Engineering Metal Halide Perovskite Nanocrystals with BODIPY Dyes for Photosensitization and Photocatalytic Applications.

The sensitization of surface-anchored organic dyes on semiconductor nanocrystals through energy transfer mechanisms has received increasing attention owing to their potential applications in photodynamic therapy, photocatalysis, and photon upconversion. Here, we investigate the sensitization mechanisms through visible-light excitation of two nanohybrids based on CsPbBr3 perovskite nanocrystals (NC) functionalized with borondipyrromethene (BODIPY) dyes, specifically 8-(4-carboxyphenyl)-1,3,5,7-tetramethyl-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BDP) and 8-(4-carboxyphenyl)-2,6-diiodo-1,3,5,7-tetramethyl-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (I2-BDP), named as NC@BDP and NC@I2-BDP, respectively. The ability of I2-BDP dyes to extract hot hole carriers from the perovskite nanocrystals is comprehensively investigated by combining steady-state and time-resolved fluorescence as well as femtosecond transient absorption spectroscopy with spectroelectrochemistry and quantum chemical theoretical calculations, which together provide a complete overview of the phenomena that take place in the nanohybrid. Förster resonance energy transfer (FRET) dominates (82%) the photosensitization of the singlet excited state of BDP in the NC@BDP nanohybrid with a rate constant of 3.8 ± 0.2 × 1010 s-1, while charge transfer (64%) mediated by an ultrafast charge transfer rate constant of 1.00 ± 0.08 × 1012 s-1 from hot states and hole transfer from the band edge is found to be mainly responsible for the photosensitization of the triplet excited state of I2-BDP in the NC@I2-BDP nanohybrid. These findings suggest that the NC@I2-BDP nanohybrid is a unique energy transfer photocatalyst for oxidizing α-terpinene to ascaridole through singlet oxygen formation.

Influence of Crystallographic Structure and Metal Vacancies on the Oxygen Evolution Reaction Performance of Ni-based Layered Hydroxides.

Nickel-based layered hydroxides (LHs) are a family of efficient electrocatalysts for the alkaline oxygen evolution reaction (OER). Nevertheless, fundamental aspects such as the influence of the crystalline structure and the role of lattice distortion of the catalytic sites remain poorly understood and typically muddled. Herein, we carried out a comprehensive investigation on ɑ-LH, ß-LH and layered double hydroxide (LDH) phases by means of structural, spectroscopical, in-silico and electrochemical studies, which suggest the key aspect exerted by Ni-vacancies in the ɑ-LH structure. Density functional theory (DFT) calculations and X-ray absorption spectroscopy (XAS) confirm that the presence of Ni-vacancies produces acute distortions of the electroactive Ni sites (reflected as the shortening of the Ni-O distances and changes in the O-Ni-O angles), triggering the appearance of Ni localised electronic states on the Fermi level, reducing the Egap, and consequently, increasing the reactivity of the electroactive sites in the ɑ-LH structure. Furthermore, post-mortem Raman and XAS measurements unveil its transformation into a highly reactive oxyhydroxide-like phase that remains stable under ambient conditions. Hence, this work pinpoints the critical role of the crystalline structure as well as the electronic properties of LH structures on their inherent electrochemical reactivity towards OER catalysis. We envision Ni-based ɑ-LH as a perfect platform for hosting trivalent cations, closing the gap toward the next generation of benchmark efficient earth-abundant electrocatalysts.

Utility guideline and considerations for the novel Hugo™ RAS (robotic-assisted surgery) system in colorectal surgery: surgical outcomes and initial experience in a tertiary center.

PURPOSE: A novel robotic platform-Hugo™ RAS (robotic-assisted surgery) system-has been introduced with several innovations that may prove advantageous for surgeons, such as an open console and four interchangeable modular arms. Our study aims to evaluate this platform's safety, efficacy, and potential impact on the surgical treatment of colorectal pathology. METHODS: Patients underwent robotic-assisted colorectal procedures with the Hugo™ RAS system at the General University Hospital of Elche from October 2023 to July 2024. Patient characteristics, intraoperative and postoperative variables, and robotic technical issues were recorded. RESULTS: Forty consecutive patients were included (14 right, 13 left, and 8 rectum neoplasms; 4 left diverticulitis; and 1 ileocecal Crohn's disease). The patients' characteristics were as follows: median age, 69.5 years; 24 males and 16 females; 45% ASA III-IV; and Charlson Comorbidity Index > 5:42.5%. We recorded four medical (2 anemia, 1 phlebitis, and 1 admission to the intensive care unit) and three surgical (1 hematoma of the incision, 1 intestinal occlusion, and 1 dehiscence of the anastomosis) postoperative complications. We had no conversions neither open nor laparoscopic surgery. The average hospital stay was 3 days, with no mortality or readmission. CONCLUSIONS: The Hugo™ RAS system is safe and feasible for colorectal procedures. The modularity of the arms provides the versatility of configurations adjusted depending on the patient's body features and the surgeon's preferences and greater adaptability to operating rooms. The open console is highly comfortable and ergonomic for the surgeon, allowing communication with the operating room environment. TRIAL REGISTRATION: NCT06512480.

A calculator for musculoskeletal injuries prediction in surgeons: a machine learning approach.

BACKGROUND: Surgical specialists experience significant musculoskeletal strain as a consequence of their profession, a domain within the healthcare system often recognized for the pronounced impact of such issues. The aim of this study is to calculate the risk of presenting musculoskeletal injuries in surgeons after surgical practice. METHODS: Cross-sectional study carried out using an online form (12/2021-03/2022) aimed at members of the Spanish Association of Surgeons. Demographic variables on physical and professional activity were recorded, as well as musculoskeletal pain (MSP) associated with surgical activity. Univariate and multivariate analysis were conducted to identify risk factors associated with the development of MSP based on personalized surgical activity. To achieve this, a risk algorithm was computed and an online machine learning calculator was created to predict them. Physiotherapeutic recommendations were generated to address and alleviate each MSP. RESULTS: A total of 651 surgeons (112 trainees, 539 specialists). 90.6% reported MSP related to surgical practice, 60% needed any therapeutic measure and 11.7% required a medical leave. In the long term, MSP was most common in the cervical and lumbar regions (52.4, 58.5%, respectively). Statistically significant risk factors (OR CI 95%) were for trunk pain, long interventions without breaks (3.02, 1.65-5.54). Obesity, indicated by BMI, to lumbar pain (4.36, 1.84-12.1), while an inappropriate laparoscopic screen location was associated with cervical and trunk pain (1.95, 1.28-2.98 and 2.16, 1.37-3.44, respectively). A predictive model and an online calculator were developed to assess MSP risk. Furthermore, a need for enhanced ergonomics training was identified by 89.6% of surgeons. CONCLUSIONS: The prevalence of MSP among surgeons is a prevalent but often overlooked health concern. Implementing a risk calculator could enable tailored prevention strategies, addressing modifiable factors like ergonomics.

Hexagonal Hybrid Bismuthene by Molecular Interface Engineering.

High-quality devices based on layered heterostructures are typically built from materials obtained by complex solid-state physical approaches or laborious mechanical exfoliation and transfer. Meanwhile, wet-chemically synthesized materials commonly suffer from surface residuals and intrinsic defects. Here, we synthesize using an unprecedented colloidal photocatalyzed, one-pot redox reaction a few-layers bismuth hybrid of "electronic grade" structural quality. Intriguingly, the material presents a sulfur-alkyl-functionalized reconstructed surface that prevents it from oxidation and leads to a tuned electronic structure that results from the altered arrangement of the surface. The metallic behavior of the hybrid is supported by ab initio predictions and room temperature transport measurements of individual nanoflakes. Our findings indicate how surface reconstructions in two-dimensional (2D) systems can promote unexpected properties that can pave the way to new functionalities and devices. Moreover, this scalable synthetic process opens new avenues for applications in plasmonics or electronic (and spintronic) device fabrication. Beyond electronics, this 2D hybrid material may be of interest in organic catalysis, biomedicine, or energy storage and conversion.

Presbylarynx: validation of a classification based on morphological characteristics.

PURPOSE: Validation of a classification to stratify presbylarynx into three types. METHODS: Evaluate the reproducibility of this classification. 30 video recordings of rigid laryngostroboscopies were presented to 20 otorhinolaryngologists from five tertiary hospitals: 10 residents and 10 specialists. Specialists with different differentiations were included. RESULTS: Among 1200 evaluations performed (30 video recordings × 20 raters, twice), average intra-rater agreement rate was 0.847 (p < 0.001). The average inter-rater reliability was 0.67 ± 0.179 on the first evaluation, and 0.691 ± 0.131 on the second evaluation. CONCLUSIONS: This study presented the validation of a classification that allows stratifying laryngeal endoscopic signs in elderly patients with presbyphonia. We believe that this classification will enrich the diagnostic protocol of the aging voice and will improve the documentation of treatment outcomes.

Geriatric otorhinolaryngology: reasons for outpatient referrals from generalists to ENT specialists.

PURPOSE: To determine the main symptoms leading to referral of geriatric patients from primary care to otorhinolaryngology. METHODS:  Retrospective, observational study performed on patients aged 65 and older, referred from Primary Care to the Otorhinolaryngology and Head and Neck Surgery department of a tertiary centre during 2019 and 2020. Symptoms leading to otorhinolaryngological referral were categorized as "Oto-neurological symptoms", "Nasal symptoms", "Pharyngolaryngeal symptoms", "Other Head and Neck symptoms" and "Other Reasons". Data regarding age, gender and whether patients maintain follow-up or have been discharged was also collected. RESULTS:  The study population included a total of 1304 patients (697 female; 607 male). Oto-neurological symptoms were found to be the most prevalent symptoms, with 65% of patients reporting oto-neurological symptoms as at least one of the reasons for referral. Hearing loss was the most commonly reported symptom, with an association found between this symptom and age (p < 0.001). Results also showed an association between the female gender and vertigo/dizziness (p < 0.001) and tinnitus (p = 0.007). An association between the male gender and nasal symptoms was also found (p = 0.018), particularly nasal obstruction (p = 0.003) and epistaxis (p = 0.028). No statistically significant associations were found among the pharyngolaryngeal group. CONCLUSIONS:  This retrospective observational study allowed for a better understanding of the type of otorhinolaryngological symptoms affecting elderly patients and driving otorhinolaryngology evaluation, cementing hearing loss as one of the major complaints among older adults and allowing for a better preparation by otorhinolaryngologists for the changing needs of this subset of the population.

Development and validation of a simple web-based tool for early prediction of COVID-19-associated death in kidney transplant recipients.

This analysis, using data from the Brazilian kidney transplant (KT) COVID-19 study, seeks to develop a prediction score to assist in COVID-19 risk stratification in KT recipients. In this study, 1379 patients (35 sites) were enrolled, and a machine learning approach was used to fit models in a derivation cohort. A reduced Elastic Net model was selected, and the accuracy to predict the 28-day fatality after the COVID-19 diagnosis, assessed by the area under the ROC curve (AUC-ROC), was confirmed in a validation cohort. The better calibration values were used to build the applicable ImAgeS score. The 28-day fatality rate was 17% (n = 235), which was associated with increasing age, hypertension and cardiovascular disease, higher body mass index, dyspnea, and use of mycophenolate acid or azathioprine. Higher kidney graft function, longer time of symptoms until COVID-19 diagnosis, presence of anosmia or coryza, and use of mTOR inhibitor were associated with reduced risk of death. The coefficients of the best model were used to build the predictive score, which achieved an AUC-ROC of 0.767 (95% CI 0.698-0.834) in the validation cohort. In conclusion, the easily applicable predictive model could assist health care practitioners in identifying non-hospitalized kidney transplant patients that may require more intensive monitoring. Trial registration: ClinicalTrials.gov NCT04494776.

A single injection of pregabalin induces short- and long-term beneficial effects on fear memory and anxiety-like behavior in rats with experimental type-1 diabetes mellitus.

Anxiety Disorders and Posttraumatic Stress Disorders (PTSD) associated with type-1 diabetes mellitus (T1DM) are increasingly common comorbidities and the treatment is quite challenging. In that sense, evidence indicates that the anticonvulsant pregabalin is highly effective in treating severe cases of anxiety, as well as PTSD and diabetic neuropathic pain which is also very prevalent in T1DM. Herein, the short- and long-term effects of a single injection of pregabalin on the acquisition of a fear extinction memory and parameters of anxiety in induced-T1DM animals were investigated. For that, we used the contextual fear conditioning (CFC) and elevated plus maze paradigms, respectively. A putative antioxidant activity was also evaluated. Our findings demonstrated that induced-T1DM animals presented greater expression of fear memory, difficulty in extinguishing this fear memory, associated with a more pronounced anxiety-like response. Pregabalin was able to induce a short and long-lasting effect by facilitating the acquisition of the fear extinction memory and inducing a later anxiolytic-like effect. Also, the increased lipid peroxidation levels in the hippocampus and prefrontal cortex of induced-T1DM rats were reduced after pregabalin injection, while the decreased levels of reduced glutathione were increased in the hippocampus. Despite the need for more studies to understand the mechanism of action of pregabalin under these conditions, our data demonstrate for the first time that a single injection of pregabalin in a specific time window was able to improve behavioral parameters in addition to inducing neuroprotective effect. Thus, pregabalin has potential worth exploring for the treatment of PTSD and/or Anxiety associated with T1DM.

Frontotemporal Lipofilling for Plagiocephaly Sequelae.

ABSTRACT: Plagiocephaly patients generally undergo corrective surgery in the first years of life, but during their growth malformative sequelae become apparent and can have a negative psychological and social impact. Volumetric filling techniques have been used to improve social balance and minimize such negative effects.We present a case of a 25 years old male with a history of plagiocephaly corrected by 8 months of age. He kept a bilateral frontotemporal defect and we performed a lipofilling of the affected areas. The aesthetic results were very satisfactory and 6 months and 1 year after the procedure he maintained a good volumetric filling. There were no complications during or after the procedure.Lipofilling provides good contouring results and has low complication rates. Its major inconvenient is adipose tissue resorption.As illustrated by this case, this type of treatment significantly improves facial appearance, raising patients' self-esteem and quality of life.