Reversible redox reactions in metal-supported porphyrin: The role of spin and oxidation state

On-surface molecular functionalization paved the way for the stabilization of chelated ions in different oxidation and spin states, allowing for the fine control of catalytic and magnetic properties of metalorganic networks. Considering two model systems, a reduced Co(i) and an open-shell Co(ii) metal-supported 2D molecular array, we investigate the interplay between the low valence oxidation and unpaired spin state in the molecular reactivity. We show that the redox reaction taking place at the cobalt tetraphenylporphyrin/Cu(100) interface, stabilizing the low-spin Co(i) state with no unpaired electrons in its valence shell, plays a pivotal role in changing the reactivity. This goes beyond the sole presence of unpaired electrons in the valence state of the Co(ii) metal-organic species, often designated as being responsible for the reactivity towards small molecules like NO and NO2. The reversible Co-NO2 interaction, established with the Co(i) leads to the stabilization of the Co(iii) oxidation state

Extended π-conjugation: a key to magnetic anisotropy preservation in highly reactive porphyrins

In this study, the magnetic anisotropy of metal complexes is explored for its crucial role in the development of molecular materials for cutting-edge applications in spintronics, memory storage, and quantum computing. The challenge of achieving maximum magnetic anisotropy for paramagnetic single nickel ion sites is addressed and realized through an on-surface thermally induced planarization reaction in tetraphenylporphyrin, which maintains the nickel species in a square planar coordination environment. At the same time, the effective ligand field reduction due to the increased π-conjugation results in a lower reactivity of the molecular species. The results herein reported showcase the synergy between magnetic anisotropy and chemical robustness in single-site magnetic materials, thus opening exciting prospects for the development of stable uniaxial anisotropy in these materials. Such a finding represents a relevant advance in the field and validates a protocol for exploring magnetic anisotropy in metal complexes

Current trends on subtotal petrosectomy with cochlear implantation in recalcitrant chronic middle ear disorders Attualità in tema di petrosectomia subtotale con impianto cocleare nelle patologie croniche dellorecchio medio recalcitranti

Obiettivo. Stabilire la sicurezza ed efficacia dell’intervento di petrosectomia subtotale con posizionamento di impianto cocleare nei pazienti affetti da patologia cronica dell’orecchio medio refrattaria a precedenti trattamenti chirurgici. Metodi. È stato svolto uno studio retrospettivo multicentrico riguardante quei pazienti af- fetti da patologie croniche dell’orecchio medio recalcitranti, sottoposti a petrosectomia subtotale con posizionamento di impianto cocleare. Le informazioni sono state raccolte dai database di 11 centri di riferimento di III livello in Italia. A complemento, è stata svolta una revisione della più recente letteratura. Risultati. Nello studio sono stati inclusi 55 pazienti con un follow-up medio di 44 mesi. Il colesteatoma ha rappresentato la più comune pato- logia ricorrente dell’orecchio medio e il 50,9% dei pazienti aveva una cavità aperta. L’80% dei pazienti è stato sottoposto ad una chirurgia a singolo stadio. Sette pazienti hanno mostrato complicanze post-operatorie, di cui un caso di espianto. Conclusioni. L’intervento di petrosectomia subtotale con posizionamento di impianto cocleare rappresenta una tecnica chirurgica di riferimento per la gestione dei pazienti affetti da otite media cronica recalcitrante. L’intervento chirurgico a singolo stadio è la strategia più frequentemente raccomandata. Il follow-up ottimale è ancora ad oggi oggetto di dibattito. Sono richiesti ulteriori studi per stabilire il ruolo di questo intervento nei pazienti pediatrici.Objective. To establish the safety and effectiveness of subtotal petrosectomy with cochlear implantation in patients affected by chronic middle ear disorders to refractory to previous surgical treatments. Methods. A multicentre, retrospective study was conducted on patients affected by recalcitrant chronic middle ear disorders who underwent cochlear implantation in combination with subtotal petrosectomy. Patients’ details were collected from databases of 11 Italian tertiary referral centres. Additionally, a review of the most updated literature was carried out. Results. 55 patients were included with a mean follow-up time of 44 months. Cholesteatoma was the most common middle ear recurrent pathology and 50.9% of patients had an open cavity. 80% of patients underwent a single stage surgery. One case of explantation for device failure was reported among the 7 patients with post-operative complications. Conclusions. Subtotal petrosectomy with cochlear implantation is a benchmark for management of patients with recalcitrant chronic middle ear disorders. A single stage procedure is the most recommended strategy. Optimal follow-up is still debated. Further studies are required to investigate the role of this surgery in paediatric patients

Ferrous to Ferric Transition in Fe-Phthalocyanine Driven by NO2 Exposure

Due to its unique magnetic properties offered by the open-shell electronic structure of the central metal ion, and for being an effective catalyst in a wide variety of reactions, iron phthalocyanine has drawn significant interest from the scientific community. Nevertheless, upon surface deposition, the magnetic properties of the molecular layer can be significantly affected by the coupling occurring at the interface, and the more reactive the surface, the stronger is the impact on the spin state. Here, we show that on Cu(100), indeed, the strong hybridization between the Fe d-states of FePc and the sp-band of the copper substrate modifies the charge distribution in the molecule, significantly influencing the magnetic properties of the iron ion. The FeII ion is stabilized in the low singlet spin state (S=0), leading to the complete quenching of the molecule magnetic moment. By exploiting the FePc/Cu(100) interface, we demonstrate that NO2 dissociation can be used to gradually change the magnetic properties of the iron ion, by trimming the gas dosage. For lower doses, the FePc film is decoupled from the copper substrate, restoring the gas phase triplet spin state (S=1). A higher dose induces the transition from ferrous to ferric phthalocyanine, in its intermediate spin state, with enhanced magnetic moment due to the interaction with the atomic ligands. Remarkably, in this way, three different spin configurations have been observed within the same metalorganic/metal interface by exposing it to different doses of NO2 at room temperature

Current trends on subtotal petrosectomy with cochlear implantation in recalcitrant chronic middle ear disorders

Objective. To establish the safety and effectiveness of subtotal petrosectomy with cochlear implantation in patients affected by chronic middle ear disorders to refractory to previous surgical treatments. Methods. A multicentre, retrospective study was conducted on patients affected by recalcitrant chronic middle ear disorders who underwent cochlear implantation in combi-nation with subtotal petrosectomy. Patients’ details were collected from databases of 11 Italian tertiary referral centres. Additionally, a review of the most updated literature was carried out. Results. 55 patients were included with a mean follow-up time of 44 months. Cholestea-toma was the most common middle ear recurrent pathology and 50.9% of patients had an open cavity. 80% of patients underwent a single stage surgery. One case of explantation for device failure was reported among the 7 patients with post-operative complications. Conclusions. Subtotal petrosectomy with cochlear implantation is a benchmark for management of patients with recalcitrant chronic middle ear disorders. A single stage procedure is the most recommended strategy. Optimal follow-up is still debated. Further studies are required to investigate the role of this surgery in paediatric patients

An improved geometric inequality via vanishing moments, with applications to singular Liouville equations

We consider a class of singular Liouville equations on compact surfaces motivated by the study of Electroweak and Self-Dual Chern-Simons theories, the Gaussian curvature prescription with conical singularities and Onsager's description of turbulence. We analyse the problem of existence variationally, and show how the angular distribution of the conformal volume near the singularities may lead to improvements in the Moser-Trudinger inequality, and in turn to lower bounds on the Euler-Lagrange functional. We then discuss existence and non-existence results.Comment: some references adde