Polymer-based antibody mimetics (iBodies) target human PD-L1 and function as a potent immune checkpoint blocker.

Immune checkpoint blockade (ICB) using monoclonal antibodies against programmed cell death protein 1 (PD-1) or programmed death-ligand 1 (PD-L1) is the treatment of choice for cancer immunotherapy. However, low tissue permeability, immunogenicity, immune-related adverse effects, and high cost could be possibly improved using alternative approaches. On the other hand, synthetic low-molecular-weight (LMW) PD-1/PD-L1 blockers have failed to progress beyond in vitro studies, mostly due to low binding affinity or poor pharmacological characteristics resulting from their limited solubility and/or stability. Here, we report the development of polymer-based anti-human PD-L1 antibody mimetics (α-hPD-L1 iBodies) by attaching the macrocyclic peptide WL12 to a N-(2-hydroxypropyl)methacrylamide copolymer. We characterized the binding properties of iBodies using surface plasmon resonance, enzyme-linked immunosorbent assay, flow cytometry, confocal microscopy, and a cellular ICB model. We found that the α-hPD-L1 iBodies specifically target human PD-L1 (hPD-L1) and block the PD-1/PD-L1 interaction in vitro, comparable to the atezolizumab, durvalumab, and avelumab licensed monoclonal antibodies targeting PD-L1. Our findings suggest that iBodies can be used as experimental tools to target hPD-L1 and could serve as a platform to potentiate the therapeutic effect of hPD-L1-targeting small molecules by improving their affinity and pharmacokinetic properties.

In-plane anisotropic and ultra-low-loss polaritons in a natural van der Waals crystal.

Polaritons-hybrid light-matter excitations-enable nanoscale control of light. Particularly large polariton field confinement and long lifetimes can be found in graphene and materials consisting of two-dimensional layers bound by weak van der Waals forces1,2 (vdW materials). These polaritons can be tuned by electric fields3,4 or by material thickness5, leading to applications including nanolasers6, tunable infrared and terahertz detectors7, and molecular sensors8. Polaritons with anisotropic propagation along the surface of vdW materials have been predicted, caused by in-plane anisotropic structural and electronic properties9. In such materials, elliptic and hyperbolic in-plane polariton dispersion can be expected (for example, plasmon polaritons in black phosphorus9), the latter leading to an enhanced density of optical states and ray-like directional propagation along the surface. However, observation of anisotropic polariton propagation in natural materials has so far remained elusive. Here we report anisotropic polariton propagation along the surface of α-MoO3, a natural vdW material. By infrared nano-imaging and nano-spectroscopy of semiconducting α-MoO3 flakes and disks, we visualize and verify phonon polaritons with elliptic and hyperbolic in-plane dispersion, and with wavelengths (up to 60 times smaller than the corresponding photon wavelengths) comparable to those of graphene plasmon polaritons and boron nitride phonon polaritons3-5. From signal oscillations in real-space images we measure polariton amplitude lifetimes of 8 picoseconds, which is more than ten times larger than that of graphene plasmon polaritons at room temperature10. They are also a factor of about four larger than the best values so far reported for phonon polaritons in isotopically engineered boron nitride11 and for graphene plasmon polaritons at low temperatures12. In-plane anisotropic and ultra-low-loss polaritons in vdW materials could enable directional and strong light-matter interactions, nanoscale directional energy transfer and integrated flat optics in applications ranging from bio-sensing to quantum nanophotonics.

Patterns of genetic divergence in the Rio Grande cooter (Pseudemys gorzugi), a riverine turtle inhabiting an arid and anthropogenically modified system.

The lower Rio Grande and Pecos River of the southwest United States have been heavily modified by human activities, profoundly impacting the integrity of their aquatic wildlife. In this context, we focused our study on the population genomics of the Rio Grande Cooter (Pseudemys gorzugi), a freshwater turtle of increasing conservation concern, residing in these two rivers and their tributaries. The genetic data revealed two distinct populations: one in the Pecos and Black Rivers of New Mexico and another in the Rio Grande and Devils River of Texas, with admixed individuals identified at the confluence of the Rio Grande and Pecos River. In addition to having a smaller geographic range, we found lower observed heterozygosity, reduced nucleotide diversity, and a smaller effective population size (Ne) in New Mexico population. Our results depict a significant isolation-by-distance pattern across their distribution, with migration being notably infrequent at river confluences. These findings are pivotal for future conservation and restoration strategies, emphasizing the need to recognize the unique needs of each population.

Population-based norms for the human papillomavirus-quality of life (HPV-QoL) questionnaire: A cross-sectional multicenter study.

INTRODUCTION: Human papillomavirus (HPV) diagnosis has a considerable emotional and psychological impact on women. To evaluate the impairment this infection leads to regarding quality of life (QoL), several scales have been suggested, such as the human-papillomavirus-quality-of-life (HPV-QoL) questionnaire. This has been validated for the Spanish population and measures the impact of HPV on health-related-quality-of-life (HR-QoL). However, normative values are yet to be developed. Thus, the objective was to describe the population-based norms of the HPV-QoL for Spanish women aged 25-65 years and to test the questionnaire's construct validity. MATERIAL AND METHODS: This was a cross-sectional nationwide multicenter study. Women from outpatient clinics in Spain aged 25-65 years, with a diagnosis of past or active HPV infection were recruited. The central tendency, dispersion, and percentiles were calculated for the total score and its dimensions for each age group. Construct validity was tested by analyzing age groups and their correlations with other related scales (12-Item General Health Questionnaire [GHQ-12], Female Sexual Function Index [FSFI], and Hospital Anxiety and Depression Scale [HADS]). RESULTS: A total of 1352 women were included in the study. The norms showed moderate and significant coefficients of correlation with other related scales. Significant differences between age strata groups were found according to educational level, sexual dysfunction, sexual activity, mental deterioration, and severity of anxiety and depression symptoms (p < 0.001 in all cases). The total score differed significantly between the groups (p = 0.006). Significant differences in the contagiousness, health, and sexuality dimensions (p < 0.05) were found among the groups. It was seen that HPV infection impaired women's QoL. Dimensions within all test age groups (p < 0.001 in all cases) were significantly different, with the health dimension being the highest contributor to women's QoL impairment, whereas social well-being was the main determinant of QoL. CONCLUSIONS: Population-based norms for the novel HPV-QoL questionnaire showed adequate validity and could be a useful tool for assessing the impact of QoL among women with HPV in Spain.

Lateral-type posterior fossa ependymomas in pediatric patients: a national collaborative study.

PURPOSE: To review a multicentric series of lateral-type posterior fossa ependymomas operated in the last ten years and to analyze the factors related to clinical evolution and tumor survival. METHODS: Descriptive, retrospective study. Active members of the Spanish Society of Pediatric Neurosurgery were invited to participate in this multicentric study. Clinical and radiological data were incorporated to an open database. The role of histologic grade, grade of resection, postoperative morbidities, and clinical follow-up was evaluated through bivariate associations (chi-square), Kaplan-Meier's curves (log-rank test), and multivariate analysis (binary logistic regression). RESULTS: Fourteen centers entered the study, and 25 cases with a minimum follow-up of 6 months were included. There were 13 boys and 12 girls with a mean age close to 3 years. Mean tumor volume at diagnosis was over 60 cc. A complete resection was achieved in 8 patients and a near-total resection in 5 cases. Fifteen tumors were diagnosed as ependymoma grade 2 and ten as ependymoma grade 3. Major morbidity occurred postoperatively in 14 patients but was resolved in twelve within 6 months. There were six cases of death and 11 cases of tumor progression along the observation period. Mean follow-up was 44.8 months. Major morbidity was significantly associated with histologic grade but not with the degree of resection. Overall and progression-free survival were significantly associated with complete surgical resection. At the last follow-up, 16 patients carried a normal life, and three displayed a mild restriction according to Lansky's scale. CONCLUSIONS: Lateral-type posterior fossa ependymomas constitute a specific pathologic and clinical tumor subtype with bad prognosis. Gross total resection is the goal of surgical treatment, for it significantly improves prognosis with no additional morbidity. Neurological deficits associated to lower cranial nerve dysfunction are common, but most are transient. Deeper genetic characterization of these tumors may identify risk factors that guide new treatments and stratification of adjuvant therapies.

Dyrk1a gene dosage in glutamatergic neurons has key effects in cognitive deficits observed in mouse models of MRD7 and Down syndrome.

Perturbation of the excitation/inhibition (E/I) balance leads to neurodevelopmental diseases including to autism spectrum disorders, intellectual disability, and epilepsy. Loss-of-function mutations in the DYRK1A gene, located on human chromosome 21 (Hsa21,) lead to an intellectual disability syndrome associated with microcephaly, epilepsy, and autistic troubles. Overexpression of DYRK1A, on the other hand, has been linked with learning and memory defects observed in people with Down syndrome (DS). Dyrk1a is expressed in both glutamatergic and GABAergic neurons, but its impact on each neuronal population has not yet been elucidated. Here we investigated the impact of Dyrk1a gene copy number variation in glutamatergic neurons using a conditional knockout allele of Dyrk1a crossed with the Tg(Camk2-Cre)4Gsc transgenic mouse. We explored this genetic modification in homozygotes, heterozygotes and combined with the Dp(16Lipi-Zbtb21)1Yey trisomic mouse model to unravel the consequence of Dyrk1a dosage from 0 to 3, to understand its role in normal physiology, and in MRD7 and DS. Overall, Dyrk1a dosage in postnatal glutamatergic neurons did not impact locomotor activity, working memory or epileptic susceptibility, but revealed that Dyrk1a is involved in long-term explicit memory. Molecular analyses pointed at a deregulation of transcriptional activity through immediate early genes and a role of DYRK1A at the glutamatergic post-synapse by deregulating and interacting with key post-synaptic proteins implicated in mechanism leading to long-term enhanced synaptic plasticity. Altogether, our work gives important information to understand the action of DYRK1A inhibitors and have a better therapeutic approach.

Implementation of Diabetic Retinopathy Screening in Adult Patients With Type 2 Diabetes in a Primary Care Setting.

Diabetic retinopathy (DR) is a microvascular complication of type 2 diabetes and the leading cause of blindness globally. Although diabetes-related eye exams are widely recognized as an effective method for early detection of DR, which can help to prevent eventual vision loss, adherence to screening exams in the United States is suboptimal. This article describes a quality improvement project to increase DR screening rates and increase knowledge and awareness of DR in adults with type 2 diabetes in a primary care setting using mobile DR screening units. This project addressed gaps of care and demonstrated that primary care settings can increase access to DR screening through a patient-centered process and thereby help to prevent irreversible outcomes of DR and improve quality of life.

Gender Gap: A Qualitative Study of Women and Leadership Acquisition in Anesthesiology.

BACKGROUND: The representation of women among leaders in the field of anesthesia continues to trail that of their male counterparts. This qualitative study was conducted to understand the pathway of leadership acquisition among women in the field of anesthesiology. METHODS: Using constructivist grounded theory, we sought to determine whether there were specific internal or external factors that were common to women in leadership in the specialty field of anesthesiology, and specifically, how they obtained leadership positions. Semistructured interviews were conducted for data collection. A total of 26 women in leadership positions in anesthesiology participated in this study. RESULTS: The analysis of these interviews resulted in the development of 4 common themes related to career pathways for these women in leadership. Each theme was examined in depth to determine the qualities necessary for individuals to advance in the field and the pathway to obtaining leadership positions. The findings of this study showed that early-career, high-value mentorship and sponsorship were important factors in leadership acquisition. Most participants (n = 20; 76%) had early mentors. Of those with early mentorship, 13 (65%) had high-value mentors, who we define as someone with power or authority. Sponsorship was the leading factor contributing to leadership acquisition. CONCLUSIONS: The results of this qualitative study may serve as a guide for encouraging female anesthesiologists with leadership aspirations. We suggest that the specialty field of anesthesiology institute targeted measures to help increase the percentage of women leadership with formal sponsorship programs at the local and national levels.

Fetal heart rate changes and labor neuraxial analgesia: a machine learning approach.

BACKGROUND: Neuraxial labor analgesia has been associated with fetal heart rate changes. Fetal bradycardia is multifactorial, and predicting it poses a significant challenge to clinicians. Machine learning algorithms may assist the clinician to predict fetal bradycardia and identify predictors associated with its presentation. METHODS: A retrospective analysis of 1077 healthy laboring parturients receiving neuraxial analgesia was conducted. We compared a principal components regression model with tree-based random forest, ridge regression, multiple regression, a general additive model, and elastic net in terms of prediction accuracy and interpretability for inference purposes. RESULTS: Multiple regression identified combined spinal-epidural (CSE) (p = 0.02), interaction between CSE and dose of phenylephrine (p < 0.0001), decelerations (p < 0.001), and the total dose of bupivacaine (p = 0.03) as associated with decrease in fetal heart rate. Random forest exhibited good predictive accuracy (mean standard error of 0.92). CONCLUSION: Use of CSE, presence of decelerations, total dose of bupivacaine, and total dose of vasopressors after CSE are associated with decreases in fetal heart rate in healthy parturients during labor. Prediction of changes in fetal heart rate can be approached with a tree-based random forest model with good accuracy with important variables that are key for the prediction, such as CSE, BMI, duration of stage 1 of labor, and dose of bupivacaine.

Sensitivity-to-change and predictive validity of the Cervantes Short-Form (C-SF) questionnaire in postmenopausal women.

OBJECTIVES: To explore, for the first time, the ability of the Cervantes Short-Form (C-SF) questionnaire to detect and to predict meaningful changes (sensitivity-to-change and predictive validity) in women with menopausal symptoms receiving any therapeutic management under routine medical care. METHODS: Postmenopausal women included in a registry study were the source of data. Sensitivity-to-change was explored by assessing the responses of C-SF to different type of treatment management: no treatment, natural therapies or systemic hormonal therapy (SHT). Predictive validity assessed the ability of baseline score to predict the reduction in the impact of menopausal symptoms in C-SF scoring equal or higher than one time its minimally important difference (MID) of improvement (response rate). RESULTS: A total of 245 women were enrolled. C-SF score was significantly reduced (better QoL) with SHT by 10.62 points versus no change or 2.32 point by natural therapies or no treatment, respectively (p < 0.001 in both cases). Women declaring better improvement after treatment showed higher significant reduction in C-SF score versus those with no self-perceived improvement or impairment: -12.49 point versus +1.06 and +12.71, respectively (p < 0,01 in both cases). Responder rate showed a significant lineal growing trend with higher C-SF scoring at baseline in women who received SHT: higher scoring showed higher response rates (lineal Chi2 = 15.9, p < 0.001), but not in the case of receiving natural therapies or no treatment. CONCLUSIONS: C-SF was shown to be sensitive-to-change when postmenopausal QOL status changes due to mainly systemic hormonal treatment, therefore, supporting the utilization of this instrument to monitor response to treatment. Likewise, pre-treatment scoring in C-SF was able to predict woman's QOL meaningful response with hormonal treatment.

Development and psychometric properties of the human papillomavirus-quality of life (HPV-QoL) questionnaire to assess the impact of HPV on women health-related-quality-of-life.

PURPOSE: The HPV-Quality-of-Life (HPV-QoL) questionnaire was developed to determine the impact of Human-Papillomavirus (HPV) infection and related interventions on women health-related quality-of-life. This study provides the development and preliminary psychometric properties of a novel HPV-QoL questionnaire for adult women with HPV. METHODS: After reviewing literature and cognitive debriefing interviews in women who had experienced HPV-related conditions, instrument items and domains were developed. A draft questionnaire was pilot tested for comprehension and ease of completion. Psychometric evaluation of the final HPV-QoL scale was conducted in a psychometric study including 252 adult women derived to our centre by a positive HPV test in the cervical cancer screening program and/or presenting genital warts. RESULTS: The present study reveals that the HPV-QoL questionnaire, structured in four domains: general well-being [including psychological well-being and social well-being subdomains], health, contagiousness and sexuality, showed good metric properties of feasibility irrespective of age or educational level, and time to administer was less than 5 min. Internal consistency and temporal stability (reliability) showed values above the acceptable standards. The instrument showed its concurrent validity by means of a significant correlation with mental and sexual existing instruments; GHQ-12 and FSFI questionnaires, respectively, and also known groups validity showing significant differences among the subgroups regarding either sexual dysfunction or mental deterioration. CONCLUSION: This study provides an HPV-QoL questionnaire with an innovative patient-reported outcomes specific measurement tool to assess HRQoL in women with HPV infection. The present study suggests this questionnaire has satisfactory psychometric properties, including validity and reliability. Results support the use of the HPV-QoL questionnaire as a HRQoL measurement instrument for daily medical practice and clinical research.

Broad spectral tuning of ultra-low-loss polaritons in a van der Waals crystal by intercalation.

Phonon polaritons-light coupled to lattice vibrations-in polar van der Waals crystals are promising candidates for controlling the flow of energy on the nanoscale due to their strong field confinement, anisotropic propagation and ultra-long lifetime in the picosecond range1-5. However, the lack of tunability of their narrow and material-specific spectral range-the Reststrahlen band-severely limits their technological implementation. Here, we demonstrate that intercalation of Na atoms in the van der Waals semiconductor α-V2O5 enables a broad spectral shift of Reststrahlen bands, and that the phonon polaritons excited show ultra-low losses (lifetime of 4 ± 1 ps), similar to phonon polaritons in a non-intercalated crystal (lifetime of 6 ± 1 ps). We expect our intercalation method to be applicable to other van der Waals crystals, opening the door for the use of phonon polaritons in broad spectral bands in the mid-infrared domain.

Management of a ruptured intraventricular aneurysm arising from distal anterior choroidal artery (AChA): pediatric case report.

Intracranial aneurysms arising from the distal anterior choroidal artery (AChA) are uncommon entities, with less than 30 cases reported. A 4-year-old boy was admitted to the Emergency Department with a sudden onset of severe headache and vomiting. CT scan of the head showed signs of intraventricular hemorrhage (IVH) and subarachnoid hemorrhage (SAH). Cerebral angiography revealed a right AChA aneurysm arising from a distal intraventricular branch with an associated microarteriovenous malformation (microAVM). Following a multidisciplinary assessment, the patient underwent surgical clipping. An ipsilateral transcortical transparietal approach was utilized. Early postoperative deficits were not found, and good clinical and radiological outcomes were assessed at long-term follow-up. Postoperative cerebral angiography showed complete exclusion and resection of both aneurysm and AVM. Surgery for intracranial aneurysms in this location can be challenging; however, good surgical and neurological outcomes can be achieved. The present work highlights the value of multidisciplinary assessment in the decision-making process in complex pediatric neurovascular pathology, especially when facing rare cases like this one, which represents the youngest case of a ruptured distal AChA aneurysm reported in the literature.

Diffuse leptomeningeal glioneuronal tumour: where to biopsy? Case report and literature review.

PURPOSE: Diffuse leptomeningeal glioneuronal tumour (DLGT) is an infrequent entity. Diagnosis is made with biopsy but with so few cases described management, prognosis remains undefined. There are not currently any articles regarding most effective place to biopsy. METHODS: Current literature review and introduction of the case of a 3-year-old male presenting at the emergency room with irritability, vomiting and nuchal rigidity. A head CT was made showing tetraventricular enlargement and a posterior fossa cyst. RESULTS: Patient underwent urgent ventriculoperitoneal shunting surgery with complete symptomp resolution. Brain MRI showed diffuse leptomeningeal enhancing, predominantly in basal cisterns, and multiple cystic-solid lesions along the neural axis. After ruling other conditions, a biopsy among intraoperative samples, was obtained of a PET positive gadolinium spinal enhancing lesion at D8 level, with the final diagnosis of DLGT. CONCLUSION: DLGT can present as acute hydrocephalus. Biopsy stablishes the diagnosis but the place to take the sample can be difficult to select. Our experience suggests that PET-CT and intraoperative biopsy analysis can improve the effectivity of a representative sample.

Disability-adjusted life expectancy lost due to pain severity and usual analgesic treatment among older adults with osteoarthritis in Spain.

BACKGROUND: Osteoarthritis (OA) is a seriously debilitating disease, which prevalence is growing in aging population becoming a substantial burden (BoD) to society. AIM: To assess disability-adjusted life expectancy (DALE) lost by pain severity and usual analgesic treatment among OA adults 65 + year in Spain. METHODS: The National Health Survey, a large, nationally representative, cross-sectional general health survey administered to 23,089 individuals was the data source. Data on subjects of 65 + years with a self-reported physician diagnosis of OA were analysed. Records were cross-classified by pain severity (no pain/mild pain, moderate pain and severe pain) and use of usual analgesics. DALE lost was used as a summary measure of BoD and expressed as both number of years of healthy life-expectancy lost due to disability and percentage of life-expectancy lost. RESULTS: 3389 records were analysed [women 73.3%; age 77.4 (SD 7.5) years]. Older OA patients showed a mean (95% CI) DALE loss of 3.5 (3.3-3.7) years, that represented on average a loss of 35.6% (33.8-37.4) as a percentage of life expectancy. Higher pain severity and analgesic treatment was statistically linked to more years of DALE lost; from 2.8 (2.3-3.2), in no/mild, to 9.0 (8.6-9.4) years in severe pain, and from 32.2% (27.5-36.9) to 90.9% (86.5-95.3) of life expectancy, respectively. DISCUSSION: In Spain, older adults with moderate to severe OA pain receiving usual analgesics showed a substantial BoD in terms of years of DALE lost and percentage of life expectancy lost. CONCLUSIONS: Patients with treated moderate to severe pain showed a more significant burden in term of DALE lost despite analgesic treatment, which apparently fails to meet pain management needs.

Twisted Nano-Optics: Manipulating Light at the Nanoscale with Twisted Phonon Polaritonic Slabs.

Recent discoveries have shown that, when two layers of van der Waals (vdW) materials are superimposed with a relative twist angle between them, the electronic properties of the coupled system can be dramatically altered. Here, we demonstrate that a similar concept can be extended to the optics realm, particularly to propagating phonon polaritons-hybrid light-matter interactions. To do this, we fabricate stacks composed of two twisted slabs of a vdW crystal (α-MoO3) supporting anisotropic phonon polaritons (PhPs), and image the propagation of the latter when launched by localized sources. Our images reveal that, under a critical angle, the PhPs isofrequency curve undergoes a topological transition, in which the propagation of PhPs is strongly guided (canalization regime) along predetermined directions without geometric spreading. These results demonstrate a new degree of freedom (twist angle) for controlling the propagation of polaritons at the nanoscale with potential for nanoimaging, (bio)-sensing, or heat management.

The city turned off: Urban dynamics during the COVID-19 pandemic based on mobile phone data.

Due to the rapid expansion of the COVID-19 pandemic, many countries ordained lockdowns, establishing different restrictions on people's mobility. Exploring to what extent these measures have been effective is critical in order to better respond to similar future scenarios. This article uses anonymous mobile phone data to study the impact of the Spanish lockdown on the daily dynamics of the Madrid metropolitan area (Spain). The analysis has been carried out for a reference week prior to the lockdown and during several weeks of the lockdown in which different restrictions were in place. During these weeks, population distribution is compared during the day and at night and presence profiles are obtained throughout the day for each type of land use. In addition, a spatial multiple regression analysis is carried out to determine the impact of the different land uses on the local population. The results in the reference week, pre-COVID-19, show how the population in activity areas increases in each time slot on a specific day and how in residential areas it decreases. However, during the lockdown, activity areas cease to attract population during the day and the residential areas therefore no longer show a decrease. Only basic essential commercial activities, or others that require the presence of workers (industrial or logistics) maintain some activity during lockdown.

Strain-Tunable Single Photon Sources in WSe2 Monolayers.

The appearance of single photon sources in atomically thin semiconductors holds great promises for the development of a flexible and ultracompact quantum technology in which elastic strain engineering can be used to tailor their emission properties. Here, we show a compact and hybrid two-dimensional semiconductor-piezoelectric device that allows for controlling the energy of single photons emitted by quantum emitters localized in wrinkled WSe2 monolayers. We demonstrate that strain fields exerted by the piezoelectric device can be used to tune the energy of localized excitons in WSe2 up to 18 meV in a reversible manner while leaving the single photon purity unaffected over a wide range. Interestingly, we find that the magnitude and, in particular, the sign of the energy shift as a function of stress is emitter dependent. With the help of finite element simulations we suggest a simple model that explains our experimental observations and, furthermore, discloses that the type of strain (tensile or compressive) experienced by the quantum emitters strongly depends on their localization across the wrinkles. Our findings are of strong relevance for the practical implementation of single photon devices based on two-dimensional materials as well as for understanding the effects of strain on their emission properties.

A Non-Heme Diiron Complex for (Electro)catalytic Reduction of Dioxygen: Tuning the Selectivity through Electron Delivery.

In the oxygen reduction reaction (ORR) domain, the investigation of new homogeneous catalysts is a crucial step toward the full comprehension of the key structural and/or electronic factors that control catalytic efficiency and selectivity. Herein, we report a unique non-heme diiron complex that can act as a homogeneous ORR catalyst in acetonitrile solution. This iron(II) thiolate dinuclear complex, [FeII2(LS)(LSH)] ([Fe2SH]+) (LS2- = 2,2'-(2,2'-bipyridine-6,6'-diyl)bis(1,1-diphenylethanethiolate)) contains a thiol group in the metal coordination sphere. [Fe2SH]+ is an efficient ORR catalyst both in the presence of a one-electron reducing agent and under electrochemically assisted conditions. However, its selectivity is dependent on the electron delivery pathway; in particular, the process is selective for H2O2 production under chemical conditions (up to ∼95%), whereas H2O is the main product during electrocatalysis (less than ∼10% H2O2). Based on computational work alongside the experimental data, a mechanistic proposal is discussed that rationalizes the selective and tunable reduction of dioxygen.

Quality indicators in gastroscopy. Gastroscopy procedure.

Within the project "Quality indicators in digestive endoscopy", pioneered by the Spanish Society for Digestive Diseases (SEPD), the objective of this research is to suggest the structure, process, and results procedures and indicators necessary to implement and assess quality in the gastroscopy setting. First, a chart was designed with the steps to be followed during a gastroscopy procedure. Secondly, a team of experts in care quality and/or endoscopy performed a qualitative review of the literature searching for quality indicators for endoscopic procedures, including gastroscopies. Finally, using a paired analysis approach, a selection of the literature obtained was undertaken. For gastroscopy, a total of nine process indicators were identified (one preprocedure, eight intraprocedure). Evidence quality was assessed with the Grading of Recommendations Assessment, Development and Evaluation (GRADE) classification scale.