Synthesis, Structural Characterisation, and Electrochemical Properties of Copper(II) Complexes with Functionalized Thiosemicarbazones Derived from 5-Acetylbarbituric Acid

The reaction between 5-acetylbarbituric acid and 4-dimethylthiosemicarbazide or 4- hexamethyleneiminyl thiosemicarbazide produces 5-acetylbarbituric-4-dimethylthiosemicarbazone (H2AcbDM) and 5-acetylbarbituric-4N-hexamethyleneiminyl thiosemicarbazone (H2Acbhexim). Eight new complexes with different copper(II) salts have been prepared and characterized using elemental analysis, molar conductance, UV–Vis, ESI-HRMS, FT-IR, magnetic moment, EPR, and cyclic voltammetry. In addition, three-dimensional molecular structures of [Cu(HAcbDM)(H2O)2](NO3)·H2O (3a), [Cu(HAcbDM)(H2O)2]ClO4 (4), and [Cu(HAcbHexim)Cl] (6) were determined by single crystal X-ray crystallography, and an analysis of their supramolecular structure was carried out. The H-bonded assemblies were further studied energetically using DFT calculations and MEP surface and QTAIM analyses. In these complexes, the thiosemicarbazone coordinates to the metal ion in an ONS-tridentate manner, in the O-enolate/S-thione form. The electrochemical behavior of the thiosemicarbazones and their copper(II) complexes has been investigated at room temperature using the cyclic voltammetry technique in DMFA. The Cu(II)/Cu(I) redox system was found to be consistent with the quasi-reversible diffusion-controlled process.Consellería de Cultura, Educación, Formación Profesional e Universidades, Xunta de Galicia (Spain), GPC GI-2197 (ED481B- 2022-068 2023/19

Supramolecular, spectroscopic and computational analysis of weak interactions in some thiosemicarbazones derived from 5-acetylbarbituric acid

A new series of 5-acetylbarbituric based thiosemicarbazones (TSC) named 5-acetylbarbituric hydrazine-1-carbothioamide (1), N-methyl-(5-acetylbarbituric)hydrazine-1-carbothioamide (2), N-ethyl-(5-acetylbarbituric)hydrazine-1-carbothioamide (3), N,N-dimethyl-(5-acetylbarbituric)hydrazine-1-carbothioamide (4), N'-piperidine-(5-acetylbarbituric)-1-carbothiohydrazide (5) and N'-hexamethyleneimine-(5-acetylbarbituric)-1-carbothiohydrazide (6), has been synthesized from 5-acetylbarbituric acid and N-unsubstituted/substituted thiosemicarbazides. The synthesized compounds were well characterized by elemental analyses, FT-IR, 1H, 13C NMR and mass spectroscopic methods. Three-dimensional molecular structures of three compounds (1⋅DMSO, 2 and 6⋅H2O) were determined by single crystal X-ray crystallography, and an analysis of their supramolecular structure was carried out. The supramolecular features of the X-ray structure were also studied using Hirshfeld surface analysis. Finally, H-bonding networks observed in the solid state X-ray structures of 1⋅DMSO, 2, and 6⋅H2O and unconventional π-stacking dimers in 6⋅H2O were further analyzed by DFT calculations in combination with molecular electrostatic potential surfaces and combined QTAIM/NCIplot computational toolsFinancial support from the Network of Excellence “Metallic Ions in Biological Systems” CTQ2017-90802-REDT [Ministerio de Economía y Competitividad (Spain) and European Regional Development Fund (EU)], and the Xunta de Galicia (Spain) [Rede de Excelencia MetalBIO ED431D 2017/01]. MICIU/AEI of Spain (project CTQ2017-85821-R FEDER) is also acknowledged for financial supportS

Málaga: Desde Málaga a playa del Ejido (Málaga) Serie B: Gestión.

Peer reviewe

Highly sensitive microsatellite instability and immunohistochemistry assessment in endometrial aspirates as a tool for cancer risk individualization in Lynch syndrome

Women with Lynch syndrome (LS) are at increased risk of endometrial cancer (EC), among other tumors, and are characterized by mismatch repair (MMR) deficiency and microsatellite instability (MSI). While risk-reducing gynecologic surgeries effectively decrease EC incidence, doubts arise regarding the appropriate timing of the surgery. We explored the usefulness of highly sensitive MSI (hs-MSI) assessment in endometrial aspirates for individualizing gynecologic surveillance in LS carriers. Ninety-three women with LS, 25 sporadic EC patients (9 MMR-proficient and 16 MMR-deficient), and 30 women with benign gynecologic disease were included in this study. hs-MSI was assessed in prospectively collected endometrial aspirates in 67 LS carriers, EC cases, and controls. MMR, PTEN, ARID1A, and PAX2 protein expression patterns were evaluated in the LS samples. Follow-up aspirates from 8 LS carriers were also analyzed. Elevated hs-MSI scores were detected in all aspirates from MMR-deficient EC cases (3 LS and 16 sporadic) and negative in aspirates from controls and MMR-proficient EC cases. Positive hs-MSI scores were also detected in all 4 LS aspirates reported as complex hyperplasia. High hs-MSI was also present in 10 of 49 aspirates (20%) from LS carriers presenting a morphologically normal endometrium, where MMR protein expression loss was detected in 69% of the samples. Interestingly, the hs-MSI score was positively correlated with MMR-deficient gland density and the presence of MMR-deficient clusters, colocalizing PTEN and ARID1A expression loss. High hs-MSI scores and clonality were evidenced in 2 samples collected up to 4 months before EC diagnosis; hs-MSI scores increased over time in 5 LS carriers, whereas they decreased in a patient with endometrial hyperplasia after progestin therapy. In LS carriers, elevated hs-MSI scores were detected in aspirates from premalignant and malignant lesions and normal endometrium, correlating with MMR protein loss. hs-MSI assessment and MMR immunohistochemistry may help individualize EC risk assessment in women with LS

Cabo de Gata: Promontorio de cabo de Gata (Almería)

Peer reviewe

Almerimar: Aguadulce a Balanegra (Almería). Serie B: Gestión

Peer reviewe

San José: Desde Las Negras a Cabo de Gata (Almería). Serie B: Gestión.

Peer reviewe

Almería: Desde cabo de Gata a Aguadulce (Almería). Serie C: Modelos y Geomorfología

Peer reviewe

Estudio de la Plataforma Continental Española. Hoja MC057-Málaga. Serie C: Modelos y Geomorfología.

Peer reviewe

Velez-Málaga: Desde Cerro y Mar a Málaga (Málaga) Serie A: Descripción.

Peer reviewe