Dehydration of alcohols catalyzed by copper(II) sulfate: type II dyotropic reactions and stepwise mechanisms.

Dehydration of alcohols in the presence of copper(II) sulfate has been analyzed computationally. Density functional theory (DFT) calculations on selected alcohols indicate that this reaction can take place via two possible mechanisms: (a) concerted - although asynchronous - type II dyotropic reactions, or (b) stepwise E1-like processes, in which cleavage of the C-O bond occurs in the first step, followed by syn proton elimination. Our calculations show the relationship between the initial alcohol structure and the preferred mechanism, which is a type II dyotropic reaction for primary alcohols, whereas a stepwise process is the favored one when stable carbocation intermediates are energetically accessible. The dehydration of dehydrolinalool (2,7-dimethyl-6-en-1-yn-3-ol, DHL) to yield different alkenes of interest in the fragrance industry is discussed as a case study of its regiochemistry.

Indomuscone-Based Sterically Encumbered Phosphines as Ligands for Palladium-Catalyzed Reactions.

The fragrance compound indomuscone is used here as a scaffold to prepare two different sterically hindered phosphines, one aromatic and another alkylic, in good yields, after four synthetic steps. The new phosphines show enhanced electronic and steric properties when compared to benchmark commercial phosphine ligands, which is reflected in the catalytic results obtained for representative palladium-catalyzed reactions such as the telomerization reaction, the Buchwald-Hartwig and Suzuki cross-coupling reactions of chloroaromatic rings, and the semi-hydrogenation reaction of an alkyne. In particular, the indomuscone-based aromatic phosphine ligand leads to the highest selectivity for the tail-to-head telomerization product between isoprene and methanol, while the indomuscone-based alkylic phosphine ligand shows extraordinary similarities with the Buchwald-type SPhos phosphine ligand.

Spectroscopic dataset of Hedione's derivatives gathered during process development.

The dataset of spectroscopic analysis performed on starting materials, intermediates, and products relating to the synthesis of Hedione are hereby presented. The data were acquired in Durham university during the period between October 2020 and September 2021 for the development of a preparative method to Dehydrohedione. The latter is a key intermediate for the synthesis of cis-Hedione, an important fragrance ingredient. Proton, Carbon-13, and Fluorine-19 Nuclear magnetic resonance of the compounds were recorded employing a Varian 600 MHz, and a Bruker Avance-400 instrument. The IR spectra were recorded in a Perkin Elmer Spectrum Two UATR Two FT-IR and the accurate mass employing a Waters QtoF premier as mass spectrometer.

Pénfigo vulgar y su manejo integral: reporte de dos casos y revisión de literatura / Pemphigus Vulgaris and its Comprehensive Management: Report of Two Cases and Literature Review

Resumen En la cavidad oral se pueden presentar lesiones en gíngiva que no están asociadas a placa bacteriana, las cuales requieren de un adecuado diagnóstico y tratamiento. La gingivitis descamativa está usualmente relacionada con desórdenes mucocutáneos, como el pénfigo vulgar (PV), donde las lesiones orales incluyendo las lesiones gingivales, pueden preceder las lesiones cutáneas. El manejo es multidisciplinario y el tratamiento incluye terapia farmacológica tópica y sistémica, se requiere un adecuado control de la placa bacteriana por parte del paciente y una estricta supervisión en el tiempo por parte del profesional para el mantenimiento y estabilidad de los tejidos gingivales. Se presentan dos casos clínicos de pacientes con diagnóstico de PV los cuales fueron manejados de manera oportuna e integral para controlar y estabilizar el factor sistémico y local.

Abstract In the oral cavity, gingiva lesions may occur that are not associated with bacterial plaque, which require adequate diagnosis and treatment. Desquamative gingivitis is usually related to mucocutaneous disorders, such as pemphigus vulgaris (PV), where oral lesions, including gingival lesions, may precede skin lesions. Management is multidisciplinary and treatment includes topical and systemic pharmacological therapy, require adequate control of dental plaque by the patient and strict supervision over time by the professional for the maintenance and stability of the gingival tissues. Two clinical cases of patients with a diagnosis of PV are presented, which were managed in a timely and integral way to control and stabilize the systemic and local factor.

Special Issue: Alternaria alternata: Should We Still Consider This Fungus as a Minor Brother in the Etiology of Respiratory Allergy?

Allergic diseases represent a major global health problem [...].

Parts-per-million of ruthenium catalyze the selective chain-walking reaction of terminal alkenes.

The chain-walking of terminal alkenes (also called migration or isomerization reaction) is currently carried out in industry with unselective and relatively costly processes, to give mixtures of alkenes with significant amounts of oligomerized, branched and reduced by-products. Here, it is shown that part-per-million amounts of a variety of commercially available and in-house made ruthenium compounds, supported or not, transform into an extremely active catalyst for the regioselective migration of terminal alkenes to internal positions, with yields and selectivity up to >99% and without any solvent, ligand, additive or protecting atmosphere required, but only heating at temperatures >150 °C. The resulting internal alkene can be prepared in kilogram quantities, ready to be used in nine different organic reactions without any further treatment.

MTNeuro: A Benchmark for Evaluating Representations of Brain Structure Across Multiple Levels of Abstraction.

There are multiple scales of abstraction from which we can describe the same image, depending on whether we are focusing on fine-grained details or a more global attribute of the image. In brain mapping, learning to automatically parse images to build representations of both small-scale features (e.g., the presence of cells or blood vessels) and global properties of an image (e.g., which brain region the image comes from) is a crucial and open challenge. However, most existing datasets and benchmarks for neuroanatomy consider only a single downstream task at a time. To bridge this gap, we introduce a new dataset, annotations, and multiple downstream tasks that provide diverse ways to readout information about brain structure and architecture from the same image. Our multi-task neuroimaging benchmark (MTNeuro) is built on volumetric, micrometer-resolution X-ray microtomography images spanning a large thalamocortical section of mouse brain, encompassing multiple cortical and subcortical regions. We generated a number of different prediction challenges and evaluated several supervised and self-supervised models for brain-region prediction and pixel-level semantic segmentation of microstructures. Our experiments not only highlight the rich heterogeneity of this dataset, but also provide insights into how self-supervised approaches can be used to learn representations that capture multiple attributes of a single image and perform well on a variety of downstream tasks. Datasets, code, and pre-trained baseline models are provided at: https://mtneuro.github.io/.

Fungi Sensitization in Spain: Importance of the Alternaria alternata Species and Its Major Allergen Alt a 1 in the Allergenicity.

Prevalence of allergy to fungi is around 3-10%. The most prevalent species involved in sensitizations are Alternaria alternata, Aspergillus fumigatus, Cladosporium herbarum, and Penicillium notatum. Our main objective was to estimate the prevalence of fungal sensitization and its variation across Spain. Following the ICH-GCP, we recruited 1156 patients from 15 allergy departments in Spain. Hospitals were selected by bioclimatic areas. Patients underwent a skin prick test (SPT) with fungi, pollens, house dust mites, and animal dander. Specific IgE to Alternaria alternata and Alt a 1 was assessed in patients with positive SPT to fungi. Of the 233 patients (20.2%) sensitized to at least one of the five fungi tested, 162 (69.5%) were sensitized to Alternaria alternata and Alt a 1, of whom 113 (69.8%) were children; 181 (77.7%) were also polysensitized to other allergens. Alternaria alternata and Alt a 1 sensitization was present in 25.4% of patients in the Continental area, 12.0% in the Mediterranean area, 7.0% in the Semidesertic area, and 2.3% in the Oceanic area. Prevalence of sensitization to the other tested sources was 63.8% to pollens, 60.5% to house dust mite, and 38.1% to animal dander. We concluded that the prevalence of fungal allergy is increasing. Fungi are still the fourth source of allergen sensitization. Alternaria alternata sensitization is the most prevalent in allergic patients to fungi. Alt a 1 is present in almost 90% of the patients sensitized to Alternaria alternata.

Tratamiento del agrandamiento gingival inducido por placa bacteriana asociado a factores locales: Reporte de un caso clínico / Treatment of Gingival Enlargement Induced by Dental Plaque Associated with Local Factors: Case Report

Resumen Los agrandamientos gingivales inducidos por placa bacteriana asociados a factores locales como el uso de aparatología ortodóntica, son frecuentemente observados en pacientes jóvenes, con un inadecuado control del biofilm dental. Dentro de la terapéutica recomendada para tratar dicha condición se encuentra la fase higiénica periodontal y el abordaje quirúrgico. Se presenta un caso clínico de un paciente de 16 años con agrandamiento gingival y su respectivo tratamiento.

Absytract Dental plaque-induced gingival enlargements associated with local factors such as the use of orthodontic appliances are frequently observed in young patients, with inadequate dental biofilm control. Among the recommended therapeutics to treat this condition is the Nonsurgical phase and the surgical approach. A clinical case of a 16-year-old patient with a gingival enlargement and its respective treatment is presented.

Síndrome de Goltz o Hipoplasia dérmica focal / Goltz Syndrome or focal dermal hypoplasia

Introducción: El síndrome de Goltz o hipoplasia dérmica focal es una enfermedad genética rara del grupo de las displasias ectodérmicas con un mecanismo de herencia dominante ligado al cromosoma X. Objetivo: Describir las características clínicas del síndrome de Goltz, su diagnóstico y tratamiento. Presentación del caso: Paciente femenina de 4 años de edad diagnosticada con síndrome de Goltz. Se valora en equipo multidisciplinario con las especialidades de genética, cirugía maxilofacial, estomatología, dermatología, oftalmología, ortopedia y el servicio de otorrinolaringología. Conclusiones: El síndrome de Goltz se caracteriza principalmente por afectación cutánea; anomalías oculares, dentales, faciales y esqueléticas; afectación del aparato gastrointestinal, urinario, cardiovascular y sistema nervioso central con grado variable de severidad. Su diagnóstico es clínico. La atención interdisciplinaria es fundamental para el adecuado diagnóstico y tratamiento; su pronóstico depende del grado de afectación(AU)

Introduction: Goltz syndrome also known as focal dermal hypoplasia is a rare genetic disease in the ectodermal dysplasia´s group and with a mechanism of dominant inheritance linked to the X chromosome. Objectives: To describe the clinical characteristics of the Goltz syndrome, its diagnosis and treatment. Case presentation: Case of a 4 year-old female patient diagnosed with Goltz syndrome. She was studied by a multidisciplinary team including Genetics, Maxillofacial Surgery, Stomatology, Dermatology, Ophthalmology, Orthopedics and ORL specialists. Conclusions: Goltz syndrome or focal dermal hypoplasia is mainly characterized by skin affectations; eyes, dental, skeletal, and face anomalies; gastrointestinal tract, urinary, cardiovascular and central nervous systems´ affections with varying degrees of severity. The diagnosis is clinical. A multidisciplinary approach is essential for a proper diagnosis and treatment; and prognosis depends on the grade of severity(AU)

Síndrome de Goltz o Hipoplasia dérmica focal / Goltz Syndrome or focal dermal hypoplasia

RESUMEN Introducción: El síndrome de Goltz o hipoplasia dérmica focal es una enfermedad genética rara del grupo de las displasias ectodérmicas con un mecanismo de herencia dominante ligado al cromosoma X. Objetivo: Describir las características clínicas del síndrome de Goltz, su diagnóstico y tratamiento. Presentación del caso: Paciente femenina de 4 años de edad diagnosticada con síndrome de Goltz. Se valora en equipo multidisciplinario con las especialidades de genética, cirugía maxilofacial, estomatología, dermatología, oftalmología, ortopedia y el servicio de otorrinolaringología. Conclusiones: El síndrome de Goltz se caracteriza principalmente por afectación cutánea; anomalías oculares, dentales, faciales y esqueléticas; afectación del aparato gastrointestinal, urinario, cardiovascular y sistema nervioso central con grado variable de severidad. Su diagnóstico es clínico. La atención interdisciplinaria es fundamental para el adecuado diagnóstico y tratamiento; su pronóstico depende del grado de afectación(AU)

ABSTRACT Introduction: Goltz syndrome also known as focal dermal hypoplasia is a rare genetic disease in the ectodermal dysplasia´s group and with a mechanism of dominant inheritance linked to the X chromosome. Objectives: To describe the clinical characteristics of the Goltz syndrome, its diagnosis and treatment. Case presentation: Case of a 4 year-old female patient diagnosed with Goltz syndrome. She was studied by a multidisciplinary team including Genetics, Maxillofacial Surgery, Stomatology, Dermatology, Ophthalmology, Orthopedics and ORL specialists. Conclusions: Goltz syndrome or focal dermal hypoplasia is mainly characterized by skin affectations; eyes, dental, skeletal, and face anomalies; gastrointestinal tract, urinary, cardiovascular and central nervous systems´ affections with varying degrees of severity. The diagnosis is clinical. A multidisciplinary approach is essential for a proper diagnosis and treatment; and prognosis depends on the grade of severity(AU)

Cocaine Allergy in Drug-Dependent Patients and Allergic People.

BACKGROUND: Adverse reactions to local anesthetics (LAs), especially esters, are not uncommon, but true allergy is rarely diagnosed. To our knowledge, currently there is no reliable method of determining IgE-mediated hypersensitivity to LAs and cocaine. OBJECTIVE: To assess the clinical value of allergy tests (prick, IgE, challenges, and arrays) in people suffering hypersensitivity reactions (asthma and anaphylaxis) during local anesthesia with cocaine derivatives and drug abusers with allergic symptoms after cocaine inhalation. METHODS: We selected cocaine-dependent patients and allergic patients who suffered severe reactions during local anesthesia from a database of 23,873 patients. The diagnostic yield (sensitivity, specificity, and predictive value) of allergy tests using cocaine and coca leaf extracts in determining cocaine allergy was assessed, taking a positive challenge as the criterion standard. RESULTS: After prick tests, specific IgE, and challenge with cocaine extract, 41 of 211 patients (19.4%) were diagnosed as sensitized to cocaine. Prick tests and IgE to coca leaves (coca tea) had a good sensitivity (95.1% and 92.7%, respectively) and specificity (92.3 and 98.8%, respectively) for the diagnosis of cocaine allergy and LA-derived allergy. CONCLUSIONS: Cocaine may be an important allergen. Drug abusers and patients sensitized to local anesthesia and tobacco are at risk. Both prick tests and specific IgE against coca leaf extract detected sensitization to cocaine. The highest levels were related to severe clinical profiles.

Biomarcadores en el fluido gingival crevicular: Revisión de literatura

os biomarcadores son moléculas que pueden ser medidas objetivamente y evaluadas como indicadores de procesos biológicos normales, procesos patológicos o respuestas farmacológicas a la intervención terapéutica. En el fluido gingival crevicular se han estudiado biomarcadores como proteínas del huésped que incluyen enzimas, inmunoglobulinas, interleuquinas, citoquinas, quimioquinas y prostaglandinas, que podrían ser de ayuda para evaluar el diagnóstico periodontal y los resultados del tratamiento, además de monitorear pacientes en riesgo de desarrollar periodontitis. El propósito de esta revisión es mostrar algunos de los biomarcadores más estudiados en la enfermedad periodontal.

iomarkers are molecules that can be objectively measured and evaluated as indicators of normal biological processes, pathological processes or pharmacological responses to therapeutic intervention. In the crevicular gingival fluid, biomarkers have been studied as host proteins including enzymes, immunoglobulins, interleukins, cytokines, chemokines and prostaglandins, which could be helpful in evaluating periodontal diagnosis and treatment outcomes, as well as monitoring patients at risk of develop periodontitis. The purpose of this review is to show some of the most studied biomarkers in periodontal disease.

Towards free 3D end-point control for robotic-assisted human reaching using binocular eye tracking.

Eye-movements are the only directly observable behavioural signals that are highly correlated with actions at the task level, and proactive of body movements and thus reflect action intentions. Moreover, eye movements are preserved in many movement disorders leading to paralysis (or amputees) from stroke, spinal cord injury, Parkinson's disease, multiple sclerosis, and muscular dystrophy among others. Despite this benefit, eye tracking is not widely used as control interface for robotic interfaces in movement impaired patients due to poor human-robot interfaces. We demonstrate here how combining 3D gaze tracking using our GT3D binocular eye tracker with custom designed 3D head tracking system and calibration method enables continuous 3D end-point control of a robotic arm support system. The users can move their own hand to any location of the workspace by simple looking at the target and winking once. This purely eye tracking based system enables the end-user to retain free head movement and yet achieves high spatial end point accuracy in the order of 6 cm RMSE error in each dimension and standard deviation of 4 cm. 3D calibration is achieved by moving the robot along a 3 dimensional space filling Peano curve while the user is tracking it with their eyes. This results in a fully automated calibration procedure that yields several thousand calibration points versus standard approaches using a dozen points, resulting in beyond state-of-the-art 3D accuracy and precision.

Asociación entre el polimorfismo FCYRIIIA-158V-F y periodontitis

s reconocida la etiología multifactorial de la periodontitis, donde factores genéticos y ambientales interactúan para producir la enfermedad y modificar su expresión clínica. El objetivo de este estudio fue determinar la asociación entre la presencia del polimorfismo para el receptor de IgG subclase III A (FCYRIIIA-158V-F) y la periodontitis severa. Se estudiaron 150 pacientes: 32 pacientes con periodontitis agresiva, 71 pacientes con periodontitis crónica, y 47 voluntarios clínicamente sanos sin periodontitis. Se obtuvieron muestras de sangre periférica, aproximadamente 20µl. La extracción de ADN se llevó a cabo desde las microtarjetas FTAelute. Los polimorfismos seleccionados fueron amplificados por PCR. Resultados: Las frecuencias genotípicas de los tres grupos evaluados cumplieron con el equilibrio Hardy-Weinberg (Test Chi cuadrado, valor-p >0.05, IC 95 %). La diferencia entre la condición de enfermo (peridontitis crónica y agresiva) y el grupo de individuos sanos fue estadísticamente significativa para la presencia del alelo T (p≤0,004), con un OR de 4,03 (IC 95%), la sensibilidad correspondió al 93% y la especificidad al 23%, con un valor predictivo positivo del 72% y un valor predictivo negativo del 61%. Conclusiones: Se determinó una asociación estadísticamente significativa entre la presencia del alelo T en el polimorfismo de FCYRIIIA-158V-F y la condición de enfermo, de manera que el poseer el alelo T presenta una mayor probabilidad de desarrollar periodontitis severa. Debido a la importancia de identificar sujetos suceptibles a la periodontitis recomendamos realizar más estudios.

he multifactorial etiology of periodontitis is recognized, where genetic and environmental factors interact to produce the disease and modify its clinical expression The aim of this study is to determine the association between the presence of the polymorphism for IgG subclass III A receptor (FCYRIIIA-158V-F) and severe periodontitis. Materials and Methods: The study sample was composed of 150 patients: 32 patients with aggressive periodontitis, 71 patients with chronic periodontitis, and 47 clinically healthy volunteers without periodontitis. Peripheral blood samples, approximately 20μl, were obtained. DNA extraction was carried out from the FTAelute micro-cards. The selected polymorphisms were amplified by PCR. Results: The genotypic frequencies of the three groups evaluated met the Hardy-Weinberg equilibrium (Chi-square test, p-value> 0.05, 95% CI). The difference between the periodontitis (chronic and aggressive peridontitis) group and the group of healthy individuals was statistically significant for the presence of the T allele (p≤0.004), with an OR of 4.03 (95% CI), the sensitivity to 93% and specificity to 23%, with a positive predictive value of 72% and a negative predictive value of 61%. Conclusions: A statistically significant association was found between the presence of the T allele in the polymorphism of FCYRIIIA-158V-F and the diseased condition (periodontitis group), suggesting that the T allele possesses a higher probability of developing severe periodontitis. Due to the importance of identifying subjects susceptible to periodontitis we recommend further studies.

Efecto del tratamiento periodontal no quirúrgico sobre los niveles de Piridinolina (ICTP) en el fluido gingival crevicular (FGC)

a enfermedad periodontal destructiva afecta los tejidos de soporte del diente, teniendo como consecuencia final la pérdida del mismo; por lo cual la investigación se dirige hacia medidas objetivas de identificación de riesgo como lo son los biomarcadores de destrucción. Debido a que los estudios realizados con biomarcadores presentes en el fluido gingival crevicular (FGC) han reportado resultados promisorios, es factible asociar marcadores de degradación tisular con la progresión de la enfermedad periodontal. El objetivo del presente estudio es determinar el efecto del tratamiento periodontal no quirúrgico, sobre los niveles de ICTP en el FGC de pacientes con periodontitis crónica. Materiales y métodos: En muestras de FGC (pre y postratamiento), tanto de sitios activos como de inactivos determinados según el método de tolerancia, se midieron los niveles de ICTP utilizando el ICTP EIA. Uni Q, los resultados se analizaron usando el programa Stata 7.0 y el student-test para las muestras no paramétricas. Resultados: Los niveles de ICTP disminuyeron significativamente después de realizar el tratamiento periodontal no quirúrgico (p= 0,0001). Conclusiones: De acuerdo con los resultados obtenidos, la ICTP puede ser un buen marcador para monitorear los efectos del tratamiento periodontal no quirúrgico.

he destructive periodontal disease affects the tissues supporting the teeth, with the final result in the loss of it; so the research is directed towards identifying objective measures of risk such as biomarkers of destruction. Because studies of biomarkers present in the gingival crevicular fluid (FGC) have reported promising results, it is posible associated markers of tissue degradation with the progression of periodontal disease. The aim of this study is to determine the effect of nonsurgical periodontal treatment on the levels of pyridinoline in the FGC patients with chronic periodontitis. Materials and Methods: FGC samples (before and after treatment), both active and inactive sites determined by the method of tolerance, ICTP levels were measured using the ICTP EIA. Uni Q, the results were analyzed using Stata 7.0 program and the student-test for nonparametric samples Results: ICTP levels decreased significantly after performing non-surgical periodontal treatment (p = 0.0001). Conclusions: According to the results, the ICTP may be a good marker to monitor the effects of nonsurgical periodontal treatment.

Segundo y tercer molar en seno maxilar / Second and third molars in maxillary sinus

Introducción: los dientes retenidos se presentan con mayor frecuencia en los adolescentes y adultos jóvenes. Cualquier diente puede estar afectado, aunque los que quedan mayormente retenidos son los terceros molares inferiores, superiores y los caninos superiores.Presentación del caso: se reportó un adolescente de 14 años de edad, masculino, que acudió a la consulta de Cirugía Maxilofacial por presentar ausencia del segundo molar superior izquierdo, que se comprobó al examen físico bucal. A través de los estudios radiográficos (vista panorámica y de senos perinasales), se observó la presencia del segundo molar retenido y tercer molar no brotado en el seno maxilar izquierdo. Se realizó tratamiento quirúrgico, para abordar la pared anterior del seno maxilar mediante técnica de Caldwell-Luc, y se visualizaron y extrajeron los dos molares. El paciente evolucionó satisfactoriamente.Conclusiones: es imprescindible el interrogatorio, el examen físico y los estudios radiológicos, para llegar a un diagnóstico y tratamiento quirúrgico efectivo en el caso de dientes retenidos(AU)