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The breaking of an interatomic bond is at the heart of chemistry yet remains a challenge to be investigated. Molecules on metal surfaces exhibit defined positions and orientations and can be characterized by scanning tunneling microscopy that moreover is able to trigger bond breaking. Until now, the bond dissociation dynamics has been studied in small molecules but not in large ones with various degrees of freedom. Here, we dissociate bromine atoms from single dibromo-terfluorene molecules on Ag(111), identifying not only the displacement but also the rotation of each fragment. It turns out that the molecular excitation that causes dissociation is not locally confined. Instead, it can propagate through the molecule, and the dynamics of the resulting fragments is uncorrelated. The fragment binds to the nearest silver atom after dissociation and dissipates its energy in rotational motion. Our findings could be useful for the precise engineering of chemical reactions with prearranged precursor molecules.

In this analytical cross-sectional method comparison study, we evaluated brain MR images in 30 dogs and cats with and without using a DICOM-based deep-learning (DL) denoising algorithm developed specifically for veterinary patients. Quantitative comparison was performed by measuring signal-to-noise (SNR) and contrast-to-noise ratios (CNR) on the same T2-weighted (T2W), T2-FLAIR, and Gradient Echo (GRE) MR brain images in each patient (native images and after denoising) in identical regions of interest. Qualitative comparisons were then conducted: three experienced veterinary radiologists independently evaluated each patient's T2W, T2-FLAIR, and GRE image series. Native and denoised images were evaluated separately, with observers blinded to the type of images they were assessing. For each image type (native and denoised) and pulse sequence type image, they assigned a subjective grade of coarseness, contrast, and overall quality. For all image series tested (T2W, T2-FLAIR, and GRE), the SNRs of cortical gray matter, subcortical white matter, deep gray matter, and internal capsule were statistically significantly higher on images treated with DL denoising algorithm than native images. Similarly, for all image series types tested, the CNRs between cortical gray and white matter and between deep gray matter and internal capsule were significantly higher on DL algorithm-treated images than native images. The qualitative analysis confirmed these results, with generally better coarseness, contrast, and overall quality scores for the images treated with the DL denoising algorithm. In this study, this DICOM-based DL denoising algorithm reduced noise in 1.5T MRI canine and feline brain images, and radiologists' perceived image quality improved., (© 2025 The Author(s). Veterinary Radiology & Ultrasound published by Wiley Periodicals LLC on behalf of American College of Veterinary Radiology.)

Purpose of Review: Prosthesis-patient mismatch (PPM) remains a significant concern in valve intervention. This review highlights the current evidence surrounding PPM, compares its impact after surgical aortic valve replacement (SAVR) and transcatheter aortic valve implantation (TAVI), and addresses ongoing debates in the literature regarding valve selection, procedural strategies, and future approaches to improve patient outcomes., Recent Findings: Recent evidence highlights that moderate to severe PPM is associated with increased mortality and adverse cardiac events, particularly in younger, active patients and those with smaller aortic annuli. Studies have emphasized the role of optimized prosthesis sizing, advanced imaging modalities, and next-generation valve technologies in mitigating PPM. Additionally, TAVI appears to outperform surgical approaches in reducing severe PPM, particularly in high-risk populations. Despite significant progress, PPM remains a persistent challenge in valve intervention procedures, particularly among patients with smaller aortic annuli and those at risk for suboptimal hemodynamic performance. Addressing this issue requires continued innovation in prosthesis design, including valves with improved hemodynamic profiles and more sizing options. Long-term research is essential to better understand the clinical impact of PPM, evaluate valve durability across various types, and develop strategies to prevent its occurrence., Competing Interests: Declarations. Human and Animal Rights and Informed Consent: This article does not contain any studies with human or animal subjects performed by any of the authors. Competing Interests: The authors declare no competing interests., (© 2025. The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature.)

Here we disclose that spiropyrans are able to undergo dynamic covalent exchange via their corresponding merocyanine isomers. In the latter, the indolinium moieties can be exchanged by a Michael-type addition-elimination sequence, in which a methylene indoline attacks a merocyanine and subsequently the initial indoline fragment is cleaved. The rate and position of the exchange equilibrium strongly depend on the reaction conditions as well as the substitution pattern on the methylene indoline fragments. Importantly, spiropyran cross exchange is catalyzed by indolinium salts and provides the opportunity for rapid in situ structural diversification of spiropyrans. This was used as synthetic tool to access various, hitherto inaccessible spiropyrans as potential dual-color photoinitiators for xolography. Moreover, we foresee application to screen dynamic covalent libraries of spiropyrans for photochromic properties and to exploit their light-sensitivity to bias the thermal equilibrium., (© 2025 The Author(s). Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Streptococcus pyogenes (Group A Streptococcus, GAS) is a human pathogen that causes local and systemic infections of the skin and mucous membranes. However, GAS is also found asymptomatically in the nasopharynx of infants. GAS infections, including pharyngitis and invasive pneumosepsis, pose significant public health concerns. Streptokinase, a key virulence factor of GAS, activates human plasminogen, facilitating bacterial dissemination. Plasminogen, traditionally known for its role in fibrinolysis, may also modulate host immune responses. We therefore aim to investigate systemic and cardiac immune cell responses during pneumonia and pneumosepsis with GAS in a murine infection model. The interaction of streptokinase with human plasminogen is species-specific, therefore the murine pneumosepsis model was developed in a transgenic mouse strain that produces human plasminogen. The data show a critical role of human plasminogen for GAS colonization and systemic spread via the nasopharynx. Due to pneumosepsis blood immune cell profiles and plasma protein levels significantly alters, indicating potential biomarkers for distinguishing local from systemic infection. In the hearts of animals with invasive infection proinflammatory immune cells significantly increased and likely displaced resident healing macrophages. The established pneumosepsis model is useful to study the pathophysiological mechanisms underlying local and invasive pneumonia caused by GAS and to investigate new therapeutic options.

A case of two separate meningiomas with concurrent subdural fluid accumulation is presented. A 13-year-old, male neutered domestic shorthair cat presented with behavior change and progressive neurologic signs localizing to the forebrain. Two extra-axial masses were seen along with a large subdural fluid collection on advanced imaging of the brain. Histology of the lesions was consistent with multiple meningiomas, while analysis of the subdural fluid was consistent with cerebrospinal fluid. A case of multiple feline meningiomas with peritumoral subdural fluid accumulation has not previously been reported., (© 2024 American College of Veterinary Radiology.)

There are few published descriptions of the MRI appearance of canine intracranial or spinal cord ependymoma. In this multicenter, retrospective, secondary analysis, case series study, three veterinary radiologists independently reviewed and recorded imaging characteristics of MRI studies in six dogs with histopathologically confirmed ependymoma (three intracranial and three spinal cord cases). A consensus was reached when there was disagreement on specific features. All intracranial ependymomas had forebrain location, heterogeneous signal intensity in T1-weighted (T1W) and T2-weighted (T2W) images, heterogeneous contrast enhancement, and hyperintensity in T2W images. Two ependymomas had an intraventricular location; one was intra-axial. Other imaging features included intralesional cyst-like structures, intralesional hemorrhage, and perilesional edema. Dogs with spinal cord ependymoma had intramedullary lesions located in the cervical or thoracic spinal cord. Spinal cord ependymomas were isointense and homogeneous in T1W images and hyperintense in T2W images. Lesion location relative to the central canal of the spinal cord was variable. All three spinal cord ependymomas had perilesional T2W hyperintensity and moderate, heterogeneous contrast enhancement. None of the spinal cord ependymomas had intralesional cyst-like structures. One spinal cord ependymoma had evidence of drop metastases (diffuse, leptomeningeal). MRI features of canine ependymomas overlap with those of other diseases of the brain and spinal cord. Ependymoma should be considered a differential diagnosis for dogs with intraventricular, intra-axial forebrain, or intramedullary spinal cord masses., (© 2024 The Author(s). Veterinary Radiology & Ultrasound published by Wiley Periodicals LLC on behalf of American College of Veterinary Radiology.)

Introduction: Head and neck squamous cell carcinoma (HNSCC) is the seventh most common cancer worldwide. Treatment options and patient outcomes have not improved significantly over the past decades, increasing the need for better preclinical models. Holistic approaches that include an intact and functional immune compartment along with the patient's individual tumor microbiome will help improve the predictive value of novel drug efficacy., Areas Covered: In this review, we describe the challenges of modeling the complex and heterogeneous tumor landscape in HNSCC and the importance of sophisticated patient-specific 3D in vitro models to pave the way for clinical trials with novel immunomodulatory drugs. We also discuss the impact of the tumor microbiome and the potential implications for prospective drug screening and validation trials., Expert Opinion: The repertoire of well-characterized preclinical 3D in vitro models continues to grow. With the increasing attention to the complex cellular, immunological, molecular, and spatio-temporal characteristics of tumors, well-designed proof-of-concept studies to test novel drug efficacy are on the verge of providing valuable, practice-changing insights for clinical trials. Bringing together expertise and improving collaboration between clinicians, academics, and regulatory agencies will facilitate the translation of preclinical findings into clinically meaningful outcomes.

Studying molecular materials at the nanoscale allows us to gain a deeper understanding of supramolecular structure formation and serves as the basis for rationally controlling the resulting interfacial properties. Here, we describe the formation of extended Moiré patterns resulting from the assembly of dipolar π-conjugated molecules on highly oriented pyrolytic graphite at the liquid-solid interface as characterized by scanning tunneling microscopy (STM). By switching the bias of the sample and thus the orientation of the external electric field in the vicinity of the STM junction, structural reorganization of the molecular building blocks and the resulting organic 2D crystal is induced and can conveniently be monitored in situ by the appearance and disappearance of the Moiré patterns. Importantly, the formation and loss of the Moiré patterns are fully reversible, providing exquisite control over epitaxial molecular crystals. Our approach provides fundamental insights into the supramolecular organization and resulting superstructure formation of incommensurable 2D lattices upon applying an electric field and enables the rational tuning of Moiré patterns as a key step toward the potential integration of organic 2D crystals in molecular nanodevices.

Background: Surgical management for neurogenic bladder requires complex decision-making by physicians, patients, and caregivers. Assessing decisional regret (DR) as a patient-reported outcome among caregivers could inform future counseling and shared decision-making., Objective: To assess DR among caregivers of children with neurogenic bladder following reconstructive bladder surgery., Study Design: A questionnaire including a validated DR survey was distributed to English-speaking caregivers of children with neurogenic bladder who had undergone reconstructive bladder surgery at Children's Hospital Colorado. DR scores range from zero to 100, with higher numbers indicating higher regret. Wilcoxon rank sum test and Spearman correlation were performed to assess differences in DR scores by patient demographic factors or disease factors., Results: Forty-five of 210 English-speaking caregivers completed the DR survey. The median DR score was 5, with 40% of subjects reporting with a DR score of zero and 24% of subjects with a DR score of 30 or higher. Patient sex and Mitrofanoff leakage were found to be associated with DR, with caregivers of male patients reporting significantly higher DR. Surgical procedure did not have a statistically significant impact on DR scores., Discussion: Sparse existing data exploring DR among patients with neurogenic bladder suggest DR following reconstructive bladder surgery is low, with few identifiable predictors of regret. While the majority of caregivers in our study report little or no DR, one quarter of caregivers report moderate to high DR. The limitations of this study include small cohort size, low response rate, exclusion of non-English speaking patients, and the potential for recall bias due to the survey design of the study., Conclusion: Caregiver DR following bladder reconstruction in children with neurogenic bladder is generally low, however a subset of caregivers reports significant DR. This study suggests that caregivers of male children may have higher DR, a finding that merits further investigation., Competing Interests: Conflict of interest The authors have no competing interests to declare., (Copyright © 2024 Journal of Pediatric Urology Company. Published by Elsevier Ltd. All rights reserved.)

Extradural neoplasms are the most common spinal tumors in small animals. A bilobed appearance of ventral extradural spinal lesions ("gullwing sign") on MRI has been described with various conditions. The objective of this retrospective study was to determine if a "gullwing sign" is more common with certain types of extradural tumors. MRI studies of dogs and cats with extradural spinal neoplasms were reviewed for the presence of a "gullwing sign". Statistical analysis was performed to evaluate a possible relationship between tumor class and the presence of a "gullwing sign". Sixty-six cases were included (5 epithelial, 31 mesenchymal, 4 neuroendocrine, and 26 round cell tumors). A "gullwing sign" was identified in 12 of 66 cases (18.2%) and was significantly more common with round cell neoplasia than other tumor types (P < .001; OR = 28.6, 95% CI [3.4, 241.1]). This information may aid radiologists in prioritizing differential diagnoses for extradural tumors in small animals., (© 2024 American College of Veterinary Radiology.)

Background: Bicuspid aortic valve (BAV) is often associated with a concomitant aortopathy. However, few studies have evaluated the effect of the aortic valve (AV) phenotype on the rate of dilation of the aorta. This study aimed to compare the progression rate of aorta dimensions according to AV phenotype (BAV vs tricuspid AV (TAV)), fusion type and sex in patients with aortic stenosis (AS)., Methods: 310 patients with AS (224 TAV and 86 BAV) recruited in the Metabolic Determinants of the Progression of Aortic Stenosis study (PROGRESSA, NCT01679431) were included in this analysis. Doppler echocardiography was performed annually to assess AS severity and measure ascending aorta (AA) dimensions. Baseline and last follow-up visit measurements were used to assess the annualised change., Results: Median AA annualised change was larger in BAV versus TAV (0.33±0.65 mm/year vs 0.21±0.56 mm/year, p=0.04). In the whole cohort, BAV phenotype and higher low-density lipoprotein (LDL) levels were significantly associated with fast progression of AA dilation in univariate analysis (OR 1.80, 95% CI 1.08 to 2.98, p=0.02; 1.37, 95% CI 1.04 to 1.80, p=0.03, respectively). AA dilation rate did not vary according to the BAV subtype (p=0.142). Predictors of AA progression rate were different between valve phenotypes, with higher apolipoprotein B/apolipoprotein A-I ratio, higher baseline peak aortic jet velocity (V peak ) and smaller baseline AA diameter in the TAV cohort (all p<0.05) versus absence of hypertension, higher LDL levels and smaller baseline AA diameter in the BAV cohort (all p<0.02). In men, higher baseline V peak and smaller baseline AA (p<0.001) were independently associated with increased annualised AA dilation, while in women, higher LDL levels (p=0.026) were independently associated with faster AA dilation., Conclusion: This study suggests that BAV is associated with faster dilation of the AA. Predictors of AA dilation are different between valve phenotype and sex, with higher LDL levels being associated with faster AA dilation in BAV., Competing Interests: Competing interests: PP holds the Canada Research Chair in Valvular Heart Diseases, Canadian Institutes of Health Research and has received funding from Edwards Lifesciences and Medtronic for echocardiography CoreLab analyses with no personal compensation. The remaining authors have nothing to disclose., (© Author(s) (or their employer(s)) 2024. Re-use permitted under CC BY-NC. No commercial re-use. See rights and permissions. Published by BMJ.)

Background: In patients with low-gradient (LG) aortic stenosis (AS), confirming disease severity and indication of intervention often requires dobutamine stress echocardiography (DSE) or aortic valve calcium scoring by computed tomography. We hypothesized that the mean transvalvular pressure gradient to effective orifice area ratio (MG/EOA, in mm Hg/cm 2 ) measured during rest echocardiography identifies true-severe AS (TSAS) and is associated with clinical outcomes in patients with low-flow, LG-AS., Objectives: The purpose of this study was to evaluate the diagnostic and prognostic value of MG/EOA ratio., Methods: The diagnostic accuracy of MG/EOA ratio to identify TSAS was retrospectively assessed in: 1) an in vitro data set obtained in a circulatory model including 93 experimental conditions; and 2) an in vivo data set of 188 patients from the TOPAS (True or Pseudo-Severe Aortic Stenosis) study (NCT01835028). Receiver operating characteristic curves were used to assess the diagnostic accuracy of MG/EOA ratio for identifying TSAS, and Cox proportional hazards regression analyses were performed to assess its association with clinical outcomes., Results: The optimal cutoff of MG/EOA ratio to identify TSAS in patients with low-flow, LG-AS was ≥25 mm Hg/cm 2 (correct classification 85%), as well as in vitro (100%). During a median follow-up of 1.41 ± 0.75 years, 146 (78%) patients met the composite endpoint of aortic valve replacement or all-cause mortality. A MG/EOA ratio ≥25 mm Hg/cm 2 was independently associated with an increased risk of the composite endpoint (adjusted HR: 2.36 [95% CI: 1.63-3.42], P  < 0.001). The Harell's C-index of MG/EOA was 0.68, equaling projected EOA (0.67) measured by DSE., Conclusions: MG/EOA ratio can be useful in low-flow, LG-AS to confirm AS severity and may complement DSE or aortic valve calcium scoring., Competing Interests: This work was supported by a grant (# MOP-57445 for TOPAS-II and # MOP-126072 and FDN-143225 for TOPAS-III) from the 10.13039/501100000024Canadian Institutes of Health Research, Ottawa, Canada. Dr Dahou was supported by a fellowship grant from “L’Agence de la santé et des services sociaux de la Capitale nationale-ADLSSS”, Québec, Québec, Canada. Dr Clavel is recopied of a national new investigator award from the heart and stroke foundation of Canada and received funding from 10.13039/100006520Edwards Lifesciences for computed tomography CoreLab analyses with no personal compensation and research grant from 10.13039/100004374Medtronic. Dr Rodes-Cabau has received institutional research grants from 10.13039/100006520Edwards Lifesciences, 10.13039/100004374Medtronic, and 10.13039/100008497Boston Scientific. Dr Pibarot holds the Canada Research Chair in Valvular Heart Diseases, 10.13039/501100000024Canadian Institutes of Health Research; and has received funding from 10.13039/100006520Edwards Lifesciences and 10.13039/100004374Medtronic for echocardiography CoreLab analyses with no personal compensation. All other authors have reported that they have no relationships relevant to the contents of this paper to disclose., (© 2024 The Authors.)

Malignant splenic lesions in dogs are common, with hemangiosarcoma diagnosed most frequently, and there have been no consistent clinicopathologic, gross, or imaging characteristics identified that differentiate malignant from benign splenic lesions. Histopathology is required for definitive diagnosis, and given the poor long-term prognosis of malignant splenic lesions, a noninvasive tool to aid in diagnosis would be valuable. This prospective cohort study utilized gadoxetate disodium, a liver-specific contrast agent (Gd-EOB-DPTA; Eovist), to identify the general lesion and pre- and postcontrast signal characteristics of benign and malignant splenic and hepatic lesions in dogs with naturally occurring disease. Twenty-five dogs were enrolled, Eovist-enhanced MRI was performed, and dogs were taken to surgery for splenectomy and other organ biopsy. All histopathology and MRI studies were evaluated by a single pathologist and a single radiologist, respectively. The associations between the tumor type and numerous variables defined on MRI were evaluated using Fisher's exact tests, and the significance was identified at a P-value of .05. Malignant splenic masses were identified in 11/25 (44%) dogs, and 5/11 malignancies represented hemangiosarcoma. The presence of abdominal effusion (P = .017) and the presence of hepatic nodules on MRI (P = .009) were associated with splenic malignancy. There were no benign T2 hyperintense and no malignant T2 hypointense lesions (P = .021). Utilization of the T2 W MRI sequence may aid in the identification of malignant splenic lesions, particularly when accompanied by abdominal effusion and hepatic lesions., (© 2024 American College of Veterinary Radiology.)

Background: The CDK4/6 inhibitor abemaciclib is an FDA-approved agent and induces T-cell-mediated immunity. Previously, we confirmed the therapeutic potential of abemaciclib on mismatch repair-deficient (dMMR) tumors in mice. Here, we applied a prophylactic administration/dosage setting using two preclinical mouse models of dMMR-driven cancer., Methods: Mlh1 -/- and Msh2 loxP/loxP mice received repeated prophylactic applications of abemaciclib mesylate (75 mg/kg bw, per oral) as monotherapy or were left untreated. Blood phenotyping and multiplex cytokine measurements were performed regularly. The tumor microenvironment was evaluated by immunofluorescence and Nanostring-based gene expression profiling. Numbers, size and immune composition and activity of extracellular vesicles (EVs) were studied at the endpoint., Findings: Prophylactic abemaciclib-administration delayed tumor development and significantly prolonged overall survival in both mouse strains (Mlh1 -/- : 50.0 wks vs. control: 33.9 wks; Msh2 loxP/loxP;TgTg(Vil1-cre : 58.4 wks vs. control 44.4 wks). In Mlh1 -/- mice, pro-inflammatory cytokines (IL-2, IL-6) significantly increased, whereas IL-10 and IL-17A decreased. Circulating and splenic exhausted and regulatory T cell numbers were significantly lower in the abemaciclib groups. Deeper analysis of late-onset tumors revealed activation of the Hedgehog and Notch signaling in Mlh1 -/- mice, and activation of the MAPK pathway in Msh2 loxP/loxP;TgTg(Vil1-cre mice. Still, arising tumors had fewer infiltrating myeloid-derived suppressor cells (vs. control). Notably, prophylactic abemaciclib-administration prevented secretion of procoagulant EVs but triggered release of immunomodulatory EVs in Mlh1 -/- mice., Interpretation: Prophylactic abemaciclib prolongs survival via global immunomodulation. Prophylactic use of abemaciclib should be considered further for individuals with inherited dMMR., Funding: This work was supported by grants from the German research foundation [DFG grant number: MA5799/2-2] and the Brigitte und Dr. Konstanze Wegener-Stiftung to CM., Competing Interests: Declaration of competing interest The authors declare that they have no competing interests., (Copyright © 2024. Published by Elsevier Inc.)

The ability to correlate the structure of a molecule with its properties is the key to the rational and accelerated design of new functional compounds and materials. Taking photoswitches as an example, the thermal stability of the metastable state is a crucial property that dictates their application in molecular systems. Indigos have recently emerged as an attractive motif for designing photoswitchable molecules due to their red-light addressability, which can be advantageous in biomedical and material applications. The lack of synthetic techniques to derivatize the abundant parent dye and a thorough understanding of the impact of structural factors on the photochemical and thermal properties hinder broad applications of this emerging photoswitch class. Herein, we report an efficient copper-catalyzed indigo N -arylation that enables the installation of a wide variety of aryl moieties carrying useful functional groups. The exclusive selectivity for monoarylation likely originates from a bimetallic cooperative mechanism through a binuclear copper-indigo intermediate. Functional N -aryl- N' -alkylindigos were prepared and shown to photoisomerize efficiently under red light. Moreover, this design allows for the modulation of thermal half-lives through N -aryl substituents, while the N' -alkyl groups enable the independent attachment of functional moieties without affecting the photochromic properties. A strong correlation between the structure of the N -aryl moiety and the thermal stability of the photogenerated Z -isomers was achieved by multivariate linear regression models obtained through a data-science workflow. This work thus builds an avenue leading to versatile red-light photoswitches and a general method for structure-property correlation that is expected to be broadly applicable to the design of photoresponsive molecules.

Objectives: The aim of the study was to investigate the potential prognostic role of preoperative measurement of erector spinae myosteatosis with Hounsfield unit average calculation as a marker for sarcopenia and frailty in patients undergoing coronary bypass surgery., Methods: Preoperative computer tomography-derived measurements of 479 consecutive patients undergoing coronary bypass surgery between January 2017 and December 2019 were retrospectively performed. The erector spinae muscle at the level of the 12th vertebra was manually outlined bilaterally on the axial computer tomography slices and Hounsfield unit average calculation was performed. The lower quartile of muscle density values was defined as myosteatotic and thus sarcopenic. Sarcopenic (n = 121) versus non-sarcopenic patients (n = 358) were compared regarding postoperative morbidity and short- and long-term mortality. Results were adjusted for age, body mass index, atrial fibrillation and hypertension using inverse probability weighting., Results: Sarcopenia was associated with higher 30-day mortality (4.1% vs 0.8%; P = 0.012), mid-term mortality after 1 year (9.3% vs 3.1%; P = 0.047) and 2 years (10.8% vs 4.2%; P = 0.047). Long-term mortality (5 years) was 20.8% for sarcopenic and 13.0% for non-sarcopenic patients but was not found to be significantly different (P = 0.089). Sarcopenia was associated with higher rates of reintubation (7.5% vs 1.1%; P < 0.001), sternal wound infections (7.5% vs 2.8%; P = 0.039) and acute kidney injury requiring haemodialysis (2.5% vs 0.4%; P = 0.021)., Conclusions: In patients undergoing coronary bypass surgery, sarcopenia was associated with increased short-term mortality, mid-term mortality and morbidity. The measurement of erector spinae myosteatosis could be an easy and useful parameter in preoperative risk assessment., (© The Author(s) 2024. Published by Oxford University Press on behalf of the European Association for Cardio-Thoracic Surgery. All rights reserved.)

Organic/inorganic hybrid systems offer great potential for novel solar cell design combining the tunability of organic chromophore absorption properties with high charge carrier mobilities of inorganic semiconductors. However, often such material combinations do not show the expected performance: while ZnO, for example, basically exhibits all necessary properties for a successful application in light-harvesting, it was clearly outpaced by TiO 2 in terms of charge separation efficiency. The origin of this deficiency has long been debated. This study employs femtosecond time-resolved photoelectron spectroscopy and many-body ab initio calculations to identify and quantify all elementary steps leading to the suppression of charge separation at an exemplary organic/ZnO interface. It is demonstrated that charge separation indeed occurs efficiently on ultrafast (350 fs) timescales, but that electrons are recaptured at the interface on a 100 ps timescale and subsequently trapped in a strongly bound (0.7 eV) hybrid exciton state with a lifetime exceeding 5 µs. Thus, initially successful charge separation is followed by delayed electron capture at the interface, leading to apparently low charge separation efficiencies. This finding provides a sufficiently large time frame for counter-measures in device design to successfully implement specifically ZnO and, moreover, invites material scientists to revisit charge separation in various kinds of previously discarded hybrid systems., (© 2024 The Author(s). Advanced Science published by Wiley‐VCH GmbH.)

Competing Interests: Mohsen Beheshti reports a relationship with Novartis Pharma GmbH that includes: board membership and consulting or advisory. Christian Pirich reports a relationship with Novartis Pharma GmbH that includes: board membership and consulting or advisory. Other authors declare that they have no conflict of intrest.

Natural photoactive systems have evolved to harness broad-spectrum light from solar radiation for critical functions such as light perception and photosynthetic energy conversion. Molecular photoswitches, which undergo structural changes upon light absorption, are artificial photoactive tools widely used for developing photoresponsive systems and converting light energy. However, photoswitches generally need to be activated by light of specific narrow wavelength ranges for effective photoconversion, which limits their ability to directly work under sunlight and to efficiently harvest solar energy. Here, focusing on azo-switches-the most extensively studied photoswitches, we demonstrate effective solar E→Z photoisomerization with photoconversions exceeding 80 % under unfiltered sunlight. These sunlight-driven azo-switches are developed by rendering the absorption of E isomers overwhelmingly stronger than that of Z isomers across a broad ultraviolet to visible spectrum. This unusual type of spectral profile is realized by a simple yet highly adjustable molecular design strategy, enabling the fine-tuning of spectral window that extends light absorption beyond 600 nm. Notably, back-photoconversion can be achieved without impairing the forward solar isomerization, resulting in unique light-reversible solar switches. Such exceptional solar chemistry of photoswitches provides unprecedented opportunities for developing sustainable light-driven systems and efficient solar energy technologies., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Objective : The objective of this study was to prospectively assess the extent to which magnetic resonance imaging (MRI) can differentiate malignant from benign lesions of the testis. Materials and Methods : All included patients underwent multiparametric testicular MRI, including diffusion-weighted imaging (DWI) and subtraction dynamic contrast-enhanced (DCE) magnetic resonance imaging (MRI). Subsequently, all patients underwent a histopathological examination via orchiectomy or testicular biopsy/partial resection. The Kolmogorov-Smirnov test, t -test, Mann-Whitney U test, Fisher's exact test, and logistic regression were applied for statistical analysis. Results : We included 48 male patients (median age 37.5 years [range 18-69]) with testicular tumors. The median tumor size on MRI was 2.0 cm for malignant tumors and 1.1 cm for benign tumors ( p < 0.05). A statistically significant difference was observed for the type (type 0-III curve, p < 0.05) and pattern of enhancement (homogeneous, heterogeneous, or rim-like, p < 0.01) between malignant and benign tumors. The minimum apparent diffusion coefficient (ADC) value was 0.9 for benign tumors and 0.7 for malignant tumors (each ×10 3 mm 2 /s, p < 0.05), while the mean ADC was 0.05. The mean ADC value was significantly lower for malignant tumors; the mean ADC value was 1.1 for benign tumors and 0.9 for malignant tumors (each ×10 3 mm 2 /s, p < 0.05). The sensitivity, specificity, positive predictive value, and negative predictive value of multiparametric MRI for differentiating malignant from benign testicular lesions were 94.3%, 76.9%, 91.7%, and 83.3%, respectively. The surgical procedures performed included orchiectomy ( n = 33; 71.7%) and partial testicular resection ( n = 11; 23.9%). Histopathology (HP) revealed malignancy in 35 patients (72.9%), including 26 with seminomas and 9 with non-seminomatous germ cell tumors (NSGCTs). The HP was benign in 13 (27.1%) patients, including 5 with Leydig cell tumors. Conclusions : Malignant and benign tumors differ in MRI characteristics in terms of the type and pattern of enhancement and the extent of diffusion restriction, indicating that MRI can be an important imaging modality for the accurate diagnosis of testicular lesions.

Transcatheter aortic valve implantation (TAVI) is now utilised as a less invasive alternative to surgical aortic valve replacement (SAVR) across the whole spectrum of surgical risk. Long-term durability of the bioprosthetic valves has become a key goal of TAVI as this procedure is now considered for younger and lower-risk populations. The purpose of this article is to present a state-of-the-art overview on the definition, aetiology, risk factors, mechanisms, diagnosis, clinical impact, and management of bioprosthetic valve dysfunction (BVD) and failure (BVF) following TAVI with a comparative perspective versus SAVR. Structural valve deterioration (SVD) is the main factor limiting the durability of the bioprosthetic valves used for TAVI or SAVR, but non-structural BVD, such as prosthesis-patient mismatch and paravalvular regurgitation, as well as valve thrombosis or endocarditis may also lead to BVF. The incidence of BVF related to SVD or other causes is low (<5%) at midterm (5- to 8-year) follow-up and compares favourably with that of SAVR. The long-term follow-up data of randomised trials conducted with the first generations of transcatheter heart valves also suggest similar valve durability in TAVI versus SAVR at 10 years, but these trials suffer from major survivorship bias, and the long-term durability of TAVI will need to be confirmed by the analysis of the low-risk TAVI versus SAVR trials at 10 years.

The artificial brain is conceived as advanced intelligence technology, capable to emulate in-memory processes occurring in the human brain by integrating synaptic devices. Within this context, improving the functionality of synaptic transistors to increase information processing density in neuromorphic chips is a major challenge in this field. In this article, Li-ion migration promoting long afterglow organic light-emitting transistors, which display exceptional postsynaptic brightness of 7000 cd m -2 under low operational voltages of 10 V is presented. The postsynaptic current of 0.1 mA operating as a built-in threshold switch is implemented as a firing point in these devices. The setting-condition-triggered long afterglow is employed to drive the photoisomerization process of photochromic molecules that mimic neurotransmitter transfer in the human brain for realizing a key memory rule, that is, the transition from long-term memory to permanent memory. The combination of setting-condition-triggered long afterglow with photodiode amplifiers is also processed to emulate the human responding action after the setting-training process. Overall, the successful integration in neuromorphic computing comprising stimulus judgment, photon emission, transition, and encoding,  to emulate the complicated decision tree of the human brain is demonstrated., (© 2024 The Authors. Advanced Materials published by Wiley‐VCH GmbH.)

Competing Interests: Die Autorinnen/Autoren geben an, dass kein Interessenkonflikt besteht.