Enhancing Haloarene Coupling Reaction Efficiency on an Oxide Surface by Metal Atom Addition.

The bottom-up synthesis of carbon-based nanomaterials directly on semiconductor surfaces allows for the decoupling of their electronic and magnetic properties from the substrates. However, the typically reduced reactivity of such nonmetallic surfaces adversely affects the course of these reactions. Here, we achieve a high polymerization yield of halogenated polyphenyl molecular building blocks on the semiconducting TiO2(110) surface via concomitant surface decoration with cobalt atoms, which catalyze the Ullmann coupling reaction. Specifically, cobalt atoms trigger the debromination of 4,4″-dibromo-p-terphenyl molecules on TiO2(110) and mediate the formation of an intermediate organometallic phase already at room temperature (RT). As the debromination temperature is drastically reduced, homocoupling and polymerization readily proceed, preventing presursor desorption from the substrate and entailing a drastic increase of the poly-para-phenylene polymerization yield. The general efficacy of this mechanism is shown with an iodinated terphenyl derivative, which exhibits similar dehalogenation and reaction yield.

On-Surface Synthesis of Five-Membered Copper Metallacycles Using Terminal Alkynes.

We present our studies on the adsorption, deprotonation, and reactions of 4,4″-diethynyl-1,1':4',1″-terphenyl on Cu(111) under ultrahigh-vacuum conditions using scanning tunneling microscopy combined with density functional theory calculations. Sequential annealing treatments induce deprotonation of pristine molecules followed by chemical reactions, resulting in branched nanostructures. Within the nanostructures, a previously unreported, double-spot linkage is observed. Our density functional theory calculations unravel that this linkage corresponds to a five-membered copper metallacycle.

Metabolic activity of Planktothrix rubescens and its consequences on oxygen dynamics in laboratory experiment: A stable isotope study.

Fluctuations in dissolved oxygen (DO) contents in natural waters can become intense during cyanobacteria blooms. In a reconnaissance study, we investigated DO concentrations and stable isotope dynamics during a laboratory experiment with the cyanobacterium Planktothrix rubescens in order to obtain insights into primary production under specific conditions. This observation was extended to sub-daily timescales with alternating light and dark phases. Dissolved oxygen concentrations and its isotopes (δ18ODO) ranged from 0.02 to 0.06 mmol · L-1 and from +9.6‰ to +23.4‰. The δ18ODO proved to be more sensitive than concentration measurements in response to metabolic variation and registered earlier shifts to dominance by respiration. Oxygen (O2) contents in the headspace and its isotopes (δ18OO2) ranged from 2.62 to 3.20 mmol · L-1 and from +9.8‰ to +21.9‰. Headspace samples showed less fluctuations in concentration and isotope trends because aquatic processes were hardly able to alter signals once the gas had reached the headspace. Headspace δ18OO2 values were corrected for gas-water equilibration and were determined to be higher than the mean δ18OH2O of -8.7‰. This finding suggests that counteracting respiration was important even during the highest photosynthetic activity. Additionally, headspace analyses led to the definition of a fractionation factor for respiration (αR) of this cyanobacterium with a value of 0.980. This value confirms the one commonly used for cyanobacteria. Our findings may become important for the management of water bodies where decreases in DO are caused by cyanobacteria.

Atomistic investigation of surface characteristics and electronic features at high-purity FeSi(110) presenting interfacial metallicity.

Iron silicide (FeSi) is a fascinating material that has attracted extensive research efforts for decades, notably revealing unusual temperature-dependent electronic and magnetic characteristics, as well as a close resemblance to the Kondo insulators whereby a coherent picture of intrinsic properties and underlying physics remains to be fully developed. For a better understanding of this narrow-gap semiconductor, we prepared and examined FeSi(110) single-crystal surfaces of high quality. Combined insights from low-temperature scanning tunneling microscopy and density functional theory calculations (DFT) indicate an unreconstructed surface termination presenting rows of Fe-Si pairs. Using high-resolution tunneling spectroscopy (STS), we identify a distinct asymmetric electronic gap in the sub-10 K regime on defect-free terraces. Moreover, the STS data reveal a residual density of states in the gap regime whereby two in-gap states are recognized. The principal origin of these features is rationalized with the help of the DFT-calculated band structure. The computational modeling of a (110)-oriented slab notably evidences the existence of interfacial intragap bands accounting for a markedly increased density of states around the Fermi level. These findings support and provide further insight into the emergence of surface metallicity in the low-temperature regime.

Male sex, revision surgery, low volume of anterior cruciate ligament remnant, and significant instability are risk factors for Posterior Root Tear of the Lateral Meniscus in patients undergoing Anterior Cruciate Ligament Reconstruction.

PURPOSE: This multicenter study aimed to determine the incidence of lateral meniscus posterior root tears (LMPRTs) in patients undergoing ACL reconstruction and identify associated risk factors. METHODS: We conducted a retrospective, multicenter study using data from the Francophone Arthroscopic Society's registry. The study included all the patients in the registry who underwent ACL reconstruction surgery between June 2020 and June 2023, we excluded incomplete data. We compared delay from injury to surgery between LMPRTs group and No LMPRTs group. Variables investigated as potential risk factors for LMPRTs included age, sex, nature of surgery (primary or revision), pivot shift test result, side-to-side laxity under anesthesia, presence of ACL remnant, occurrence of medial meniscal tear, and presence of collateral ligament injury. Risk factors were analyzed using a logistic regression model. RESULTS: Among the 5359 patients analyzed, LMPRTs occurred in 7.0% (n=375) of cases during ACL reconstruction. Mean age at surgery was 29.3 +/- 10.3 years old [11-77]. Concerning delay to surgery, the mean time was 8.4 +/- 23.1 weeks [0.0-347.2] in the No LMPRTs group and 6.5 +/- 10.2 weeks [0.2-61.6] in the LMPRTs group (p = 0.109). Univariate analysis revealed that male sex (p < 0.001), revision surgery (p < 0.001), medial meniscal injury (p = 0.007), ACL remnant (0% vs > 70%, <10% vs > 70%, 10 to 30% vs > 70%, 30 to 50% vs > 70%, 50 to 70% vs > 70%; p < 0.001) and higher pivot shift grade (p = 0.011) were significantly associated with a presence of LMPRTs. Age, side-to-side laxity, and collateral ligament injury were not found to be significant risk factor In multivariate analysis : male sex, revision surgery, pivot shift test result and a low volume of ACL remnant remained significant. Side to side laxity was also a significant factor in multivariate analysis. CONCLUSION: This study identified male sex, revision surgery, low volume of ACL remnant, side to side laxity and higher grade of pivot shift as significant risk factors for LMPRTs during ACL reconstruction.

Risk factors and prevalence of ramp lesions in ACL ruptures: An analysis from the registry of the Francophone Arthroscopic Society.

PURPOSE: The study aimed to estimate the prevalence of ramp lesions among patients undergoing anterior cruciate ligament (ACL) reconstruction and identify risk factors associated with these lesions. METHODS: A retrospective, multicentre cohort study was conducted using data from the Francophone Arthroscopic Society's registry, including 5359 patients who underwent ACL reconstruction (ACLR) from June 2020 to June 2023. Potential risk factors for ramp lesion such as patient demographics, revision surgery, pivot shift, side-to-side anteroposterior laxity, medial collateral ligament (MCL) injury, lateral meniscal tear and the volume of ligament remnant were evaluated using multivariate regression analyses. BMI and delay to surgery were also assessed. RESULTS: Ramp lesions were identified in 822 patients (15.3%). Univariate analysis identified male sex, younger age, revision surgery, lateral meniscal injury, percentage of ACL remnant (all p < 0.0001) and pivot shift (p = 0.0103) as significant risk factors. MCL injury was associated with a lower risk (p < 0.0001). In multivariate analysis, male sex, younger age, revision surgery, lateral meniscal injury and percentage of ACL remnants remained significant risk factors, while MCL injury remained a protective factor. The anteroposterior laxity wasn't a significant predictor in either analysis. In subgroup analysis, there were no differences concerning body mass index (n.s) and the delay to surgery (n.s). CONCLUSION: The study identified male sex, younger age, revision surgery, lateral meniscal injury and pourcentage of ACL remnant as significant risk factors for ramp lesions, with MCL injury acting as a protective factor. This will help regarding the suspicion and identification of ramp lesions. LEVEL OF EVIDENCE: Level III.

Clinical Results and CT Analysis of ISA Stemless at a Minimum Follow-up of 2 Years.

INTRODUCTION: The utilization of stemless anatomic total shoulder arthroplasty is on the rise. Epiphyseal fixation leads to radiological bone remodeling, which has been reported to exceed 40% in certain studies series. The aim of this study was to present the clinical and radiological outcomes of a stemless implant with asymmetric central epiphyseal fixation at an average follow-up of 31 months. MATERIALS: This retrospective multicenter study examined prospective data of patients undergoing total anatomic arthroplasty with ISA Stemless implant and followed up at least 2 years. Clinical assessment included preoperative and final follow-up measurements of active range of motion (ROM), Constant score, and Subjective Shoulder Value (SSV). Anatomical epiphyseal reconstruction and bone remodeling at the 2-year follow-up were assessed by standardized Computed Tomography Scanner (CT scan). Statistical analysis employed unpaired Student's t-test or chi-squared test depending on the variable type, conducted using EasyMedStat software (version 3.22; www.easymedstat.com). RESULTS: Fifty patients (mean age 68 years, 62% females) were enrolled, with an average follow-up of 31 months (24-44). Primary osteoarthritis (68%) with type A glenoid (78%) was the prevailing indication. The mean Constant score and SSV improved significantly from 38 ± 11 to 76 ± 11 (p<0.001) and from 31% ± 16 to 88% ± 15 (p<0.001) respectively at the last follow-up. Forward elevation, external rotation and internal rotation ROM increased by 39° ± 42, 28° ± 21 and 3,2 ± 2,5 points respectively, surpassing the Minimally Clinically Important Difference (MCID) after total shoulder arthroplasty. No revisions were necessary. CT scans identified 30% osteolysis in the posterior-medial calcar region, devoid of clinical repercussions. No risk factors were associated with bone osteolysis. CONCLUSION: At an average follow-up of 31 months, ISA Stemless implant provided favorable clinical results. CT analysis revealed osteolysis-like remodeling in the posterior-medial zone of the calcar (30%), without decline in clinical outcomes and revisions. Long-term follow-up studies are mandated to evaluate whether osteolysis is associated with negative consequences.

The relevance of knee arthroscopy photographs in medicolegal proceedings.

PURPOSE: Whether photographs included in the operative report of knee arthroscopies can make the surgeon liable in the event of a legal investigation remains unknown. The main objective of this study was to establish inter-observer reliability in determining the presence or absence of lesions of the cartilage, meniscus and anterior cruciate ligament (ACL). Secondary objective was to assess the inter-observer reliability in classifying lesions. METHOD: A retrospective observational study was conducted in a continuous serie of 60 patients who underwent knee arthroscopy from the same operator. The photographs of each patient's operative report were presented separately to three experts, blinded to each other. Each expert had to decide on the presence or absence of injuries to the following structures: meniscal, cartilage and ACL and then, classify it. Primary and secondary endpoints were evaluated using the Fleiss' kappa index. RESULTS: Inter-observer reliability for lesion detection was between 0.4 and 0.61 for all structures with three exceptions: for cartilage, it was low (0.15) at the lateral tibial plateau and poor (-0.01) at the external condyle. On the contrary, the concordance was almost perfect (0.8) for the ACL. For classifying cartilaginous and meniscal lesions, inter-observer reliability was poor (from 0.03 to 0.14), except for at the lateral meniscus (0.65). CONCLUSION: Inter-observer reliability of arthroscopic knee diagnoses is poor when photographs alone are used. In the event of a legal investigation following knee arthroscopy, the photographs included in the operative report should not be used alone to hold the surgeon liable.

On-Surface Isomerization of Indigo within 1D Coordination Polymers.

Natural products are attractive components to tailor environmentally friendly advanced new materials. We present surface-confined metallosupramolecular engineering of coordination polymers using natural dyes as molecular building blocks: indigo and the related Tyrian purple. Both building blocks yield identical, well-defined coordination polymers composed of (1 dehydroindigo : 1 Fe) repeat units on two different silver single crystal surfaces. These polymers are characterized atomically by submolecular resolution scanning tunnelling microscopy, bond-resolving atomic force microscopy and X-ray photoelectron spectroscopy. On Ag(100) and on Ag(111), the trans configuration of dehydroindigo results in N,O-chelation in the polymer chains. On the more inert Ag(111) surface, the molecules additionally undergo thermally induced isomerization from the trans to the cis configuration and afford N,N- plus O,O-chelation. Density functional theory calculations confirm that the coordination polymers of the cis-isomers on Ag(111) and of the trans-isomers on Ag(100) are energetically favoured. Our results demonstrate post-synthetic linker isomerization in interfacial metal-organic nanosystems.

Photoresponse of Solution-Synthesized Graphene Nanoribbon Heterojunctions on Diamond Indicating Phototunable Photodiode Polarity.

Graphene nanoribbon heterostructures and heterojunctions have attracted interest as next-generation molecular diodes with atomic precision. Their mass production via solution methods and prototypical device integration remains to be explored. Here, the bottom-up solution synthesis and characterization of liquid-phase-processable graphene nanoribbon heterostructures (GNRHs) are demonstrated. Joint photoresponsivity measurements and simulations provide evidence of the structurally defined heterostructure motif acting as a type-I heterojunction. Real-time, time-dependent density functional tight-binding simulations further reveal that the photocurrent polarity can be tuned at different excitation wavelengths. Our results introduce liquid-phase-processable, self-assembled heterojunctions for the development of nanoscale diode circuitry and adaptive hardware.

MRI sequences at different degrees of flexion to investigate knee popping: an unusual way to diagnose an isolated pigmented villonodular synovitis lesion.

Knee popping is a frequent symptom among knee disorders which requires further investigation in case of a recent evolution of the symptom or pathological associated ones. This article reports a rare presentation of pigmented villonodular synovitis (PVNS), identified as the cause of knee popping symptoms, by performing MRI sequences at various degrees of knee flexion for a patient complaining from a gradual onset of knee popping, occurring when bending the knee over 120° of flexion. MRI sequences were performed just before the popping occurs (flexion 90°) and right after it had occurred (flexion 120°). The latter confirmed the origin of the symptom as the lesion moved forward, passing brutally through the interstice between the PCL and the ACL at 120° of flexion, explaining the popping. Treatment decision was to perform an arthroscopic resection of the lesion. Diagnosis of isolated PVNS was confirmed after anatomopathological analysis.

On-Surface Synthesis of Polyphenylene Wires Comprising Rigid Aliphatic Bicyclo[1.1.1]Pentane Isolator Units.

Bicyclo[1.1.1]pentane (BCP) motifs are of growing importance to the pharmaceutical industry as sp3 -rich bioisosteres of benzene rings and as molecular building blocks in materials science. Herein we explore the behavior of 1,3-disubstituted BCP moieties on metal surfaces by combining low-temperature scanning tunneling microscopy / non-contact atomic force microscopy studies with density functional theory modeling. We examine the configuration of individual BCP-containing precursors on Au(111), their supramolecular assembly and thermally activated dehalogenative coupling reactions, affording polymeric chains with incorporated electronically isolating units. Our studies not only provide the first sub-molecular insights of the BCP scaffold behavior on surfaces, but also extend the potential application of BCP derivatives towards integration in custom-designed surface architectures.

Navigate Flying Molecular Elephants Safely to the Ground: Mass-Selective Soft Landing up to the Mega-Dalton Range by Electrospray Controlled Ion-Beam Deposition.

The prototype of a highly versatile and efficient preparative mass spectrometry system used for the deposition of molecules in ultrahigh vacuum (UHV) is presented, along with encouraging performance data obtained using four model species that are thermolabile or not sublimable. The test panel comprises two small organic compounds, a small and very large protein, and a large DNA species covering a 4-log mass range up to 1.7 MDa as part of a broad spectrum of analyte species evaluated to date. Three designs of innovative ion guides, a novel digital mass-selective quadrupole (dQMF), and a standard electrospray ionization (ESI) source are combined to an integrated device, abbreviated electrospray controlled ion-beam deposition (ES-CIBD). Full control is achieved by (i) the square-wave-driven radiofrequency (RF) ion guides with steadily tunable frequencies, including a dQMF allowing for investigation, purification, and deposition of a virtually unlimited m/z range, (ii) the adjustable landing energy of ions down to ∼2 eV/z enabling integrity-preserving soft landing, (iii) the deposition in UHV with high ion beam intensity (up to 3 nA) limiting contaminations and deposition time, and (iv) direct coverage control via the deposited charge. The maximum resolution of R = 650 and overall efficiency up to Ttotal = 4.4% calculated from the solution to UHV deposition are advantageous, whereby the latter can be further enhanced by optimizing ionization performance. In the setup presented, a scanning tunneling microscope (STM) is attached for in situ UHV investigations of deposited species, demonstrating a selective, structure-preserving process and atomically clean layers.

Remplissage Yields Similar 2-Year Outcomes, Fewer Complications, and Low Recurrence Compared to Latarjet Across a Wide Range of Preoperative Glenoid Bone Loss.

PURPOSE: The purpose of this study was to compare functional outcome, return to sport, satisfaction, postoperative recurrence, and complications in patients undergoing primary arthroscopic Bankart repair with remplissage (ABR) to primary Latarjet. METHODS: A multicenter retrospective study was performed on patients undergoing primary ABR or open Latarjet between 2013 and 2019 who had a minimum 2-year follow-up. Baseline and two-year range of motion (ROM), patient-reported outcomes (PROs: Western Ontario Shoulder Instability Index [WOSI], Single Assessment Numeric Evaluation [SANE], and visual analog scale [VAS] for pain) recurrence, return to sport, satisfaction, and complications were reviewed. RESULTS: This study included 258 patients, including 70 ABRs and 188 Latarjet procedures. Baseline demographics, ROM, and PROs were similar. Mean preop glenoid bone loss (GBL) (12.3% ± 10.9% vs 7.6% ± 9%; P < .001) and off-track lesions (23% vs 13%; P = .046) were higher in the ABR group, while preoperative GBL range was similar (0-42% vs 0-47%). Changes in the VAS (1.9 vs 0.9; P = .019) and WOSI (1096 vs 805; P < .001) were improved in ABR. The percentage of patients who achieved a minimal clinically important difference was improved in WOSI for ABR and PASS for ABR in SANE, VAS, and WOSI scores. The ABR cohort reported worse changes in external rotation (ER) (-4° vs +19°; P < .001). Return to sport among overhead and contact athletes favored ABR (91.5% vs 72.7%; P = .007). Satisfaction and recurrent dislocation were similar. Surgical complications were observed in 0% of ABR cases, compared to 5.9% in the Latarjet group. CONCLUSION: Primary ABR resulted in 2-year functional outcomes that were as good or superior to primary Latarjet, with higher return to sport for overhead and contact activities, fewer complications, and comparably low recurrence rates, even despite greater bipolar bone loss in the ABR cohort. However, this comes at the expense of decreased external rotation, which may be considered in individual patients. LEVEL OF EVIDENCE: III, retrospective comparative study.

Abiotic Formation of an Amide Bond via Surface-Supported Direct Carboxyl-Amine Coupling.

Amide bond formation is one of the most important reactions in biochemistry, notably being of crucial importance for the origin of life. Herein, we combine scanning tunneling microscopy and X-ray photoelectron spectroscopy studies to provide evidence for thermally activated abiotic formation of amide bonds between adsorbed precursors through direct carboxyl-amine coupling under ultrahigh-vacuum conditions by means of on-surface synthesis. Complementary insights from temperature-programmed desorption measurements and density functional theory calculations reveal the competition between cross-coupling amide formation and decarboxylation reactions on the Au(111) surface. Furthermore, we demonstrate the critical influence of the employed metal support: whereas on Au(111) the coupling readily occurs, different reaction scenarios prevail on Ag(111) and Cu(111). The systematic experiments signal that archetypical bio-related molecules can be abiotically synthesized in clean environments without water or oxygen.

Depositing Molecular Graphene Nanoribbons on Ag(111) by Electrospray Controlled Ion Beam Deposition: Self-Assembly and On-Surface Transformations.

The chemical processing of low-dimensional carbon nanostructures is crucial for their integration in future devices. Here we apply a new methodology in atomically precise engineering by combining multistep solution synthesis of N-doped molecular graphene nanoribbons (GNRs) with mass-selected ultra-high vacuum electrospray controlled ion beam deposition on surfaces and real-space visualisation by scanning tunnelling microscopy. We demonstrate how this method yields solely a controllable amount of single, otherwise unsublimable, GNRs of 2.9 nm length on a planar Ag(111) surface. This methodology allows for further processing by employing on-surface synthesis protocols and exploiting the reactivity of the substrate. Following multiple chemical transformations, the GNRs provide reactive building blocks to form extended, metal-organic coordination polymers.

N-Heterocyclic Carbenes: Molecular Porters of Surface Mounted Ru-Porphyrins.

Ru-porphyrins act as convenient pedestals for the assembly of N-heterocyclic carbenes (NHCs) on solid surfaces. Upon deposition of a simple NHC ligand on a close packed Ru-porphyrin monolayer, an extraordinary phenomenon can be observed: Ru-porphyrin molecules are transferred from the silver surface to the next molecular layer. We have investigated the structural features and dynamics of this portering process and analysed the associated binding strengths and work function changes. A rearrangement of the molecular layer is induced by the NHC uptake: the NHC selective binding to the Ru causes the ejection of whole porphyrin molecules from the molecular layer on silver to the layer on top. This reorganisation can be reversed by thermally induced desorption of the NHC ligand. We anticipate that the understanding of such mass transport processes will have crucial implications for the functionalisation of surfaces with carbenes.

Surface-Mediated Ring-Opening and Porphyrin Deconstruction via Conformational Distortion.

The breakdown of macrocyclic compounds is of utmost importance in manifold biological and chemical processes, usually proceeding via oxygenation-induced ring-opening reactions. Here, we introduce a surface chemical route to selectively break a prototypical porphyrin species, cleaving off one pyrrole unit and affording a tripyrrin derivative. This pathway, operational in an ultrahigh vacuum environment at moderate temperature is enabled by a distinct molecular conformation achieved via the specific interaction between the porphyrin and its copper support. We provide an atomic-level characterization of the surface-anchored tripyrrin, its reaction intermediates, and byproducts by bond-resolved atomic force microscopy, unequivocally identifying the molecular skeletons. The ring-opening is rationalized by the distortion reducing the macrocycle's stability. Our findings open a route to steer ring-opening reactions by conformational design and to study intriguing tetrapyrrole catabolite analogues on surfaces.

Actinide Coordination Chemistry on Surfaces: Synthesis, Manipulation, and Properties of Thorium Bis(porphyrinato) Complexes.

Actinide-based metal-organic complexes and coordination architectures encompass intriguing properties and functionalities but are still largely unexplored on surfaces. We introduce the in situ synthesis of actinide tetrapyrrole complexes under ultrahigh-vacuum conditions, on both a metallic support and a 2D material. Specifically, exposure of a tetraphenylporphyrin (TPP) multilayer to an elemental beam of thorium followed by a temperature-programmed reaction and desorption of surplus molecules yields bis(porphyrinato)thorium (Th(TPP)2) assemblies on Ag(111) and hexagonal boron nitride/Cu(111). A multimethod characterization including X-ray photoelectron spectroscopy, scanning tunneling microscopy, temperature-programmed desorption, and complementary density functional theory modeling provides insights into conformational and electronic properties. Supramolecular assemblies of Th(TPP)2 as well as individual double-deckers are addressed with submolecular precision, e.g., demonstrating the reversible rotation of the top porphyrin in Th(TPP)2 by molecular manipulation. Our findings thus demonstrate prospects for actinide-based functional nanoarchitectures.