activate strong C-H bonds through a mechanism that remains largely unknown. Herein, we investigated the role of a conserved glutamine/glutamate in the second coordination sphere. Mutation of the Gln in AA9C to Glu, Asp, or Asn showed that the nature and distance of the headgroup to the copper fine-tune LPMO functionality and copper reactivity.

Syntheses and Structures of 5-Membered Heterocycles Featuring 1,2-Diphospha-1,3-Butadiene and Its Radical Anion.

LGa(P OC)cAAC 2 features a 1,2-diphospha-1,3-butadiene unit with a delocalized π-type HOMO and a π*-type LUMO according to DFT calculations. [LGa(P OC)cAAC][K(DB-18-c-6)] 3[K(DB-18-c-6] containing the 1,2-diphospha-1,3-butadiene radical anion 3⋅ was isolated from the reaction of 2 with KC and dibenzo-18-crown-6. 3 reacted with [Fc][B(C F ) ] (Fc=ferrocenium) to 2 and with TEMPO to [L Ga(P OC)cAAC][K(DB-18-c-6)] 4[K(DB-18-c-6] containing the 1,2-diphospha-1,3-butadiene anion 4 .

D-π-A Structured Porphyrin and Organic Dyes with Easily Synthesizable Donor Units for Low-Cost and Efficient Dye-Sensitized Solar Cells.

This study aimed to develop low-cost D-π-A structured porphyrin and organic dyes with easily synthesizable donor units instead of the conventional complex multistep synthetic donor unit of [bis(7-(2,4-bis(hexyloxy)phenyl)-9,9-dimethyl-9H-fluoren-2-yl)amine] used in and as well-known record cosensitizers with an extremely high power conversion efficiency (PCE). The design strategy concerned the easier synthesis of low-cost donor units with inversion structures in donor groups via donor structural engineering, particularly by changing the position of the fluorene and phenylene units in the donor moiety while keeping the π-bridge and acceptor unit unchanged, leading to the synthesis of two D-π-A structured porphyrins [ and ] and one D-π-A structured organic sensitizer [] for dye-sensitized solar cells (DSSCs). Specifically, porphyrin incorporated two hexyl chains into the 9-position of each fluorene, while and substituted two hexyloxy chain units to the terminal position of each fluorene in the donor groups of porphyrin dyes.