165 research outputs found

    Electrochemical surface science of tungsten and molybdenum oxide clusters on boron nitride nanomesh

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    In the pursuit of more efficient heterogeneous catalysts and electrocatalysts, the real-space observation of active sites at the atomic scale under reaction conditions opens exciting possibilities for establishing detailed composition–structure–reactivity relationships. In this work, we focus on the study of small oxide clusters of the early transition metals tungsten and molybdenum using electrochemical scanning tunnelling microscopy (EC-STM). The metal oxide clusters are generated directly in the aqueous electrolyte, with the metals acting as ‘electrochemical evaporator’, and this process is studied through a combination of cyclic voltammetry, electrochemical impedance spectroscopy, inductively coupled plasma–optical emission spectroscopy and high-resolution mass spectrometry. Once the transition metal oxide clusters are generated, we immobilise them on boron nitride nanomesh, a corrugated monolayer of hexagonal boron nitride on Rh(111) with unique molecular trapping properties. The immobilisation of the oxide clusters is experimentally verified using ex situ X-ray photoelectron and Raman spectroscopy, also gauging any chemical changes of the clusters compared to the dispersed state in aqueous environment. Finally, we use EC-STM to directly observe the tungsten and molybdenum oxide cluster-decorated nanomesh surface in the presence of electrolyte under electrochemical potential control. To the best of our knowledge, this is the first study where molybdenum tips have been used for EC-STM observation. By imaging tungsten oxide clusters with Mo tips and vice versa, we explore the stable combinations of substrate and tip materials and potentials towards chemically selective imaging at the atomic scale. Moving forward, we will use this knowledge to develop operando electrochemical imaging while an electrocatalytic reaction is ongoing

    Origins, evolution, domestication and diversity of Saccharomyces beer yeasts

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    Yeasts have been used for food and beverage fermentations for thousands of years. Today, numerous different strains are available for each specific fermentation process. However, the nature and extent of the phenotypic and genetic diversity and specific adaptations to industrial niches have only begun to be elucidated recently. In Saccharomyces, domestication is most pronounced in beer strains, likely because they continuously live in their industrial niche, allowing only limited genetic admixture with wild stocks and minimal contact with natural environments. As a result, beer yeast genomes show complex patterns of domestication and divergence, making both ale (S. cerevisiae) and lager (S. pastorianus) producing strains ideal models to study domestication and, more generally, genetic mechanisms underlying swift adaptation to new niches

    Optimization of Scan Strategies in Selective Laser Melting of Aluminum Parts With Downfacing Areas

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    Selective laser melting (SLM) is an additive manufacturing technique in which metal products are manufactured in a layer-by-layer manner. One of the main advantages of SLM is the large geometrical design freedom. Because of the layered build, parts with inner cavities can be produced. However, complex structures, such as downfacing areas, influence the process behavior significantly. The downfacing areas can be either horizontal or inclined structures. The first part of this work describes the process parameter optimization for noncomplex, upfacing structures to obtain relative densities above 99%. In the second part of this research, parameters are optimized for downfacing areas, both horizontal and inclined. The experimental results are compared to simulations of a thermal model, which calculates the melt pool dimensions based on the material properties (such as thermal conductivity) and process parameters (such as laser power and scan speed). The simulations show a great similarity between the thermal model and the actual process

    Close-range hyperspectral image analysis for the early detection of stress responses in individual plants in a high-throughput phenotyping platform

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    The potential of close-range hyperspectral imaging (HSI) as a tool for detecting early drought stress responses in plants grown in a high-throughput plant phenotyping platform (HTPPP) was explored. Reflectance spectra from leaves in close-range imaging are highly influenced by plant geometry and its specific alignment towards the imaging system. This induces high uninformative variability in the recorded signals, whereas the spectral signature informing on plant biological traits remains undisclosed. A linear reflectance model that describes the effect of the distance and orientation of each pixel of a plant with respect to the imaging system was applied. By solving this model for the linear coefficients, the spectra were corrected for the uninformative illumination effects. This approach, however, was constrained by the requirement of a reference spectrum, which was difficult to obtain. As an alternative, the standard normal variate (SNV) normalisation method was applied to reduce this uninformative variability. Once the envisioned illumination effects were eliminated, the remaining differences in plant spectra were assumed to be related to changes in plant traits. To distinguish the stress-related phenomena from regular growth dynamics, a spectral analysis procedure was developed based on clustering, a supervised band selection, and a direct calculation of a spectral similarity measure against a reference. To test the significance of the discrimination between healthy and stressed plants, a statistical test was conducted using a one-way analysis of variance (ANOVA) technique. The proposed analysis techniques was validated with HSI data of maize plants (Zea mays L.) acquired in a HTPPP for early detection of drought stress in maize plant. Results showed that the pre-processing of reflectance spectra with the SNV effectively reduces the variability due to the expected illumination effects. The proposed spectral analysis method on the normalized spectra successfully detected drought stress from the third day of drought induction, confirming the potential of HSI for drought stress detection studies and further supporting its adoption in HTPPP

    Reversible Redox‐Driven Crystallization in a Paracyclophane Monolayer at a Solid–Liquid Interface

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    The development and integration of cyclophanes into future functional materials require a detailed understanding of the physicochemical principles that underlie their properties, phase behavior, and in particular the relationship between structure and function. Here, electrochemically switchable crystallization of a ferrocene‐bearing 3D Janus tecton (M‐Fc) at the interface between highly oriented pyrolytic graphite (HOPG) and an electrolyte solution is demonstrated. The M‐Fc adlayer is successfully visualized under both ambient and electrochemical conditions using scanning tunneling microscopy. Voltammetric measurements show a surface‐confined redox process for the M‐Fc modified surface that drives the phase transition between a visible 2D ordered linear phase (M‐Fc0, with ferrocene in the neutral state) and an invisible gas‐like adsorption layer with high mobility when ferrocene is oxidized, M‐Fc+, and a “square scheme” mechanism explains the data. Analogous experiments in a ferrocene‐free tecton adlayer show no phase transition and confirm that the dynamics in M‐Fc are redox‐driven. On‐surface 3D nanoarchitectures are also demonstrated by forming inclusion complexes between M‐Fc and β‐cyclodextrin and device behavior through electrochemical scanning tunneling spectroscopy (STS). These results showcase the functional potential of this class of cyclophanes, which can find use in actuators, optical crystals, and other smart materials

    Membranous urethral length measurement on preoperative MRI to predict incontinence after radical prostatectomy:a literature review towards a proposal for measurement standardization

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    Objectives: To investigate the membranous urethral length (MUL) measurement and its interobserver agreement, and propose literature-based recommendations to standardize MUL measurement for increasing interobserver agreement. MUL measurements based on prostate MRI scans, for urinary incontinence risk assessment before radical prostatectomy (RP), may influence treatment decision-making in men with localised prostate cancer. Before implementation in clinical practise, MRI-based MUL measurements need standardization to improve observer agreement. Methods: Online libraries were searched up to August 5, 2022, on MUL measurements. Two reviewers performed article selection and critical appraisal. Papers reporting on preoperative MUL measurements and urinary continence correlation were selected. Extracted information included measuring procedures, MRI sequences, population mean/median values, and observer agreement. Results: Fifty papers were included. Studies that specified the MRI sequence used T2-weighted images and used either coronal images (n = 13), sagittal images (n = 18), or both (n = 12) for MUL measurements. ‘Prostatic apex’ was the most common description of the proximal membranous urethra landmark and ‘level/entry of the urethra into the penile bulb’ was the most common description of the distal landmark. Population mean (median) MUL value range was 10.4–17.1 mm (7.3–17.3 mm), suggesting either population or measurement differences. Detailed measurement technique descriptions for reproducibility were lacking. Recommendations on MRI-based MUL measurement were formulated by using anatomical landmarks and detailed descriptions and illustrations. Conclusions: In order to improve on measurement variability, a literature-based measuring method of the MUL was proposed, supported by several illustrative case studies, in an attempt to standardize MRI-based MUL measurements for appropriate urinary incontinence risk preoperatively. Clinical relevance statement: Implementation of MUL measurements into clinical practise for personalized post-prostatectomy continence prediction is hampered by lack of standardization and suboptimal interobserver agreement. Our proposed standardized MUL measurement aims to facilitate standardization and to improve the interobserver agreement. Key Points: • Variable approaches for membranous urethral length measurement are being used, without detailed description and with substantial differences in length of the membranous urethra, hampering standardization. • Limited interobserver agreement for membranous urethral length measurement was observed in several studies, while preoperative incontinence risk assessment necessitates high interobserver agreement. • Literature-based recommendations are proposed to standardize MRI-based membranous urethral length measurement for increasing interobserver agreement and improving preoperative incontinence risk assessment, using anatomical landmarks on sagittal T2-weighted images.</p

    Ambient Bistable Single Dipole Switching in a Molecular Monolayer

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    Reported here is a molecular dipole that self‐assembles into highly ordered patterns at the liquid‐solid interface, and it can be switched at room temperature between a bright and a dark state at the single‐molecule level. Using a scanning tunneling microscope (STM) under suitable bias conditions, binary information can be written at a density of up to 41 Tb cm−2 (256 Tb/in2). The written information is stable during reading at room temperature, but it can also be erased at will, instantly, by proper choice of tunneling conditions. DFT calculations indicate that the contrast and switching mechanism originate from the stacking sequence of the molecular dipole, which is reoriented by the electric field between the tip and substrate
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