Use of dipicolinate-based complexes for producing ion-imprinted polystyrene resins for the extraction of yttrium-90 and heavy lanthanide cations

Highly selective separation of yttrium (and lanthanides) is of interest for the design of radiopharmaceuticals, and an efficient method based on the ion-imprinting concept is proposed here. The synthesis and structural, thermodynamic and photophysical characterization of complexes of trivalent yttrium and lanthanides with two new vinyl derivatives of dipicolinic acid, HL1 and L2, are described. The feasibility of using ion-imprinted resins for yttrium and lanthanide separation is demonstrated. The resins were obtained by copolymerization with styrene and divinylbenzene and subsequent acid treatment to remove the metal ion. High-resolution Eu luminescence experiments revealed that the geometry of the complexation sites is well preserved in the imprinted polymers. The ion-imprinted polymer based on HL1 proved to be particularly well adapted for yttrium extraction, having a sizeable capacity (8.9 +- 0.2 g/mg resin) and a fast rate of extraction (t1/2 = 1.7 min). In addition, lighter and heavier lanthanide ions are separated. Finally, the resin displays high selectivity for yttrium and lanthanide cations against alkali and alkaline earth metals. For instance, in a typical experiment, 10 mg of yttrium was extracted from 5 g of milk ash sample by 2 g of the resin. The good separation properties displayed by the resin based on HL1 open interesting perspectives for the production of highly pure 90Y and radiolanthanides for medical applications, and for trace analysis of these radiochemicals in food and in the environment

Cabergoline as an adjuvant to standard heart failure treatment in peripartum cardiomyopathy: a case report and review of the literature

Introduction: Peripartum cardiomyopathy (PPCM) is a rare and idiopathic form of dilated cardiomyopathy presenting late in pregnancy or early postpartum. Since the 16-kDa fragment of prolactin has been identified as a key factor in the pathophysiology of PPCM, prolactin inhibitors have been used as an adjuvant to standard heart failure treatment. Although bromocriptine is the current first choice, promising results have been reported with cabergoline, albeit scant. Case Presentation: We presented the case of a 41-year-old woman who received a diagnosis of PPCM one week after delivery and was successfully treated with cabergoline, finally experiencing a complete recovery. Conclusion: The case adds to the scant evidence supporting the use of cabergoline in PPCM patients. We argue that the favorable pharmacokinetic and metabolic profiles of this drug should prompt its consideration as a valid alternative prolactin inhibitor in these critical patients

Changing Style in Style-Changing Industries: The Role of Critics as Gatekeepers in High-End Fashion

Mastering aesthetics is a precious source of competitive advantage in creative industries. In fashion, innovation is reflected by how and how much styles change. Elite designers claim to be the only endogenous force shaping fashion innovation season by season. Yet, each season, fashion critics vet the new collections these designers introduce, assessing what is original as opposed toreworked and uninspired, in this way playing a fundamental role as gatekeepers in setting taste within the industry. In this research, we document how stylistic innovation, vis-`a-vis the styles premier design houses introduced each season, is impacted, among the others, by the specific exogenous force of critics’ assessments of designers’ past work. Our data, which include 61 measures detailing the styles introduced by 38 prestigious Italian and French design houses over a nine-year period, suggest designers move further away from styles reviewed less favourably while adhering more closely to styles reviewed more positively. Additionally, the styles a designer introduces are shown to depend on critical assessments of competing designers’ styles, revealing how design houses attend to each other’s work. This work documents the strong correlation between style dynamics and critics’ feedback. It also has important implications for any company trying to find a balance between independence and conformity in setting its own unique positioning into the market

Ethynyl Benziodoxolones for the Direct Alkynylation of Heterocycles: Structural Requirement, Improved Procedure for Pyrroles, and Insights into the Mechanism

This report describes a full study of the gold-catalyzed direct alkynylation of indoles, pyrroles, and thiophenes using alkynyl hypervalent iodine reagents, especially the study of the structural requirements of alkynyl benziodoxolones for an efficient acetylene transfer to heterocycles. An improved procedure for the alkynylation of pyrroles using pyridine as additive is also reported. Nineteen alkynyl benziodoxol(on)es were synthesized and evaluated in the direct alkynylation of indoles and/or thiophenes. Bulky silyl groups as acetylene substituents were optimal. Nevertheless, transfer of aromatic acetylenes to thiophene was achieved for the first time. An accelerating effect of a methyl substituent in both the 3- and 6-position of triisopropylsilylethynyl-1,2-benziodoxol-3(1H)-one (TIPS-EBX) on the reaction rate was observed. Competitive experiments between substrates of different nucleophilicity, deuterium labeling experiments, as well as the regioselectivity observed are all in agreement with electrophilic aromatic substitution. Gold(III) 2-pyridinecarboxylate dichloride was also an efficient catalyst for the reaction. Investigations indicated that gold(III) could be eventually reduced to gold(I) during the process. As a result of these investigations, a p activation or an oxidative mechanism are most probable for the alkynylation reaction

Mitochondrial enzyme GLUD2 plays a critical role in glioblastoma progression

Background: Glioblastoma (GBM) is the most frequent and malignant primary brain tumor in adults and despite the progress in surgical procedures and therapy options, the overall survival remains very poor. Glutamate and α-KG are fundamental elements necessary to support the growth and proliferation of GBM cells. Glutamate oxidative deamination, catalyzed by GLUD2, is the predominant pathway for the production of α-KG. Methods: GLUD2 emerged from the RNA-seq analysis of 13 GBM patients, performed in our laboratory and a microarray analysis of 77 high-grade gliomas available on the Geo database. Thereafter, we investigated GLUD2 relevance in cancer cell behavior by GLUD2 overexpression and silencing in two different human GBM cell lines. Finally, we overexpressed GLUD2 in-vivo by using zebrafish embryos and monitored the developing central nervous system. Findings: GLUD2 expression was found associated to the histopathological classification, prognosis and survival of GBM patients. Moreover, through in-vitro functional studies, we showed that differences in GLUD2 expression level affected cell proliferation, migration, invasion, colony formation abilities, cell cycle phases, mitochondrial function and ROS production. In support of these findings, we also demonstrated, with in-vivo studies, that GLUD2 overexpression affects glial cell proliferation without affecting neuronal development in zebrafish embryos. Interpretation: We concluded that GLUD2 overexpression inhibited GBM cell growth suggesting a novel potential drug target for control of GBM progression. The possibility to enhance GLUD2 activity in GBM could result in a blocked/reduced proliferation of GBM cells without affecting the survival of the surrounding neurons

Behavior of a forest of NiFe nanowires in KOH and NaCl solution for water electrolysis

The present work investigates the behavior of nanostructured electrodes consisting of an array of nanowires of NiFe alloy in KOH + 0.5 M NaCl solution. The aim is to explore the possibility of using these electrodes for hydrogen production by seawater electrolysis. Seawater splitting requires a highly selective electrode on the anode side, where the evolution of molecular chlorine or the formation of other active chlorine compounds can compete with the oxygen evolution reaction. Nanostructured electrodes, obtained by template electrosynthesis, were tested at room temperature in KOH + 0.5 M NaCl solution, and the results were compared with those obtained in pure KOH. The results showed that the presence of NaCl does not affect the electrocatalytic behavior of the nanostructured NiFe alloy. Furthermore, the chemical–physical characterizations carried out after the long-term galvanostatic tests, have shown that the nanostructured electrodes are also stable in terms of morphology and composition. In addition, the solution used to perform the long-term galvanostatic tests was analyzed to investigate the possible formation of chlorine compounds. The absence of these compounds, together with the measured potential value measured for the oxygen evolution reaction, which was always lower than the thermodynamic redox potential for the hypochlorite formation reaction, leads us to conclude that these electrodes are potentially suitable for seawater electrolysis

Assessing the effect of mercury pollution on cultured benthic foraminifera community using morphological and eDNA metabarcoding approaches

none14sìMercury (Hg) is a highly toxic element for living organisms and is known to bioaccumulate and biomagnify. Here, we analyze the response of benthic foraminifera communities cultured in mesocosm and exposed to different concentrations of Hg. Standard morphological analyses and environmental DNA metabarcoding show evidence that Hg pollution has detrimental effects on benthic foraminifera. The molecular analysis provides a more complete view of foraminiferal communities including the soft-walled single-chambered monothalamiids and small-sized hard-shelled rotaliids and textulariids than the morphological one. Among these taxa that are typically overlooked in morphological studies we found potential bioindicators of Hg pollution. The mesocosm approach proves to be an effective method to study benthic foraminiferal responses to various types and concentrations of pollutants over time. This study further supports foraminiferal metabarcoding as a complementary and/or alternative method to standard biomonitoring program based on the morphological identification of species communities.openFrontalini, Fabrizio; Greco, Mattia; Di Bella, Letizia; Lejzerowicz, Franck; Reo, Emanuela; Caruso, Antonio; Cosentino, Claudia; Maccotta, Antonella; Scopelliti, Giovanna; Nardelli, Maria Pia; Losada, Maria Teresa; Armynot du Châtelet, Eric; Coccioni, Rodolfo; Pawlowski, JanFrontalini, Fabrizio; Greco, Mattia; Di Bella, Letizia; Lejzerowicz, Franck; Reo, Emanuela; Caruso, Antonio; Cosentino, Claudia; Maccotta, Antonella; Scopelliti, Giovanna; Nardelli, Maria Pia; Losada, Maria Teresa; Armynot du Châtelet, Eric; Coccioni, Rodolfo; Pawlowski, Ja

Brilliant Photoluminescence and Triboluminescence from Ternary Complexes of Dy-III and Tb-III with 3-Phenyl-4-propanoy1-5-isoxazolonate and a Bidentate Phosphine Oxide Coligand

Three new lanthanide heterocyclic beta-diketonate complexes [Dy(PPI)(3)(EtOH)(2)] (1), [Dy(PPI)(3)(DPEPO)] (2), and [Tb(PPI)(3)(DPEPO)] (3) [where HPPI = 3-pheny1-4-propanoyl-5-isoxazolone and DPEPO = bis(2(diphenylphosphino)phenyl)ether oxide] have been synthesized and fully characterized. Single-crystal X-ray diffraction analyses reveal that these complexes are mononuclear and that the central Ln(III) ion is coordinated to eight oxygen atoms that are provided by three bidentate beta-diketonate ligands and ethanol or bidentate DPEPO in a distorted square antiprismatic geometry. These complexes have high molar absorption coefficients (up to 3 X 10(4) M-1 cm(-1) at 285 nm) and display strong visible and, for Dy-III, NIR luminescence upon irradiation at the ligand-centered band in the range 250-350 nm. The emission quantum yields and the luminescence lifetimes at room temperature are 3 +/- 0.5% and 15 +/- 1 us for 1, 12 +/- 2% and 33 +/- 1 mu s for 2, and 42 +/- 6% and 795 +/- 1 mu s for 3. Moreover, the crystals of 2 and 3 exhibit brilliant triboluminescence, visible in daylight

ANKRd44 gene silencing: A putative role in trastuzumab resistance in HER2-like breast cancer

Trastuzumab is an effective therapeutic treatment for Her2-like breast cancer; despite this most of these tumors develop resistance to therapy due to specific gene mutations or alterations in gene expression. Understanding the mechanisms of resistance to Trastuzumab could be a useful tool in order to identify combinations of drugs that elude resistance and allow a better response for the treated patients. Twelve primary biopsies of Her2+/hormone receptor negative (ER-/PgR-) breast cancer patients were selected based on the specific response to neoadjuvant therapy with Trastuzumab and their whole exome was sequenced leading to the identification of 18 informative gene mutations that discriminate patients selectively based on response to treatment. Among these genes, we focused on the study of the ANKRD44 gene to understand its role in the mechanism of resistance to Trastuzumab. The ANKRD44 gene was silenced in Her2-like breast cancer cell line (BT474), obtaining a partially Trastuzumab-resistant breast cancer cell line that constitutively activates the NF-kb protein via the TAK1/AKT pathway. Following this activation an increase in the level of glycolysis in resistant cells is promoted, also confirmed by the up-regulation of the LDHB protein and by an increased TROP2 protein expression, found generally associated with aggressive tumors. These results allow us to consider the ANKRD44 gene as a potential gene involved in Trastuzumab resistance