Intramolecular C(sp²)−H bond activation in 6,6′-dimethoxy-2,2′-bipyridine with gold(III): crystal and molecular structure of the first N′,C(3) “rollover” cycloaurated derivative

Treatment of 6,6′-dimethoxy-2,2′-bipyridine (bipy2OMe) with gold(III) acetate results in the exclusive formation of a cyclometalated gold(III) derivative arising from activation of the C(3)−H bond of a pyridine ring

Gold(III) adducts with chiral pyridinyl-oxazolines: synthesis, reactivity of the coordinated ligands, and structural characterizations

Novel gold(III) pyridinyl-oxazoline cationic complexes [Au(pyoxR)Cl2][X] [pyoxR = (S)-4-R-2-(pyridin-2-yl)-4,5-dihydrooxazole, with R = iPr, Bn, and (R)-4-phenyl-2-(pyridin-2-yl)-4,5-dihydrooxazole; X = PF6, AuCl4, or mixtures of the two anions] were synthesized and structurally characterized. Reaction of the adducts with NaOAc in aqueous solution afforded the neutral complexes [Au(N,N′,O)Cl] of the deprotonated ligands N-(1-hydroxy-3-R-2-yl)pyridine-2-carboxamide (R = iPr, Ph), N,N′H,OH, resulting from ring-opening of the bound pyox ligand by hydroxide ions and incorporation of hydroxide into the ring-opened products. Reaction of [Au(N,N′,O)Cl] (R = iPr) with HX (X = Cl, BF4, OTf) in aqueous solution resulted in protonation of the coordinated alkoxo group and its displacement from the coordination sphere to give the adducts [Au(N,N′,OH)ClX] (X = OTf, Cl) or the aquo complex [Au(N,N′,OH)(OH2)Cl]+ (X = BF4). Crystal structure characterizations were carried out on both [Au(N,N′,O)Cl] and [Au(N,N′,OH)Cl2] (R = iPr). Equimolar mixtures of the ring-opened derivative [Au(N,N′,O)Cl] (R = iPr) and either silver salts or HBF4 were found to promote, under mild conditions, polymerization of styrenes

[Au₂(phen^2Me)₂(&#956;<b>-</b>O)₂](PF₆)₂, a novel dinuclear gold(III) complex showing excellent antiproliferative properties

A novel dioxo-bridged dinuclear gold(III) complex with two 2,9-dimethylphenanthroline ligands was synthesized and thoroughly characterized. Its crystal structure was solved, and its solution behavior assessed. Remarkably, this compound revealed excellent antiproliferative properties in vitro against a wide panel of 36 cancer cell lines, combining a high cytotoxic potency to pronounced tumor selectivity. Very likely, these properties arise from an innovative mode of action (possibly involving histone deacetylase inhibition), as suggested by COMPARE analysis. In turn, electrospray ionization&#8722;mass spectrometry studies provided valuable insight into its molecular mechanisms of activation and of interaction with protein targets. Gold(III) reduction, dioxo bridge disruption, coordinative gold(I) binding to the protein, and concomitant release of the phenanthroline ligand were proposed to occur upon interaction with superoxide dismutase, used here as a model protein. Because of the reported results, this new gold(III) compound qualifies itself as an optimal candidate for further pharmacological testing

[Au-2(phen(2Me))2(mu-O)2](PF6)2, a novel dinuclear gold(III) complex showing excellent antiproliferative properties

A novel dioxo-bridged dinuclear gold(III) complex with two 2,9-dimethylphenanthroline ligands was synthesized and thoroughly characterized. Its crystal structure was solved, and its solution behavior assessed. Remarkably, this compound revealed excellent antiproliferative properties in vitro against a wide panel of 36 cancer cell lines, combining a high cytotoxic potency to pronounced tumor selectivity. Very likely, these properties arise from an innovative mode of action (possibly involving histone deacetylase inhibition), as suggested by COMPARE analysis. In turn, electrospray ionization−mass spectrometry studies provided valuable insight into its molecular mechanisms of activation and of interaction with protein targets. Gold(III) reduction, dioxo bridge disruption, coordinative gold(I) binding to the protein, and concomitant release of the phenanthroline ligand were proposed to occur upon interaction with superoxide dismutase, used here as a model protein. Because of the reported results, this new gold(III) compound qualifies itself as an optimal candidate for further pharmacological testing

Il male invisibile sempre più visibile

Se non dovesse risultare chiaro il titolo - a dire il vero non immediatamente evidente - di questo volume, più chiaro è il sottotitolo che si riferisce alle conseguenze immediate e striscianti di questa presenza sull'ambiente nel quale viviamo e sulla nostra salute. Parliamo della logica militare che pervade sempre più il nostro tessuto sociale, con un sistema di valori che desta repulsione nella nostra coscienza civile. Parliamo delle conseguenze devastanti sulla salute e sull'ambiente delle popolazioni cosiddette "nemiche". Parliamo delle conseguenze altrettanto devastanti sui corpi e sulle menti dei "nostri", di chi il militare e la guerra è mandato o comandato a farli senza sapere. Parliamo di un tumore sociale quale il drenaggio delle nostre risorse e del nostro lavoro, un tumore sociale che non fa altro che generare tumori reali: non solo nei nostri corpi, ma anche nella mente nostra e delle generazioni a venire. Crediamo sia arrivato il momento di sollevare il velo di censure, compiacenze, ignoranza coltivata ad arte che ricopre il mondo militare. Vogliamo contribuire a rendere visibile e vivido questo male invisibile che avvelena la nostra società. Occorre andare avanti nello studio e nella ricerca, occorre andare oltr

Il male invisibile sempre più visibile

Se non dovesse risultare chiaro il titolo – a dire il vero non immediatamente evidente – di questo volume, più chiaro è il sottotitolo che si riferisce alle conseguenze immediate e striscianti di questa presenza sull’ambiente nel quale viviamo e sulla nostra salute. Parliamo della logica militare che pervade sempre più il nostro tessuto sociale, con un sistema di valori che desta repulsione nella nostra coscienza civile. Parliamo delle conseguenze devastanti sulla salute e sull’ambiente delle popolazioni cosiddette “nemiche”. Parliamo delle conseguenze altrettanto devastanti sui corpi e sulle menti dei “nostri”, di chi il militare e la guerra è mandato o comandato a farli senza sapere. Parliamo di un tumore sociale quale il drenaggio delle nostre risorse e del nostro lavoro, un tumore sociale che non fa altro che generare tumori reali: non solo nei nostri corpi, ma anche nella mente nostra e delle generazioni a venire. Crediamo sia arrivato il momento di sollevare il velo di censure, compiacenze, ignoranza coltivata ad arte che ricopre il mondo militare. Vogliamo contribuire a rendere visibile e vivido questo male invisibile che avvelena la nostra società. Occorre andare avanti nello studio e nella ricerca, occorre andare oltre

Carotid artery stenting during endovascular thrombectomy for acute ischemic stroke with tandem occlusion: the Italian Registry of Endovascular Treatment in Acute Stroke

Purpose The management of tandem extracranial internal carotid artery and intracranial large vessel occlusion during endovascular thrombectomy (EVT) for acute ischemic stroke (AIS) has been under-investigated. We sought to investigate outcomes of AIS patients with tandem occlusion (TO) treated with carotid artery stenting (CAS) compared to those not treated with CAS (no-CAS) during EVT. Methods We performed a cohort study using data from AIS patients enrolled in the Italian Registry of Endovascular Treatment in Acute Stroke. Outcomes were 3 months' mortality, functional outcome, complete and successful recanalization, any intracranial hemorrhage, parenchymal hematoma and symptomatic intracerebral hemorrhage. Results Among 466 AIS patients with TO, CAS patients were 122 and no-CAS patients were 226 (118 excluded). After adjustment for unbalanced variables, CAS was associated with a lower rate of 3 months' mortality (OR 0.407, 95% CI 0.171-0.969, p = 0.042). After adjustment for pre-defined variables, CAS was associated with a lower rate of 3 months' mortality (aOR 0.430, 95% CI 0.187-0.989, p = 0.047) and a higher rate of complete recanalization (aOR 1.986, 95% CI 1.121-3.518, p = 0.019), successful recanalization (aOR 2.433, 95% CI 1.263-4.686, p = 0.008) and parenchymal hematoma (aOR 2.876, 95% CI 1.173-7.050, p = 0.021). CAS was associated with lower 3 months mortality (OR 0.373, 95% CI 0.141-0.982, p = 0.046) and higher rates of successful recanalization (OR 2.082, 95% CI 1.099-3.942, p = 0.024) after adjustment for variables associated with 3 months' mortality and successful recanalization, respectively. Conclusions Among AIS patients with TO, CAS during EVT was associated with a higher rate of successful reperfusion and a lower rate of 3 months' mortality