Evolution of the ionisation energy with the stepwise growth of chiral clusters of [4]helicene.

Polycyclic aromatic hydrocarbons (PAHs) are widely established as ubiquitous in the interstellar medium (ISM), but considering their prevalence in harsh vacuum environments, the role of ionisation in the formation of PAH clusters is poorly understood, particularly if a chirality-dependent aggregation route is considered. Here we report on photoelectron spectroscopy experiments on [4]helicene clusters performed with a vacuum ultraviolet synchrotron beamline. Aggregates (up to the heptamer) of [4]helicene, the smallest PAH with helical chirality, were produced and investigated with a combined experimental and theoretical approach using several state-of-the-art quantum-chemical methodologies. The ionisation onsets are extracted for each cluster size from the mass-selected photoelectron spectra and compared with calculations of vertical ionisation energies. We explore the complex aggregation topologies emerging from the multitude of isomers formed through clustering of P and M, the two enantiomers of [4]helicene. The very satisfactory benchmarking between experimental ionisation onsets vs. predicted ionisation energies allows the identification of theoretically predicted potential aggregation motifs and corresponding energetic ordering of chiral clusters. Our structural models suggest that a homochiral aggregation route is energetically favoured over heterochiral arrangements with increasing cluster size, hinting at potential symmetry breaking in PAH cluster formation at the scale of small grains.

Influence of a Concomitant Medial Meniscus Injury on Knee Joint Function and Osteoarthritis Presence after Anterior Cruciate Ligament Reconstruction.

(1) Background: The aim of this study was to investigate how a medial meniscus injury accompanying an anterior cruciate ligament rupture affects the clinical outcome 10 years after ACL reconstruction. (2) Methods: A total of 37 patients who received anterior cruciate ligament reconstruction (ACLR) were included in this retrospective study. Two groups were analyzed at a single follow-up of 10 years: (i) "isolated (ACLR)" (n = 20) and (ii) "ACLR with medial meniscal injury" (n = 17). The following clinical scores were recorded: International Knee Documentation Committee (IKDC), the Knee Injury and Osteoarthritis Outcome Score (KOOS), Lysholm Score and Tegner Activity Score. To determine the degree of osteoarthritis the Kellgren-Lawrence score was used. (3) Results: The "isolated ACLR" study group scored significantly higher (p < 0.05) on the IKDC subjective questionnaire (mean: 88.4) than the "ACLR with medial meniscus injury" group (mean: 81). The KOOS category "activities of daily living" showed significantly better results in the isolated ACLR group (p < 0.05). The "ACLR with medial meniscus injury" group had significantly higher degree of osteoarthritis (p < 0.05). No significant differences were found in all the other clinical scores. (4) Conclusions: The results of this study further indicate that patients with a concomitant medial meniscus injury have slightly more discomfort in everyday life and increased risk of developing osteoarthritis 10 years after surgery.

Charge Regulation at the Nanoscale as Evidenced from Light-Responsive Nanoemulsions.

Emulsions are indispensable in everyday life, and the demand for emulsions' diversity and control of properties is therefore substantial. As emulsions possess a high internal surface area, an understanding of the oil/water (o/w) interfaces at the molecular level is fundamental but often impaired by experimental limitations to probe emulsion interfaces in situ. Here, we have used light-responsive surfactants (butyl-AAP) that can photoisomerize between E and Z isomers by visible and UV light irradiation to tune the emulsion interfaces. This causes massive changes in the interface tension at the extended o/w interfaces in macroemulsions and a drastic shift in the surfactants' critical micelle concentration, which we show can be used to control both the stability and phase separation. Strikingly different from macroemulsions are nanoemulsions (RH ∼90 nm) as these are not susceptible to E/Z photoisomerization of the surfactants in terms of changes in their droplet size or ζ-potential. However, in situ second-harmonic scattering and pulsed-field gradient nuclear magnetic resonance (NMR) experiments show dramatic and reversible changes in the surface excess of surfactants at the nanoscopic interfaces. The apparent differences in ζ-potentials and surface excess provide evidence for a fixed charge to particle size ratio and the need for counterion condensation to renormalize the particle charge to a critical charge, which is markedly different compared to the behavior of very large particles in macroemulsions. Thus, our findings may have broader implications as the electrostatic stabilization of nanoparticles requires much lower surfactant concentrations, allowing for a more sustainable use of surfactants.

Triplet Excitation-Energy Transfer Couplings from Subsystem Time-Dependent Density-Functional Theory.

We present an implementation of triplet excitation-energy transfer (TEET) couplings based on subsystem-based time-dependent density-functional theory (sTDDFT). TEET couplings are systematically investigated by comparing "exact" and approximate variants of sTDDFT. We demonstrate that, while sTDDFT utilizing explicit approximate non-additive kinetic energy (NAKE) density functionals is well-suited for describing singlet EET processes, it is inadequate for characterizing TEET. However, we show that projection-based embedding (PbE)-based sTDDFT addresses the challenges faced by NAKE-sTDDFT and emerges as a promising method for accurately describing electronic couplings in TEET processes. We also introduce the mixed PbE-/NAKE-embedding procedure to investigate the TEET effects in solvated pairs of chromophores. This approach offers a good balance between accuracy and efficiency, enabling comprehensive studies of TEET processes in complex environments.

Accelerating Analytic-Continuation GW Calculations with a Laplace Transform and Natural Auxiliary Functions.

We present a simple and accurate GW implementation based on a combination of a Laplace transform (LT) and other acceleration techniques used in post-self-consistent field quantum chemistry, namely, natural auxiliary functions and the frozen-core approximation. The LT-GW approach combines three major benefits: (a) a small prefactor for computational scaling, (b) easy integration into existing molecular GW implementations, and (c) significant performance improvements for a wide range of possible applications. Illustrating these advantages for systems consisting of up to 352 atoms and 7412 basis functions, we further demonstrate the benefits of this approach combined with an efficient implementation of the Bethe-Salpeter equation.

Infra-patellar fat pad-derived mesenchymal stem cells maintain their chondrogenic differentiation potential after arthroscopic harvest with blood-product supplementation.

PURPOSE: Mesenchymal stem cells/medicinal signaling cells (MSCs) possess therapeutic potential and are used in regenerative orthopaedics. The infra-patellar fat pad (IFP) is partially resected during knee arthroscopy (KASC) and contains MSCs. Heat, irrigation, and mechanical stress during KASC may decrease MSC's therapeutic potential. This study assessed MSCs' regenerative potential after arthroscopic IFP harvest and potential effects of two blood products (BP) (platelet-rich plasma (PRP), hyperacute serum (HAS)) on MSCs' viability and chondrogenic differentiation capacity. METHODS: IFP was arthroscopically harvested, isolated, and counted (n = 5). Flow cytometry was used to assess cell viability via staining with annexin V/7-AAD and stemness markers via staining for CD90, CD73, and CD105. MSCs were incubated with blood products, and metabolic activity was determined via an XTT assay. Deposition of cartilage extracellular matrix was determined in histologic sections of chondrogenically differentiated 3D pellet cultures via staining with Alcian Blue. Expression of cartilage-specific genes (SOX9, MMP3/13, ACAN, COL1/2) was analyzed via quantitative PCR. RESULTS: MSC isolation from IFP yielded 2.66*106 ± 1.49*106 viable cells from 2.7 (0.748) g of tissue. MSC markers (CD 90/105/73) were successfully detected and annexin V staining showed 81.5% viable cells. XTT showed increased metabolic activity. Within the BP groups, this increase was significant (days 0-14, p < 0.05). PCR showed expression of cartilage-specific genes in each group. COL2 (p < 0.01) as well as ACAN (p < 0.001) expression levels were significantly higher in the HAS group. Histology showed successful differentiation. CONCLUSION: Arthroscopic harvest of IFP-MSCs yields sufficient cells with maintained regenerative potential and viability. Blood products further enhance MSCs' viability.

Sterically Allowed H-type Supramolecular Polymerizations.

The functionalization of π-conjugated scaffolds with sterically demanding substituents is a widely used tactic to suppress cofacial (H-type) stacking interactions, which may even inhibit self-assembly. Contrary to expectations, we demonstrate herein that increasing steric effects can result in an enhanced thermodynamic stability of H-type supramolecular polymers. In our approach, we have investigated two boron dipyrromethene (BODIPY) dyes with bulky phenyl (2) and mesityl (3) meso-substituents and compared their self-assembly in nonpolar media with that of a parent meso-methyl BODIPY 1 lacking bulky groups. While the enhanced steric demand induces pathway complexity, the superior thermodynamic stability of the H-type pathways can be rationalized in terms of additional enthalpic gain arising from intermolecular C-H⋅⋅⋅F-B interactions of the orthogonally arranged aromatic substituents, which overrule their inherent steric demand. Our findings underline the importance of balancing competing non-covalent interactions in self-assembly.

Automatic Generation of Auxiliary Basis Sets in Spherical Representation Using the Cholesky Decomposition.

Density fitting techniques that use automatically generated auxiliary basis sets generally rely on the formation of basis function products. Recently, Lehtola [ J. Chem. Theory Comput. 2021, 17, 6886-6900] presented a procedure making use of a purely spherical representation by adding auxiliary basis functions coupled to the required angular momentum quantum numbers for the product of spherical harmonics and then removing linear dependencies by means of a Cholesky decomposition. In this work, we extend this idea by making use of the explicit equations for the product of two spherical harmonics in the angular part of the basis function product. Some of the resulting terms are not directly accessible when popular standard integral libraries are used, which could prevent the widespread use of the exact product form. For these terms, we introduce four approximations of increasing sophistication that require integrals involving only standard Gaussian-type orbitals and thus can be computed with standard libraries. We assess the accuracy of the different schemes in the context of the aCD for the reconstruction of the electron repulsion integral matrix and absolute and relative single point energies and in the framework of optimally tuned range-separated hybrid functionals.

Unicompartmental Knee Arthroplasty Provides Superior Clinical and Radiological Outcomes Compared to High Tibial Osteotomy at a Follow-Up of 5-8 Years.

BACKGROUND: Knee Osteoarthritis (OA) is a debilitating disease. Initially, the medial compartments are affected in most cases. For this pathology, joint preservation is preferable. Two surgical procedures aim to meet this goal: high-tibial osteotomy (HTO) and unicompartmental knee arthroplasty (UKA). The aim was to compare clinical and radiological outcomes of HTO versus UKA in patients with unicompartmental, medial OA. METHOD: Retrospective case series. A total of 86 (61 UKA, 25 HTO) patients that received either treatment at a single, specialized center were assessed pre-operatively and at a single follow-up examination at 77.13 months (±8.170). The Knee Society Score (KSS), range of motion (ROM), SF36 questionnaire and the Tegner score were used. The Kellgren-Lawrence score was assessed pre- and post-surgically. Survivorship with the endpoint "revision" was assessed. RESULTS: The UKA group showed significantly better improvements in KSS scores for pain (p < 0.006) and function (p < 0.001). OA progression (p < 0.02) and survivorship (p < 0.018) differed, significantly favoring UKA. ROM, SF36 and Tegner score did not differ significantly. CONCLUSIONS: The presented mid-to long-term data suggest that UKA provides superior results in selected outcomes. Nevertheless, significant differences in the demographics of treatments indicate the challenge of comparing these two treatments.

Light-enabled deracemization of cyclopropanes by Al-salen photocatalysis.

Privileged chiral catalysts-those that share common structural features and are enantioselective across a range of reactions-continue to transform the chemical-research landscape1. In recent years, new reactivity modes have been achieved through excited-state catalysis, processes activated by light, but it is unclear if the selectivity of ground-state privileged catalysts can be matched. Although the interception of photogenerated intermediates by ground-state cycles has partially addressed this challenge2, single, chiral photocatalysts that simultaneously regulate reactivity and selectivity are conspicuously scarce3. So far, precision donor-acceptor recognition motifs remain crucial in enantioselective photocatalyst design4. Here we show that chiral Al-salen complexes, which have well-defined photophysical properties, can be used for the efficient photochemical deracemization5 of cyclopropyl ketones (up to 98:2 enantiomeric ratio (e.r.)). Irradiation at λ = 400 nm (violet light) augments the reactivity of the commercial catalyst to enable reactivity and enantioselectivity to be regulated simultaneously. This circumvents the need for tailored catalyst-substrate recognition motifs. It is predicted that this study will stimulate a re-evaluation of many venerable (ground-state) chiral catalysts in excited-state processes, ultimately leading to the identification of candidates that may be considered 'privileged' in both reactivity models.

Mid-Term Migration Behavior of an Uncemented Proximally Anchored Straight Stem-A Retrospective EBRA Migration Analysis.

BACKGROUND: Aseptic loosening is one of the most-common causes of the failure of cementless stems. Einzel Bild Röntgen Analyse-Femoral Component Analysis (EBRA-FCA) allows the diagnosis of stem migration, which can be considered a factor in predicting implant survival. The current study aimed to present the migration behavior of a tapered proximally anchored straight stem. METHODS: This retrospective study reviewed all consecutive patients who received a cementless CBC straight stem (Mathys AG, Bettlach, Switzerland) between 2005 and 2019. We analyzed the migration pattern using the EBRA-FCA software and reviewed their medical histories. In addition, periprosthetic radiolucency was rated according to the Gruen zones and femoral configuration according to Dorr. RESULTS: A total of 333 stems in 332 patients (female 191; male 141) met our inclusion criteria. The mean age at surgery was 63 (range 21-87) years. Migration analysis by EBRA-FCA showed a mean subsidence of 1.6 mm at final follow-up at 96 months with a maximum noted mean subsidence of 2.0 mm at 72 and 84 months. Dorr Type A showed a tendency of less subsidence than did Dorr Type B and was statistically significant at 6 (p = 0.0396) and 72 months (p = 0.0127). The body mass index (BMI) and increased subsidence were not found to correlate (p > 0.05). For this cohort, the overall femoral revision-free rate was 95.2% and the revision-free rate for aseptic loosening was 99.1%. CONCLUSIONS: The results showed migration behavior in cementless stems with initial increased migration and subsequent secondary stabilization, suggesting an excellent long-term outcome. Stem migration of this tapered proximally anchored stem might be lower in Dorr Type A than in Dorr Type B femurs without being statistically significant at all time points.

Midterm Results of High-Dose-Rate Intraoperative Brachytherapy in the Treatment of Soft Tissue Sarcomas.

INTRODUCTION: According to the literature only sparse data are available on the use of high-dose-rate intraoperative brachytherapy (IOHDR-BT) as a boost to external-beam irradiation (EBRT) in combination with a wide resection in patients with high-grade soft tissue sarcomas (STS). MATERIALS AND METHODS: Applying a retrospective study design, we investigated all patients who between 2010 and 2016 underwent marginal resection of a high-grade STS and intraoperative radiotherapy, followed by EBRT. We included only patients with a traceable follow-up time of at least two years. Of 89 patients, 35 met our inclusion criteria and showed an average follow-up of four years. RESULTS: We found an overall 2-year local control rate of 94.3%. The local recurrence rate for R0 resections was 6%, whereas recurrences occurred in 13% of R1 resections and in 100% of R2 resections. One affected patient received only intraoperative radiotherapy. The recurrence rate by tumour entity was 36% for LPS, 11% for myxofibrosarcoma and 17% for undifferentiated pleomorphic sarcoma. CONCLUSION: The treatment regimen consisting of limb-preserving surgery, IORT and pre- or postoperative radiotherapy consistently shows excellent local control rates.

Which Physical Phenomena Determine the Ionization Potential of Liquid Water?

Understanding and predicting the properties of molecular liquids from the corresponding properties of the individual molecules is notoriously difficult because there is cooperative behavior among the molecules in the liquid. This is particularly relevant for water, where even the most fundamental molecular properties, such as the dipole moment, are radically different in the liquid compared to the gas phase. In this work, we focus on the ionization potential (IP) of liquid water by dissecting its individual contributions from the individual molecules making up the liquid. This is achieved by using periodic subsystem DFT, a state-of-the-art electronic structure method based on density embedding. We identify and evaluate four important electronic contributions to the IP of water: (1) mean-field, evaluated at the Hartree-Fock level; (2) electronic correlation, incorporated via DFT and wave function-based methods; (3) interaction with and (4) polarization of the environment, both evaluated ab initio with density embedding. Furthermore, we analyze their impact on the IP relative to the structural fluctuation of liquid water, revealing unexpected, hidden correlations, confirming that the broadening of the photoelectron spectra is mostly caused by intermolecular interactions confined in the first solvation shell.

Incidence of alpine skiing and snowboarding injuries.

BACKGROUND: The incidence of injuries on alpine ski slopes have been assessed using various methods. A decline in injury rate has been observed throughout the literature; however, the actual incidence remains unclear. The purpose of this study was therefore to evaluate the incidence of skiing and snowboarding injuries using large-sample data from an entire geographic state. METHODS: Data on alpine injuries over the course of five winter seasons between 2017 and 2022 were prospectively collected from the emergency service dispatch center of Tyrol (Austria). The incidence of injuries was assessed in relation to the number of skier days, which was obtained from the chamber of commerce. RESULTS: A total of 43,283 cases were identified, and a total of 98.1 Mio skier days were registered during the inclusion period of our study, resulting in an overall incidence of 0.44 injuries per 1,000 skier days. This is significantly less than reported from previous studies. From 2017/18 to 2021/22 there was a slight increase in injuries per 1000 skier days with an exception only for the COVID-19 related season 2020/21. CONCLUSION: Our study showed a significant reduction in the incidence of alpine skiing and snowboarding injuries in comparison with previous studies and should be considered a benchmark for future studies. Long-term studies on the efficacy of safety gear, as well as the influence of ski patrol and air-borne rescues on patient outcome are warranted.

Brachytherapy in the Treatment of Soft-Tissue Sarcomas of the Extremities-A Current Concept and Systematic Review of the Literature.

INTRODUCTION: Evidence on the use of brachytherapy in soft-tissue sarcoma (STS) is sparse. Therapy regimens are determined more by local interdisciplinary tumor conferences than by standardized protocols. Patient-specific factors complicate the standardized application of therapy protocols. The individuality of the treatment makes it difficult to compare results. MATERIALS AND METHODS: A comprehensive literature search was conducted, whereby the literature from a period of almost 44 years (1977-2021) was graded and included in this systematic review. For this purpose, PubMed was used as the primary database. Search string included "soft-tissue sarcoma", "brachytherapy", and "extremity." Four independent researchers reviewed the literature. Only full-text articles written in English or German were included. RESULTS: Of the 175 identified studies, 70 were eligible for analysis based on the inclusion and exclusion criteria. The key points to compare were local complications, recurrence rate and correlation with margins of resection, and the use of brachytherapy regarding tumor grading. CONCLUSION: Brachytherapy represents an important subset of radiotherapy techniques used in STSs, whose indications and applications are constantly evolving, and for which a local control rate of 50% to 96% has been reported as monotherapy, depending on risk factors. However, the best benefit is seen in the combination of further resection and brachytherapy, and most authors at many other centers agree with this treatment strategy.

Artificial-Intelligence-Aided Radiographic Diagnostic of Knee Osteoarthritis Leads to a Higher Association of Clinical Findings with Diagnostic Ratings.

BACKGROUND: Radiographic knee osteoarthritis (OA) severity and clinical severity are often dissociated. Artificial intelligence (AI) aid was shown to increase inter-rater reliability in radiographic OA diagnosis. Thus, AI-aided radiographic diagnoses were compared against AI-unaided diagnoses with regard to their correlations with clinical severity. METHODS: Seventy-one DICOMs (m/f = 27:42, mean age: 27.86 ± 6.5) (X-ray format) were used for AI analysis (KOALA software, IB Lab GmbH). Subjects were recruited from a physiotherapy trial (MLKOA). At baseline, each subject received (i) a knee X-ray and (ii) an assessment of five main scores (Tegner Scale (TAS); Knee Injury and Osteoarthritis Outcome Score (KOOS); International Physical Activity Questionnaire; Star Excursion Balance Test; Six-Minute Walk Test). Clinical assessments were repeated three times (weeks 6, 12 and 24). Three physicians analyzed the presented X-rays both with and without AI via KL grading. Analyses of the (i) inter-rater reliability (IRR) and (ii) Spearman's Correlation Test for the overall KL score for each individual rater with clinical score were performed. RESULTS: We found that AI-aided diagnostic ratings had a higher association with the overall KL score and the KOOS. The amount of improvement due to AI depended on the individual rater. CONCLUSION: AI-guided systems can improve the ratings of knee radiographs and show a stronger association with clinical severity. These results were shown to be influenced by individual readers. Thus, AI training amongst physicians might need to be increased. KL might be insufficient as a single tool for knee OA diagnosis.

On the accuracy of orbital based multi-level approaches for closed-shell transition metal chemistry.

In this work, we investigate the accuracy of the local molecular orbital molecular orbital (LMOMO) scheme and projection-based wave function-in-density functional theory (WF-in-DFT) embedding for the prediction of reaction energies and barriers of typical reactions involving transition metals. To analyze the dependence of the accuracy on the system partitioning, we apply a manual orbital selection for LMOMO as well as the so-called direct orbital selection (DOS) for both approaches. We benchmark these methods on 30 closed shell reactions involving 16 different transition metals. This allows us to devise guidelines for the manual selection as well as settings for the DOS that provide accurate results within an error of 2 kcal mol-1 compared to local coupled cluster. To reach this accuracy, on average 55% of the occupied orbitals have to be correlated with coupled cluster for the current test set. Furthermore, we find that LMOMO gives more reliable relative energies for small embedded regions than WF-in-DFT embedding.

EBRA Migration Analysis of a Modular, Distally Fixed Stem in Hip Revision Arthroplasty: A Clinical and Radiological Study.

Background: Massive osteolysis of the proximal femur makes stem revision a challenging procedure. EBRA-FCA provides the opportunity to determine stem migration, which is considered a predictive factor for implant survival. In this study, we aimed to analyze the migration behavior of a modular, distally fixed reconstruction prosthesis. Methods: Applying a retrospective study design, we reviewed all consecutive patients who received a cementless MP reconstruction prosthesis (Waldemar Link GmbH & Co. KG, Hamburg, Germany) at our Department between 2005 and 2019. We reviewed medical histories and performed radiological measurements using EBRA-FCA software. Results: A total of 67 stems in 62 patients (female 26; male 36) fulfilled our inclusion criteria. Mean age at surgery was 68.0 (range 38.7−88.44) years. EBRA migration analysis showed a median subsidence of 1.6 mm (range 0.0−20.6) at 24 months. The angle between stem and femur axis was 0.3° (range 0.0°−2.9°) at final follow-up. No correlation between body mass index and increased subsidence was found (p > 0.05). Overall revision-free rate amounted to 92.5% and revision-free rate for aseptic loosening to 98.5%. Furthermore, no case of material breakage was detected. Conclusions: In summary, the MP reconstruction prosthesis showed low subsidence and reduction in the migration rate over the investigated follow-up. Based on this, the modular stem can be considered as a good therapy option in challenging stem revisions offering various options to address the individual anatomical situation.

Subsystem density-functional theory: A reliable tool for spin-density based properties.

Subsystem density-functional theory compiles a set of features that allow for efficiently calculating properties of very large open-shell radical systems such as organic radical crystals, proteins, or deoxyribonucleic acid stacks. It is computationally less costly than correlated ab initio wave function approaches and can pragmatically avoid the overdelocalization problem of Kohn-Sham density-functional theory without employing hard constraints on the electron-density. Additionally, subsystem density-functional theory calculations commonly start from isolated fragment electron densities, pragmatically preserving a priori specified subsystem spin-patterns throughout the calculation. Methods based on subsystem density-functional theory have seen a rapid development over the past years and have become important tools for describing open-shell properties. In this Perspective, we address open questions and possible developments toward challenging future applications in connection with subsystem density-functional theory for spin-dependent properties.