Single-Spin Sensing: A Molecule-on-Tip Approach.

Magnetometry plays a pivotal role in addressing the requirements of ultradense storage technology and overcoming challenges associated with downscaled spin qubits. A promising approach for atomic-scale single-spin sensing involves utilizing a magnetic molecule as a spin sensor, although such a realization is still in its early stages. To tackle this challenge and underscore the potential of this method, we combined a nickelocene molecule with scanning tunneling microscopy to perform versatile spin-sensitive imaging of magnetic surfaces. We investigated model Co islands on Cu(111) of different thicknesses having variable magnetic properties. Our method demonstrates robustness and reproducibility, providing atomic-scale sensitivity to spin polarization and magnetization orientation, owing to a direct exchange coupling between the nickelocene-terminated tip and the Co surfaces. We showcase the accessibility of magnetic exchange maps using this technique, revealing unique signatures in magnetic corrugation, which are well described by computed spin-density maps. These advancements significantly improve our capacity to probe and visualize magnetism at the atomic level.

Submolecular-scale control of phototautomerization.

Optically activated reactions initiate biological processes such as photosynthesis or vision, but can also control polymerization, catalysis or energy conversion. Methods relying on the manipulation of light at macroscopic and mesoscopic scales are used to control on-surface photochemistry, but do not offer atomic-scale control. Here we take advantage of the confinement of the electromagnetic field at the apex of a scanning tunnelling microscope tip to drive the phototautomerization of a free-base phthalocyanine with submolecular precision. We can control the reaction rate and the relative tautomer population through a change in the laser excitation wavelength or through the tip position. Atomically resolved tip-enhanced photoluminescence spectroscopy and hyperspectral mapping unravel an excited-state mediated process, which is quantitatively supported by a comprehensive theoretical model combining ab initio calculations with a parametric open-quantum-system approach. Our experimental strategy may allow insights in other photochemical reactions and proof useful to control complex on-surface reactions.

Ten-Year Minimum Follow-up Study of First Metatarsophalangeal Joint Fusion in Young vs Old Patients.

BACKGROUND: Painful degenerative joint disease (DJD) of the first metatarsophalangeal joint (MTP I), or hallux rigidus, mainly occurs in later stages of life. For end-stage hallux rigidus, MTP I arthrodesis is considered the gold standard. As young and active patients are affected considerably less frequently, it currently remains unclear, whether they benefit to the same extent. We hypothesized that MTP I arthrodesis in younger patients would lead to an inferior outcome with decreased rates of overall with lower rates of patient postoperative pain and function compared to an older cohort. METHODS: All patients aged <50 years who underwent MTP I arthrodesis at our institution between 1995 and 2012 were included in this study. This group was then matched and compared with a group of patients aged >60 years. Minimum follow-up was 10 years. Outcome measures were Tegner activity score (TAS), a "Virtual Tegner activity score" (VTAS), the visual analog scale (VAS), and the Foot Function index (FFI). RESULTS: Sixty-one MTP I fusions (n = 28 young, n = 33 old) in 46 patients were included in our study at an average of 14 years after surgery. Younger patients experienced significantly more pain relief as reflected by changes in VAS and FFI Pain subscale scores. No difference in functional outcomes was found with change in the FFI function subscale or in the ability to have desired functional outcomes using the ratio of TAS to VTAS. Revision rate did not differ between the two groups apart from hardware removal, which was significantly more likely in the younger group. CONCLUSION: In patients below the age of 50 years with end-stage DJD of the first metatarsal joint, MTP I arthrodesis not only yielded highly satisfactory postoperative results at least equal outcome compared to an older cohort of patients aged >60 years at an average 14 years' follow-up. Based on these findings, we consider first metatarsal joint fusion even for young patients is a valid option to treat end-stage hallux rigidus. LEVEL OF EVIDENCE: Level III, a case-control study.

Many-Body Description of STM-Induced Fluorescence of Charged Molecules.

A scanning tunneling microscope is used to study the fluorescence of a model charged molecule (quinacridone) adsorbed on a sodium chloride (NaCl)-covered metallic sample. Fluorescence from the neutral and positively charged species is reported and imaged using hyperresolved fluorescence microscopy. A many-body model is established based on a detailed analysis of voltage, current, and spatial dependences of the fluorescence and electron transport features. This model reveals that quinacridone adopts a palette of charge states, transient or not, depending on the voltage used and the nature of the underlying substrate. This model has a universal character and clarifies the transport and fluorescence mechanisms of molecules adsorbed on thin insulators.

Tip-induced excitonic luminescence nanoscopy of an atomically resolved van der Waals heterostructure.

The electronic and optical properties of van der Waals heterostructures are strongly influenced by the structuration and homogeneity of their nano- and atomic-scale environments. Unravelling this intimate structure-property relationship is a key challenge that requires methods capable of addressing the light-matter interactions in van der Waals materials with ultimate spatial resolution. Here we use a low-temperature scanning tunnelling microscope to probe-with atomic-scale resolution-the excitonic luminescence of a van der Waals heterostructure, made of a transition metal dichalcogenide monolayer stacked onto a few-layer graphene flake supported by a Au(111) substrate. Sharp emission lines arising from neutral, charged and localized excitons are reported. Their intensities and emission energies vary as a function of the nanoscale topography of the van der Waals heterostructure, explaining the variability of the emission properties observed with diffraction-limited approaches. Our work paves the way towards understanding and controlling optoelectronic phenomena in moiré superlattices with atomic-scale resolution.

Topologically localized excitons in single graphene nanoribbons.

Intrinsic optoelectronic properties of atomically precise graphene nanoribbons (GNRs) remain largely unexplored because of luminescence quenching effects that are due to the metallic substrate on which the ribbons are grown. We probed excitonic emission from GNRs synthesized on a metal surface with atomic-scale spatial resolution. A scanning tunneling microscope (STM)-based method to transfer the GNRs to a partially insulating surface was used to prevent luminescence quenching of the ribbons. STM-induced fluorescence spectra reveal emission from localized dark excitons that are associated with the topological end states of the GNRs. A low-frequency vibronic emission comb is observed and attributed to longitudinal acoustic modes that are confined to a finite box. Our study provides a path to investigate the interplay between excitons, vibrons, and topology in graphene nanostructures.

Chest CT Findings and SARS-CoV-2 Infection in Trauma Patients-Is There a Prediction towards Higher Complication Rates?

Background: Polytrauma patients with SARS-CoV-2 infections may be associated with an increased complication rate. The main goal of this study was to analyze the clinical course of trauma patients with COVID infection and a positive CT finding. Methods: This was a retrospective in-hospital study. Polytrauma patients diagnosed with SARS-CoV-2 infections were included in our analysis. The outcome parameters were pulmonary complication during admission, pulmonary embolism, pleural effusion, pneumonia, mortality, length of stay and readmission < 30 days. Results: 48 patients were included in the study. Trauma patients in the age-adjusted matched-pair analysis with typical changes in SARS-CoV-2 infection in CT findings showed significantly more pulmonary complications in general and significantly more cases of pneumonia (complications: 56% vs. 11%, p = 0.046; pneumonia 44% vs. 0%, p = 0.023). In addition, the clinical course of polytrauma patients with SARS-CoV-2 infection showed a high rate of pulmonary complications in the inpatient course (53%). Conclusion: The results of our study show that the changes in the CT findings of trauma patients with SARS-CoV-2 infection are a good indicator of further inpatient outcomes. Similarly, polytrauma patients with a SARS-CoV-2 infection and positive CT findings are shown to have increased risk for pulmonary complications.

Internal Stark effect of single-molecule fluorescence.

The optical properties of chromophores can be efficiently tuned by electrostatic fields generated in their close environment, a phenomenon that plays a central role for the optimization of complex functions within living organisms where it is known as internal Stark effect (ISE). Here, we realised an ISE experiment at the lowest possible scale, by monitoring the Stark shift generated by charges confined within a single chromophore on its emission energy. To this end, a scanning tunneling microscope (STM) functioning at cryogenic temperatures is used to sequentially remove the two central protons of a free-base phthalocyanine chromophore deposited on a NaCl-covered Ag(111) surface. STM-induced fluorescence measurements reveal spectral shifts that are associated to the electrostatic field generated by the internal charges remaining in the chromophores upon deprotonation.

X-ray magnetic dichroism and tunnel magneto-resistance study of the magnetic phase in epitaxial CrVOxnanoclusters.

Epitaxial clusters of chromium and chromium-vanadium oxides are studied by tunnel magneto-resistivity measurements, x-ray absorption spectrometry and circular magnetic circular dichroism. They turn out to carry a small magnetic moment that follows a super-paramagnetic behavior. The chromium ion contribution to this magnetization is mainly due to an original magnetic Cr2O3-like phase, whereas usual Cr2O3is known to be anti-ferromagnetic in the bulk. For mixed clusters, vanadium ions also contribute to the total magnetization and they are coupled to the chromium ion spins. By measuring the dichroic signal at different temperatures, we get insight into the possible spin configurations of vanadium and chromium ions: we propose that the magnetic dipoles observed in the clusters assembly could be related to ionic spins that couple at a very short range, as for instance in short one-dimensional spins chains.

Energy funnelling within multichromophore architectures monitored with subnanometre resolution.

The funnelling of energy within multichromophoric assemblies is at the heart of the efficient conversion of solar energy by plants. The detailed mechanisms of this process are still actively debated as they rely on complex interactions between a large number of chromophores and their environment. Here we used luminescence induced by scanning tunnelling microscopy to probe model multichromophoric structures assembled on a surface. Mimicking strategies developed by photosynthetic systems, individual molecules were used as ancillary, passive or blocking elements to promote and direct resonant energy transfer between distant donor and acceptor units. As it relies on organic chromophores as the elementary components, this approach constitutes a powerful model to address fundamental physical processes at play in natural light-harvesting complexes.

Single-molecule tautomerization tracking through space- and time-resolved fluorescence spectroscopy.

Tautomerization, the interconversion between two constitutional molecular isomers, is ubiquitous in nature1, plays a major role in chemistry2 and is perceived as an ideal switch function for emerging molecular-scale devices3. Within free-base porphyrin4, porphycene5 or phthalocyanine6, this process involves the concerted or sequential hopping of the two inner hydrogen atoms between equivalent nitrogen sites of the molecular cavity. Electronic and vibronic changes6 that result from this NH tautomerization, as well as details of the switching mechanism, were extensively studied with optical spectroscopies, even with single-molecule sensitivity7. The influence of atomic-scale variations of the molecular environment and submolecular spatial resolution of the tautomerization could only be investigated using scanning probe microscopes3,8-11, at the expense of detailed information provided by optical spectroscopies. Here, we combine these two approaches, scanning tunnelling microscopy (STM) and fluorescence spectroscopy12-15, to study the tautomerization within individual free-base phthalocyanine (H2Pc) molecules deposited on a NaCl-covered Ag(111) single-crystal surface. STM-induced fluorescence (STM-F) spectra exhibit duplicate features that we assign to the emission of the two molecular tautomers. We support this interpretation by comparing hyper-resolved fluorescence maps15-18(HRFMs) of the different spectral contributions with simulations that account for the interaction between molecular excitons and picocavity plasmons19. We identify the orientation of the molecular optical dipoles, determine the vibronic fingerprint of the tautomers and probe the influence of minute changes in their atomic-scale environment. Time-correlated fluorescence measurements allow us to monitor the tautomerization events and to associate the proton dynamics to a switching two-level system. Finally, optical spectra acquired with the tip located at a nanometre-scale distance from the molecule show that the tautomerization reaction occurs even when the tunnelling current does not pass through the molecule. Together with other observations, this remote excitation indicates that the excited state of the molecule is involved in the tautomerization reaction path.

The influence of obesity and gender on outcome after reversed L-shaped osteotomy for hallux valgus.

BACKGROUND: Hallux valgus deformity (HV) affects around every fourth individual, and surgical treatment is performed in every thousandth person. There is an ongoing quest for the best surgical management and reduction of undesirable outcomes. The aim was to explore associations of obesity and gender with radiological and clinical outcome after reversed L-shaped osteotomy (ReveL) for HV. MATERIALS AND METHODS: This study was carried out in a retrospective cohort design at a single University Hospital in Switzerland between January 2004 and December 2013. It included adult patients treated with ReveL for HV. The primary exposure was body mass index (BMI) at the time of ReveL. The secondary exposure was gender. The primary outcome was radiological relapse of HV (HV angle [HVA] > 15 degrees [°]) at the last follow-up. Secondary outcomes were improvable patient satisfaction, complication, redo surgery, and optional hardware removal. Logistic regression analysis adjusted for confounders. RESULTS: The median weight, height, and BMI were 66.0 (interquartile range [IQR] 57.0-76.0) kilograms (kg), 1.65 (IQR 1.60-1.71) metres (m), and 24.0 (IQR 21.3-27.8) kg/m2. Logistic regression analysis did not show associations of relapse with BMI, independent of age, gender, additional technique, and preoperative HVA (adjusted odds ratio [ORadjusted] = 1.10 [95% (%) confidence interval (CI) = 0.70-1.45], p = 0.675). Relapse was 91% more likely in males (ORadjusted = 1.91 [95% CI = 1.19-3.06], p = 0.007). Improvable satisfaction was 79% more likely in males (ORadjusted = 1.79 [CI = 1.04-3.06], p = 0.035). Hardware removal was 47% less likely in males (ORadjusted = 0.53 [95% CI 0.30-0.94], p = 0.029). CONCLUSIONS: In this study, obesity was not associated with unsatisfactory outcomes after ReveL for HV. This challenges the previous recommendation that preoperative weight loss may be necessary for a successful surgical treatment outcome. Males may be informed about potentially higher associations with unfavourable outcomes. Due to the risk of selection bias and lack of causality, findings may need to be confirmed with clinical trials.

Radiological and Clinical Outcome After Reversed L-Shaped Osteotomy: A Large Retrospective Swiss Cohort Study.

The objective was to report radiological and clinical outcomes after reversed L-shaped osteotomy (ReveL) for hallux valgus (HV). A retrospective cohort study was performed between January 2004 and December 2013. The primary outcome was radiological recurrence of HV (HV angle [HVA] >15°). There were various exposure and secondary outcome variables. The results showed a median follow-up of 12.0 months (N = 827). Radiological recurrence, limited patient satisfaction, complication, revision surgery, and elective hardware removal were found in 25.0%, 15.3%, 4.6%, 2.5%, and 26.7%. Median pre- to postoperative changes were highest for HVA (delta = -16.7°). Recurrence was more likely in cases with preoperative HVA ≥40° (adjusted odds ratio [ORadjusted]) 3.63, p < .001). Revisions were more likely with concomitant diseases and bilateral surgery (ORadjusted 12.53, p = .010; ORadjusted 3.35, p = .030). Hardware removal was less likely in patients ≥50 years (ORadjusted 0.67, p = .014). In conclusion, ReveL was a good surgical option for HV because of the relatively low rates of unfavorable outcomes.

Linking Electronic Transport through a Spin Crossover Thin Film to the Molecular Spin State Using X-ray Absorption Spectroscopy Operando Techniques.

One promising route toward encoding information is to utilize the two stable electronic states of a spin crossover molecule. Although this property is clearly manifested in transport across single molecule junctions, evidence linking charge transport across a solid-state device to the molecular film's spin state has thus far remained indirect. To establish this link, we deploy materials-centric and device-centric operando experiments involving X-ray absorption spectroscopy. We find a correlation between the temperature dependencies of the junction resistance and the Fe spin state within the device's [Fe(H2B(pz)2)2(NH2-phen)] molecular film. We also factually observe that the Fe molecular site mediates charge transport. Our dual operando studies reveal that transport involves a subset of molecules within an electronically heterogeneous spin crossover film. Our work confers an insight that substantially improves the state-of-the-art regarding spin crossover-based devices, thanks to a methodology that can benefit device studies of other next-generation molecular compounds.

Electrofluorochromism at the single-molecule level.

The interplay between the oxidation state and the optical properties of molecules is important for applications in displays, sensors, and molecular-based memories. The fundamental mechanisms occurring at the level of a single molecule have been difficult to probe. We used a scanning tunneling microscope (STM) to characterize and control the fluorescence of a single zinc-phthalocyanine radical cation adsorbed on a sodium chloride-covered gold (111) sample. The neutral and oxidized states of the molecule were identified on the basis of their fluorescence spectra, which revealed very different emission energies and vibronic fingerprints. The emission of the charged molecule was controlled by tuning the thickness of the insulator and the plasmons localized at the apex of the STM tip. In addition, subnanometric variations of the tip position were used to investigate the charging and electroluminescence mechanisms.

Fano Description of Single-Hydrocarbon Fluorescence Excited by a Scanning Tunneling Microscope.

The detection of fluorescence with submolecular resolution enables the exploration of spatially varying photon yields and vibronic properties at the single-molecule level. By placing individual polycyclic aromatic hydrocarbon molecules into the plasmon cavity formed by the tip of a scanning tunneling microscope and a NaCl-covered Ag(111) surface, molecular light emission spectra are obtained that unravel vibrational progression. In addition, light spectra unveil a signature of the molecule even when the tunneling current is injected well separated from the molecular emitter. This signature exhibits a distance-dependent Fano profile that reflects the subtle interplay between inelastic tunneling electrons, the molecular exciton and localized plasmons in at-distance as well as on-molecule fluorescence. The presented findings open the path to luminescence of a different class of molecules than investigated before and contribute to the understanding of single-molecule luminescence at surfaces in a unified picture.

The influence of the number of screws and additional surgical procedures on outcome in hallux valgus treatment.

BACKGROUND: Surgical treatment of hallux valgus (HV) is one of the major flagships of orthopedic surgeons. Due to relatively unsatisfactory radiological and clinical outcomes, the search for the best surgical technique and causes for unsatisfactory outcomes continues. The objective was to investigate associations of the number of screws and additional surgical techniques for HV with radiological and clinical outcome after reversed L-shaped osteotomy (ReveL). METHODS: A retrospective cohort study of adults from a single University Hospital between 2004 and 2013 was performed. The primary exposure was the number of screws (one vs two) used for osseous fixation after ReveL. The secondary exposure was an additional surgical technique for HV (e.g., Akin osteotomy). The primary outcome was a radiological recurrence of HV (HV angle (HVA) > 15°) at last follow-up. The secondary outcomes were limited patient satisfaction, complication, revision surgery, and elective hardware removal. Odds ratio (OR) and 95% confidence interval (CI) were estimated by logistic regression adjusting for confounders. RESULTS: The recurrence was 45% less likely with the use of one screw, independent of age, sex, additional technique, and preoperative HVA (odds ratio (ORadjusted) = 0.55 [95% CI 0.30-0.98], p = 0.043). The recurrence was 162% more likely with an additional surgical technique for HV (ORadjusted = 2.62 [1.24-5.52], p = 0.011). CONCLUSION: In ReveL for HV, a single screw (instead of two screws) may be sufficient enough for a similar or even better outcome, which may also reduce costs. Additional surgical procedures for HV may be refrained from if possible. Due to limitations of a retrospective study, results may need validation with clinical trials.

Bright Electroluminescence from Single Graphene Nanoribbon Junctions.

Thanks to their highly tunable band gaps, graphene nanoribbons (GNRs) with atomically precise edges are emerging as mechanically and chemically robust candidates for nanoscale light emitting devices of modulable emission color. While their optical properties have been addressed theoretically in depth, only few experimental studies exist, limited to ensemble measurements and without any attempt to integrate them in an electronic-like circuit. Here we report on the electroluminescence of individual GNRs suspended between the tip of a scanning tunneling microscope (STM) and a Au(111) substrate, constituting thus a realistic optoelectronic circuit. Emission spectra of such GNR junctions reveal a bright and narrow band emission of red light, whose energy can be tuned with the bias voltage applied to the junction, but always lying below the gap of infinite GNRs. Comparison with ab initio calculations indicates that the emission involves electronic states localized at the GNR termini. Our results shed light on unpredicted optical transitions in GNRs and provide a promising route for the realization of bright, robust, and controllable graphene-based light-emitting devices.

Vibronic Spectroscopy with Submolecular Resolution from STM-Induced Electroluminescence.

A scanning tunneling microscope is used to generate the electroluminescence of phthalocyanine molecules deposited on NaCl/Ag(111). Photon spectra reveal an intense emission line at ≈1.9 eV that corresponds to the fluorescence of the molecules, and a series of weaker redshifted lines. Based on a comparison with Raman spectra acquired on macroscopic molecular crystals, these spectroscopic features can be associated with the vibrational modes of the molecules and provide a detailed chemical fingerprint of the probed species. Maps of the vibronic features reveal submolecularly resolved structures whose patterns are related to the symmetry of the probed vibrational modes.

Probing a Device's Active Atoms.

Materials science and device studies have, when implemented jointly as "operando" studies, better revealed the causal link between the properties of the device's materials and its operation, with applications ranging from gas sensing to information and energy technologies. Here, as a further step that maximizes this causal link, the paper focuses on the electronic properties of those atoms that drive a device's operation by using it to read out the materials property. It is demonstrated how this method can reveal insight into the operation of a macroscale, industrial-grade microelectronic device on the atomic level. A magnetic tunnel junction's (MTJ's) current, which involves charge transport across different atomic species and interfaces, is measured while these atoms absorb soft X-rays with synchrotron-grade brilliance. X-ray absorption is found to affect magnetotransport when the photon energy and linear polarization are tuned to excite FeO bonds parallel to the MTJ's interfaces. This explicit link between the device's spintronic performance and these FeO bonds, although predicted, challenges conventional wisdom on their detrimental spintronic impact. The technique opens interdisciplinary possibilities to directly probe the role of different atomic species on device operation, and shall considerably simplify the materials science iterations within device research.