Alteration of Gut Microbiota Composition in the Progression of Liver Damage in Patients with Metabolic Dysfunction-Associated Steatotic Liver Disease (MASLD).

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.

Three-Dimensional Digital Image Correlation Based on Speckle Pattern Projection for Non-Invasive Vibrational Analysis.

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.

Atomic-Scale Structural Fluctuations of a Plasmonic Cavity.

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.

Gigahertz Frame Rate Imaging of Charge-Injection Dynamics in a Molecular Light Source.

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.

Crystalline lens gradient refractive index distribution in the guinea pig.

PURPOSE: The crystalline lens undergoes morphological and functional changes with age and may also play a role in eye emmetropisation. Both the geometry and the gradient index of refraction (GRIN) distribution contribute to the lens optical properties. We studied the lens GRIN in the guinea pig, a common animal model to study myopia. METHODS: Lenses were extracted from guinea pigs (Cavia porcellus) at 18 days of age (n = 4, three monolaterally treated with negative lenses and one untreated) and 39 days of age (n = 4, all untreated). Treated eyes were myopic (-2.07 D on average) and untreated eyes hyperopic (+3.3 D), as revealed using streak retinoscopy in the live and cyclopeged animals. A custom 3D spectral domain optical coherence tomography (OCT) system (λ = 840 nm, Δλ = 50 nm) was used to image the enucleated crystalline lens at two orientations. Custom algorithms were used to estimate the lens shape and GRIN was modelled with four variables that were reconstructed using the OCT data and a minimisation algorithm. Ray tracing was used to calculate the optical power and spherical aberration assuming a homogeneous refractive index or the estimated GRIN. RESULTS: Guinea pig lenses exhibited nearly parabolic GRIN profiles. When comparing the two age groups (18- and 39 day-old) there was a significant increase in the central thickness (from 3.61 to 3.74 mm), and in the refractive index of the surface (from 1.362 to 1.366) and the nucleus (from 1.443 to 1.454). The presence of GRIN shifted the spherical aberration (-4.1 µm on average) of the lens towards negative values. CONCLUSIONS: The guinea pig lens exhibits a GRIN profile with surface and nucleus refractive indices that increase slightly during the first days of life. GRIN plays a major role in the lens optical properties and should be incorporated into computational guinea pig eye models to study emmetropisation, myopia development and ageing.

Charge Carrier Injection Electroluminescence with CO-Functionalized Tips on Single Molecular Emitters.

We investigate electroluminescence of single molecular emitters on NaCl on Ag(111) and Au(111) with submolecular resolution in a low-temperature scanning probe microscope with tunneling current, atomic force, and light detection capabilities. The role of the tip state is studied in the photon maps of a prototypical emitter, zinc phthalocyanine (ZnPc), using metal and CO-metal tips. CO-functionalization is found to have an impact on the resolution and contrast of the photon maps due to the localized overlap of the p-orbitals on the tip with the molecular orbitals of the emitter. The possibility of using the same CO-functionalized tip for tip-enhanced photon detection and high resolution atomic force is demonstrated. We study the electroluminescence of ZnPc, induced by charge carrier injection at sufficiently high bias voltages. We propose that the distinct level alignment of the ZnPc frontier orbitals with the Au(111) and Ag(111) Fermi levels governs the primary excitation mechanisms as the injection of electrons and holes from the tip into the molecule, respectively. These findings put forward the importance of the tip status in the photon maps and contribute to a better understanding of the photophysics of organic molecules on surfaces.

A Single Hydrogen Molecule as an Intensity Chopper in an Electrically Driven Plasmonic Nanocavity.

Photon statistics is a powerful tool for characterizing the emission dynamics of nanoscopic systems and their photophysics. Recent advances that combine correlation spectroscopy with scanning tunneling microscopy induced luminescence (STML) have allowed the measurement of the emission dynamics from individual molecules and defects, demonstrating their nature as single-photon emitters. The application of correlation spectroscopy to the analysis of the dynamics of a well-characterized adsorbate system in an ultrahigh vacuum remained to be demonstrated. Here, we combine single-photon time correlations with STML to measure the dynamics of individual H2 molecules between a gold tip and an Au(111) surface. An adsorbed H2 molecule performs recurrent excursions below the tip apex. We use the fact that the presence of the H2 molecule in the junction modifies plasmon emission to study the adsorbate dynamics. Using the H2 molecule as a chopper for STM-induced optical emission intensity, we demonstrate bunching in the plasmonic photon train in a single measurement over 6 orders of magnitude in the time domain (from microseconds to seconds) that takes only a few seconds. Our findings illustrate the power of using photon statistics to measure the diffusion dynamics of adsorbates with STML.

On-Surface Driven Formal Michael Addition Produces m-Polyaniline Oligomers on Pt(111).

On-surface synthesis is emerging as a highly rational bottom-up methodology for the synthesis of molecular structures that are unattainable or complex to obtain by wet chemistry. Here, oligomers of meta-polyaniline, a known ferromagnetic polymer, were synthesized from para-aminophenol building-blocks via an unexpected and highly specific on-surface formal 1,4 Michael-type addition at the meta position, driven by the reduction of the aminophenol molecule. We rationalize this dehydrogenation and coupling reaction mechanism with a combination of in situ scanning tunneling and non-contact atomic force microscopies, high-resolution synchrotron-based X-ray photoemission spectroscopy and first-principles calculations. This study demonstrates the capability of surfaces to selectively modify local molecular conditions to redirect well-established synthetic routes, such as Michael coupling, towards the rational synthesis of new covalent nanostructures.

Atomic-Scale Imaging and Spectroscopy of Electroluminescence at Molecular Interfaces.

The conversion of electric power to light is an important scientific and technological challenge. Advanced experimental methods have provided access to explore the relevant microscopic processes at the nanometer scale. Here, we review state-of-the-art studies of electroluminescence induced on the molecular scale by scanning tunneling microscopy. We discuss the generation of excited electronic states and electron-hole pairs (excitons) at molecular interfaces and address interactions between electronic states, local electromagnetic fields (tip-induced plasmons), and molecular vibrations. The combination of electronic and optical spectroscopies with atomic-scale spatial resolution is able to provide a comprehensive picture of energy conversion at the molecular level. A recently developed aspect is the characterization of electroluminescence emitters as quantum light sources, which can be studied with high time resolution, thus providing access to picosecond dynamics at the atomic scale.

Validation of an Affordable Handheld Wavefront Autorefractor.

SIGNIFICANCE: There is a critical need for tools that increase the accessibility of eye care to address the most common cause of vision impairment: uncorrected refractive errors. This work assesses the performance of an affordable autorefractor, which could help reduce the burden of this health care problem in low-resource communities. PURPOSE: The purpose of this study was to validate the commercial version of a portable wavefront autorefractor for measuring refractive errors. METHODS: Refraction was performed without cycloplegia using (1) a standard clinical procedure consisting of an objective measurement with a desktop autorefractor followed by subjective refraction (SR) and (2) with the handheld autorefractor. Agreement between both methods was evaluated using Bland-Altman analysis and by comparing the visual acuity (VA) with trial frames set to the resulting measurements. RESULTS: The study was conducted on 54 patients (33.9 ± 14.1 years of age) with a spherical equivalent (M) refraction determined by SR ranging from -7.25 to 4.25 D (mean ± SD, -0.93 ± 1.95 D). Mean differences between the portable autorefractor and SR were 0.09 ± 0.39, -0.06 ± 0.13, and 0.02 ± 0.12 D for M, J0, and J45, respectively. The device agreed within 0.5 D of SR in 87% of the eyes for spherical equivalent power. The average VAs achieved from trial lenses set to the wavefront autorefractor and SR results were 0.02 ± 0.015 and 0.015 ± 0.042 logMAR units, respectively. Visual acuity resulting from correction based on the device was the same as or better than that achieved by SR in 87% of the eyes. CONCLUSIONS: This study found excellent agreement between the measurements obtained with the portable autorefractor and the prescriptions based on SR and only small differences between the VA achieved by either method.

Single Charge and Exciton Dynamics Probed by Molecular-Scale-Induced Electroluminescence.

Excitons and their constituent charge carriers play the central role in electroluminescence mechanisms determining the ultimate performance of organic optoelectronic devices. The involved processes and their dynamics are often studied with time-resolved techniques limited by spatial averaging that obscures the properties of individual electron-hole pairs. Here, we overcome this limit and characterize single charge and exciton dynamics at the nanoscale by using time-resolved scanning tunneling microscopy-induced luminescence (TR-STML) stimulated with nanosecond voltage pulses. We use isolated defects in C60 thin films as a model system into which we inject single charges and investigate the formation dynamics of a single exciton. Tunable hole and electron injection rates are obtained from a kinetic model that reproduces the measured electroluminescent transients. These findings demonstrate that TR-STML can track dynamics at the quantum limit of single charge injection and can be extended to other systems and materials important for nanophotonic devices.

Nanoscale Imaging of Charge Carrier and Exciton Trapping at Structural Defects in Organic Semiconductors.

Charge carrier and exciton trapping in organic semiconductors crucially determine the performance of organic (opto-)electronic devices such as organic field-effect transistors, light-emitting diodes, or solar cells. However, the microscopic origin of the relevant traps generally remains unclear, as most spectroscopic techniques are unable to simultaneously probe the electronic and morphological structure of individual traps. Here, we employ low-temperature scanning tunneling microscopy (STM) and spectroscopy (STS) as well as tight-binding calculations derived from ab initio calculations to image the localized electronic states arising at structural defects in thin C60 films (<10 ML). The spatially and spectrally resolved STM-induced luminescence at these states reveals an enhanced radiative decay of excitons, which is interpreted in terms of the local symmetry lowering and the trapping of excitons by an X-trap. The combined mapping of the STM-induced luminescence, electronic structure, and morphology thus provides new insights into the origin and characteristics of individual exciton traps in organic semiconductors and offers new avenues to study charge carrier and exciton dynamics on molecular scales.

Three-dimensional evaluation of accommodating intraocular lens shift and alignment in vivo.

OBJECTIVE: To quantify 3-dimensionally the anterior segment geometry, biometry, and lens position and alignment in patients before and after implantation of the Crystalens-AO (Bausch & Lomb, Rochester, NY) accommodating intraocular lens (A-IOL). DESIGN: Prospective, observational study. PARTICIPANTS: Ten patients (20 eyes) with cataract before and after implantation of the Crystalens-AO A-IOL. METHODS: Custom full anterior segment 3-dimensional (3-D) spectral optical coherence tomography (OCT) provided with quantification tools was used to image the cornea, iris, and natural lens preoperatively and intraocular lens postoperatively. Measurements were obtained under phenylephrine preoperatively and under natural viewing conditions and phenylephrine (for accommodative efforts ranging from 0 to 2.5 diopters [D]) and pilocarpine postoperatively. MAIN OUTCOME MEASURES: Three-dimensional quantitative anterior segment images, corneal geometry and power, anterior chamber depth (ACD), lens thickness, pupil diameter, A-IOL shift with accommodative effort or drug-induced accommodation, and A-IOL alignment. RESULTS: Crystalline lens and IOLs were visualized and quantified 3-dimensionally. The average ACD were 2.64±0.24 and 3.65±0.35 mm preoperatively and postoperatively (relaxed state), respectively, and they were statistically significantly correlated (although their difference was not statistically correlated with lens thickness). The A-IOL did not shift systematically with accommodative effort, with 9 lenses moving forward and 11 lenses moving backward (under natural conditions). The average A-IOL shift under stimulated accommodation with pilocarpine was -0.02±0.20 mm. The greatest forward shift occurred bilaterally in 1 patient (-0.49 mm in the right eye and -0.52 mm in the left eye, under pilocarpine). The high right/left symmetry in the horizontal tilt of the crystalline lens is disrupted on IOL implantation. Accommodative IOLs tend to be slightly more vertically tilted than the crystalline lens, with increasing tendency with accommodative effort. Two subjects showed postoperative IOL tilts >9 degrees. Changes in pupillary diameter correlated with pilocarpine-induced A-IOL axial shift. Intermediate accommodative demands (1.25 D) elicited the greater shifts in axial A-IOL location and tilt and pupil diameter. CONCLUSIONS: Quantitative 3-D anterior segment OCT allows full evaluation of the geometry of eyes implanted with A-IOLs preoperatively and postoperatively. High-resolution OCT measurements of the Crystalens 3-D positioning revealed small (and in many patients backward) A-IOL axial shifts with both natural or drug-induced accommodation, as well as tilt changes with respect to natural lens and accommodative effort.

Resonant Tip-Enhanced Raman Spectroscopy of a Single-Molecule Kondo System.

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.

Ray tracing optimization: a new method for intraocular lens power calculation in regular and irregular corneas.

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.

Correction: In situ observation of the on-surface thermal dehydrogenation of n-octane on Pt(111).

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.

In situ observation of the on-surface thermal dehydrogenation of n-octane on Pt(111).

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.

Graphene functionalisation with a conjugated poly(fluorene) by click coupling: striking electronic properties in solution.

Graphene flakes covalently modified with a conjugated polymer, poly[(9,9-dihexylfluorene)-co-alt-(9,9-bis-(6-azidohexyl)fluorene)] (PFA), were efficiently synthesised by a Cu-catalysed Huisgen 1,3-dipolar cycloaddition between alkyne-modified graphene and an azide-functionalised polymer. Two approaches for the modification of graphene with alkyne groups were investigated (coupling with a diazonium salt generated in situ or an amidation reaction) and the optimum conditions determined. The success of the click-coupling approach was confirmed by FTIR, (1)H NMR, Raman, and X-ray photoelectron spectroscopy (XPS). The absorption and emission spectra of the click product show a strong solvent dependency.

Scleral changes induced by atropine in chicks as an experimental model of myopia.

PURPOSE: To determine the effects of intravitreal atropine on scleral growth in the form-deprived chick as an experimental model of myopia. METHODS: Five groups of five chicks were studied from day 0-12 post-hatching. One group remained untreated (C), and four were form-deprived by monocular light diffusers to induce myopia. Two groups (RL and A) wore diffusers for 9 days, and the other two groups (D and D + A) wore diffusers throughout the study. Group D received no further treatment (myopia positive control). Groups A and D + A received intravitreal injections of atropine for days 9-12. Measurements of refractive error and axial length were performed on days 0, 9, and 12. Sclera changes were assessed in cartilaginous and fibrous layers by histological analysis. RESULTS: All form-deprived eyes had a myopic refractive error on day 9. All atropine-treated groups were hyperopic on day 12. The effect of atropine was most evident in Group D + A in which diffusers were maintained throughout treatment and changes in refractive error were statistically significant. The observed changes in axial length were in line with the changes in refractive error. The scleral fibrous layer thickness increased, and the sceral cartilaginous layer underwent a slight thinning compared to Group D, the myopia positive control. CONCLUSIONS: If the signals that induce growth remain during atropine treatment, morphological changes in sclera are produced: the scleral fibrous layer thickened, and the sceral cartilaginous layer thinned. These changes resulted in refractive error recovery, and the ocular growth was stopped. The data suggested the atropine was acting throughout the scleral fibrous layer.

Real Space Visualization of Entangled Excitonic States in Charged Molecular Assemblies.

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.