Large heterometallic coordination cages with gyrobifastigium-like geometry

Large (Mw > 10 kDa) heterometallic coordination cages with gyrobifastigium-like geometry are obtained by using metalloligands with sterically demanding FeII clathrochelate cores and four divergent pyridyl groups. Upon reaction with cis-blocked PtII and PdII complexes, MII8L4 cages are formed. The gyrobifastigium geometry of these cages is in contrast to the barrel-like structures which are typically observed for metallasupramolecular assemblies with M8L4 stoichiometry

The Intricate Structural Chemistry of MII2nLn-Type Assemblies

The reaction of cis-blocked, square-planar M-II complexes with tetratopic N-donor ligands is known to give metallasupramolecular assemblies of the formula M2nLn. These assemblies typically adopt barrel-like structures, with the ligands paneling the sides of the barrels. However, alternative structures are possible, as demonstrated by the recent discovery of a Pt8L4 cage with unusual gyrobifastigium-like geometry. To date, the factors that govern the assembly of (M2nLn)-L-II complexes are not well understood. Herein, we provide a geometric analysis of M2nLn complexes, and we discuss how size and geometry of the ligand is expected to influence the self-assembly process. The theoretical analysis is complemented by experimental studies using different cis-blocked Pt-II complexes and metalloligands with four divergent pyridyl groups. Mononuclear metalloligands gave mainly assemblies of type Pt8L4, which adopt barrel- or gyrobifastigium-like structures. Larger assemblies can also form, as evidenced by the crystallographic characterization of a Pt10L5 complex and a Pt16L8 complex. The former adopts a pentagonal barrel structure, whereas the latter displays a barrel structure with a distorted square orthobicupola geometry. The Pt16L8 complex has a molecular weight of more than 23 kDa and a diameter of 4.5 nm, making it the largest, structurally characterized M2nLn complex described to date. A dinuclear metalloligand was employed for the targeted synthesis of pentagonal Pt10L5 barrels, which are formed in nearly quantitative yields

Il linguaggio mentalistico nell'autismo. Risultati di un intervento di teatroterapia

Il Progetto IDEAS \ue8 nato con l\u2019intento di promuovere, attraverso la teatroterapia, lo sviluppo delle competenze sociali di bambini e ragazzi con Disturbi dello Spettro Autistico (Autism Spectrum Disorders \u2013 ASD). Il teatro, infatti, aiuta a comprendere meglio le dinamiche relazionali e favorisce lo sviluppo delle competenze legate alla teoria della mente. Partendo da queste evidenze, abbiamo analizzato la produzione di linguaggio mentalistico in un campione formato da sette ragazzi, cinque con ASD e due con alcuni tratti autistici. Gli incontri sono stati suddivisi in due situa- zioni, una sperimentale, composta dalle attivit\ue0 teatrali, e una di controllo, in cui i ragazzi sono stati coinvolti in giochi da tavolo. I risultati hanno evidenziato una produzione significativamente maggiore di termini riferiti a stati mentali durante gli esercizi teatrali rispetto alla condizione di controllo. Il teatro, inoltre, ha elicitato una modalit\ue0 d\u2019uso pi\uf9 evoluta di queste parole, che implica una riflessione sugli stati mentali

Mente e linguaggio: esempi da popolazioni atipiche

Il contributo ha l\u2019obiettivo di esplorare il rapporto tra teoria della mente e linguaggio, con particolare attenzione alle persone con disturbi dello spettro autistico e con disabilit\ue0 uditiva. Tali tematiche vengono introdotte con riferimento a contributi teorici classici e recenti. Vengono inoltre riportati alcuni risultati di uno studio pilota sull\u2019utilizzo di termini mentali in sette bambini con sintomatologia autistica coinvolti in un\u2019esperienza di teatro-terapia: da tale studio emerge come in situazione teatrale vengano prodotti pi\uf9 termini mentalistici, soprattutto cognizioni e desideri, e in modo pi\uf9 spontaneo rispetto a una situazione di controllo. Per quanto riguarda la sordit\ue0, si sottolinea il ruolo dell\u2019esperienza nel favorire l\u2019accesso alla teoria della mente e si forniscono indicazioni concrete connesse ai principi del metodo Dre\u17eani

Effect of interface type in the VR-based acquisition of pedestrian skills in persons with ASD

Possession of 'social' skills is crucial for persons with autism spectrum disorders (ASD) to maintain a certain independence and a better quality of life, and interaction with virtual environments seems an effective learning aid. In a previous study, we reported that in adults with ASD interaction with a virtual environment (a virtual city) is beneficial to the acquisition of pedestrian skills (street crossing and street navigation). Interaction was based on a gesture-based interface (Microsoft Kinect). Here we compare the learning performance when the same virtual environment is operated by a gamepad interface. We used exactly the same training protocol and data analysis than the original study. We found that both interface types are effective in the acquisition of street crossing and city navigation skills. The gamepad interface seems easier to use (thus leading to faster interaction), but gesture-based interfaces are superior in terms of transfer of the learned skills to real road environments (as reported by parents and caregivers)

Modeling of Anechoic Chambers With Equivalent Materials and Equivalent Sources

Numerical simulation of anechoic chambers is an important topic nowadays, since it can provide useful data about the performance of an electromagnetic compatibility site. However, the mathematical nature of the problem, the physical dimensions of the simulated sites, and the frequency ranges pose nontrivial challenges to the numerical simulation. Computational requirements, in particular, will quickly become unmanageable if adequate techniques are not employed. In this paper, we describe a novel approach, based on equivalent elements, that enables the simulation of large chambers with modest computational resources. Themethod is then validated against 558 real measurement results

The Intricate Structural Chemistry of M^II_2<i>n</i>L_<i>n</i>‑Type Assemblies

The reaction of <i>cis</i>-blocked, square-planar M^II complexes with tetratopic N-donor ligands is known to give metallasupramolecular assemblies of the formula M_2<i>n</i>L_<i>n</i>. These assemblies typically adopt barrel-like structures, with the ligands paneling the sides of the barrels. However, alternative structures are possible, as demonstrated by the recent discovery of a Pt₈L₄ cage with unusual gyrobifastigium-like geometry. To date, the factors that govern the assembly of M^II_2<i>n</i>L_<i>n</i> complexes are not well understood. Herein, we provide a geometric analysis of M_2<i>n</i>L_<i>n</i> complexes, and we discuss how size and geometry of the ligand is expected to influence the self-assembly process. The theoretical analysis is complemented by experimental studies using different <i>cis</i>-blocked Pt^II complexes and metalloligands with four divergent pyridyl groups. Mononuclear metalloligands gave mainly assemblies of type Pt₈L₄, which adopt barrel- or gyrobifastigium-like structures. Larger assemblies can also form, as evidenced by the crystallographic characterization of a Pt₁₀L₅ complex and a Pt₁₆L₈ complex. The former adopts a pentagonal barrel structure, whereas the latter displays a barrel structure with a distorted square orthobicupola geometry. The Pt₁₆L₈ complex has a molecular weight of more than 23 kDa and a diameter of 4.5 nm, making it the largest, structurally characterized M_2<i>n</i>L_<i>n</i> complex described to date. A dinuclear metalloligand was employed for the targeted synthesis of pentagonal Pt₁₀L₅ barrels, which are formed in nearly quantitative yields