P2-Type Na0.84Li0.1Ni0.27Mn0.63O2-Layered Oxide Na-Ion Battery Cathode: Structural Insights and Electrochemical Compatibility with Room-Temperature Ionic Liquids.

Modern technologies that can replace state-of-the-art Li-ion batteries (LIBs), such as Na-ion batteries (NIBs), are currently driving new advancements in energy storage research. Developing functional active materials having sustainable features and enhanced performances able to assess their exploitation in the large-scale market represents a major challenge. Rationally designed P2-type layered transition metal (TM) oxides can enable high-energy NIB cathodes, where the tailored composition directly tunes the electrochemical and structural properties. Such positive electrodes need stable electrolytes, and exploration of unconventional room-temperature ionic liquid (RTIL)-based formulations paves the route toward safer options to flammable organic solvents. Notwithstanding the fact that Li+ doping in these materials has been proposed as a viable strategy to improve structural issues, an in-depth understanding of structure-property relationship as well as electrochemical testing with innovative RTIL-based electrolytes is still missing. Herein, we propose the solid-state synthesis of P2-Na0.84Li0.1Ni0.27Mn0.63O2 (NLNMO) cathode material, which exhibits promising structural reversibility and superior capacity retention upon cycling when tested in combination with RTIL-based electrolytes (EMI-, PYR14-, and N1114-FSI) compared to the standard NaClO4/PC. As unveiled from DFT calculations, lattice integrity is ensured by the reduced Jahn-Teller distortion upon Na removal exerted by Mn4+ and Li+ sublattices, while the good redox reversibility is mainly associated with the electrochemically active Ni2+/Ni3+/Ni4+ series burdening the charge compensation upon desodiation. By declaring the electrochemical compatibility of the P2-NLNMO cathode with three RTIL-based electrolytes and dissecting the role of Li/Ni/Mn sublattices in determining the electrochemical behavior, our comprehensive study enlightens the potential application of this electrode/electrolyte setup for future high-energy NIB prototype cells.

Azobenzene-based optoelectronic transistors for neurohybrid building blocks.

Exploiting the light-matter interplay to realize advanced light responsive multimodal platforms is an emerging strategy to engineer bioinspired systems such as optoelectronic synaptic devices. However, existing neuroinspired optoelectronic devices rely on complex processing of hybrid materials which often do not exhibit the required features for biological interfacing such as biocompatibility and low Young's modulus. Recently, organic photoelectrochemical transistors (OPECTs) have paved the way towards multimodal devices that can better couple to biological systems benefiting from the characteristics of conjugated polymers. Neurohybrid OPECTs can be designed to optimally interface neuronal systems while resembling typical plasticity-driven processes to create more sophisticated integrated architectures between neuron and neuromorphic ends. Here, an innovative photo-switchable PEDOT:PSS was synthesized and successfully integrated into an OPECT. The OPECT device uses an azobenzene-based organic neuro-hybrid building block to mimic the retina's structure exhibiting the capability to emulate visual pathways. Moreover, dually operating the device with opto- and electrical functions, a light-dependent conditioning and extinction processes were achieved faithful mimicking synaptic neural functions such as short- and long-term plasticity.

Structural Evolution of Air-Exposed Layered Oxide Cathodes for Sodium-Ion Batteries: An Example of Ni-doped NaxMnO2.

Sodium-ion batteries have recently aroused the interest of industries as possible replacements for lithium-ion batteries in some areas. With their high theoretical capacities and competitive prices, P2-type layered oxides (NaxTMO2) are among the obvious choices in terms of cathode materials. On the other hand, many of these materials are unstable in air due to their reactivity toward water and carbon dioxide. Here, Na0.67Mn0.9Ni0.1O2 (NMNO), one of such materials, has been synthesized by a classic sol-gel method and then exposed to air for several weeks as a way to allow a simple and reproducible transition toward a Na-rich birnessite phase. The transition between the anhydrous P2 to the hydrated birnessite structure has been followed via periodic XRD analyses, as well as neutron diffraction ones. Extensive electrochemical characterizations of both pristine NMNO and the air-exposed one vs sodium in organic medium showed comparable performances, with capacities fading from 140 to 60 mAh g-1 in around 100 cycles. Structural evolution of the air-exposed NMNO has been investigated both with ex situ synchrotron XRD and Raman. Finally, DFT analyses showed similar charge compensation mechanisms between P2 and birnessite phases, providing a reason for the similarities between the electrochemical properties of both materials.

New Insights on Singlet Oxygen Release from Li-Air Battery Cathode: Periodic DFT Versus CASPT2 Embedded Cluster Calculations.

Li-air batteries are a promising energy storage technology for large-scale applications, but the release of highly reactive singlet oxygen (1O2) during battery operation represents a main concern that sensibly limits their effective deployment. An in-depth understanding of the reaction mechanisms underlying the 1O2 formation is crucial to prevent its detrimental reactions with the electrolyte species. However, describing the elusive chemistry of highly correlated species such as singlet oxygen represents a challenging task for state-of-the-art theoretical tools based on density functional theory. Thus, in this study, we apply an embedded cluster approach, based on CASPT2 and effective point charges, to address the evolution of 1O2 at the Li2O2 surface during oxidation, i.e., the battery charging process. Based on recent hypothesis, we depict a feasible O22-/O2-/O2 mechanisms occurring from the (112̅0)-Li2O2 surface termination. Our highly accurate calculations allow for the identification of a stable superoxide as local minimum along the potential energy surface (PES) for 1O2 release, which is not detected by periodic DFT. We find that 1O2 release proceeds via a superoxide intermediate in a two-step one-electron process or another still accessible pathway featuring a one-step two-electron mechanism. In both cases, it represents a feasible product of Li2O2 oxidation upon battery charging. Thus, tuning the relative stability of the intermediate superoxide species can enable key strategies aiming at controlling the detrimental development of 1O2 for new and highly performing Li-air batteries.

First-principles design of nanostructured electrode materials for Na-ion batteries: challenges and perspectives.

Post-lithium batteries are emerging as viable solutions for sustainable energy transition. Effective deployment in the market calls for great research efforts in the identification of novel component materials and the assessment of related working principles. Computational modelling can be a key player in boosting innovation and development by enabling rational strategies for the design of appropriately tuned materials with optimized activity towards battery operating processes. By gaining access to the structural and electronic features of functional electrodes, state-of-the-art DFT methods can unveil the subtle structure-property relationship that affects the uptake, transport, and storage efficiency. Hereby, we aim at reviewing the research status of theoretical advances in the field of Na-ion batteries (NIBs) and illustrating to what extent atomistic insights into sodiation/desodiation mechanisms of nanostructured materials can assist the development of effective anodes and cathodes for stable and highly performing devices. Thanks to increasing computer power and fruitful cooperation between theory and experiments, the route for effective design methodologies is being paved and will feed the upcoming developments in NIB technology.

d-Glucose Adsorption on the TiO2 Anatase (100) Surface: A Direct Comparison Between Cluster-Based and Periodic Approaches.

Titanium dioxide (TiO2) has been extensively studied as a suitable material for a wide range of fields including catalysis and sensing. For example, TiO2-based nanoparticles are active in the catalytic conversion of glucose into value-added chemicals, while the good biocompatibility of titania allows for its application in innovative biosensing devices for glucose detection. A key process for efficient and selective biosensors and catalysts is the interaction and binding mode between the analyte and the sensor/catalyst surface. The relevant features regard both the molecular recognition event and its effects on the nanoparticle electronic structure. In this work, we address both these features by combining two first-principles methods based on periodic boundary conditions and cluster approaches (CAs). While the former allows for the investigation of extended materials and surfaces, CAs focus only on a local region of the surface but allow for using hybrid functionals with low computational cost, leading to a highly accurate description of electronic properties. Moreover, the CA is suitable for the study of reaction mechanisms and charged systems, which can be cumbersome with PBC. Here, a direct and detailed comparison of the two computational methodologies is applied for the investigation of d-glucose on the TiO2 (100) anatase surface. As an alternative to the commonly used PBC calculations, the CA is successfully exploited to characterize the formation of surface and subsurface oxygen vacancies and to determine their decisive role in d-glucose adsorption. The results of such direct comparison allow for the selection of an efficient, finite-size structural model that is suitable for future investigations of biosensor electrocatalytic processes and biomass conversion catalysis.

First-Principles Study of Na Intercalation and Diffusion Mechanisms at 2D MoS2/Graphene Interfaces.

Na-ion batteries (NIBs) are emerging as promising energy storage devices for large-scale applications. Great research efforts are devoted to design new effective NIB electrode materials, especially for the anode side. A hybrid 2D heterojunction with graphene and MoS2 has been recently proposed for this purpose: while MoS2 has shown good reversible capacity as a NIB anode, graphene is expected to improve conductivity and resistance to mechanical stress upon cycling. The most relevant processes for the anode are the intercalation and diffusion of the large Na ion, whose complex mechanisms are determined by the structural and electronic features of the MoS2/graphene interface. Understanding these processes and mechanisms is crucial for developing new nanoscale anodes for NIBs with high performances. To this end, here we report a state-of-the-art DFT study to address (a) the structural and electronic properties of heterointerfaces between the MoS2 monolayers and graphene, (b) the most convenient insertion sites for Na, and (c) the possible diffusion paths along the interface and the corresponding energy barrier heights. We considered two MoS2 polymorphs: 1T and 3R. Our results show that 1T-MoS2 interacts more strongly with graphene than 3R-MoS2. In both cases, the best Na host site is found at the MoS2 side of the interface, and the band structure reveals a proper n-type character of the graphene moiety, which is responsible for electronic conduction. Minimum-energy paths for Na diffusion show very low barrier heights for the 3R-MoS2/graphene interface (<0.25 eV) and much higher values for its 1T counterpart (∼0.7 eV). Analysis of structural features along the diffusion transition states allows us to identify the strong coordination of Na with the exposed S atoms as the main feature hindering an effective diffusion in the 1T case. These results provide new hints on the physicochemical details of Na intercalation and diffusion mechanisms at complex 2D heterointerfaces and will help further development of advanced electrode materials for efficient NIBs.

Sodium diffusion in ionic liquid-based electrolytes for Na-ion batteries: the effect of polarizable force fields.

Understanding the transport of sodium ions in ionic liquids is key to designing novel electrolyte materials for sodium-ion batteries. In this work, we combine molecular dynamics simulation and experiments to study how molecular interactions and local ordering affect relevant physico-chemical properties. Ionic transport and local solvation environments are investigated in electrolytes composed of sodium bis(fluorosulfonyl)imide, (Na[FSI]), in N,N-methylpropylpyrrolidinium bis(fluorosulfonyl)imide, [C3C1pyr][FSI], at different salt concentrations. The electrolyte systems are modelled by means of molecular dynamic simulations using a polarizable force field. We show that including polarization effects explicitly in the molecular simulations is required in order to attain a reliable description of the transport properties of sodium in the [C3C1pyr][FSI] electrolyte. The validation of the computational results upon comparison with experimental data allows us to assess the suitability of polarizable force fields in describing and interpreting the structure and dynamics of the sodium salt-ionic liquid system, which is essential to enable the application of IL-based electrolytes in novel energy-storage technologies.

Reorganization of a Nuclear Medicine Department in Northern Italy During a 2-Month Lockdown for COVID-19 Pandemic.

Coronavirus disease (COVID-19) outbreak has profoundly changed the organization of hospital activities. We present our experience of reorganization of a nuclear medicine service settled in Northern Italy during the pandemic period of March and April 2020 characterized a government-mandated lockdown. Our service remained open during the whole period, performing approximately 80% of the routine practice, while maintaining it COVID-free despite the geographical context characterized by a high risk of infection. Reorganization involved all aspects of a nuclear medicine department, following local, national, and international guidelines for prioritizing patients, telephone and physical triages, deployment of appropriate personal protective equipment, social distancing, and logistic changes for scheduling examinations and disinfection procedures. All staff remained COVID-19-negative despite the unintentional admission of 4 patients who later turned out to be positive for the severe acute respiratory syndrome coronavirus 2. These adopted measures would serve as the basis for safe nuclear medicine services in the post-lockdown phase.

First-principles study of Na insertion at TiO2 anatase surfaces: new hints for Na-ion battery design.

Na-ion batteries (NIBs) are attracting widespread interest as a potentially more convenient alternative to current state-of-the-art Li-ion batteries (LIBs), chiefly for large-scale energy storage from renewables. Developing novel active materials is essential for the deployment of NIBs, especially in terms of negative electrodes that can accommodate the larger sodium ions. We focus on TiO2 anatase, which has been proposed as a promising anode material for the overall balance of performance, stability and cost. As the exposed crystal facets in different morphologies of nanostructured anatase can affect the electrochemical performances, here we report a theoretical investigation of Na+ adsorption and migration through (101), (100) and (001) surface terminations, thus explaining the different activities toward sodiation reported in the literature. Energy barriers computed by means of the CI-NEB method at the DFT+U level of theory show that the (001) surface is the most effective termination for Na+ insertion. We also provide a detailed analysis to elucidate that the energy barriers are due to structural modifications of the lattice upon sodiation. From these results we derive new design directions for the development of cheap and effective oxide-based nanostructured electrode materials for advanced NIBs.

A new mobile self-dispensing and administering system for 18F-FDG: evaluation of operator dose reduction.

PURPOSE: Recently new mobile systems for dispensing positron emitters have been produced, designed to guarantee dispensing cycles in an aseptic environment. The aim of the present work was to assess the advantage of one of these systems in radiation protection of operators in clinical settings. METHODS: Recently, in our centre the new self-dispensing system named KARL100 by Tema Sinergie was adopted for 18F-FDG radiopharmaceuticals. The system is associated with an automatic Rad-inject infuser. The system that was previously used was a fixed isolator NMC DSI (Tema Sinergie), equipped with a µDDS-An activity fractioning system, together with a pneumatic post for the syringe delivery. The dosimetric evaluations on both systems were carried out through environmental measurements with an ionisation chamber and with the use of personal dosimeters. RESULTS: The operations of preparation and administration of 18F-FDG dose to the patient, with the use of Karl100 + RadInject, involve exposures much lower than those obtained by the fixed isolator. The average body exposure of the technician was reduced by 31%, and for the physician by 77%. On the extremities, the equivalent dose to the hands of the technician was reduced by 78%, and for the physician by 96%. Also the additional dosimeters worn by the technician confirmed the estimated environmental assessments. CONCLUSIONS: The exposures of the working personnel were significantly reduced with the introduction of the new KARL100 system.

Ab initio study of PbCr(1-x)S x O4 solid solution: an inside look at Van Gogh Yellow degradation.

Van Gogh Yellow refers to a family of lead chromate pigments widely used in the 19th century and often mixed with lead sulfate to obtain different yellow hues. Unfortunately, some paintings, such as the famous Sunflowers series, suffered degradation problems due to photoactivated darkening of once bright yellow areas, especially when irradiated with UV light. Recent advanced spectroscopic analyses have proved that this process occurs mostly where the pigment presents a sulfur-rich orthorhombic phase of a PbCr(1-x)S x O4 solid solution, while chromium-rich monoclinic phases are lightfast. However, the question of whether degradation is purely a surface phenomenon or if the bulk properties of sulfur-rich pigments trigger the process is still open. Here, we use first-principles calculations to unveil the role of sulfur in determining important bulk features such as structure, stability, and optical properties. From our findings, we suggest that degradation occurs via an initial local segregation of lead sulfate that absorbs at UV light wavelengths and provides the necessary energy for subsequent reduction of chromate ions into the greenish chromic oxide detected in experiments. In perspective, our results set reliable scientific foundations for further studies on surface browning phenomena and can help to chose the best strategy for the proper conservation of art masterpieces.

Optimized protocol for (18)F-choline PET/CT in patients with biochemically relapsed prostate cancer: experiences on 250 consecutive cases.

PURPOSE: We review acquisition F-choline PET/CT methodology, evaluate a new F-choline acquisition protocol for prostate cancer (PC), and propose a standardized acquisition protocol on F-choline in PC patients. MATERIALS: Two hundred fifty consecutive PC patients (mean age 72 years, mean PSA 7.9 ng/mL) were prospectively evaluated with F-choline PET/CT. An early scan of the pelvis (1 bed position of 4 minutes) was followed by a whole-body scan at 1 hour. Early and 1 delayed hour images of the pelvis were compared. RESULTS: Twenty-one percent of patients (n = 57) with positive F-choline demonstrated abnormal local uptake; 18% of patients (n = 45) showed distant localization only; 23% of patients (n = 53) had both local and distant localization; 38% of patients (n = 38) did not show any pathological uptake. All early images showed absence of radioactive urine in ureters, bladder, or urethra with satisfactory visualization of the prostatic region. Considering the group of patients with local uptake only, the prostatic region uptake, confirmed by late images, was better visualized in the early phase in 32/57 cases (SUVmax 12.4 ± 3.2 vs. 7.3 ± 5.2, P <0.01). Instead distant lesions were visualized on both early and late images with similar uptakes values (SUVmax 9.8 ± 4.1 vs. 10.3 ± 4.5, P = N.S.). CONCLUSION: Early F-choline images improve pelvic prostate cancer lesion clarity. All pathologic pelvic deposits (prostate, lymph nodes, bone) were visualized both in the early and late images.

New acquisition protocol of 18F-choline PET/CT in prostate cancer patients: review of the literature about methodology and proposal of standardization.

PURPOSE: (1) To evaluate a new acquisition protocol of (18)F-choline (FCH) PET/CT for prostate cancer patients (PC), (2) to review acquisition (18)F-choline PET/CT methodology, and (3) to propose a standardized acquisition protocol on FCH PET/CT in PC patients. MATERIALS: 100 consecutive PC patients (mean age 70.5 years, mean PSA 21.35 ng/mL) were prospectively evaluated. New protocol consisted of an early scan of the pelvis immediately after the injection of the tracer (1 bed position of 4 min) followed by a whole body scan at one 1 hour. Early and 1 hour images were compared for interfering activity and pathologic findings. RESULTS: The overall detection rate of FCH PET/CT was 64%. The early static images of the pelvis showed absence of radioactive urine in ureters, bladder, or urethra which allowed a clean evaluation of the prostatic fossae. Uptake in the prostatic region was better visualized in the early phase in 26% (7/30) of cases. Other pelvic pathologic findings (bone and lymph nodes) were visualized in both early and late images. CONCLUSION: Early (18)F-choline images improve visualization of abnormal uptake in prostate fossae. All pathologic pelvic deposits (prostate, lymph nodes, and bone) were visualized in both early and late images.

Role of 18F-choline PET/CT in biochemically relapsed prostate cancer after radical prostatectomy: correlation with trigger PSA, PSA velocity, PSA doubling time, and metastatic distribution.

PURPOSE: The aim of this study was to evaluate the efficacy of ¹8F-choline PET/CT (18FCH-PET/CT) in restaging patients previously treated by radical prostatectomy for a prostate cancer, presenting with biochemical relapse during follow-up (FU). PATIENTS AND METHODS: Three hundred thirty-one patients referred to us from January 2009 to April 2011 to perform 18FCH PET/CT were evaluated: 233 of them (mean age 69.7 years) met the inclusion criteria of the study: (1) biochemical relapse after radical prostatectomy (trigger PSA>0.2 ng/mL) (n=224) and (2) high risk for relapse (elevated Gleason score≥8) in spite PSA<0.1 ng/mL during FU (n=9). Trigger PSA was available for all patients (mean 8 ng/mL) and in 44 of them also PSA kinetic (PSA velocity-PSAvel; PSA doubling time-PSAdt). Correlation between 18FCH PET/CT detection rate and trigger PSA, PSAvel, PSAdt, and tumoral spread distribution were evaluated by univariate and multivariate analysis. Subsequent minimum FU was 1 year (mean 26 months, range 12-40). RESULTS: Overall detection rate of 18FCH PET/CT was 54%, which significantly increased when the trigger PSA increases (P<0.001). PET-positive patients presented a "fast" PSA kinetic (mean PSAdt=6 months and mean PSAvel=9.3 ng/mL/yr), while PET-negative patients presented a "slow" PSA kinetic (mean PSAdt=15.4 months and mean PSAvel=0.9 ng/mL/yr). Disease relapse was local in 17% of cases, distant in 66%, and combined in 17%. CONCLUSIONS: Overall 18FCH PET/CT detection rate was 54% (ie, similar to that reported in literature with ¹¹C-choline), which increases with the increase in trigger PSA: this condition was particularly true in patients with accelerated PSA kinetic. In about 20% of patients, 18FCH PET/CT demonstrated local relapses early enough to offer locoregional radiation therapy.

Phantom study of the impact of reconstruction parameters on the detection of mini- and micro-volume lesions with a low-dose PET/CT acquisition protocol.

PURPOSE: Every PET scanner suffers of the partial volume effect (PVE), that is a loss of contrast in small lesions causing a worsening in standardized uptake value (SUV) accuracy, that is critical if quantitative PET/CT imaging is used for diagnosis and therapy. METHODS: In order to quantify PVE and optimize our clinical protocols to minimize this effect in a last generation PET/CT scanner, we utilized a cylindrical phantom equipped with ten mini- and micro-volume hollow spheres. The lesion detectability and the SUV accuracy were evaluated at a fixed spheres to background intrinsic contrast (activity concentration ratio 8:1) but in different scan conditions: (a) acquisition modality (3D vs. 2D), (b) number of subset per iteration, (c) type of post-reconstruction filter and (d) activity concentration (i.e. total counts). Also the effect of different absorber thickness was evaluated. RESULTS: Small lesion detectability resulted better in images acquired in 3D mode rather than 2D, mainly because of the lower noise produced by the fully-3D algorithm. The number of reconstruction iterations and the post-processing filter used affected both the contrast underestimation and the spatial resolution. Decreasing the (18)F activity injected according to the low-dose protocol, the small lesions could be distinguished from the background down to a diameter of 6.2mm and the SUV accuracy did not deteriorate. Adding absorber thickness around the phantom, the image noise slightly increased while SUV accuracy did not change. CONCLUSIONS: The hybrid PET/CT scanner we evaluated showed good performances, mainly in 3D acquisition modality. The phantom measurements showed that the most appropriate reconstruction protocol derived from a compromise between the contrast accuracy and the noise variance in PET images. The low-dose protocol clinically used demonstrated no loss in SUV accuracy and an adequate lesion detectability for lesions down to 6.2mm in diameter.

A very rare case of nonfunctioning pituitary adenoma incidentally disclosed at 18F-FDG PET/CT.

This is a case of a 48-year-old man treated with surgery and (131)I for papillary thyroid carcinoma: a follow-up (18)F-FDG PET/CT incidentally evidenced pituitary uptake, also seen in (111)In-octreoscan as increased uptake in the sellar area. MRI confirmed a pituitary mass. The patient did not show any signs or symptoms related to this lesion; 1 year later, both PET/CT and MRI findings remained unchanged. Surgery confirmed nonfunctioning benign pituitary adenoma. This single case observed in 12,873 consecutive patients scanned in our center confirms the possibility that nonfunctioning benign pituitary adenomas may be FDG-avid: uptake mechanisms remain unknown, and targeted studies are needed.

Mini-invasive videoassisted thyroid lobectomy for neonatal hyperfunctioning adenoma related to a somatic TSHr gene mutation.

We report here a case of a paediatric hyperthyroidism due to a micro-macro-follicular thyroid adenoma in the presence of heterozygous point mutation of TSH receptor (TSHr). We describe the case from the initial diagnosis, through laboratoristic examinations and imaging techniques, until the radical surgical treatment made by a mini-cervicotomic videoassisted technique. We also explained the genetic work-up from peripheral blood and thyroid adenoma tissue.