Nell'Ombra della Fiaba Le espressioni di Eros e Thanatos nella letteratura per l'infanzia

Questo lavoro sarà dedicato alla fiaba, uno dei generi narrativi più diffusi; nella tradizione orale esiste fin dai tempi più antichi; successivamente trascritta, ha assunto un valore letterario a cominciare dai lavori di Giambattista Basile in Italia e di Perrault in Francia nel Seicento, e successivamente in Germania con la raccolta di fiabe popolari dei fratelli Grimm, per diventare nell'ultimo secolo anche soggetto di film. Nel primo capitolo si cercherà di evidenziare, sulla scorta degli studi condotti da Propp, le funzioni e la struttura che la caratterizzano; nel secondo centrale sarà il rapporto tra fiaba e interpretazione psicoanalitica. Nel terzo capitolo l'attenzione si concentrerà su un aspetto particolare, presente in tutti i testi presi in esame in questo lavoro: Thanatos, la pulsione di morte e distruzione, l'ostacolo costante, che può assumere varie forme e che il protagonista deve affrontare e superare per raggiungere l'Eros finale. Quest'ultimo non è da intendersi unicamente nell'accezione più conosciuta, bensì come una condizione di benessere, di equilibrio e raggiungimento di totalità. Sebbene Thanatos sia notoriamente antagonista rispetto ad Eros, in questo lavoro si tenterà, tuttavia, di analizzarne anche la carica positiva, che permette al protagonista alla fine di riunirsi al Bene. Fiabe di tutto il mondo e di ogni tempo raccontano di personaggi costretti a subire incantesimi maligni, sortilegi, maledizioni, fino ad essere, in alcuni casi, trasformati in animali; e del percorso che tocca fare a principi e re (bagni purificatori, omicidi e atti estremi) per sottrarsi a Thanatos, tornare alla vita e trovare un nuovo l'equilibrio finale. Questa successione di eventi può essere letta come un alternarsi delle due “pulsioni freudiane” Eros e Thanatos, rispettivamente la pulsione di vita e la pulsione di morte che dominano il personaggio e le sue azioni. Questa dicotomia, che invade il testo nella sua struttura, ma anche negli elementi che la compongono, crea un continuo incontro-scontro tra le due pulsioni. Alla fine della fiaba il lettore si trova di fronte, nella maggior parte dei casi, ad un esito positivo delle vicende, che vede trionfare il Bene, Eros, se però ci si ferma ad osservare meglio il testo e gli ostacoli che il protagonista ha dovuto affrontare, ci si renderà presto conto che la presenza di Thanatos ha assunto il ruolo principale rispetto al rinomato “happy ending” (...e vissero felici e contenti). Lo sviluppo delle vicende si conferma, ad un'analisi più profonda, quasi sempre dominato dalla pulsione negativa, che riesce ad occupare nel testo spazi descrittivo-narrativi più lunghi e dettagliati, mentre i passaggi in cui emerge Eros, e soprattutto il finale che lo vede trionfare, sono trattati in maniera più sbrigativa e meno accurata. La presenza di Thanatos nelle fiabe e nei racconti destinati ad un pubblico di bambini è, quindi, da considerarsi di importanza assoluta e strategica. A dimostrazione di questa tesi verranno analizzati i testi più conosciuti della letteratura infantile a partire dai primi dell'800 fino ad arrivare ai giorni nostri: la raccolta di fiabe dei fratelli Grimm, Alice nel paese delle meraviglie di Lewis Carroll, Pinocchio di Collodi, Peter Pan di J.M. Barrie, Il Piccolo Principe di Antoine de Saint-Exupéry e nell'ultimo sottocapitolo le storie di Luis Sepúlveda. L'analisi verrà svolta seguendo un criterio cronologico per poter dimostrare come, nonostante in questo arco di tempo si succedano varie generazioni di autori e di “piccoli e grandi lettori”, le tematiche affrontate rimangano le stesse, e soprattutto come la presenza di Thanatos sia non solo una costante in questo genere letterario, ma acquisisca addirittura un ruolo positivo all'interno delle vicende, creando le condizioni e le dinamiche affinché il protagonista le possa volgere ad un esito positivo, fino a raggiungere l'equilibrio tanto desiderato

Ligand-interchange reactions between M(iv) (M = Ti, V) oxide bis-acetylacetonates and halides of high-valent group 4 and 5 metals. A synthetic and electrochemical study

The reactions of M’O(acac)2[M’ = Ti, V; acac = acetylacetonato anion] with equimolar amounts of MF5 (M = Nb, Ta) in CH2Cl2 afforded Ti(acac)2F2, 1a, and [V(acac)3][MF6] (M = Nb,4a;M=Ta,4b), respectively. MOF3 (M = Nb, 2a; M=Ta,2b) were co-produced from MF5/TiO(acac)2. The intermediate species [TaF4{OTi(acac)2}2][TaF6], 3, was intercepted in the course of the formation of 1a from TiO(acac)2/TaF5. NbCl5 reacted with TiO(acac)2 yielding selectively the previously reported [NbO(acac)Cl2]x, 5, and Ti2(acac)2(μ-Cl)2Cl4, 6. Complex 6 was alternatively obtained from the addition of a two-fold excess of TiCl4 to VO(acac)2. The 1 : 1 reactions of TiX4 (X = F, Cl) with TiO(acac)2 in dichloromethane gave Ti(acac)2X2 (X = F,1a; X = Cl, 1b) and TiOX2 (X = F, 7a; X = Cl, 7b). The 1 : 1 combination of TiX4 (X = F, Cl) with VO(acac)2 led to 1a, band VOX2 (X = F, 8a; X = Cl, 8b). The μ-oxido compounds (C6F5)3B–O–M’(acac)2(M’ = Ti, V) underwent fragmentation by [PF6]- in chlorinated solvent, yielding POF3, 9, and [B(C6F5)3F]-, 10, according to NMR studies; 1a and V(acac)3+, respectively, were detected as the metal-containing species. Electrochemical studies were carried out aiming at the full characterization of the products and the observation of possible degradation pathways

On the Chiroptical Behavior of Conjugated Multichromophoric Compounds of a New Pseudoaromatic Class: Bicolchicides and Biisocolchicides

It is well known that, stemming from the mutual interplay between chromophores, circular dichroism (CD) is a powerful technique to deal with structural problems for both the small organic molecule and the biopolymer. However, quantitative interpretations of the spectroscopic and structural terms that give rise to the exciton couplet are usually presented for ideal cases, or a few CD bands only are taken into account, overlooking the role of the solvent medium. Circular dichroism and UV absorption spectra were carried out for colchicide (3) and isocolchicide (6), as well as their coupling products, 10,10'-bicolchicide (2) and 9,9'-biisocolchicide (5), in both hydrogen bonding and non hydrogen bonding solvents, as well as MeCN/H(2)O mixtures. A dramatic control by the solvent emerged, as even tiny changes in the composition of solvent mixtures, at ca 1 water molar fraction, induced a dramatic modification of their CD bands. A mutarotation phenomenon--long known for isocolchicine (8)--was also observed for 5, and can be attributed to the interconversion between atropisomers (R(a),7S),(R(a),7'S)-5a and (R(a),7S),(S(a),7'S)-5b. Our data show that with molecules built on two structurally identical moieties which embody both hydrophilic and hydrophobic groups, even tiny changes in the composition of solvent mixtures cause a dramatic modification of the CD bands. Their analysis arrives at a qualitative rationalization of the observed CD couplets from the coupling of high energy transitions, while attempts at a quantitative interpretation of these phenomena through time-dependent density functional theory allowed to reproduce satisfactorily the CD spectrum in the 300-450 nm region only. Failure with higher energies probably reflects currently inadequate specific theoretical treatments of the solvent medium

Universalità spirituale di Cicerone

The article reviews Cicero's early education and his major works (in chronological order) to explore his spiritual universalism. In fact, the studies that he carried out not only in Rome, but also in Greece, led him to follow the Roman tendency towards cultural openness, also evident in the Circle of the Scipios; he was, for example, deeply influenced by Philo's, Diodotus's and Antiochus's philosophical doctrines. Cicero is presented here as the first example in the ancient world of a substantial union between political and artistic activity, a union that stands out particularly in his rhetorical works and especially in De oratore (considered the key treatise for understanding Cicero the orator). Ciceronian universalism thus appears as the synthesis of Hellenic and Roman spirituality and is strongly rooted in the conception of humanitas.   [Sara Busceti, Stefano Pellegrin A.S.L. 2022 Liceo Cavour Torino]L'articolo passa in rassegna la formazione giovanile di Cicerone e le sue opere maggiori (in ordine cronologico) per trattare del suo universalismo spirituale. Gli anni di studio svolti non solo a Roma, ma anche in Grecia, lo indussero infatti a seguire la tendenza romana all'apertura culturale, evidente anche nel Circolo degli Scipioni; egli fu per esempio profondamente influenzato dal pensiero filosofico di Filone, Diodoto e Antioco. Cicerone viene qui presentato come primo esempio nel mondo antico di unione sostanziale tra attività politica ed artistica, connubio che risalta particolarmente nelle opere retoriche e soprattutto nel De oratore (considerato il trattato chiave per comprendere del tutto il Cicerone oratore). L'universalismo ciceroniano appare dunque come la sintesi tra spiritualità ellenica e romana ed è fortemente radicato nella concezione dell'humanitas

Synthesis and characterization of non-bridging mono- and bis-σ-η1-alkynyl derivatives of the phosphido-bridged hexaplatinum core [Pt6(μ-PBut2)4(CO)4]2+

Several mono- or bis-alkynyl derivatives of general formula Pt6(μ-PBut2)4(CO)4X(CC–R), Pt6(μ-PBut2)4(CO)4(CC–R)2 or Pt6(μ-PBut2)4(CO)4(CC–R)(CC–R′) were obtained under Sonogashira type conditions. The new clusters have been characterized with microanalysis and using IR and multinuclear NMR spectroscopy. The crystal and molecular structures of Pt6(μ-PBut2)4(CO)4(CC–R)2 (R = H, C6H4-4-n-C5H11) are presented and electrochemical and spectroelectrochemical studies of some representative compounds are also reported

Modular chiral Eu(iii) complexes for efficient circularly polarized OLEDs

Achieving both high dissymmetry factors and strong emission in circularly polarized (CP) luminescent materials and, at the same time, compatibility with manufacturing processes for organic electronic devices, is a crucial issue for reliable applications of CP emitters in many fields, such as chiral electronics and optoelectronics. In this communication, we show that the independent choice of the sensitizing and the chirality inducing ligands allows europium(III) complexes to meet the multiple requirements for solution processed efficient CP electroluminescent devices

Atomically Precise Ni-Pd Alloy Carbonyl Nanoclusters: Synthesis, Total Structure, Electrochemistry, Spectroelectrochemistry, and Electrochemical Impedance Spectroscopy

The molecular nanocluster [Ni36-xPd5+x(CO)46]6- (x = 0.41) (16-) was obtained from the reaction of [NMe3(CH2Ph)]2[Ni6(CO)12] with 0.8 molar equivalent of [Pd(CH3CN)4][BF4]2 in tetrahydrofuran (thf). In contrast, [Ni37-xPd7+x(CO)48]6- (x = 0.69) (26-) and [HNi37-xPd7+x(CO)48]5- (x = 0.53) (35-) were obtained from the reactions of [NBu4]2[Ni6(CO)12] with 0.9-1.0 molar equivalent of [Pd(CH3CN)4][BF4]2 in thf. After workup, 35- was extracted in acetone, whereas 26- was soluble in CH3CN. The total structures of 16-, 26-, and 35- were determined with atomic precision by single-crystal X-ray diffraction. Their metal cores adopted cubic close packed structures and displayed both substitutional and compositional disorder, in light of the fact that some positions could be occupied by either Ni or Pd. The redox behavior of these new Ni-Pd molecular alloy nanoclusters was investigated by cyclic voltammetry and in situ infrared spectroelectrochemistry. All three compounds 16-, 26-, and 35- displayed several reversible redox processes and behaved as electron sinks and molecular nanocapacitors. Moreover, to gain insight into the factors that affect the current-potential profiles, cyclic voltammograms were recorded at both Pt and glassy carbon working electrodes and electrochemical impedance spectroscopy experiments performed for the first time on molecular carbonyl nanoclusters

When ferrocene and diiron organometallics meet: triiron vinyliminium complexes exhibit strong cytotoxicity and cancer cell selectivity

Cationic triiron complexes resulting from the conjugation of the ferrocenyl skeleton (Fc) with a diiron bis-cyclopentadienyl core through a variable vinyliminium linker, [Fe2Cp2(CO)(mu-CO){mu-eta(1):eta(3)-C(Fc)CHCN(R)(R')}]CF3SO3 ([2a-i]CF3SO3, Cp = eta(5)-C5H5, R, R'= alkyl, aryl), were synthesised in 70-94% yield, and the homologous nitrate salt was also prepared in one case ([2h]NO3). The neutral derivatives [Fe2Cp2(CO)(mu-CO){mu-eta(1):eta(3)-C(Fc)CHC(CN)NMe2}], 3, and [FeCp(CO){CN(Me)(Xyl)CHC(Fc)C(=O)}], 4 (Xyl = 2,6-C6H3Me2), were obtained in ca. 70% yield by reactions of the respective precursors [2h]CF3SO3 and [2i]CF3SO3 with NBu4CN and pyrrolidine, respectively. All products were purified by alumina chromatography and fully characterised by analytical and spectroscopic methods, and by single crystal X-ray diffraction in the cases of [2a]CF3SO3 and 3. The cytotoxicity of the complexes was assessed on A2780, A2780cisR and BxPC-3 cancer cell lines, and the nontumoral Balb/3T3 clone A31. Most of the cationic complexes display IC50 values in the low micromolar/nanomolar range concerning the cancer cell lines, and up to 35 times higher values on the nontumoral cells. In order to shed light on the mode of action, selected complexes were further characterised by cyclic voltammetry and spectroelectrochemical experiments, and assessed for their potential to trigger ROS production and to interact with a range of biomolecules, i.e. a synthetic dodecapeptide as a simplified model for thioredoxin reductase (TrxR-pept), some model proteins (cytochrome c, hen egg-white lysozyme, ubiquitin, bovine serum albumin, superoxide dismutase and human carbonic anhydrase) and one single-stranded oligonucleotide (ODN2)

An Italian multicenter retrospective real-life analysis of patients with brain metastases from renal cell carcinoma: the BMRCC study

Background: The treatment of patients with brain-spread renal cell carcinoma (RCC) is an unmet clinical need, although more recent therapeutic strategies have significantly improved RCC patients' life expectancy. Our multicenter, retrospective, observational study investigated a real-world cohort of patients with brain metastases (BM) from RCC (BMRCC). Patients and methods: A total of 226 patients with histological diagnosis of RCC and radiological evidence of BM from 22 Italian institutions were enrolled. Univariate and multivariate models were performed to investigate the impact of clinicopathological features and multimodal treatments on both overall survival (OS) from the BM diagnosis and intracranial progression-free survival (iPFS). Results: The median OS from the BM diagnosis was 18.8 months (interquartile range: 6.2-43 months). Multivariate analysis confirmed the following as positive independent prognostic factors: a Karnofsky Performance Status >70% [hazard ratio (HR) = 0.49, 95% confidence interval (CI) 0.26-0.92, P = 0.0026] and a single BM (HR = 0.51, 95% CI 0.31-0.86, P = 0. 0310); in contrast, the following were confirmed as worse prognosis factors: progressive extracranial disease (HR = 1.66, 95% CI 1.003-2.74, P = 0.00181) and only one line of systemic therapy after the BM occurrence (HR = 2.98, 95% CI 1.62-5.49, P = 0.029). Subgroup analyses showed no difference in iPFS according to the type of the first systemic treatment [immunotherapy (IT) or targeted therapy (TT)] carried out after the BM diagnosis (HR = 1.033, 95% CI 0.565-1.889, P = 0.16), and revealed that external radiation therapy (eRT) significantly prolonged iPFS when combined with IT (10.7 months, 95% CI 4.9-48 months, P = 0.0321) and not when combined with TT (9.01 months, 95% CI 2.7-21.2 months, P = 0.59). Conclusions: Our results suggest a potential additive effect in terms of iPFS for eRT combined with IT and encourage a more intensive multimodal therapeutic strategy in a multidisciplinary context to improve the survival of BMRCC patients