ESI : (E)nfoques (S)ituados (I)mprescindibles para una educación otra

En el presente trabajo integrador final nos propusimos analizar el desarrollo y la inserción del Programa de Educación Sexual Integral en el sistema educativo nacional y su impacto en el mismo, desde una perspectiva feminista descolonial. Con este propósito recontruimos la perspectiva feminista descolonial y expusimos cómo concibe al sistema educativo en el proyecto moderno colonial recurriendo a la misma como herramienta para repensar la educación. A partir de esta delimitación, tomamos el Programa de Educación Sexual Integral, desarrollando un apartado que se esfuerza por dar cuenta de los aspectos prioritarios para finalmente tensionar y proponer cuatro modos de comprender la ESI que, a nuestro entender, habilitan a pensar una educación más feminista y descolonial.Fil: Morandi, Mariela. Universidad Nacional de Rosario. Facultad de Ciencia Política y Relaciones Internacionales. Escuela de Trabajo Social; Argentina.Fil: Tiberi, Renzo. Universidad Nacional de Rosario. Facultad de Ciencia Política y Relaciones Internacionales. Escuela de Trabajo Social; Argentina

Surprising Complexity of the [Gd(AAZTA)(H2O)2]− Chelate Revealed by NMR in the Frequency and Time Domains

[Abstract] Typically, Ln(III) complexes are isostructural along the series, which enables studying one particular metal chelate to derive the structural features of the others. This is not the case for [Ln(AAZTA)(H2O)x]− (x = 1, 2) systems, where structural variations along the series cause changes in the hydration number of the different metal complexes, and in particular the loss of one of the two metal-coordinated water molecules between Ho and Er. Herein, we present a 1H field-cycling relaxometry and 17O NMR study that enables accessing the different exchange dynamics processes involving the two water molecules bound to the metal center in the [Gd(AAZTA)(H2O)2]− complex. The resulting picture shows one Gd-bound water molecule with an exchange rate ∼6 times faster than that of the other, due to a longer metal–water distance, in accordance with density functional theory (DFT) calculations. The substitution of the more labile water molecule with a fluoride anion in a diamagnetic-isostructural analogue of the Gd-complex, [Y(AAZTA)(H2O)2]−, allows us to follow the chemical exchange process by high-resolution NMR and to describe its thermodynamic behavior. Taken together, the variety of tools offered by NMR (including high-resolution 1H, 19F NMR as a function of temperature, 1H longitudinal relaxation rates vs B0, and 17O transverse relaxation rates vs T) provides a complete description of the structure and exchange dynamics of these Ln-complexes along the series.This research was supported by the Università del Piemonte Orientale (Ricerca locale FAR2019). F.C., L.T., and M.B. acknowledge the financial support from the Ministero dell’Università e della Ricerca (PRIN 2017A2KEPL project “Rationally designed nanogels embedding paramagnetic ions as MRI probes”). This work was carried out within the framework of the COST CA15209 Action “European Network on NMR Relaxometry”Italia. Ministero dell'Università e della Ricerca; PRIN-2017A2KEP

Soluble Variants of Human Recombinant Glutaminyl Cyclase

Soluble variants QPC

Myxedema coma in a patient with type 1 neurofibromatosis: rare association

Myxedema coma, a rare but fatal emergency, is an extreme expression of hypothyroidism. We describe a 51-year-old male patient who has discontinued hypothyroidism treatment 10 months earlier and developed lethargy, edema, and cold intolerance symptoms. He also had a previous diagnosis of neurofibromatosis. After admission, he progressed to respiratory insufficiency and coma. The prompt recognition of the condition, thyroid hormone replacement, and management of the complications (hypoventilation, cardiogenic shock associated with swinging heart, adrenal and renal insufficiency and sepsis), resulted in a favorable evolution.O coma mixedematoso (CM) é uma emergência endocrinológica rara, porém letal e consiste na expressão extrema do hipotireoidismo. Relatamos o caso de um paciente do sexo masculino, 51 anos, que abandonou tratamento do hipotireoidismo por 10 meses e evoluiu com sintomas de letargia, edema e intolerância ao frio que culminaram em insuficiência respiratória e coma. Apresentava também diagnóstico prévio de neurofibromatose. O diagnóstico precoce do coma mixedematoso aliado à instituição imediata do tratamento com levotiroxina e ao manejo adequado de complicações, como insuficiência respiratória, choque cardiogênico associado a swinging heart, insuficiências adrenal e renal agudas e sepse, permitiu a evolução favorável do quadro.74374

Understanding the Effect of the Electron Spin Relaxation on the Relaxivities of Mn(II) Complexes with Triazacyclononane Derivatives

[Abstract] Investigating the relaxation of water ¹H nuclei induced by paramagnetic Mn(II) complexes is important to understand the mechanisms that control the efficiency of contrast agents used in diagnostic magnetic resonance imaging (MRI). Herein, a series of potentially hexadentate triazacyclononane (TACN) derivatives containing different pendant arms were designed to explore the relaxation of the electron spin in the corresponding Mn(II) complexes by using a combination of ¹H NMR relaxometry and theoretical calculations. These ligands include 1,4,7-triazacyclononane-1,4,7-triacetic acid (H₃NOTA) and three derivatives in which an acetate group is replaced by sulfonamide (H₃NOƨASAm), amide (H₂NOƨAM), or pyridyl (H₂NOƨAPy) pendants. The analogue of H₃NOTA containing three propionate pendant arms (H₃NOTPrA) was also investigated. The X-ray structure of the derivative containing two acetate groups and a sulfonamide pendant arm [Mn(NOƨASAm)]⁻ evidenced six-coordination of the ligand to the metal ion, with the coordination polyhedron being close to a trigonal prism. The relaxivities of all complexes at 20 MHz and 25 °C (1.1–1.3 mM⁻¹ s⁻¹) are typical of systems that lack water molecules coordinated to the metal ion. The nuclear magnetic relaxation profiles evidence significant differences in the relaxivities of the complexes at low fields (<1 MHz), which are associated with different spin relaxation rates. The zero field splitting (ZFS) parameters calculated by using DFT and CASSCF methods show that electronic relaxation is relatively insensitive to the nature of the donor atoms. However, the twist angle of the two tripodal faces that delineate the coordination polyhedron, defined by the N atoms of the TACN unit (lower face) and the donor atoms of the pendant arms (upper face), has an important effect in the ZFS parameters. A twist angle close to the ideal value for an octahedral coordination (60°), such as that in [Mn(NOTPrA)]⁻, leads to a small ZFS energy, whereas this value increases as the coordination polyhedron approaches to a trigonal prism.C.P.-I., D.E.-G., and A.R.-R. thank Ministerio de Ciencia e Innovación (Grants CTQ2016-76756-P and PID2019-108352RJ-I00) and Xunta de Galicia (Grants ED431B 2017/59 and ED431D 2017/01) for generous financial support. R.U.-V. thanks Xunta de Galicia (Grant ED481A-2018/314) for funding her PhD contractXunta de Galicia; ED431B 2017/59Xunta de Galicia; ED431D 2017/01Xunta de Galicia; ED481A-2018/31

Three-dimensional deuterium-carbon correlation experiments for high-resolution solid-state MAS NMR spectroscopy of large proteins

Well-resolved 2H-13C correlation spectra, reminiscent of 1H-13C correlations, are obtained for perdeuterated ubiquitin and for perdeuterated outer-membrane protein G (OmpG) from E. coli by exploiting the favorable lifetime of 2H double-quantum (DQ) states. Sufficient signal-to-noise was achieved due to the short deuterium T 1, allowing for high repetition rates and enabling 3D experiments with a 2H-13C transfer step in a reasonable time. Well-resolved 3D 2HDQ-13C-13C correlations of ubiquitin and OmpG were recorded within 3.5days each. An essentially complete assignment of 2HDQα shifts and of a substantial fraction of 2HDQβ shifts were obtained for ubiquitin. In the case of OmpG, 2HDQα and 2HDQβ chemical shifts of a considerable number of threonine, serine and leucine residues were assigned. This approach provides the basis for a general heteronuclear 3D MAS NMR assignment concept utilizing pulse sequences with 2HDQ-13C transfer steps and evolution of deuterium double-quantum chemical shift

Mn2+ complexes containing sulfonamide groups with pH-responsive relaxivity

We present two ligands containing a N-ethyl-4-(trifluoromethyl)benzenesulfonamide group attached to either a 6,6'-(azanediylbis(methylene))dipicolinic acid unit (H3DPASAm) or a 2,2'-(1,4,7-triazonane-1,4-diyl)diacetic acid macrocyclic platform (H3NO2ASAm). These ligands were designed to provide pH-dependent relaxivity response upon complexation with Mn2+ in aqueous solution. The protonation constants of the ligands and the stability constants of the Mn2+ complexes were determined using potentiometric titrations complemented by spectrophotometric experiments. The deprotonation of the sulfonamide groups of the ligands are characterized by protonation constants of logKiH = 10.36 and 10.59 for DPASAm3 and HNO2ASAm2 , respectively. These values decrease dramatically to logKiH = 6.43 and 5.42 in the presence of Mn2+ due to the coordination of the negatively charged sulfonamide groups to the metal ion. The higher logKiH value in [Mn(DPASAm)] is related to the formation of a seven-coordinate complex, while the metal ion in [Mn(NO2ASAm)] is six-coordinated. The X ray crystal structure of Na[Mn(DPASAm)(H2O)]·2H2O confirms the formation of a seven-coordinate complex, where the coordination environment is fulfilled by the donor atoms of the two picolinate groups, the amine N at-om, the N atom of the sulfonamide group and a coordinated water molecule. The lower conditional stability of the [Mn(NO2ASAm)] complex and the lower protonation constant of the sulfonamide group results in complex dissociation at relatively high pH (< 7.0). However, protonation of the sulfonamide group in [Mn(DPASAm)] falls into the physiologically relevant pH window and causes a significant increase in relaxivity from r1p = 3.8 mM 1 s 1 at pH 9.0 to r1p = 8.9 mM 1 s 1 at pH 4.0 (10 MHz, 25 ºC).Agencia Estatal de Investigación | Ref. CTQ2016-76756-PXunta de Galicia | Ref. ED431B 2017/59Xunta de Galicia | Ref. ED431D 2017/01Xunta de Galicia | Ref. ED481A-2018/314Universitá degli Studi del Piemonte OrientaleMinisterio de Ciencia, Innovación y Universidades | Ref. BEAGAL18/0014