Studying the Intrinsic Reactivity of Chromanes by Gas-Phase Infrared Spectroscopy.

Tandem mass spectrometry is routinely used for the structural analysis of organic molecules, but many fragmentation reactions are not well understood. Because several potential structures can correspond to a measured mass, the assignment of product ions is ambiguous using mass spectrometry alone. Here, we combine mass spectrometry with high-resolution gas-phase infrared spectroscopy and computational chemistry tools to identify product ion structures and derive collision-induced fragmentation mechanisms of the chromane derivatives Trolox and Methyltrolox. We find that protonated Trolox and Methyltrolox fragment identically via dehydration and decarbonylation, while deprotonated ions display substantially diverging reactivities. For deprotonated Methyltrolox, we observe unusual radical fragmentation reactions and suggest a [1,2]-Wittig rearrangement involving aryl migration in the gas phase. Overall, the combined experimental and theoretical approach presented here revealed complex proton dynamics and intramolecular rearrangement reactions, which expand our understanding on structure-reactivity relationships of isolated molecules in different protonation states.

Investigation of the Proton-Bound Dimer of Dihydrogen Phosphate and Formate Using Infrared Spectroscopy in Helium Droplets.

Understanding the structural and dynamic properties of proton-bound complexes is crucial for elucidating fundamental aspects of chemical reactivity and molecular interactions. In this work, the proton-bound complex between dihydrogen phosphate and formate, and its deuterated counterparts, is investigated using IR action spectroscopy in helium droplets. Contrary to the initial expectation that the stronger phosphoric acid would donate a proton to formate, both experiment and theory show that all exchangeable protons are located in the phosphate moiety. The experimental spectra show good agreement with both scaled harmonic and VPT2 anharmonic calculations, indicating that anharmonic effects are small. Some H-bending modes of the nondeuterated complex are found to be sensitive to the helium environment. In the case of the partially deuterated complexes, the experiments indicate that internal dynamics leads to isomeric interconversion upon IR excitation.

Infrared Spectroscopy of Fluorenyl Cations at Cryogenic Temperatures.

The notion of (anti)aromaticity is a successful concept in chemistry to explain the structure and stability of polycyclic hydrocarbons. Cyclopentadienyl and fluorenyl cations are among the most studied classical antiaromatic systems. In this work, fluorenyl cations are investigated by high-resolution gas-phase infrared spectroscopy in helium droplets. Bare fluorenyl cations are generated in the gas phase by electrospray ionization. After mass-to-charge selection, ions are captured in ultracold helium nanodroplets and probed by infrared spectroscopy using a widely tunable free-electron laser in the 600-1700 cm-1 range. The highly resolved cryogenic infrared spectra confirm, in combination with DFT computations, that all cations are present in their singlet states.

The Many Faces of JAKs and STATs Within the COVID-19 Storm.

The positive-sense single stranded RNA virus, Severe Acute Respiratory Syndrome Coronavirus 2 (SARS-CoV-2), resulted in a global pandemic with horrendous health and economic consequences not seen in a century. At a finer scale, immunologically, many of these devastating effects by SARS-CoV-2 can be traced to a "cytokine storm" resulting in the simultaneous activation of Janus Kinases (JAKs) and Signal Transducers and Activators of Transcription (STAT) proteins downstream of the many cytokine receptor families triggered by elevated cytokines found in Coronavirus Disease 2019 (COVID-19). In this report, cytokines found in the storm are discussed in relation to the JAK-STAT pathway in response to SARS-CoV-2 and the lessons learned from RNA viruses and previous Coronaviruses (CoVs). Therapeutic strategies to counteract the SARS-CoV-2 mediated storm are discussed with an emphasis on cell signaling and JAK inhibition.

Treatment decision for transcatheter aortic valve implantation: the role of the heart team : Position statement paper of the Dutch Working Group of Transcatheter Heart Interventions.

The current paper presents a position statement of the Dutch Working Group of Transcatheter Heart Valve Interventions that describes which patients with aortic stenosis should be considered for transcatheter aortic valve implantation and how this treatment proposal/decision should be made. Given the complexity of the disease and the assessment of its severity, in particular in combination with the continuous emergence of new clinical insights and evidence from physiological and randomised clinical studies plus the introduction of novel innovative treatment modalities, the gatekeeper of the treatment proposal/decision and, thus, of qualification for cost reimbursement is the heart team, which consists of dedicated professionals working in specialised centres.

De la Finca a la Escuela: Promoviendo el consumo de frutas y vegetales en escuelas de Guatemala y Costa Rica / From the Farm to the School: Promoting the consumption of fruits and vegetables in schools in Guatemala and Costa Rica

El objetivo del proyecto fue aumentar el consumo de frutas y vegetales en escolares de las ciudades de Guatemala y San José, Costa Rica, mediante la implementación de un sistema de provisión de frutas y vegetales sostenido en el ambiente escolar, con el fin de establecer hábitos alimentarios saludables a edades tempranas. Una de las estrategias del proyecto fue establecer vínculos entre productores de frutas y vegetales; y establecimientos educativos

Material Didáctico para la Promoción del Consumo de Frutas / Didactic material for the promotion of fruit consumption

Los objetivos de los materiales son: • Promover hábitos alimentarios saludables desde la infancia • Dar a conocer la importancia del consumo de frutas y las consecuencias de un consumo insuficiente • Fomentar el consumo de frutas en la escuela y el hogar Los materiales educativos se acompañan de una guía docente que detalla el uso adecuado de cada una de las actividades propuestas, sus objetivos y las competencias ejercitadas en cada una de ellas. El presente documento incluye un resumen de la metodología seguida para la elaboración de los materiales educativos y la versión final de los mismos

Takotsubo cardiomyopathy following radioiodine therapy for toxic multinodular goitre.

We report on a 73-year-old man with a toxic multinodular goitre, which was treated with radioiodine therapy (I-131) without pretreatment with an antithyroid drug. Four weeks later he presented with rapidly progressive dyspnoea and a significant increase in free thyroxin. The electrocardiogram showed ST -segment elevation, and echocardiography demonstrated apical akinesia and a left ventricular ejection fraction of only 25%. However, direct coronary catheterisation showed no evidence of coronary artery disease. Left ventricular angiography showed apical ballooning consistent with the diagnosis of takotsubo cardiomyopathy. Following treatment of the cardiomyopathy and thyrotoxicosis, he experienced a complete recovery. To the best of our knowledge, this is the first report of a takotsubo cardiomyopathy associated with thyrotoxicosis resulting from radiation thyroiditis induced by radioiodine. Three other cases of takotsubo cardiomyopathy associated with Graves' disease have been described in literature.

Guía alimentaria frontera sur de Nicaragua / Guides alimentary south frontier of Nicaragua

Ofrece información sobre la promoción de prácticas alimentarias en la población y esta dirigido a las personas, instituciones y organismos que desarrollan actividades de alimentación y nutrición. Prporciona los conceptos básicos de alimentación y nutrición, el valor nutrivo de los alimentos y los efectos en estado nutricional

Situación de los programa de fortificación de alimentos / Situation of the programs of fortification of food year 2000

El documento presenta la situación de los programas de fortificación de alimentos en el año 2,000 en Nicaragua. La informacion proviene de la II Encuesta Nacional de Micronutrientes. Aunque la información no tiene el rigor estadístico para cada uno de los departamentos. El documento también proporciona datos provenientes de las actividades de inspección realizadas por el Departamento de Control de Alimentos del Ministerio de Salud en el año 2,000, tanto en plantas procesadoras como en sitios de expendios, que aunque sin seguir un patrón sistématico y periódico, es información útil e importante de ser conocida

Comparison of left ventricular function at rest and post-stress in patients with myocardial infarction: Evaluation with gated SPECT.

BACKGROUND: Quantitative electrocardiogram-gated single photon emission computed tomography (SPECT) myocardial imaging (QGS) is a means of providing functional information about the left ventricle and myocardial perfusion. However, the functional information derived 30 minutes post-stress may be different from the left ventricular (LV) function determined at rest. This study determined whether LV function post-stress would be different from LV function at rest in patients with an earlier myocardial infarction. METHODS AND RESULTS: LV perfusion and ejection fraction (LVEF), were determined by means of both the rest and post-stress acquisition in 58 patients with an earlier myocardial infarction and in 23 patients with a low likelihood of coronary artery disease by using technetium-99m tetrofosmin and the QGS program. The interobserver and intraobserver variability of LVEF was excellent, within a margin of 2%. No significant differences in LVEF were observed between post-stress and rest in the 23 patients with a low likelihood of disease (DeltaLVEF, 0.04% +/- 3.2%, P = not significant). Conversely, the patients with an earlier myocardial infarction showed a significantly lower LVEF post-stress, compared with that at rest (DeltaLVEF, -1.9% +/- 4.2%, P =.002). In 33 patients (57%), the LVEF post-stress was 2% or more lower than the LVEF at rest. Furthermore, reversible ischemia, which was present in 16 patients (28%), did not interact with the DeltaLVEF post-stress, compared with the DeltaLVEF at rest (P = not significant). Parameters such as the stress modality (adenosine stress or exercise), the number of stenosed vessels, or the perfusion defect severity score did not influence the DeltaLVEF post-stress, compared with the DeltaLVEF at rest. CONCLUSIONS: In patients with an earlier myocardial infarction, LV function post-stress may not represent the true resting LV function. Consequently, this result justifies the stratification of patients before starting the gated SPECT study. In patients with an earlier myocardial infarction, the gated acquisition should be performed during the rest study.