3-Thiophenemalonic Acid Additive Enhanced Performance in Perovskite Solar Cells.

The development of ambient-air-processable organic-inorganic halide perovskite solar cells (OIHPSCs) is a challenge necessary for the transfer of laboratory-scale technology to large-scale and low-cost manufacturing of such devices. Different approaches like additives, antisolvents, composition engineering, and different deposition techniques have been employed to improve the morphology of the perovskite films. Additives that can form Lewis acid-base adducts are known to minimize extrinsic impacts that trigger defects in ambient air. In this work, we used the 3-thiophenemalonic acid (3-TMA) additive, which possesses thiol and carboxyl functional groups, to convert PbI2, PbCl2, and CH3NH3I to CH3NH3PbI3 completely. This strategy is effective in regulating the kinetics of crystallization and improving the crystallinity of the light-absorbing layer under high relative humidity (RH) conditions (30-50%). As a result, the 3-TMA additive increases the yield of the power conversion efficiency (PCE) from 14.9 to 16.5% and its stability under the maximum power point. Finally, we found that the results of this work are highly relevant and provide additional inputs to the ongoing research progress related to additive engineering as one of the efficient strategies to reduce parasitic recombination and enhance the stability of inverted OIHPSCs in ambient environment processing.

Pinaceae Pine Resins (Black Pine, Shore Pine, Rosin, and Baltic Amber) as Natural Dielectrics for Low Operating Voltage, Hysteresis-Free, Organic Field Effect Transistors.

Four pinaceae pine resins analyzed in this study: black pine, shore pine, Baltic amber, and rosin demonstrate excellent dielectric properties, outstanding film forming, and ease of processability from ethyl alcohol solutions. Their trap-free nature allows fabrication of virtually hysteresis-free organic field effect transistors operating in a low voltage window with excellent stability under bias stress. Such green constituents represent an excellent choice of materials for applications targeting biocompatibility and biodegradability of electronics and sensors, within the overall effort of sustainable electronics development and environmental friendliness.

Machine learning and DFT investigation of CO, CO2 and CH4 adsorption on pristine and defective two-dimensional magnesene.

Adsorption study of environmentally toxic small gas molecules on two-dimensional (2D) materials plays a significant role in analyzing the performance of sensors. In this work, density functional theory (DFT) and machine learning (ML) techniques have been employed to systematically study the adsorption properties of CO, CO2, and CH4 gas molecules on the pristine and defective planar magnesium monolayer, known as magnesene (2D-Mg). The DFT analysis showed that mechanically robust 2D-Mg retains its metallicity in the presence of both mono and di-vacancy defects. Our observations have shown that 2D-Mg, whether defective or pristine, exhibits distinct adsorption behaviors towards CO, CO2, and CH4 gas molecules, including varying chemisorption and physisorption, charge transfer, and distance from the gas molecules. When analyzing the recovery time of gas molecules at room temperature, it is clear that adsorption energy has a direct correlation with the adsorption-desorption cycles, and CH4 possesses an ultra-low recovery time (15.27 ps) compared to CO2 (1.04 ns) and CO (0.90 µs) molecules. The analysis showed that defects do not have a significant impact on the work function of 2D-Mg. However, the work function decreased upon adsorption of CH4, resulting in improved sensitivity due to changes in the electronic properties. Additionally, we explored supervised ML regression models to evaluate their ability to act as a surrogate for the DFT-based adsorption energy calculation. Using both system statistics and smooth overlap of atomic position (SOAP)-based featurization, we observed that adsorption energies can be predicted with a mean absolute error of 0.10 eV.

Elucidating the Origins of High Preferential Crystal Orientation in Quasi-2D Perovskite Solar Cells.

Incorporating large organic cations to form 2D and mixed 2D/3D structures significantly increases the stability of perovskite solar cells. However, due to their low electron mobility, aligning the organic sheets to ensure unimpeded charge transport is critical to rival the high performances of pure 3D systems. While additives such as methylammonium chloride (MACl) can enable this preferential orientation, so far, no complete description exists explaining how they influence the nucleation process to grow highly aligned crystals. Here, by investigating the initial stages of the crystallization, as well as partially and fully formed perovskites grown using MACl, the origins underlying this favorable alignment are inferred. This mechanism is studied by employing 3-fluorobenzylammonium in quasi-2D perovskite solar cells. Upon assisting the crystallization with MACl, films with a degree of preferential orientation of 94%, capable of withstanding moisture levels of 97% relative humidity for 10 h without significant changes in the crystal structure are achieved. Finally, by combining macroscopic, microscopic, and spectroscopic studies, the nucleation process leading to highly oriented perovskite films is elucidated. Understanding this mechanism will aid in the rational design of future additives to achieve more defect tolerant and stable perovskite optoelectronics.

Sensitive and high laser damage threshold substrates for surface-enhanced Raman scattering based on gold and silver nanoparticles.

Surface-enhanced Raman scattering (SERS) is a sensitive and fast technique for sensing applications such as chemical trace analysis. However, a successful, high-throughput practical implementation necessitates the availability of simple-to-use and economical SERS substrates. In this work, we present a robust, reproducible, flexible and yet cost-effective SERS substrate suited for the sensitive detection of analytes at near-infrared (NIR) excitation wavelengths. The fabrication is based on a simple dropcast deposition of silver or gold nanomaterials on an aluminium foil support, making the design suitable for mass production. The fabricated SERS substrates can withstand very high average Raman laser power of up to 400 mW in the NIR wavelength range while maintaining a linear signal response of the analyte. This enables a combined high signal enhancement potential provided by (i) the field enhancement via the localized surface plasmon resonance introduced by the noble metal nanomaterials and (ii) additional enhancement proportional to an increase of the applicable Raman laser power without causing the thermal decomposition of the analyte. The application of the SERS substrates for the trace detection of melamine and rhodamine 6G is demonstrated, which shows limits of detection smaller than 0.1 ppm and analytical enhancement factors on the order of 104 as compared to bare aluminium foil.

Direct Electrochemical CO2 Capture Using Substituted Anthraquinones in Homogeneous Solutions: A Joint Experimental and Theoretical Study.

Electrochemical capture of carbon dioxide (CO2) using organic quinones is a promising and intensively studied alternative to the industrially established scrubbing processes. While recent studies focused only on the influence of substituents having a simple mesomeric or nucleophilicity effect, we have systematically selected six anthraquinone (AQ) derivatives (X-AQ) with amino and hydroxy substituents in order to thoroughly study the influence thereof on the properties of electrochemical CO2 capture. Experimental data from cyclic voltammetry (CV) and UV-Vis spectroelectrochemistry of solutions in acetonitrile were analyzed and compared with innovative density functional tight binding computational results. Our experimental and theoretical results provide a coherent explanation of the influence of CO2 on the CV data in terms of weak and strong binding nomenclature of the dianions. In addition to this terminology, we have identified the dihydroxy substituted AQ as a new class of molecules forming rather unstable [X-AQ-(CO2) n ]2- adducts. In contrast to the commonly used dianion consideration, the results presented herein reveal opposite trends in stability for the X-AQ-CO2 •- radical species for the first time. To the best of our knowledge, this study presents theoretically calculated UV-Vis spectra for the various CO2-AQ reduction products for the first time, enabling a detailed decomposition of the spectroelectrochemical data. Thus, this work provides an extension of the existing classification with proof of the existence of X-AQ-CO2 species, which will be the basis of future studies focusing on improved materials for electrochemical CO2 capture.

Machine Learning and Optoelectronic Materials Discovery: A Growing Synergy.

Novel optoelectronic materials have the potential to revolutionize the ongoing green transition by both providing more efficient photovoltaic (PV) devices and lowering energy consumption of devices like LEDs and sensors. The lead candidate materials for these applications are both organic semiconductors and more recently perovskites. This Perspective illustrates how novel machine learning techniques can help explore these materials, from speeding up ab initio calculations toward experimental guidance. Furthermore, based on existing work, perspectives around machine-learned molecular dynamics potentials, physically informed neural networks, and generative methods are outlined.

Wide-bandgap organic solar cells with a novel perylene-based non-fullerene acceptor enabling open-circuit voltages beyond 1.4 V.

A perylene-based acceptor (PMI-FF-PMI), consisting of two perylene monoimide (PMI) units bridged with a dihydroindeno[1,2-b]fluorene molecule was developed as a potential non-fullerene acceptor (NFA) for organic solar cells (OSCs). The synthesized NFA was combined with the high-performance donor polymer D18 to fabricate efficient OSCs. With an effective bandgap of 2.02 eV, the D18:PMI-FF-PMI blend can be categorized as a wide-bandgap OSC and is an attractive candidate for application as a wide-bandgap sub-cell in all-organic triple-junction solar cell devices. Owing to their large effective bandgap, D18:PMI-FF-PMI solar cells are characterized by an extremely high open-circuit voltage (V OC) of 1.41 V, which to the best of our knowledge is the highest reported value for solution-processed OSCs so far. Despite the exceptionally high V OC of this blend, a comparatively large non-radiative voltage loss (ΔV non-rad OC) of 0.25 V was derived from a detailed voltage loss analysis. Measurements of the electroluminescence quantum yield (ELQY) of the solar cell reveal high ELQY values of ∼0.1%, which contradicts the ELQY values derived from the non-radiative voltage loss (ΔV non-rad OC = 0.25 V, ELQY = 0.0063%). This work should help to raise awareness that (especially for BHJ blends with small ΔHOMO or ΔLUMO offsets) the measured ELQY cannot be straightforwardly used to calculate the ΔV non-rad OC. To avoid any misinterpretation of the non-radiative voltage losses, the presented ELQY discrepancies for the D18:PMI-FF-PMI system should encourage OPV researchers to primarily rely on the ΔV non-rad OC values derived from the presented voltage loss analysis based on EQEPV and J-V measurements.

Patients return to sports and to work after successful treatment of septic arthritis following anterior cruciate ligament reconstruction.

PURPOSE: To determine specific return to sports (RTS) and return to work (RTW) rates of patients with septic arthritis following anterior cruciate ligament reconstruction (ACLR), and to assess for factors associated with a diminished postoperative return to physical activity after successful eradication of the infection. METHODS: In this study, patients who were treated for postoperative septic arthritis of the knee following anterior cruciate ligament reconstruction between 2006 and 2018 were evaluated at a minimum follow-up (FU) of 2 years. Patients' outcomes were retrospectively analyzed using standardized patient-reported outcome scores including the Lysholm score and the subjective IKDC score, as well as return to sports and return to work questionnaires to assess for the types, number, and frequency of sports performed pre- and postoperatively and to evaluate for potential occupational changes due to septic arthritis following ACLR. To assess for the signifiance of the graft at follow-up, outcomes were compared between patients with a functioning graft at FU and those without, as well as between patients with initial graft retention and those with graft removal and consecutive revision ACLR. RESULTS: Out of 44 patients eligible for inclusion, 38 (86%) patients at a mean age of 36.2 ± 10.3 years were enrolled in this study. At a mean follow-up of 60.3 ± 39.9 months, the Lysholm score and the subjective IKDC score reached 80.0 ± 15.1 and 78.2 ± 16.6 points, respectively. The presence of a graft at FU yielded statistically superior results only on the IKDC score (p = 0.014). There were no statistically significant differences on the Lysholm score (n.s.) or on the IKDC score (n.s.) between patients with initial graft retention and those with initial removal who had undergone revision ACLR. All of the included 38 patients were able to return to sports at a median time of 8 (6-16) months after their last surgical intervention. Among patients who performed pivoting sports prior to their injury, 23 (62.2%) returned to at least one pivoting sport postoperatively. Overall, ten patients (26.3%) returned to all their previous sports at their previous frequency. The presence of a graft at FU resulted in a significantly higher RTS rate (p = 0.010). Comparing patients with initial graft retention and those with graft removal and consecutive revision ACLR, there was no statistically significant difference concerning the RTS rate (n.s.). Thirty-one patients (83.8%) were able to return to their previous work. CONCLUSION: Successful eradication of septic arthritis following anterior cruciate ligament reconstruction allows for a postoperative return to sports and a return to work particularly among patients with ACL-sufficient knees. However, the patients' expectations should be managed carefully, as overall return rates at the pre-injury frequency are relatively low. LEVEL OF EVIDENCE: IV.

NHR-8 and P-glycoproteins uncouple xenobiotic resistance from longevity in chemosensory C. elegans mutants.

Longevity is often associated with stress resistance, but whether they are causally linked is incompletely understood. Here we investigate chemosensory-defective Caenorhabditis elegans mutants that are long-lived and stress resistant. We find that mutants in the intraflagellar transport protein gene osm-3 were significantly protected from tunicamycin-induced ER stress. While osm-3 lifespan extension is dependent on the key longevity factor DAF-16/FOXO, tunicamycin resistance was not. osm-3 mutants are protected from bacterial pathogens, which is pmk-1 p38 MAP kinase dependent, while TM resistance was pmk-1 independent. Expression of P-glycoprotein (PGP) xenobiotic detoxification genes was elevated in osm-3 mutants and their knockdown or inhibition with verapamil suppressed tunicamycin resistance. The nuclear hormone receptor nhr-8 was necessary to regulate a subset of PGPs. We thus identify a cell-nonautonomous regulation of xenobiotic detoxification and show that separate pathways are engaged to mediate longevity, pathogen resistance, and xenobiotic detoxification in osm-3 mutants.

Global Property Prediction: A Benchmark Study on Open-Source, Perovskite-like Datasets.

Screening combinatorial space for novel materials, such as perovskite-like ones for photovoltaics, has resulted in a high amount of simulated high-throughput data and analysis thereof. This study proposes a comprehensive comparison of structural fingerprint-based machine learning models on seven open-source databases of perovskite-like materials to predict band gaps and energies. It shows that none of the given methods, including graph neural networks, are able to capture arbitrary databases evenly, while underlining that commonly used metrics are highly database-dependent in typical workflows. In addition, the applicability of variance selection and autoencoders to significantly reduce fingerprint size indicates that models built with common fingerprints only rely on a submanifold of the available fingerprint space.

Protein kinase A controls the hexosamine pathway by tuning the feedback inhibition of GFAT-1.

The hexosamine pathway (HP) is a key anabolic pathway whose product uridine 5'-diphospho-N-acetyl-D-glucosamine (UDP-GlcNAc) is an essential precursor for glycosylation processes in mammals. It modulates the ER stress response and HP activation extends lifespan in Caenorhabditis elegans. The highly conserved glutamine fructose-6-phosphate amidotransferase 1 (GFAT-1) is the rate-limiting HP enzyme. GFAT-1 activity is modulated by UDP-GlcNAc feedback inhibition and via phosphorylation by protein kinase A (PKA). Molecular consequences of GFAT-1 phosphorylation, however, remain poorly understood. Here, we identify the GFAT-1 R203H substitution that elevates UDP-GlcNAc levels in C. elegans. In human GFAT-1, the R203H substitution interferes with UDP-GlcNAc inhibition and with PKA-mediated Ser205 phosphorylation. Our data indicate that phosphorylation affects the interactions of the two GFAT-1 domains to control catalytic activity. Notably, Ser205 phosphorylation has two discernible effects: it lowers baseline GFAT-1 activity and abolishes UDP-GlcNAc feedback inhibition. PKA controls the HP by uncoupling the metabolic feedback loop of GFAT-1.

[Acute rupture of the pectoralis major muscle at the musculotendinous junction : Case report of a rare injury and literature review]. / Akute muskulotendinöse Ruptur des M. pectoralis major : Fallbericht einer seltenen Verletzung und Literaturübersicht.

Rupture of the pectoralis major muscle (PMR) is a rare injury that occurs primarily during strength training. The case of a 31-year-old professional basketball player who suffered a rupture of the pectoralis major muscle (PM) at the myotendinous junction while performing bench presses is presented. Due to persistent pain and decreased muscle function, surgery was performed 3 weeks after the initial trauma. The patient returned to playing basketball pain-free with full range of motion 3 months following refixation of the PM. This article discusses the distinct characteristics of this injury in the context of the current literature and the operative approach is presented in detail.

High prevalence of a deep lateral femoral notch sign in patients with anterior cruciate ligament (ACL) and concomitant posterior root tears of the lateral meniscus.

PURPOSE: To determine the prevalence of a deep lateral femoral notch sign (LFNS) in magnetic resonance imaging (MRI) in patients with anterior cruciate ligament (ACL) and concomitant posterior root tears of the lateral meniscus (PLRT). METHODS: A retrospective chart review was conducted to identify all patients undergoing ACL reconstruction between 2016 and 2018. Based on the arthroscopic appearance of the lateral meniscus, patients were assorted to one of three groups: isolated ACL tear (ACL-Group), ACL tear with concomitant lateral meniscus tear not involving the posterolateral root (Meniscus-Group), and ACL tear with concomitant PLRT (PLRT-Group). Incidence and depth of a LFNS on preoperative MRI was compared between the three cohorts. RESULTS: 115 patients (mean age: 29.5 ± 11.3 years) were included in the study, with 58 patients (50.4%) assorted to the ACL-Group, 24 patients (20.9%) to the Meniscus-Group, and 33 patients (28.7%) to the PLRT-Group. The prevalence of a LFNS was significantly higher in the PLRT-Group (39.4%), when compared to the ACL- (5.2%) or Meniscus-Groups (25.0%; p < 0.001, respectively). Additionally, logistic regression analysis demonstrated that patients with PLRT were 5.3 times more likely to have a LFNS as compared to those without a lateral root tear (p < 0.001). CONCLUSION: In patients with ACL tears, the presence of a LFNS on preoperative MRI may be predictive for a PLRT. As the LFNS occurs in almost 40% of the patients with combined ACL tears and PLRT, the LFNS may be a useful secondary diagnostic finding in early MRI diagnostic. Identifying PLRT on MRI is clinically relevant, as it prevents misdiagnosis and facilitates surgical decision-making, thus avoiding subsequent delayed treatment. LEVEL OF EVIDENCE: Level IV.

Anti-Stokes photoluminescence study on a methylammonium lead bromide nanoparticle film.

Photon cooling via anti-Stokes photoluminescence (ASPL) is a promising approach to realize all-solid-state cryo-refrigeration by photoexcitation. Photoluminescence quantum yields close to 100% and a strong coupling between phonons and excited states are required to achieve net cooling. We have studied the anti-Stokes photoluminescence of thin films of methylammonium lead bromide nanoparticles. We found that the anti-Stokes photoluminescence is thermally activated with an activation energy of ∼80 meV. At room temperature the ASPL up-conversion efficiency is ∼60% and it depends linearly on the excitation intensity. Our results suggest that upon further optimization of their optical properties, the investigated particles could be promising candidates for the demonstration of photon cooling in thin solid films.

Oxygen Reduction Activities of Strained Platinum Core-Shell Electrocatalysts Predicted by Machine Learning.

Core-shell nanocatalyst activities are chiefly controlled by bimetallic material composition, shell thickness, and nanoparticle size. We present a machine learning framework predicting strain with site-specific precision to rationalize how strain on Pt core-shell nanocatalysts can enhance oxygen reduction activities. Large compressive strain on Pt@Cu and Pt@Ni induces optimal mass activities at 1.9 nm nanoparticle size. It is predicted that bimetallic Pt@Au and Pt@Ag have the best mass activities at 2.8 nm, where active sites are exposed to weak compressive strain. We demonstrate that optimal strain depends on the nanoparticle size; for instance, strengthening compressive strain on 1.92 nm sized Pt@Cu and Pt@Ni, or weakening compressive strain on 2.83 nm sized Pt@Ag and Pt@Au, can lead to further enhanced mass activities.

Partial Anterior Cruciate Ligament Ruptures: Advantages by Intraligament Autologous Conditioned Plasma Injection and Healing Response Technique-Midterm Outcome Evaluation.

The historical treatment options for partial anterior cruciate ligament (ACL) ruptures were conservative therapy or ACL reconstruction by injured bundle or entire ACL replacement. In awareness of the regenerative potential of biologic agents such as mesenchymal stem cells or platelet rich plasma (PRP), the healing response technique was developed to preserve the injured ACL with better outcomes than the conservative therapy. Further improvement of this technique seems to be obtained by the additional application of PRP products. Thus, the aim of this study was to evaluate the midterm outcome after intraligament autologous conditioned plasma (ACP) by a clinical, scoring, and functional performance assessment. 42 patients were evaluated in this study. The failure rate was 9.5%. Outcome evaluation showed good to excellent results. The scores were IKDC subjective 83.2 (SD 14.5), Lysholm 85.5 (SD 15.5), Tegner 4.7 (SD 1.7), and Cincinnati 85.4 (SD 15.5) after a mean follow-up of 33 months. Clinical examination showed stable Lachman test, negative pivot shift phenomenon, and a significant reduction in AP-laxity compared to preoperative status (rolimeter preoperative: 1.9 (SD1.4); postoperative 0.6 (SD1.8), p=0.001) in all patients. Functional performance testing showed no significant differences between the injured and healthy side. Return to sport was achieved after a mean of 5.8 months (SD 3.6) in 71.1% of the included patients. In summary, this new treatment option revealed in midterm follow-up promising results to treat partial ACL lesions with a reduced need for conversion to ACL reconstruction and with a high percentage of return to preinjury sport activity.

Correction to: Intra-ligamentary autologous conditioned plasma and healing response to treat partial ACL ruptures.

With regards to Berardo Di Matteo, second author. The author's name is incorrectly listed on Pub-Med. The first and last name have been mixed up.

Intra-ligamentary autologous conditioned plasma and healing response to treat partial ACL ruptures.

INTRODUCTION: Conservative treatment of partial ACL ruptures is associated with a high failure rate, and often patients undergo ACL reconstruction. ACL preservation by trephination of the ACL origin and application of Autologous Conditioned Plasma (ACP) seems to be an intriguing new treatment option to favour ACL tissue healing and avoid traditional reconstruction. The aim of this study was to describe the mid-term outcomes of this new ACL preserving technique. MATERIALS AND METHODS: Twenty-four patients (mean age 41.8 years) affected by partial rupture of one or both ACL bundles were included in the present trial. The partial ACL tears were arthroscopically assessed and classified according to a new five step grading system. All patients were treated by trephination of the femoral ACL stump and intra-ligamentary application of ACP. The postoperative outcome was evaluated by both subjective scores and stability testing up to a mean of 25.1 months' follow-up. Adverse events and failure rate were also documented. RESULTS: Clinical outcome was good to excellent with IKDC subjective 82.7 (SD 11.8), Lysholm 87.6 (SD 8.1), Tegner 5.3 (SD 2.1), Cincinnati 88.7 (SD 14.8). The failure rate (i.e. persisting knee instability assessed clinically or by rolimeter) was 12.5%. At objective measurements, knee joints showed a firm endpoint in Lachman test, negative pivot shift phenomenon and a significant reduction in AP-laxity compared to pre-operative status by rolimeter testing (p = 0.002). Return to sport practice was achieved after mean 4.8 months (SD 4.1). CONCLUSIONS: ACL stump trephination and concomitant intra-ligamentary application of ACP revealed promising results at mid-term follow-up to treat partial ACL lesions.