Fitting Multiplet Simulations to L-Edge XAS Spectra of Transition-Metal Complexes Using an Adaptive Grid Algorithm.

A new methodology based on an adaptive grid algorithm followed by an analysis of the ground state from the fit parameters is presented to analyze and interpret experimental XAS L2,3-edge data. The fitting method is tested first in a series of multiplet calculations for d0-d7 systems and for which the solution is known. In most cases, the algorithm is able to find the solution, except for a mixed-spin Co2+ Oh complex, where it instead revealed a correlation between the crystal field and the electron repulsion parameters near spin-crossover transition points. Furthermore, the results for the fitting of previously published experimental data sets on CaO, CaF2, MnO, LiMnO2, and Mn2O3 are presented and their solution discussed. The presented methodology has allowed the evaluation of the Jahn-Teller distortion in LiMnO2, which is consistent with the observed implications in the development of batteries, which use this material. Moreover, a follow-up analysis of the ground state in Mn2O3 has demonstrated an unusual ground state for the highly distorted site which would be impossible to optimize in a perfect octahedral environment. Ultimately, the presented methodology can be used in the analysis of X-ray absorption spectroscopy data measured at the L2,3-edge for a large number of materials and molecular complexes of first-row transition metals and can be expanded to the analysis of other X-ray spectroscopic data in future studies.

Factores de riesgo de persistencia en pacientes con tratamiento quirúrgico de hiperparatiroidismo primario / Risk factors for surgical failure in patients undergoing surgery for primary hyperparathyroidism

Introducción El hiperparatiroidismo primario es la tercera enfermedad endócrina más frecuente. El objetivo de este estudio fue determinar los resultados a largo plazo y los factores de riesgo de persistencia en pacientes operados por hiperparatiroidismo primario. Métodos Estudio retrospectivo de pacientes operados de paratiroidectomía entre 2009-2019. Se definió cura como el restablecimiento de la homeostasis normal del calcio durante un mínimo de seis meses, persistencia como la continuidad de hipercalcemia por más de seis meses postoperatorios, y recurrencia como la reaparición de hipercalcemia luego de un intervalo normocalcémico mayor a seis meses postoperatorios. Se realizó un análisis más detallado en pacientes con normocalcemia y hormona paratiroidea (HPT) elevada postoperatoria. Las variables independientemente relacionadas a persistencia fueron analizadas mediante análisis multivariante. Resultados Se incluyeron 212 pacientes. La edad media fue 59 años y 83% fueron mujeres. Se observó cura en 204 pacientes (96,2%), persistencia en ocho (3,8%) y recurrencia en tres (1,4%). Cuatro pacientes (1,9%) presentaron normocalcemia y HPT persistentemente elevada luego de la cirugía. Todos presentaron patología paratiroidea (dos adenoma y dos hiperplasia). En el seguimiento se observaron tres pacientes con fallo renal crónico (FRC) y uno con déficit de vitamina D. La persistencia se asoció independientemente con hiperplasia (Odds ratio=12,6; IC 95%: 1,28-124; p = 0,030) y tejido paratiroideo normal (Odds ratio=188; IC 95%: 9,33- 379; p = 0,001) en el estudio histopatológico. Conclusión La paratiroidectomía es un procedimiento seguro en términos de morbilidad y resultados a largo plazo. La hiperplasia y el tejido paratiroideo normal en el estudio histopatológico son factores de riesgo de persistencia (AU)

Introduction Primary hyperparathyroidism is the third most common endocrine disease. The aim of our study was to determine long-term outcomes and risk factors for persistence in patients undergoing parathyroidectomy for primary hyperparathyroidism. Methods Retrospective study including patients undergoing parathyroidectomy between 2009- 2019. Cure was defined as reestablishment of normal calcium homeostasis lasting a minimum of 6 months. Persistence was defined by ongoing hypercalcemia more than 6 months after surgery. Recurrent PHTP was defined by recurrence of hypercalcemia after a normocalcemic interval at more than 6 months after surgery. A more detailed analysis was performed on patients with normocalcemia and persistently elevated PTH levels after surgery. Variables independently related to persistence were analyzed by multivariate analysis. Results We included 212 patients. Mean age was 59 years and 83% were women. Cure was observed in 204 patients (96.2%), persistence in 8 (3.8%) and recurrence in 3 (1.4%). Four patients (1.9%) presented normocalcemia and persistently elevated PTH after surgery. All presented parathyroid pathology (2 adenomas and 2 hyperplasia). In follow-up we observed that adenoma subgroup presented one patient with CKD and one with vitamin D deficiency while in the hyperplasia subgroup two patients presented CKD. Persistence was independently associated with hyperplasia (Odds ratio=12.6, IC95%=1.28-124, p=0.030) and normal parathyroid tissue (Odds ratio=188, IC95%=9.33-379, p=0.001) on histopathological report. Conclusión Primary hyperparathyroidism is a safe procedure in terms of morbidity and long-term outcomes. Hyperplasia and normal parathyroid tissue on histopathological report are risk factors for persistence. An interdisciplinary diagnostic and therapeutic approach is required to prevent persistence (AU)

Patterns of Volatility Across the Spike Protein Accurately Predict the Emergence of Mutations within SARS-CoV-2 Lineages

Mutations in the spike glycoprotein of SARS-CoV-2 allow the virus to probe the sequence space in search of higher-fitness states. New sublineages of SARS-CoV-2 variants-of-concern (VOCs) continuously emerge with such mutations. Interestingly, the sites of mutation in these sublineages vary between the VOCs. Whether such differences reflect the random nature of mutation appearance or distinct evolutionary spaces of spike in the VOCs is unclear. Here we show that each position of spike has a lineage-specific likelihood for mutations to appear and dominate descendent sublineages. This likelihood can be accurately estimated from the lineage-specific mutational profile of spike at a protein-wide level. The mutability environment of each position, including adjacent sites on the protein structure and neighboring sites on the network of comutability, accurately forecast changes in descendent sublineages. Mapping of imminent changes within the VOCs can contribute to the design of immunogens and therapeutics that address future forms of SARS-CoV-2.

Effects of the age/rage axis in the platelet activation.

Platelet activity is essential in cardiovascular diseases. Therefore our objective was to evaluate the main effects of activating RAGE in platelets which are still unknown. A search for RAGE expression in different databases showed poor or a nonexistent presence in platelets. We confirmed the expression in platelets and secreted variable of RAGE (sRAGE). Platelets from elderly adults expressed in resting showed 3.2 fold more RAGE from young individuals (p < 0.01) and 3.3 fold with TRAP-6 (p < 0.001). These results could indicate that the expression of RAGE is more inducible in older adults. Then we found that activating RAGE with AGE-BSA-derived from methylglyoxal and subthreshold TRAP-6, showed a considerable increase with respect to the control in platelet aggregation and expression of P-selectin (respectively, p < 0.01). This effect was almost completely blocked by using a specific RAGE inhibitor (FSP-ZM1), confirming that RAGE is important for the function and activation platelet. Finally, we predict the region stimulated by AGE-BSA is located in region V of RAGE and 13 amino acids are critical for its binding. In conclusion, the activation of RAGE affects platelet activation and 13 amino acids are critical for its stimulation, this information is crucial for future possible treatments for CVD.

How soon should urgent EEG be performed following a first epileptic seizure?

PURPOSE: Patients with a first unprovoked epileptic seizure are often seen in emergency services. Electroencephalography (EEG) is indicated for diagnosing epilepsy, but the optimal time to perform this test has not been defined. This study aimed to determine the time interval following a seizure within which EEG has the greatest diagnostic yield. METHODS: We conducted a retrospective study of all adult patients with a first unprovoked seizure who had undergone emergency EEG (July 2014-December 2019). Data collection included demographics, seizure type, time interval to EEG study, EEG pattern identified, and the prescription after emergency assessment. An optimal cut-off point for time to EEG was obtained, and an adjusted regression model was performed to establish associations with the presence of epileptiform abnormalities. RESULTS: A total of 170 patients were included (mean age: 50.7 years, 40.6% women). Epileptiform discharges were identified in 34.1% of recordings, nonepileptiform abnormalities in 46.5%, and normal findings in 19.4%. A lower latency from seizure to EEG was associated with a higher probability of finding epileptiform discharges (median: 12.7 in the epileptiform EEGs vs. 20 h in the nonepileptiform EEGs, p < 0.001). The time interval associated with the highest probability of detecting an epileptiform EEG pattern was within the first 16 h after seizure onset: 52.1% of recordings performed before the 16-h cut-off showed these abnormal patterns compared with 20.2% performed after (p < 0.001). These findings were not related to the presence of an epileptogenic lesion in neuroimaging or to other clinical variables. The finding of epileptiform abnormalities was followed by a greater prescription of antiseizure drugs (96.4% vs. 66% in nonepileptiform patterns, p < 0.001). CONCLUSION: The diagnostic yield of EEG following a first unprovoked epileptic seizure is highest when this test is performed within the first 16 h after onset of the event.

Galactose-α-1,3-galactose (alpha-gal) allergy: first pediatric case in a series of patients in Spain.

INTRODUCTION AND OBJECTIVES: Allergy to galactose-α-1,3-galactose (alpha-gal) is a peculiar form of food allergy generally manifesting as an anaphylactic reaction hours after mammalian meat consumption, due to the presence of specific IgE against this oligosaccharide. In addition, immediate anaphylaxis may develop after exposure to other sources of alpha-gal, such as monoclonal antibody cetuximab, vaccines, plasma expanders or anti-snake venoms. Sensitization to alpha-gal has also been implicated in the rapid degeneration of biological valve implants, and recognized as a cause of occupational disease in cattle raisers. The implication of tick bites in this type of sensitization has been accepted by all the research groups dedicated to this disease. PATIENTS AND METHOD: The present study describes the clinical and sensitization characteristics of 39 patients diagnosed with alpha-gal allergy in the hospitals of our province (Lugo, Monforte de Lemos and Burela, Spain). RESULTS: Most patients were middle-age males. Of note, is the fact that the series includes the first pediatric patient reported in Spain to date. The predominant clinical manifestations were urticaria or delayed anaphylaxis after consumption of mammalian meat. Seventy-four percent of the patients reported having suffered a previous tick bite, and the clinical presentation of anaphylaxis was significantly more prevalent in those with a persistent local reaction following the bite than in those with no such reaction (p = 0.032). CONCLUSIONS: A review is also made of the disorder which, due to its variable clinical expression, is referred to as alpha-gal syndrome. The study concludes that a diagnosis of alpha-gal allergy should be considered in patients with urticaria-anaphylaxis of uncertain origin or manifesting after the administration of vaccines or products of bovine/porcine origin.

Consensus on the prevention, diagnosis, and treatment of Clostridium difficile infection. / Consenso sobre prevención, diagnóstico y tratamiento de la infección por Clostridium difficile.

In recent decades, Clostridium difficile infection (CDI) has become a worldwide health problem. Mexico is no exception, and therefore the Asociación Mexicana de Gastroenterología brought together a multidisciplinary group (gastroenterologists, endoscopists, internists, infectious disease specialists, and microbiologists) to carry out the "Consensus on the prevention, diagnosis, and treatment of Clostridium difficile infection", establishing useful recommendations (in relation to the adult population) for the medical community. Said recommendations are presented herein. Among them, it was recognized that CDI should be suspected in subjects with diarrhea that have a history of antibiotic and/or immunosuppressant use, but that it can also be a community-acquired infection. A 2-step diagnostic algorithm was proposed, in which a highly sensitive test, such as glutamate dehydrogenase (GDH), is first utilized, and if positive, confirmed by the detection of toxins through immunoassay or nucleic acid detection tests. Another recommendation was that CDI based on clinical evaluation be categorized as mild-moderate, severe, and complicated severe, given that such a classification enables better therapeutic decisions to be made. In mild-moderate CDI, oral vancomycin is the medication of choice, and metronidazole is recommended as an alternative treatment. In addition, fecal microbiota transplantation was recognized as an efficacious option in patients with recurrence or in the more severe cases of infection, and surgery should be reserved for patients with severe colitis (toxic megacolon), in whom all medical treatment has failed.

[Efficacy and safety of transcranial magnetic stimulation in patients with non-fluent aphasia, following an ischaemic stroke. A controlled, randomised and double-blind clinical trial]. / Eficacia y seguridad de la estimulacion magnetica transcraneal en pacientes con afasia no fluente, posterior a ictus isquemico. Ensayo clinico controlado, aleatorizado y doble ciego.

INTRODUCTION: Non-fluent aphasia is a frequent complication in post-ischemic stroke patients, with repetitive transcranial magnetic stimulation (rTMS) being one of the possible treatment alternatives. AIM: To assess the efficacy and safety of rTMS in patients with non-fluent after-ischemic stroke aphasia. PATIENTS AND METHODS: Double blind, randomized controlled clinical trial in post-stroke patients who were assigned to receive 10 sessions (one daily) of active treatment or placebo of rTMS, without the addition of language therapy. The baseline characteristics were compared initially and the efficacy between the active group versus the placebo group at day 30 was evaluated through a Mann-Whitney U test. RESULTS: 82 patients were included: active group (n = 41) and placebo group (n = 41). At baseline, statistically significant differences were found between the groups in favor of the placebo in the domains of the Boston test of auditory compression (p = 0.024), denomination (p = 0.014) and praxis (p = 0.026), and also occurred on the 30th day in the naming domains (p = 0.037) and reading (p = 0.001). There were 39 adverse reactions: 23 (26.83%) in the active group vs 16 (21.96%) in the placebo group (p = 0.290); the majority corresponded to episodes of mild headache. CONCLUSION: rTMS is a safe therapy, however, given the conditions of this study, we could not demonstrate the efficacy of rTMS versus placebo in patients with non-fluent aphasia with involvement of Broca's area after an ischemic stroke.

TITLE: Eficacia y seguridad de la estimulacion magnetica transcraneal en pacientes con afasia no fluente, posterior a ictus isquemico. Ensayo clinico controlado, aleatorizado y doble ciego.Introduccion. La afasia no fluente es una complicacion frecuente en pacientes postictus isquemico y la estimulacion magnetica transcraneal repetitiva (EMTr) representa una de las posibles alternativas de tratamiento. Objetivo. Evaluar la eficacia y la seguridad de la EMTr en pacientes con afasia no fluente postictus isquemico. Pacientes y metodos. Ensayo clinico controlado doble ciego, aleatorizado, en pacientes postictus isquemico que fueron asignados a recibir 10 sesiones (una diaria) de tratamiento activo o placebo de EMTr, sin adicion de terapia del lenguaje. Las caracteristicas basales fueron comparadas inicialmente, y la eficacia entre el grupo activo frente al grupo placebo el dia 30 se evaluo a traves de una prueba U de Mann-Whitney. Resultados. Se incluyo a 82 pacientes: grupo activo (n = 41) y grupo placebo (n = 41). Se encontraron diferencias basales estadisticamente significativas entre los grupos a favor del placebo en los dominios del test de Boston de compresion auditiva (p = 0,024), denominacion (p = 0,014) y praxis (p = 0,026), e igualmente ocurrio el dia 30 en los dominios de denominacion (p = 0,037) y lectura (p = 0,001). Se presentaron 39 reacciones adversas, 23 en el grupo activo (26,83%) frente a 16 (21,96%) en el grupo placebo (p = 0,290), y la mayoria correspondia a episodios de cefalea leve. Conclusion. La EMTr es una terapia segura, pero dadas las condiciones de este estudio, no pudo demostrarse la eficacia de la EMTr frente al placebo en pacientes con afasia no fluente con afectacion del area de Broca posterior a un ictus isquemico.

Regulación en la práctica de la neuropsicología clínica en México / Regulation in the practice of clinical neuropsychology in Mexico

En México, no existe una adecuada regulación legal de la práctica profesional de la neuropsicología, a pesar de que existen pautas a nivel internacional donde se estipula que el profesional debe tener una formación teórica-práctica sobre neurociencias, psicología clínica y psicometría, además de destreza en habilidades clínicas y formulación de programas de intervención sólidamente fundamentados en estudios empíricos. Por lo tanto, es necesario que los profesionistas estén capacitados para desarrollar su labor, pues de lo contrario estaría atentando contra derechos fundamentales del ser humano. Por lo que las autoridades en materia de salud mental, al tener facultades suficientes para actualizar y legalizar en relación con la práctica clínica, deberán implementar medidas más específicas y rígidas en cuanto a los requisitos que deben reunir los profesionales en materia de neuropsicología. Finalmente, se debe impulsar el consenso entre las asociaciones, universidades y profesionales del campo, para establecer vías de comunicación que tenga como objetivo la regulación y reconocimiento de la profesionalización en neuropsicología clínica.

In Mexico, there is a lack of legal regulation of the professional practice of neuropsychology, even though there are international guidelines on the practice of neuropsychology which stipulate to have theoretical-practical training in neuroscience, clinical psychology and psychometrics, as well as skills in clinical and formulation of intervention programs solidly based on empirical studies. Therefore, it is a necessity that the professionals are properly trained, because otherwise it would be attacking the fundamental rights of the human being. Thus, the mental health authorities should update and legalize in relation to clinical practice more specific measures on the requirements to practice clinical neuropsychology. Finally, consensus among associations, universities, and professionals in the field should be encouraged to establish a communication that aims to regulate and recognize the practice in clinical neuropsychology.

Thiophene and its sulfur inhibit indenoindenodibenzothiophene diradicals from low-energy lying thermal triplets.

Many qualitative structure-property correlations between diradical character and emerging molecular properties are known. For example, the increase of diradical character further decreases the singlet-triplet energy gap. Here we show that inclusion of thiophenes within a quinoidal polycyclic hydrocarbon imparts appreciable diradical character yet retains the large singlet-triplet energy gap, a phenomenon that has no precedent in the literature. The low aromatic character of thiophene and its electron-rich nature are the key properties leading to these unique findings. A new indenoindenodibenzothiophene scaffold has been prepared and fully characterized by several spectroscopies, magnetic measurements, solid-state X-ray and state-of-the-art quantum chemical calculations, all corroborating this unique dichotomy between the diradical input and the emerging magnetic properties. New structure-property relationships such as these are not only extremely important in the field of diradical chemistry and organic electronics, but also provide new insights into the versatility of π-electron chemical bonding.

Risk factors for Clostridium difficile infection in intestinal transplant recipients during the first year post-transplant.

BACKGROUND: Clostridium difficile is the most common cause of healthcare-associated infectious diarrhea. Risk factors for C. difficile infections (CDI) in intestinal transplant recipients (ITR) are not well-defined. The aim of our study was to assess specific risk factors for CDI in ITR. METHODS: This is a 1:3 case-control study that included 29 ITR who developed CDI (cases) and 87 ITR without CDI (controls) observed during the first year post-transplantation. Wilcoxon rank sum and Fisher's exact tests were used to compare variables. Univariate and multivariable conditional logistic regressions analysis were performed to identify risk factors for CDI. RESULTS: The multivariable conditional logistic regression analysis showed that proton pump inhibitors (PPI) administration (odds ratio [OR] = 0.06; 95% confidence interval [CI]: 0.007-0.52; P = .01) was the only factor associated with lower rates of CDI. Outcomes for cases vs controls: rejection episodes 24.14% vs 20.69% (P = .7), graft loss 0% vs 2.3% (P = .99), and survival rate 1 year post-transplantation 79.3% (59.6-90.1%) vs 87.2% (78.1-92.7%) (P = .38). CONCLUSIONS: Proton pump inhibitor administration might be protective for CDI in ITR. Risks factors for CDI might be different in ITR compared to other populations; anatomical differences and medications administered in the post-transplantation period may affect intestinal microbiota.

Prognosis of status epilepticus in elderly patients.

PURPOSE: To evaluate the clinical features and prognosis of status epilepticus (SE) in patients above 70 years old. METHODS: Retrospective analysis of all patients ≥70 years old with SE registered prospectively during 4 years. Follow-up after discharge was performed. RESULTS: Ninety patients were evaluated. Acute symptomatic etiology was the most prevalent. The mean number of antiepileptic drugs (AEDs) used was 2.7 ± 1.2, and 21% of the patients required sedation. A poor outcome was considered when death (31.1%) or developing of new neurological impairment at discharge (32.2%) occurred. After multivariate analysis, four variables predicted a poor outcome: acute symptomatic etiology (OR: 6.320; 95% CI: 1.976-20.217; P = .002), focal motor SE type (OR: 9.089; 95% CI: 2.482-33.283; P = .001), level of consciousness (OR: 4.596; 95% CI: 1.903-11.098; P = .001), and SE duration >12 hours (OR: 3.763; 95% CI: 1.130-12.530; P = .031). Independent predictive factors of mortality were SE duration >12 hours (OR: 4.306; 95% CI: 1.044-17.757; P = .043), modified Status Epilepticus Severity Score (mSTESS) (OR: 2.216; 95% CI: 1.313-3.740; P = .003), and development of complications (OR: 3.334; 95% CI: 1.004-11.070, P = .049). Considering long-term mortality, age (HR 1.036; 95% CI 1.001-1.071; P = .044), a potentially fatal underlying cause (HR 2.609; 95% CI 1.497- 4.548; P = .001), and mSTESS score >4 (HR 1.485; 95% CI 1.158-1.903; P = .002) remained as predictive factors. There was no association between sedation and the number of AEDs used with outcome at discharge or long-term mortality (P > .05). CONCLUSIONS: SE above 70 years old has a high morbimortality. Prognosis is not related to treatment aggressiveness.

Seroprevalence and risk factors associated with Brucella seropositivity in dairy and mixed cattle herds from Ecuador.

An extensive cross-sectional study to determine the seroprevalence of and associated risk factors for Brucella infection was performed in dairy and mixed (dairy-beef) cattle herds in Ecuador. A total of 2666 serum samples from 386 farms were analyzed using Rose Bengal test and a blocking ELISA test. In addition, a questionnaire with 57 variables related to management, feeding, facilities, biosecurity, and animal health was filled in every cattle farm. A Generalized Estimating Equations model was used to determine the factors associated with Brucella seropositivity. The true prevalence of Brucella seropositivity in dairy and mixed cattle from Ecuador reached 17.0% (CI95% 15.6-18.4%). The herd prevalence was 45.1% (174/386) (CI95% 40.1-50.1%), and the within-herd prevalence ranged from 10 to 100% (mean 38.9%; Q1 14.3%, Q2 26.8%, Q3 52.5%). Seven factors were included in the GEE model for Brucella seropositivity: the nominal variables sex (OR 2.03; CI95% 1.32-3.13), herd type (dairy) (OR 1.79; CI95% 1.11-2.87), closed facilities in the farm (OR 1.80; CI95% 1.19-2.74), and ad libitum feeding (OR: 0.32; CI95%: 0.19-0.54), and the quantitative variables age (OR 1.005; CI95% 1.001-1.009), average slope in the farm (%) (OR 1.013; CI95% 1.002-1.024), and annual abortion rate (OR 1.016; CI95% 1.002-1.031). This study remarks the high spread of Brucella infection in cattle farms from Ecuador. In addition, it reports the risk factors associated to this infection in the predominant extensive system existent in this country.

Laryngospasm, central and obstructive apnea during seizures: Defining pathophysiology for sudden death in a rat model.

Seizure spread into the autonomic nervous system can result in life-threatening cardiovascular and respiratory dysfunction. Here we report on a less-studied consequence of such autonomic derangements-the possibility of laryngospasm and upper-airway occlusion. We used parenteral kainic acid to induce recurring seizures in urethane-anesthetized Sprague Dawley rats. EEG recordings and combinations of cardiopulmonary monitoring, including video laryngoscopy, were performed during multi-unit recordings of recurrent laryngeal nerve (RLN) activity or head-out plethysmography with or without endotracheal intubation. Controlled occlusions of a tracheal tube were used to study the kinetics of cardiac and respiratory changes after sudden obstruction. Seizure activity caused significant firing increases in the RLN that were associated with abnormal, high-frequency movements of the vocal folds. Partial airway obstruction from laryngospasm was evident in plethysmograms and was prevented by intubation. Complete glottic closure (confirmed by laryngoscopy) occurred in a subset of non-intubated animals in association with the largest increases in RLN activity, and cessation of airflow was followed in all obstructed animals within tens of seconds by ST-segment elevation, bradycardia, and death. Periods of central apnea occurred in both intubated and non-intubated rats during seizures for periods up to 33s and were associated with modestly increased RLN activity, minimal cardiac derangements, and an open airway on laryngoscopy. In controlled complete airway occlusions, respiratory effort to inspire progressively increased, then ceased, usually in less than 1min. Respiratory arrest was associated with left ventricular dilatation and eventual asystole, an elevation of systemic blood pressure, and complete glottic closure. Severe laryngospasm contributed to the seizure- and hypoxemia-induced conditions that resulted in sudden death in our rat model, and we suggest that this mechanism could contribute to sudden death in epilepsy.

A Biradical Balancing Act: Redox Amphoterism in a Diindenoanthracene Derivative Results from Quinoidal Acceptor and Aromatic Donor Motifs.

The reduced and oxidized states of an open-shell diindeno[b,i]anthracene (DIAn) derivative have been investigated by experimental and theoretical techniques. As a result of moderate biradical character and the ability of cyclopenta-fused scaffolds to stabilize both positive and negative charges, DIAn exhibits rich redox chemistry with four observable and isolable charged states. Structural and electronic properties of the DIAn system are brought to light by UV-vis-NIR and Raman spectroelectrochemical measurements. Aromatization of the diindeno-fused anthracene core upon successive single-electron injections is revealed through single-crystal X-ray diffraction of radical anion and dianion salts. We present a rare case where the pseudoaromatic/quinoidal ground state of a neutral biradical polycyclic hydrocarbon leads to a stable cascade of five redox states. Our detailed investigation of the transformation of molecular structure along all four redox events provides a clearer understanding of the nature of charge carriers in ambipolar organic field-effect transistors.

Diindeno-fusion of an anthracene as a design strategy for stable organic biradicals.

The consequence of unpaired electrons in organic molecules has fascinated and confounded chemists for over a century. The study of open-shell molecules has been rekindled in recent years as new synthetic methods, improved spectroscopic techniques and powerful computational tools have been brought to bear on this field. Nonetheless, it is the intrinsic instability of the biradical species that limits the practicality of this research. Here we report the synthesis and characterization of a molecule based on the diindeno[b,i]anthracene framework that exhibits pronounced open-shell character yet possesses remarkable stability. The synthetic route is rapid, efficient and possible on the gram scale. The molecular structure was confirmed through single-crystal X-ray diffraction. From variable-temperature Raman spectroscopy and magnetic susceptibility measurements a thermally accessible triplet excited state was found. Organic field-effect transistor device data show an ambipolar performance with balanced electron and hole mobilities. Our results demonstrate the rational design and synthesis of an air- and temperature-stable biradical compound.

A new clinical score for the prognosis of status epilepticus in adults.

BACKGROUND AND PURPOSE: The severity of status epilepticus (SE) has an important impact in clinical outcomes. The Status Epilepticus Severity Score (STESS) is a score for predicting mortality in SE at admission. The baseline modified Rankin Scale (mRS) might be a prognostic factor for assessing the short-tem outcomes of SE. Therefore, our aim was to evaluate the effectiveness of mRS and whether its addition to the STESS improves the prediction of mortality. METHODS: Consecutive patients with SE and aged >16 years were recruited during 3 years. Receiver operating characteristic curves and a logistic regression model were developed to estimate the scores of the new score, designated as modified STESS (mSTESS), and it was subsequently compared with the STESS. RESULTS: In all, 136 patients were included. Mean age was 62.01 ± 17.62 (19-95) years, and 54% were male. The capacity of the STESS to predict mortality was 74.3% (95% confidence interval 63.8%-81.8%), whilst the capacity of the mRS to predict mortality was 65.2% (95% confidence interval 54.2%-76.2%). The logistic regression model and receiver operating characteristic curves enabled the classification of mRS as follows: 0, mRS = 0; 1, mRS = 1-3; and 2, mRS > 3. These values, when added to the other items of the STESS, resulted in the mSTESS with scores between 0 and 8 points. The capacity of the mSTESS to predict mortality was 80.1%. An mSTESS > 4 established an overall accuracy of 81.8% for predicting mortality, which was considerably higher than the overall accuracy of STESS ≥ 3 (59.6%). CONCLUSIONS: The baseline mRS was associated with high mortality risk. It is proposed to use mSTESS to improve the prediction of mortality risk in SE.