<i>ent</i>-Labdane Diterpenoids from the Aerial Parts of <i>Eupatorium obtusissmum</i>

Six new <i>ent</i>-labdane diterpenoids, uasdlabdanes A–F (<b>1</b>–<b>6</b>), were isolated from the aerial parts of <i>Eupatorium obtusissmum</i>. The new structures were elucidated through spectroscopic and spectrometric data analyses. The absolute configurations of compounds <b>1</b> and <b>2</b> were established by X-ray crystallography, and those of <b>3</b>–<b>6</b>, by comparison of experimental and calculated electronic circular dichroism spectra. The antiproliferative activity of the compounds was studied in a panel of six representative human solid tumor cell lines and showed GI₅₀ values ranging from 19 to >100 μM

Positional Isomerism and Steric Effects in the Self-Assemblies of Phenylene Bis-Monothiooxalamides

The potential interplay of steric and substitution pattern effects of the monothiooxalamide side arms on the structure, conformational features, and self-assembly of a series of phenylene bis-monothiooxalamides was investigated. Herein we have demonstrated that phenylene bis-monothiooxalamides self-associate in the solid state, through intermolecular hydrogen bonding as <i>meso</i>-helices when the thioamide NR group is ^<i>s</i>Bu and through dispersive CO···CX (X = O, S, π), S···S, and C–H···S interactions when R is ^<i>t</i>Bu, independently from the substitution pattern in the phenyl ring. The helical structures are exclusively developed through N_CSH···O hydrogen bonding. The steric strain imposed by the <i>ortho</i>-substitution pattern has the effect of moving both monothiooxalyl units out of the phenyl plane enabling dimerization through strong N_COH···O intermolecular hydrogen bonds and promotes the formation of <i>meso</i>-helices. The steric demand of the thioamide NR group rules the conformation adopted by <i>meta</i>-substituted derivatives and the self-association arrangement of <i>para</i>-substituted derivatives. Infrared data support the blue-shifted nature of the N_CSH···O hydrogen bond. NMR data in solution agree with the extensive intramolecular hydrogen bonding scheme. Results are supported by density functional theory theoretical calculations. Monothiooxalamide unit offers considerable potential as a key moiety for crystal engineering

Exceptional avian pellet from the Paleocene of Patagonia and description of its content: a new species of calyptocephalellid (Neobatrachia) anuran

A fossil gastric pellet from the Danian ‘Banco Negro Inferior’ of the Salamanca Formation at Punta Peligro Locality (Chubut, Argentina) and its 3D preserved fossil content is studied herein. The structure of the pellet and the condition of the enclosed bones suggest that it was produced by a bird of prey, although birds of any kind are as yet unknown from osteological remains in the Banco Negro ecosystem. The content of the pellet originated from a single anuran individual, representing a new species of the genus Calyptocephalella, is described herein as C. sabrosa sp. nov. The new find highlights the broad temporal, geographical and taxonomic diversity of this frog genus in Patagonia's geological past.Fil: Muzzopappa, Paula. Fundación de Historia Natural Félix de Azara; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Parque Centenario. Museo Argentino de Ciencias Naturales "Bernardino Rivadavia"; ArgentinaFil: Martinelli, Agustín Guillermo. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Parque Centenario. Museo Argentino de Ciencias Naturales "Bernardino Rivadavia"; ArgentinaFil: Garderes, Juan Pablo. Fundación de Historia Natural Félix de Azara; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Rougier, Guillermo Walter. University of Louisville; Estados Unido

COVID-19 vaccine safety during pregnancy and breastfeeding in women with autoimmune diseases: results from the COVAD study

Objectives: We investigated COVID-19 vaccine safety in pregnant and breastfeeding women with autoimmune diseases (AID) in the COVID-19 Vaccination in Autoimmune Diseases (COVAD) study. Methods: Delayed-onset (>7 days) vaccine-related adverse events (AE), disease flares (DF), and AID-related treatment modifications were analyzed upon diagnosis of AID versus healthy controls (HC) and the pregnancy/breastfeeding status at the time of at least one dose of vaccine. Results: Among the 9201 participants to the self-administered online survey, 6787 (73.8%) were women. Forty pregnant and 52 breastfeeding patients with AID were identified, of whom the majority had received at least one dose of COVID-19 vaccine (100% and 96.2%, respectively). AE were reported significantly more frequently in pregnant than in non-pregnant patients (overall AE 45% vs 26%, p= 0.01; minor AE 40% vs 25.9%, p= 0.03; major AE 17.5% vs 4.6%, p< 0.01), but no difference was found in comparison with pregnant HC. No difference was observed between breastfeeding patients and HC with respect to AE. Post-vaccination DF were reported by 17.5% of pregnant and 20% of breastfeeding patients, and by 18.3% of age- and disease-matched non-pregnant and non-breastfeeding patients (n = 262). All pregnant/breastfeeding patients who experienced a DF were managed with glucocorticoids; 28.6% and 20% of them required initiation or change in immunosuppressants, respectively. Conclusion: This study provides reassuring insights into the safety of COVID-19 vaccines administered to women with AID during the gestational and post-partum periods, helping overcome hesitant attitudes, as the benefits for the mother and the fetus by passive immunization appear to outweigh potential risks