Atomic-precision control of plasmon-induced single-molecule switching in a metal-semiconductor nanojunction.

Atomic-scale control of photochemistry facilitates extreme miniaturisation of optoelectronic devices. Localised surface plasmons, which provide strong confinement and enhancement of electromagnetic fields at the nanoscale, secure a route to achieve sub-nanoscale reaction control. Such local plasmon-induced photochemistry has been realised only in metallic structures so far.

Single-molecule tip-enhanced Raman spectroscopy of C on the Si(111)-(7 × 7) surface.

Tip-enhanced Raman spectroscopy (TERS), combined with low-temperature scanning tunnelling microscopy (STM), has emerged as a highly sensitive method for chemical characterization, offering even sub-molecular resolution. However, its exceptional sensitivity is generally limited to molecules adsorbed onto plasmonic surfaces. Here we demonstrate single-molecule TERS for fullerene (C) adsorbed on the Si(111)-(7 × 7) reconstructed surface.

Toward Realistic Models of the Electrocatalytic Oxygen Evolution Reaction.

The electrocatalytic oxygen evolution reaction (OER) supplies the protons and electrons needed to transform renewable electricity into chemicals and fuels. However, the OER is kinetically sluggish; it operates at significant rates only when the applied potential far exceeds the reversible voltage. The origin of this overpotential is hidden in a complex mechanism involving multiple electron transfers and chemical bond making/breaking steps.

Structure and Conformation Determine Gas-Phase Infrared Spectra of Detergents.

Native mass spectrometry of membrane proteins relies on non-ionic detergents which protect the protein during transfer from solution into the gas phase. Once in the gas phase, the detergent micelle must be efficiently removed, which is usually achieved by collision-induced dissociation (CID). Recently, infrared multiple photon dissociation (IRMPD) has emerged as an alternative activation method for the analysis of membrane proteins, which has led to a growing interest in detergents that efficiently absorb infrared light.

Reversible metal cluster formation on Nitrogen-doped carbon controlling electrocatalyst particle size with subnanometer accuracy.

Copper and nitrogen co-doped carbon catalysts exhibit a remarkable behavior during the electrocatalytic CO reduction (CORR), namely, the formation of metal nanoparticles from Cu single atoms, and their subsequent reversible redispersion. Here we show that the switchable nature of these species holds the key for the on-demand control over the distribution of CORR products, a lack of which has thus far hindered the wide-spread practical adoption of CORR. By intermitting pulses of a working cathodic potential with pulses of anodic potential, we were able to achieve a controlled fragmentation of the Cu particles and partial regeneration of single atom sites.

Studying the Intrinsic Reactivity of Chromanes by Gas-Phase Infrared Spectroscopy.

Tandem mass spectrometry is routinely used for the structural analysis of organic molecules, but many fragmentation reactions are not well understood. Because several potential structures can correspond to a measured mass, the assignment of product ions is ambiguous using mass spectrometry alone. Here, we combine mass spectrometry with high-resolution gas-phase infrared spectroscopy and computational chemistry tools to identify product ion structures and derive collision-induced fragmentation mechanisms of the chromane derivatives Trolox and Methyltrolox.

Revealing the structure of the active sites for the electrocatalytic CO reduction to CO over Co single atom catalysts using operando XANES and machine learning.

Transition-metal nitrogen-doped carbons (TM-N-C) are emerging as a highly promising catalyst class for several important electrocatalytic processes, including the electrocatalytic CO reduction reaction (CORR). The unique local environment around the singly dispersed metal site in TM-N-C catalysts is likely to be responsible for their catalytic properties, which differ significantly from those of bulk or nanostructured catalysts. However, the identification of the actual working structure of the main active units in TM-N-C remains a challenging task due to the fluctional, dynamic nature of these catalysts, and scarcity of experimental techniques that could probe the structure of these materials under realistic working conditions.

Terahertz Spin-Conductance Spectroscopy: Probing Coherent and Incoherent Ultrafast Spin Tunneling.

Thin-film stacks | consisting of a ferromagnetic-metal layer and a heavy-metal layer are spintronic model systems. Here, we present a method to measure the ultrabroadband spin conductance across a layer between and at terahertz frequencies, which are the natural frequencies of spin-transport dynamics. We apply our approach to MgO tunneling barriers with thickness = 0-6 Å.

Accessing Ultrafast Spin-Transport Dynamics in Copper Using Broadband Terahertz Spectroscopy.

We study the spatiotemporal dynamics of ultrafast electron spin transport across nanometer-thick copper layers using ultrabroadband terahertz emission spectroscopy. Our analysis of temporal delays, broadening, and attenuation of the spin-current pulse reveals ballisticlike propagation of the pulse peak, approaching the Fermi velocity, and diffusive features including a significant velocity dispersion. A comparison to the frequency-dependent Fick's law identifies the diffusion-dominated transport regime for distances >2  nm.

Obtaining Robust Density Functional Tight-Binding Parameters for Solids across the Periodic Table.

The density functional tight-binding (DFTB) approach allows electronic structure-based simulations at length and time scales far beyond what is possible with first-principles methods. This is achieved by using minimal basis sets and empirical approximations. Unfortunately, the sparse availability of parameters across the periodic table is a significant barrier to the use of DFTB in many cases.

Chemokine Oligomers and the Impact of Fondaparinux Binding.

Heparin, a widely used clinical anticoagulant, is generally well-tolerated; however, approximately 1% of patients develop heparin-induced thrombocytopenia (HIT), a serious side effect. While efforts to understand the role of chemokines in HIT development are ongoing, certain aspects remain less studied, such as the stabilization of chemokine oligomers by heparin. Here, we conducted a combined ion mobility-native mass spectrometry study to investigate the stability of chemokine oligomers and their complexes with fondaparinux, a synthetic heparin analog.

Investigation of the Proton-Bound Dimer of Dihydrogen Phosphate and Formate Using Infrared Spectroscopy in Helium Droplets.

Understanding the structural and dynamic properties of proton-bound complexes is crucial for elucidating fundamental aspects of chemical reactivity and molecular interactions. In this work, the proton-bound complex between dihydrogen phosphate and formate, and its deuterated counterparts, is investigated using IR action spectroscopy in helium droplets. Contrary to the initial expectation that the stronger phosphoric acid would donate a proton to formate, both experiment and theory show that all exchangeable protons are located in the phosphate moiety.

Correlative In Situ Spectro-Microscopy of Supported Single CuO Nanoparticles: Unveiling the Relationships between Morphology and Chemical State during Thermal Reduction.

The activity, selectivity, and lifetime of nanocatalysts critically depend on parameters such as their morphology, support, chemical composition, and oxidation state. Thus, correlating these parameters with their final catalytic properties is essential. However, heterogeneity across nanoparticles (NPs) is generally expected.

Operando Raman spectroscopy uncovers hydroxide and CO species enhance ethanol selectivity during pulsed CO electroreduction.

Pulsed CO electroreduction (CORR) has recently emerged as a facile way to in situ tune the product selectivity, in particular toward ethanol, without re-designing the catalytic system. However, in-depth mechanistic understanding requires comprehensive operando time-resolved studies to identify the kinetics and dynamics of the electrocatalytic interface. Here, we track the adsorbates and the catalyst state of pre-reduced CuO nanocubes ( ~ 30 nm) during pulsed CORR using sub-second time-resolved operando Raman spectroscopy.

Facet Dependence of the Oxygen Evolution Reaction on CoO, CoFeO, and FeO Epitaxial Film Electrocatalysts.

The main obstacle for the electrocatalytic production of "green hydrogen" is finding suitable electrocatalysts which operate highly efficiently over extended periods of time. The topic of this study is the oxygen evolution reaction (OER), one of the half-reactions of water splitting. It is complex and has intricate kinetics, which impairs the reaction efficiency.

Labeling of Mucin-Type -Glycans for Quantification Using Liquid Chromatography and Fluorescence Detection.

-glycosylation is a common post-translational modification that is essential for the defensive properties of mucus barriers. Incomplete and altered -glycosylation is often linked to severe diseases, such as cancer, cystic fibrosis, and chronic obstructive pulmonary disease. Originating from a nontemplate-driven biosynthesis, mucin-type -glycan structures are very complex.

Cation Effects on the Acidic Oxygen Reduction Reaction at Carbon Surfaces.

Hydrogen peroxide (HO) is a widely used green oxidant. Until now, research has focused on the development of efficient catalysts for the two-electron oxygen reduction reaction (2e ORR). However, electrolyte effects on the 2e ORR have remained little understood.

Spiral packing and chiral selectivity in model membranes probed by phase-resolved sum-frequency generation microscopy.

Since the lipid raft model was developed at the end of the last century, it became clear that the specific molecular arrangements of phospholipid assemblies within a membrane have profound implications in a vast range of physiological functions. Studies of such condensed lipid islands in model systems using fluorescence and Brewster angle microscopies have shown a wide range of sizes and morphologies, with suggestions of substantial in-plane molecular anisotropy and mesoscopic structural chirality. Whilst these variations can significantly alter many membrane properties including its fluidity, permeability and molecular recognition, the details of the in-plane molecular orientations underlying these traits remain largely unknown.

Compression of a Stearic Acid Surfactant Layer on Water Investigated by Ambient Pressure X-ray Photoelectron Spectroscopy.

We present a combined Langmuir-Pockels trough and ambient pressure X-ray photoelectron spectroscopy (APXPS) study of the compression of stearic acid surfactant layers on neat water. Changes in the packing density of the molecules are directly determined from C 1s and O 1s APXPS data. The experimental data are fit with a 2D model for the stearic acid coverage.

Ion mobility-tandem mass spectrometry of mucin-type O-glycans.

The dense O-glycosylation of mucins plays an important role in the defensive properties of the mucus hydrogel. Aberrant glycosylation is often correlated with inflammation and pathology such as COPD, cancer, and Crohn's disease. The inherent complexity of glycans and the diversity in the O-core structure constitute fundamental challenges for the analysis of mucin-type O-glycans.

Infrared Multiphoton Dissociation Enables Top-Down Characterization of Membrane Protein Complexes and G Protein-Coupled Receptors.

Membrane proteins are challenging to analyze by native mass spectrometry (MS) as their hydrophobic nature typically requires stabilization in detergent micelles that are removed prior to analysis via collisional activation. There is however a practical limit to the amount of energy which can be applied, which often precludes subsequent characterization by top-down MS. To overcome this barrier, we have applied a modified Orbitrap Eclipse Tribrid mass spectrometer coupled to an infrared laser within a high-pressure linear ion trap.

Enhanced Methanol Synthesis from CO Hydrogenation Achieved by Tuning the Cu-ZnO Interaction in ZnO/CuO Nanocube Catalysts Supported on ZrO and SiO.

The nature of the Cu-Zn interaction and especially the role of Zn in Cu/ZnO catalysts used for methanol synthesis from CO hydrogenation are still debated. Migration of Zn onto the Cu surface during reaction results in a Cu-ZnO interface, which is crucial for the catalytic activity. However, whether a Cu-Zn alloy or a Cu-ZnO structure is formed and the transformation of this interface under working conditions demand further investigation.

Role of Fe decoration on the oxygen evolving state of CoO nanocatalysts.

The production of green hydrogen through alkaline water electrolysis is the key technology for the future carbon-neutral industry. Nanocrystalline CoO catalysts are highly promising electrocatalysts for the oxygen evolution reaction and their activity strongly benefits from Fe surface decoration. However, limited knowledge of decisive catalyst motifs at the atomic level during oxygen evolution prevents their knowledge-driven optimization.