ABSTRACT
The influence of surface morphology and the oxidation state on the electrocatalytic activity of nanostructured electrodes is well recognized, yet disentangling their individual roles in specific reactions remains challenging. Here, we investigated the electrooxidation of sulfite ions in an alkaline environment using cyclic voltammetry on copper oxide nanostructured electrodes with different oxidation states and morphologies but with similar active areas. To this aim, we synthesized nanostructured Cu films made of nanoparticles or nanorods on top of glassy carbon electrodes. Our findings showed an enhanced sensitivity and a lower detection threshold when utilizing Cu(I) over Cu(II). Density functional theory-based thermochemical analysis revealed the underlying oxidation mechanism, indicating that while the energy gain associated with the process is comparable for both oxide surfaces, the desorption energy barrier for the resulting sulfate molecules is three times higher on Cu(II). This becomes the limiting step of the reaction kinetics and diminishes the overall electrooxidation efficiency. Our proposed mechanism relies on the tautomerization of hydroxyl groups confined on the surface of Cu-based electrodes. This mechanism might be applicable to electrochemical reactions involving other sulfur compounds that hold technological significance.
ABSTRACT
Tip-enhanced Raman spectroscopy (TERS) under ultrahigh vacuum and cryogenic conditions enables exploration of the relations between the adsorption geometry, electronic state, and vibrational fingerprints of individual molecules. TERS capability of reflecting spin states in open-shell molecular configurations is yet unexplored. Here, we use the tip of a scanning probe microscope to lift a perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) molecule from a metal surface to bring it into an open-shell spin one-half anionic state. We reveal a correlation between the appearance of a Kondo resonance in differential conductance spectroscopy and concurrent characteristic changes captured by the TERS measurements. Through a detailed investigation of various adsorbed and tip-contacted PTCDA scenarios, we infer that the Raman scattering on suspended PTCDA is resonant with a higher excited state. Theoretical simulation of the vibrational spectra enables a precise assignment of the individual TERS peaks to high-symmetry Ag modes, including the fingerprints of the observed spin state. These findings highlight the potential of TERS in capturing complex interactions between charge, spin, and photophysical properties in nanoscale molecular systems and suggest a pathway for designing single-molecule spin-optical devices.
ABSTRACT
Metabolic dysfunction-associated steatotic liver disease (MASLD) is a complex disorder whose prevalence is rapidly growing in South America. The disturbances in the microbiota-gut-liver axis impact the liver damaging processes toward fibrosis. Gut microbiota status is shaped by dietary and lifestyle factors, depending on geographic location. We aimed to identify microbial signatures in a group of Chilean MASLD patients. Forty subjects were recruited, including healthy controls (HCs), overweight/obese subjects (Ow/Ob), patients with MASLD without fibrosis (MASLD/F-), and MASLD with fibrosis (MASLD/F+). Both MASLD and fibrosis were detected through elastography and/or biopsy, and fecal microbiota were analyzed through deep sequencing. Despite no differences in α- and ß-diversity among all groups, a higher abundance of Bilophila and a lower presence of Defluviitaleaceae, Lachnospiraceae ND3007, and Coprobacter was found in MASLD/F- and MASLD/F+, compared to HC. Ruminococcaceae UCG-013 and Sellimonas were more abundant in MASLD/F+ than in Ow/Ob; both significantly differed between MASLD/F- and MASLD/F+, compared to HC. Significant positive correlations were observed between liver stiffness and Bifidobacterium, Prevotella, Sarcina, and Acidaminococcus abundance. Our results show that MASLD is associated with changes in bacterial taxa that are known to be involved in bile acid metabolism and SCFA production, with some of them being more specifically linked to fibrosis.
Subject(s)
Gastrointestinal Microbiome , Humans , Male , Female , Middle Aged , Adult , Liver Cirrhosis/microbiology , Liver Cirrhosis/metabolism , Liver Cirrhosis/pathology , Feces/microbiology , Liver/metabolism , Liver/pathology , Fatty Liver/microbiology , Fatty Liver/metabolism , Fatty Liver/pathology , Disease Progression , Obesity/microbiology , Obesity/complications , Obesity/metabolism , Chile , Bacteria/classification , Bacteria/isolation & purification , Bacteria/genetics , Bacteria/metabolism , AgedABSTRACT
Correction for 'In situ observation of the on-surface thermal dehydrogenation of n-octane on Pt(111)' by Daniel Arribas et al., Nanoscale, 2023, https://doi.org/10.1039/d3nr02564k.
ABSTRACT
The catalytic dehydrogenation of alkanes constitutes a key step for the industrial conversion of these inert sp3-bonded carbon chains into other valuable unsaturated chemicals. To this end, platinum-based materials are among the most widely used catalysts. In this work, we characterize the thermal dehydrogenation of n-octane (n-C8H18) on Pt(111) under ultra-high vacuum using synchrotron-radiation X-ray photoelectron spectroscopy, temperature-programmed desorption and scanning tunneling microscopy, combined with ab initio calculations. At low activation temperatures, two different dehydrogenation stages are observed. At 330 K, n-C8H18 effectively undergoes a 100% regioselective single C-H bond cleavage at one methyl end. At 600 K, the chemisorbed molecules undergo a double dehydrogenation, yielding double bonds in their carbon skeletons. Diffusion of the dehydrogenated species leads to the formation of carbon molecular clusters, which represents the first step towards poisoning of the catalyst. Our results reveal the chemical mechanisms behind the first stages of alkane dehydrogenation on a platinum model surface at the atomic scale, paving the way for designing more efficient dehydrogenation catalysts.
ABSTRACT
To develop a novel algorithm based on ray tracing, simulated visual performance and through-focus optimization for an accurate intraocular lens (IOL) power calculation. Custom-developed algorithms for ray tracing optimization (RTO) were used to combine the natural corneal higher-order aberrations (HOAs) with multiple sphero-cylindrical corrections in 210 higher order statistical eye models for developing keratoconus. The magnitude of defocus and astigmatism producing the maximum Visual Strehl was considered as the optimal sphero-cylindrical target for IOL power calculation. Corneal astigmatism and the RMS HOAs ranged from - 0.64 ± 0.35D and 0.10 ± 0.04 µm (0-months) to - 3.15 ± 1.38D and 0.82 ± 0.47 µm (120-months). Defocus and astigmatism target was close to neutral for eyes with low amount of HOAs (0 and 12-months), where 91.66% of eyes agreed within ± 0.50D in IOL power calculation (RTO vs. SRK/T). However, corneas with higher amounts of HOAs presented greater visual improvement with an optimized target. In these eyes (24- to 120-months), only 18.05% of eyes agreed within ± 0.50D (RTO vs. SRK/T). The power difference exceeded 3D in 42.2% while the cylinder required adjustments larger than 3D in 18.4% of the cases. Certain amounts of lower and HOAs may interact favourably to improve visual performance, shifting therefore the refractive target for IOL power calculation.
Subject(s)
Astigmatism , Keratoconus , Lenses, Intraocular , Phacoemulsification , Humans , Visual Acuity , Refraction, Ocular , Cornea , Optics and PhotonicsABSTRACT
Non-contact vibration measurements are relevant for non-invasively characterizing the mechanical behavior of structures. This paper presents a novel methodology for full-field vibrational analysis at high frequencies using the three-dimensional digital image correlation technique combined with the projection of a speckle pattern. The method includes stereo calibration and image processing routines for accurate three-dimensional data acquisition. Quantitative analysis allows the extraction of several deformation parameters, such as the cross-correlation coefficients, shape and intensity, as well as the out-of-plane displacement fields and mode shapes. The potential of the methodology is demonstrated on an Unmanned Aerial Vehicle wing made of composite material, followed by experimental validation with reference accelerometers. The results obtained with the projected three-dimensional digital image correlation show a percentage of error below 5% compared with the measures of accelerometers, achieving, therefore, high sensitivity to detect the dynamic modes in structures made of composite material.
Subject(s)
Imaging, Three-Dimensional , Vibration , Calibration , Imaging, Three-Dimensional/methodsABSTRACT
Interplay between motion of nuclei and excitations has an important role in molecular photophysics of natural and artificial structures. Here we provide a detailed analysis of coupling between quantized librational modes (librons) and charged excited states (trions) on single phthalocyanine dyes adsorbed on a surface. By means of tip-induced electroluminescence performed with a scanning probe microscope, we identify libronic signatures in spectra of chirally adsorbed phthalocyanines and find that these signatures are absent from spectra of symmetrically adsorbed species. We create a model of the libronic coupling based on the Franck-Condon principle to simulate the spectral features. Experimentally measured librational spectra match very well the theoretically calculated librational eigenenergies and peak intensities (Franck-Condon factors). Moreover, the comparison reveals an unexpected depopulation channel for the zero libron of the excited state that can be effectively controlled by tuning the size of the nanocavity. Our results showcase the possibility of characterizing the dynamics of molecules by their low-energy molecular modes using µeV-resolved tip-enhanced spectroscopy.
ABSTRACT
[This corrects the article DOI: 10.1371/journal.pone.0240933.].
ABSTRACT
Given the relevance of the effects that weight loss can generate on the physical performance in athletes, this study performed a systematic review with meta-analysis of the published literature on rapid weight loss (RWL) and examined its impact on the physical performance in Official Olympic combat sports athletes. The "Preferred Reporting Items for Systematic Reviews and Meta-Analysis" (PRISMA) guidelines were followed to ensure an ethical and complete reporting of the findings. PubMed, SPORT Discus, and EBSCO were the electronic databases explored for article retrieval and selection. The following string was applied: "RWL" OR "weight loss" OR "weight reduction" AND "judo" OR "wrestling" or "taekwondo" or "boxing" AND "performance." Based on the quality analysis, conducted according to the "Tool for the assessment of study quality and reporting in exercise training studies" (TESTEX), ten articles achieved a score >6 points. The meta-analysis showed a significant difference in pre- vs. post-weight loss (p = 0.003) and no effects in pre- vs. post-power and strength performance analysis (p > 0.05 for both results). Based on our systematic review and meta-analysis of the literature, RWL up to ≤5% of the body mass in less than 7 days does not influence performance outcomes in Official Olympic combat athletes with weight classes, considering the strength and power measures.
ABSTRACT
Purpose: The purpose of this study was to assess the impact of different intracorneal ring segments (ICRS) combinations on corneal morphology and visual performance on patients with keratoconus. Methods: A total of 124 eyes from 96 patients who underwent ICRS surgery were analyzed and classified into 7 groups based on ICRS disposition and the diameter of the surgical zone (5- and 6-mm). Pre- and postoperative complete ophthalmological examinations were conducted. Corneal geometry, volume, and symmetry were studied. Zernike polynomials were used to build a virtual ray-tracing model to evaluate optical aberrations and the Visual Strehl (VS). Results: ICRS induced significant flattening across the cornea, being more pronounced on the anterior (+0.38 mm, P < 0.001) than on the posterior (+0.15 mm, P < 0.001) corneal radius. Asphericity experienced a larger change for a 6-mm surgical zone diameter (from -1.23 ± 1.1 to -1.86 ± 1.2, P < 0.001) than for a 5-mm zone (from -1.99 ± 1.1 to -2.10 ± 1.5, P = 0.536). Mean astigmatism was reduced by 2.05 D (P < 0.001). Combination four was the most effective in reducing astigmatism. Coma decreased by 30% on average and combination one produced an average reduction by 51% (P < 0.05). Patients experienced significant improvement in visual performance, best corrected visual acuity increased from 0.57 ± 0.21 to 0.69 ± 0.21 and VS changed from 0.049 ± 0.02 to 0.065 ± 0.041. Conclusions: ICRS combinations implanted within 5 mm diameter zone are more effective in flattening the cornea, whereas those implanted on 6 mm diameter are as effective in reducing astigmatism and are a good choice if the asymmetry and the intended flattening are smaller. Combinations with asymmetrical implants are the best option to regularize corneal surface. Translational Relevance: This study uses methods and metrics of optical research applied to daily clinical practice.
Subject(s)
Astigmatism , Keratoconus , Astigmatism/surgery , Corneal Stroma/diagnostic imaging , Corneal Stroma/surgery , Corneal Topography , Eye, Artificial , Humans , Keratoconus/surgery , Prosthesis Implantation/methods , Refraction, Ocular , Visual AcuityABSTRACT
The use of physical vapor deposition methods in the fabrication of catalyst layers holds promise for enhancing the efficiency of future carbon capture and utilization processes such as the CO2 reduction reaction (CO2RR). Following that line of research, we report in this work the application of a sputter gas aggregation source (SGAS) and a multiple ion cluster source type apparatus, for the controlled synthesis of CuOx nanoparticles (NPs) atop gas diffusion electrodes. By varying the mass loading, we achieve control over the balance between methanation and multicarbon formation in a gas-fed CO2 electrolyzer and obtain peak CH4 partial current densities of -143 mA cm-2 (mass activity of 7.2 kA/g) with a Faradaic efficiency (FE) of 48% and multicarbon partial current densities of -231 mA cm-2 at 76% FE (FEC2H4 = 56%). Using atomic force microscopy, electron microscopy, and quasi in situ X-ray photoelectron spectroscopy, we trace back the divergence in hydrocarbon selectivity to differences in NP film morphology and rule out the influence of both the NP size (3-15 nm, >20 µg cm-2) and in situ oxidation state. We show that the combination of the O2 flow rate to the aggregation zone during NP growth and deposition time, which affect the NP production rate and mass loading, respectively, gives rise to the formation of either densely packed CuOx NPs or rough three-dimensional networks made from CuOx NP building blocks, which in turn affects the governing CO2RR mechanism. This study highlights the potential held by SGAS-generated NP films for future CO2RR catalyst layer optimization and upscaling, where the NPs' tunable properties, homogeneity, and the complete absence of organic capping agents may prove invaluable.
ABSTRACT
Entanglement of excitons holds great promise for the future of quantum computing, which would use individual molecular dyes as building blocks of their circuitry. Studying entangled excitonic eigenstates emerging in coupled molecular assemblies in the near-field with submolecular resolution has the potential to bring insight into the photophysics of these fascinating quantum phenomena. In contrast to far-field spectroscopies, near-field spectroscopic mapping permits direct identification of the individual eigenmodes, type of exciton coupling, including excited states otherwise inaccessible in the far field (dark states). Here we combine tip-enhanced spectromicroscopy with atomic force microscopy to inspect delocalized single-exciton states of charged molecular assemblies engineered from individual perylenetetracarboxylic dianhydride (PTCDA) molecules. Hyperspectral mapping of the eigenstates and comparison with calculated many-body optical transitions reveals a second low-lying excited state of the anion monomers and its role in the exciton entanglement within the assemblies. We demonstrate control over the exciton coupling by switching the assembly charge states. Our results reveal the possibility of tailoring excitonic properties of organic dye aggregates for advanced functionalities and establish the methodology to address them individually at the nanoscale.
ABSTRACT
Development of sustainable processes for hydrocarbons synthesis is a fundamental challenge in chemistry since these are of unquestionable importance for the production of many essential synthetic chemicals, materials and carbon-based fuels. Current industrial processes rely on non-abundant metal catalysts, temperatures of hundreds of Celsius and pressures of tens of bars. We propose an alternative gas phase process under mild reaction conditions using only atomic carbon, molecular hydrogen and an inert carrier gas. We demonstrate that the presence of CH2 and H radicals leads to efficient C-C chain growth, producing micron-length fibres of unbranched alkanes with an average length distribution between C23-C33. Ab-initio calculations uncover a thermodynamically favourable methylene coupling process on the surface of carbonaceous nanoparticles, which is kinematically facilitated by a trap-and-release mechanism of the reactants and nanoparticles that is confirmed by a steady incompressible flow simulation. This work could lead to future alternative sustainable synthetic routes to critical alkane-based chemicals or fuels.
ABSTRACT
Optical spectromicroscopies, which can reach atomic resolution due to plasmonic enhancement, are perturbed by spontaneous intensity modifications. Here, we study such fluctuations in plasmonic electroluminescence at the single-atom limit profiting from the precision of a low-temperature scanning tunneling microscope. First, we investigate the influence of a controlled single-atom transfer from the tip to the sample on the plasmonic properties of the junction. Next, we form a well-defined atomic contact of several quanta of conductance. In contact, we observe changes of the electroluminescence intensity that can be assigned to spontaneous modifications of electronic conductance, plasmonic excitation, and optical antenna properties all originating from minute atomic rearrangements at or near the contact. Our observations are relevant for the understanding of processes leading to spontaneous intensity variations in plasmon-enhanced atomic-scale spectroscopies such as intensity blinking in picocavities.
ABSTRACT
The interest in the research of the structural and electronic properties between graphene and lithium has bloomed since it has been proven that the use of graphene as an anode material in lithium-ion batteries ameliorates their performance and stability. Here, we investigate an alternative route to intercalate lithium underneath epitaxially grown graphene on iridium by means of photon irradiation. We grow thin films of LiCl on top of graphene on Ir(111) and irradiate the system with soft X-ray photons, which leads to a cascade of physicochemical reactions. Upon LiCl photodissociation, we find fast chlorine desorption and a complex sequence of lithium intercalation processes. First, it intercalates, forming a disordered structure between graphene and iridium. On increasing the irradiation time, an ordered Li(1 × 1) surface structure forms, which evolves upon extensive photon irradiation. For sufficiently long exposure times, lithium diffusion within the metal substrate is observed. Thermal annealing allows for efficient lithium desorption and full recovery of the pristine G/Ir(111) system. We follow in detail the photochemical processes using a multitechnique approach, which allows us to correlate the structural, chemical, and electronic properties for every step of the intercalation process of lithium underneath graphene.
ABSTRACT
Constant-amplitude bias modulation over a broad range of microwave frequencies is a prerequisite for application in high-resolution spectroscopic techniques in a tunneling junction as e.g. electron spin resonance spectroscopy or optically detected paramagnetic resonance. Here, we present an optical method for determining the frequency-dependent magnitude of the transfer function of a dedicated high-frequency line integrated with a scanning probe microscope. The method relies on determining the energy cutoff of the plasmonic electroluminescence spectrum, which is linked to the energies of the electrons inelastically tunneling across the junction. We develop an easy-to-implement procedure for effective compensation of an RF line and determination of the transfer function magnitude in the GHz range. We test our method with conventional electronic calibration and find a perfect agreement.
ABSTRACT
Light sources on the scale of single molecules can be addressed and characterized at their proper sub-nanometer scale by scanning tunneling microscopy-induced luminescence (STML). Such a source can be driven by defined short charge pulses while the luminescence is detected with sub-nanosecond resolution. We introduce an approach to concurrently image the molecular emitter, which is based on an individual defect, with its local environment along with its luminescence dynamics at a resolution of a billion frames per second. The observed dynamics can be assigned to the single electron capture occurring in the low-nanosecond regime. While the emitter's location on the surface remains fixed, the scanning of the tip modifies the energy landscape for charge injection into the defect. The principle of measurement is extendable to fundamental processes beyond charge transfer, like exciton diffusion.
ABSTRACT
Charged optical excitations (trions) generated by charge carrier injection are crucial for emerging optoelectronic technologies as they can be produced and manipulated by electric fields. Trions and neutral excitons can be efficiently induced in single molecules by means of tip-enhanced spectromicroscopic techniques. However, little is known of the exciton-trion dynamics at single molecule level as this requires methods permitting simultaneous subnanometer and subnanosecond characterization. Here, we investigate exciton-trion dynamics by phase fluorometry, combining radio frequency modulated scanning tunnelling luminescence with time-resolved single photon detection. We generate excitons and trions in single Zinc Phthalocyanine (ZnPc) molecules on NaCl/Ag(111), and trace the evolution of the system in the picosecond range. We explore the dependence of effective lifetimes on bias voltage and describe the conversion mechanism from neutral excitons to trions, via charge capture, as the primary pathway to trion formation. We corroborate the dynamics of the system by a causally deterministic four-state model.
ABSTRACT
Silicon is present in interstellar dust grains, meteorites and asteroids, and to date thirteen silicon-bearing molecules have been detected in the gas-phase towards late-type stars or molecular clouds, including silane and silane derivatives. In this work, we have experimentally studied the interaction between atomic silicon and hydrogen under physical conditions mimicking those at the atmosphere of evolved stars. We have found that the chemistry of Si, H and H2 efficiently produces silane (SiH4), disilane (Si2H6) and amorphous hydrogenated silicon (a-Si:H) grains. Silane has been definitely detected towards the carbon-rich star IRC+10216, while disilane has not been detected in space yet. Thus, based on our results, we propose that gas-phase reactions of atomic Si with H and H2 are a plausible source of silane in C-rich AGBs, although its contribution to the total SiH4 abundance may be low in comparison with the suggested formation route by catalytic reactions on the surface of dust grains. In addition, the produced a-Si:H dust analogs decompose into SiH4 and Si2H6 at temperatures above 500 K, suggesting an additional mechanism of formation of these species in envelopes around evolved stars. We have also found that the exposure of these dust analogs to water vapor leads to the incorporation of oxygen into Si-O-Si and Si-OH groups at the expense of SiH moieties, which implies that, if this type of grains are present in the interstellar medium, they will be probably processed into silicates through the interaction with water ices covering the surface of dust grains.