Scaffold diversity for enhanced activity of glycosylated inhibitors of fungal adhesion.

is one of the most prevalent fungal pathogens involved in hospital acquired infections. It binds to glycans at the surface of epithelial cells and initiates infection. This process can be blocked by synthetic carbohydrates that mimic the structure of cell surface glycans.

Vibrational Perturbation of the [FeFe] Hydrogenase H-Cluster Revealed by CH-ADT Labeling.

[FeFe] hydrogenases are highly active catalysts for the interconversion of molecular hydrogen with protons and electrons. Here, we use a combination of isotopic labeling, Fe nuclear resonance vibrational spectroscopy (NRVS), and density functional theory (DFT) calculations to observe and characterize the vibrational modes involving motion of the 2-azapropane-1,3-dithiolate (ADT) ligand bridging the two iron sites in the [2Fe] subcluster. A -CH- ADT labeling in the synthetic diiron precursor of [2Fe] produced isotope effects observed throughout the NRVS spectrum.

Rational design of tandem catalysts using a core-shell structure approach.

A facile and rational approach to synthesize bimetallic heterogeneous tandem catalysts is presented. Using core-shell structures, it is possible to create spatially controlled ensembles of different nanoparticles and investigate coupled chemocatalytic reactions. The CO hydrogenation to methane and light olefins was tested, achieving a tandem process successfully.

Ligand-Metal Charge Transfer Induced Adjustment of Textural Properties Controls the Performance of Single-Atom Catalysts during Photocatalytic Degradation.

Because of their peculiar nitrogen-rich structure, carbon nitrides are convenient polydentate ligands for designing single atom-dispersed photocatalysts. However, the relation between catalysts' textural properties and their photophysical-photocatalytic properties is rarely elaborated. Herein, we report the preparation and characterization of a series of single-atom heterogeneous catalysts featuring highly dispersed Ag and Cu species on mesoporous graphitic CN.

The Role of Nitrogen-doping in the Catalytic Transfer Hydrogenation of Phenol to Cyclohexanone with Formic Acid over Pd supported on Carbon Nanotubes.

Highly selective one-step hydrogenation of phenol to cyclohexanone, an important intermediate in the production of nylon 6 and nylon 66, is desirable but remains a challenge. Pd nanoparticles supported on nitrogen- and oxygen-functionalized carbon nanotubes (NCNTs, OCNTs) were prepared, characterized, and applied in the hydrogenation of phenol to cyclohexanone to study the effect of N-doping. Almost full conversion of phenol with high selectivity to cyclohexanone was achieved over Pd/NCNT under mild reaction conditions using either H or formic acid (FA) as a hydrogen source.

Towards a unified understanding of the copper sites in particulate methane monooxygenase: an X-ray absorption spectroscopic investigation.

The enzymatic conversion of the greenhouse gas, methane, to a liquid fuel, methanol, is performed by methane monooxygenases (MMOs) under mild conditions. The copper stoichiometry of particulate MMO (pMMO) has been long debated, with a dicopper site previously proposed on the basis of a 2.51 Å Cu-Cu feature in extended X-ray absorption fine structure (EXAFS) data.

AgCu Bimetallic Electrocatalysts for the Reduction of Biomass-Derived Compounds.

The electrochemical transformation of biomass-derived compounds (e.g., aldehyde electroreduction to alcohols) is gaining increasing interest due to the sustainability of this process that can be exploited to produce value-added products from biowastes and renewable electricity.

An electrochemical cell for in operando C nuclear magnetic resonance investigations of carbon dioxide/carbonate processes in aqueous solution.

In operando nuclear magnetic resonance (NMR) spectroscopy is one method for the online investigation of electrochemical systems and reactions. It allows for real-time observations of the formation of products and intermediates, and it grants insights into the interactions of substrates and catalysts. An in operando NMR setup for the investigation of the electrolytic reduction of at silver electrodes has been developed.

True Nature of the Transition-Metal Carbide/Liquid Interface Determines Its Reactivity.

Compound materials, such as transition-metal (TM) carbides, are anticipated to be effective electrocatalysts for the carbon dioxide reduction reaction (CORR) to useful chemicals. This expectation is nurtured by density functional theory (DFT) predictions of a break of key adsorption energy scaling relations that limit CORR at parent TMs. Here, we evaluate these prospects for hexagonal MoC in aqueous electrolytes in a multimethod experiment and theory approach.

Structure-Spectroscopy Correlations for Intermediate Q of Soluble Methane Monooxygenase: Insights from QM/MM Calculations.

The determination of the diiron core intermediate structures involved in the catalytic cycle of soluble methane monooxygenase (sMMO), the enzyme that selectively catalyzes the conversion of methane to methanol, has been a subject of intense interest within the bioinorganic scientific community. Particularly, the specific geometry and electronic structure of the intermediate that precedes methane binding, known as intermediate Q (or MMOH), has been debated for over 30 years. Some reported studies support a bis-μ-oxo-bridged Fe(IV)O closed-core conformation Fe(IV)O core, whereas others favor an open-core geometry, with a longer Fe-Fe distance.

Stable Acidic Water Oxidation with a Cobalt-Iron-Lead Oxide Catalyst Operating via a Cobalt-Selective Self-Healing Mechanism.

The instability and expense of anodes for water electrolyzers with acidic electrolytes can be overcome through the implementation of a cobalt-iron-lead oxide electrocatalyst, [Co-Fe-Pb]O , that is self-healing in the presence of dissolved metal precursors. However, the latter requirement is pernicious for the membrane and especially the cathode half-reaction since Pb and Fe precursors poison the state-of-the-art platinum H evolving catalyst. To address this, we demonstrate the invariably stable operation of [Co-Fe-Pb]O in acidic solutions through a cobalt-selective self-healing mechanism without the addition of Pb and Fe and investigate the kinetics of the process.

Tuning of Reciprocal Carbon-Electrode Properties for an Optimized Hydrogen Evolution.

Closing the material cycle for harmful and rare resources is a key criterion for sustainable and green energy systems. The concept of using scalable biomass-derived carbon electrodes to produce hydrogen from water was proposed here, satisfying the need for sustainability in the field of chemical energy conversion. The carbon electrodes exhibited not only water oxidation activity but also a strong self-oxidation when being used as anode for water splitting.

Applying Unconventional Spectroscopies to the Single-Molecule Magnets, Co(PPh ) X (X=Cl, Br, I): Unveiling Magnetic Transitions and Spin-Phonon Coupling.

Large separation of magnetic levels and slow relaxation in metal complexes are desirable properties of single-molecule magnets (SMMs). Spin-phonon coupling (interactions of magnetic levels with phonons) is ubiquitous, leading to magnetic relaxation and loss of memory in SMMs and quantum coherence in qubits. Direct observation of magnetic transitions and spin-phonon coupling in molecules is challenging.

Catalytic Oxygenation of Hydrocarbons by Mono-μ-oxo Dicopper(II) Species Resulting from O-O Cleavage of Tetranuclear Cu /Cu Peroxo Complexes.

One of the challenges of catalysis is the transformation of inert C-H bonds to useful products. Copper-containing monooxygenases play an important role in this regard. Here we show that low-temperature oxygenation of dinuclear copper(I) complexes leads to unusual tetranuclear, mixed-valent μ -peroxo [Cu /Cu ] complexes.

Reversible H Oxidation and Evolution by Hydrogenase Embedded in a Redox Polymer Film.

Efficient electrocatalytic energy conversion requires the devices to function reversibly, deliver a significant current at minimal overpotential. Redox-active films can effectively embed and stabilise molecular electrocatalysts, but mediated electron transfer through the film typically makes the catalytic response irreversible. Here, we describe a redox-active film for bidirectional (oxidation or reduction) and reversible hydrogen conversion, consisting of [FeFe] hydrogenase embedded in a low-potential, 2,2'-viologen modified hydrogel.

andelectron microscopy in heterogeneous catalysis-insights into multi-scale chemical dynamics.

This review features state-of-the-artandelectron microscopy (EM) studies of heterogeneous catalysts in gas and liquid environments during reaction. Heterogeneous catalysts are important materials for the efficient production of chemicals/fuels on an industrial scale and for energy conversion applications. They also play a central role in various emerging technologies that are needed to ensure a sustainable future for our society.

Metal Nanoparticles Immobilized on Molecularly Modified Surfaces: Versatile Catalytic Systems for Controlled Hydrogenation and Hydrogenolysis.

The synthesis and use of supported metal nanoparticle catalysts have a long-standing tradition in catalysis, typically associated with the field of heterogeneous catalysis. More recently, the development and understanding of catalytic systems composed of metal nanoparticles (NPs) that are synthesized from organometallic precursors on molecularly modified surfaces (MMSs) have opened a conceptually new approach to the design of multifunctional catalysts (NPs@MMS). These complex yet fascinating materials bridge molecular ("homogeneous") and material ("heterogeneous") approaches to catalysis and provide access to catalytic systems with tailor-made reactivity through judicious combinations of supports, molecular modifiers, and nanoparticle precursors.

Exploiting the Acceleration Voltage Dependence of EMCD.

Energy-loss magnetic chiral dichroism (EMCD) is a versatile method for measuring magnetism down to the atomic scale in transmission electron microscopy (TEM). As the magnetic signal is encoded in the phase of the electron wave, any process distorting this characteristic phase is detrimental for EMCD. For example, elastic scattering gives rise to a complex thickness dependence of the signal.

Spectroscopic Investigation of a Metal-Metal-Bonded Fe Single-Molecule Magnet with an Isolated = / Giant-Spin Ground State.

The metal-metal-bonded molecule [BuN][(L)Fe(dmf)] (Fe) was previously shown to possess a thermally isolated spin = / ground state and found to exhibit slow magnetization relaxation below a blocking temperature of ∼5 K [ , , 13949-13956]. Here, we present a comprehensive spectroscopic investigation of this unique single-molecule magnet (SMM), combining ultrawideband field-swept high-field electron paramagnetic resonance (EPR) with frequency-domain Fourier-transform terahertz EPR to accurately quantify the spin Hamiltonian parameters of Fe. Of particular importance is the near absence of a 4th-order axial zero-field splitting term, which is known to arise because of quantum mechanical mixing of spin states on account of the relatively weak spin-spin (superexchange) interactions in traditional polynuclear SMMs such as the celebrated Mn-acetate.

Calculating metalation in cells reveals CobW acquires Co for vitamin B biosynthesis while related proteins prefer Zn.

Protein metal-occupancy (metalation) in vivo has been elusive. To address this challenge, the available free energies of metals have recently been determined from the responses of metal sensors. Here, we use these free energy values to develop a metalation-calculator which accounts for inter-metal competition and changing metal-availabilities inside cells.

Comment on "Structural evidence for a dynamic metallocofactor during N reduction by Mo-nitrogenase".

Kang (Reports, 19 June 2020, p. 1381) report a structure of the nitrogenase MoFe protein that is interpreted to indicate binding of N or an N-derived species to the active-site FeMo cofactor. Independent refinement of the structure and consideration of biochemical evidence do not support this claim.

B-Cu-Zn Gas Diffusion Electrodes for CO Electroreduction to C Products at High Current Densities.

Electroreduction of CO to multi-carbon products has attracted considerable attention as it provides an avenue to high-density renewable energy storage. However, the selectivity and stability under high current densities are rarely reported. Herein, B-doped Cu (B-Cu) and B-Cu-Zn gas diffusion electrodes (GDE) were developed for highly selective and stable CO conversion to C  products at industrially relevant current densities.

The Asp1 pyrophosphatase from S. pombe hosts a [2Fe-2S] cluster in vivo.

The Schizosaccharomyces pombe Asp1 protein is a bifunctional kinase/pyrophosphatase that belongs to the highly conserved eukaryotic diphosphoinositol pentakisphosphate kinase PPIP5K/Vip1 family. The N-terminal Asp1 kinase domain generates specific high-energy inositol pyrophosphate (IPP) molecules, which are hydrolyzed by the C-terminal Asp1 pyrophosphatase domain (Asp1). Thus, Asp1 activities regulate the intracellular level of a specific class of IPP molecules, which control a wide number of biological processes ranging from cell morphogenesis to chromosome transmission.

Probing Physical Oxidation State by Resonant X-ray Emission Spectroscopy: Applications to Iron Model Complexes and Nitrogenase.

The ability of resonant X-ray emission spectroscopy (XES) to recover physical oxidation state information, which may often be ambiguous in conventional X-ray spectroscopy, is demonstrated. By combining Kβ XES with resonant excitation in the XAS pre-edge region, resonant Kβ XES (or 1s3p RXES) data are obtained, which probe the 3d final-state configuration. Comparison of the non-resonant and resonant XES for a series of high-spin ferrous and ferric complexes shows that oxidation state assignments that were previously unclear are now easily made.

Localized and Delocalized States of a Diamine Cation: Resolution of a Controversy.

Recent Rydberg spectroscopy measurements of a diamine molecule, ,'-dimethylpiperazine (DMP), indicate the existence of a localized electronic state as well as a delocalized electronic state. This implies that the cation, DMP, can similarly have its positive charge either localized on one of the N atoms or delocalized over both. This interpretation of the experiments has, however, been questioned based on coupled cluster calculations.