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Triplet state reactivity of iminium ions in organocatalytic asymmetric [2 + 2] photocycloadditions
No full textOrganic transformations mediated by the transient formation of iminium
ions have shown remarkable synthetic potential for the construction of
enantioenriched molecules. The possibility to access their first singlet
excited state (S1) under light irradiation has led to the development of
previously inaccessible transformations. However, the triplet state (T1)
reactivity remains limited and typically requires external photosensitizers.
Here we show that structurally modified chiral iminium ions, integrated
into extended π-systems, directly engage in T1 reactivity. This modified
conjugated architecture was designed to overcome the intrinsic
photophysical limitations of conventional iminium ion chemistry, enabling
access to previously inaccessible excited-state reaction manifolds.
The resulting system allows organocatalytic enantioselective [2 + 2]
photocycloadditions without the need for external sensitizers. Mechanistic
studies, involving spectroscopic techniques and computational methods,
elucidate the role of the T1 intermediate as the key reactive intermediate.Organic transformations mediated by the transient formation of iminium ions have shown remarkable synthetic potential for the construction of enantioenriched molecules. The possibility to access their first singlet excited state (S1) under light irradiation has led to the development of previously inaccessible transformations. However, the triplet state (T1) reactivity remains limited and typically requires external photosensitizers. Here we show that structurally modified chiral iminium ions, integrated into extended π-systems, directly engage in T1 reactivity. This modified conjugated architecture was designed to overcome the intrinsic photophysical limitations of conventional iminium ion chemistry, enabling access to previously inaccessible excited-state reaction manifolds. The resulting system allows organocatalytic enantioselective [2 + 2] photocycloadditions without the need for external sensitizers. Mechanistic studies, involving spectroscopic techniques and computational methods, elucidate the role of the T1 intermediate as the key reactive intermediate. (Figure presented.
To ablate or not to ablate? Outcomes of local ablative treatments (LAT) for oncogene addicted (OA) oligo-metastatic (OM) non-small cell lung cancer (NSCLC): A systematic review
No full text: Oncogene-addicted non-small cell lung cancer (NSCLC) encompasses distinct molecular phenotypes, each associated with specific clinical behavior and variable sensitivity to targeted therapies. Therapeutic advancements in the field enhanced clinical outcomes and overall prognostic improvement. Beyond the molecular profile, disease burden serves as a predictive marker for treatment response and overall prognostic outcomes. The current disease staging categorizes patients based on the number and sites of metastatic involvement. In this context, the addition of local ablative therapies (LAT) is candidate to enhance or prolong the effectiveness of standard systemic therapies. Our systematic review aims to summarize current evidence dealing with the outcomes of LAT in the context of oncogene addicted NSCLC. Over response results, we also reported side effects whenever available.Oncogene-addicted non-small cell lung cancer (NSCLC) encompasses distinct molecular phenotypes, each associated with specific clinical behavior and variable sensitivity to targeted therapies. Therapeutic advancements in the field enhanced clinical outcomes and overall prognostic improvement. Beyond the molecular profile, disease burden serves as a predictive marker for treatment response and overall prognostic outcomes. The current disease staging categorizes patients based on the number and sites of metastatic involvement. In this context, the addition of local ablative therapies (LAT) is candidate to enhance or prolong the effectiveness of standard systemic therapies. Our systematic review aims to summarize current evidence dealing with the outcomes of LAT in the context of oncogene addicted NSCLC. Over response results, we also reported side effects whenever available
Pitfalls of insomnia management in the elderly: A narrative review
No full textIntroduction: Insomnia is a common sleep disorder characterized by difficulty initiating or maintaining sleep, significantly impacting daytime functioning and quality of life. Its chronic nature, high prevalence among older adults, and association with multiple comorbidities make it a pressing health concern. Here, we provide an overview of insomnia in the elderly, highlighting the gap between scientific guidelines and real-world clinical practice and the common pitfalls in managing this fragile patient population. Methods: We performed a comprehensive literature review to synthesize recent findings on insomnia pathophysiology, diagnosis, and treatment in the aging population. Results: Insomnia in the elderly is frequently intertwined with comorbidities, which both contribute to and are exacerbated by sleep disturbances. The diagnostic process is complex, requiring differentiation between primary insomnia and conditions influenced by comorbidities, medications, and age-related sleep changes. A comprehensive clinical assessment remains the cornerstone of diagnosis. Treatment prioritizes non-pharmacological strategies, with cognitive-behavioral therapy for insomnia as the first-line approach, though accessibility remains a challenge. Pharmacotherapy should be reserved for short-term use, with careful consideration of adverse effects. However, pharmacological treatment often becomes chronic and deviates from clinical recommendations, relying on off-label medications. Insomnia management is further complicated by polypharmacy, which disrupts sleep and increases the risk of drug interactions and side effects, including falls and cognitive decline. Conclusions: A multidimensional, patient-centered approach is essential for managing insomnia in older adults. Addressing comorbidities, optimizing pharmacological strategies, and improving access to non-pharmacological treatments are crucial steps towards enhancing outcomes and quality of life in this vulnerable population
Dealing with the left atrial appendage during open heart surgery: To exclude or not to exclude in patients with Sinus Rhythm?
No full textFar from a vestigial structure, the LAA contributes
to atrial reservoir function, pressure-volume modulation,
and endocrine secretion during sinus rhythm (SR). Despite
increased POAF, the study demonstrates a significant reduc-
tion in 5-year stroke or thromboembolis
Upcycled materials for water treatment and emerging contaminant recovery: a preliminary study on waste-derived magnetic zeolites
No full textThis study explores the applicability of magnetic zeolites from industrial waste-specifically fly ash (FA) combined with either synthetic Fe-based nanoparticles (FANPs1 and FANPs2) or red mud (RM) in differing ratios (FA1RM1 and FA4RM1)-for the removal and recovery of emerging water contaminants. FA and RM originate from coal combustion in thermoelectric power plants and alumina extraction from bauxite, respectively. The resulting materials were first assessed for acute toxicity on a freshwater model organism, revealing no acute effects. They were then tested under environmentally relevant conditions for the removal of ofloxacin (OFL), a fluoroquinolone antibiotic selected as a representative water-persistent contaminant. Subsequently, three extraction techniques-ultrasound-assisted extraction (UsAE), microwave-assisted extraction (MwAE), and magnetic hyperthermia-assisted extraction (MhAE)-were applied to recover the adsorbed OFL. All materials exhibited high OFL loading efficiencies (80-95%). Among the extraction techniques, MwAE yielded the highest OFL recovery (>80% for FANPs2 and FA4RM1), while UsAE and MhAE achieved lower efficiencies (up to similar to 60%), regardless of the adsorbent used. Post-loading and post-extraction characterization studies provided insights into the adsorption mechanism and revealed significant OFL resorption across all zeolite types. Preliminary tests also confirmed the ability of these materials to capture endocrine-disrupting compounds (EDCs), underscoring their potential for water remediation and recovery applications
Benchmarking a DNN for aortic valve calcium lesions segmentation on FPGA-based DPU using the vitis AI toolchain
No full textSemantic segmentation assigns a class to every pixel of an image to automatically locate objects in the context of computer vision applications for autonomous vehicles, robotics, agriculture, gaming, and medical imaging. Deep Neural Network models, such as Convolutional Neural Networks (CNNs), are widely used for this purpose. Among the plethora of models, the U-Net is a standard in biomedical imaging. Nowadays, GPUs efficiently perform segmentation and are the reference architectures for running CNNs, and FPGAs compete for inferences among alternative platforms, promising higher energy efficiency and lower latency solutions. In this contribution, we evaluate the performance of FPGA-based Deep Processing Units (DPUs) implemented on the AMD Alveo U55C for the inference task, using calcium segmentation in cardiac aortic valve computer tomography scans as a benchmark. We design and implement a U-Net-based application, optimize the hyperparameters to maximize the prediction accuracy, perform pruning to simplify the model, and use different numerical quantizations to exploit low-precision operations supported by the DPUs and GPUs to boost the computation time. We describe how to port and deploy the U-Net model on DPUs, and we compare accuracy, throughput, and energy efficiency achieved with four generations of GPUs and a recent dual 32-core high-end CPU platform. Our results show that a complex DNN like the U-Net can run effectively on DPUs using 8-bit integer computation, achieving a prediction accuracy of approximately 95% in Dice and 91% in IoU scores. These results are comparable to those measured when running the floating-point models on GPUs and CPUs. On the one hand, in terms of computing performance, the DPUs achieves a inference latency of approximately 3.5 ms and a throughput of approximately 4.2 kPFS, boosting the performance of a 64-core CPU system by approximately 10% in terms of latency and a factor 2X in terms of throughput, but still do not overcoming the performance of GPUs when using the same numerical precision. On the other hand, considering the energy efficiency, the improvements are approximately a factor 6.7X compared to the CPU, and 1.6X compared to the P100 GPU manufactured with the same technological process (16 nm)
Initial performance results of the JUNO detector
No full textThe Jiangmen Underground Neutrino Observatory (JUNO) started physics data taking on 26 August 2025. JUNO consists of a 20-kton liquid scintillator central detector, surrounded by a 35 kton water pool serving as a Cherenkov veto, and almost 1000 m of plastic scintillator veto on top. The detector is located in a shallow underground laboratory with an overburden of 1800 m.w.e. This paper presents the performance results of the detector, extensively studied during the commissioning of the water phase, the subsequent liquid scintillator filling phase, and the first physics runs. The liquid scintillator achieved an attenuation length of 20.6 m at 430 nm, while the high coverage PMT system and scintillator together yielded about 1785 photoelectrons per MeV of energy deposit at the detector centre, measured using the 2.223 MeV from neutron captures on hydrogen with an Am-C calibration source. The reconstructed energy resolution is 3.4% for two 0.511 MeV at the detector centre and 2.9% for the 0.93 MeV quenched Po-214 alpha decays from natural radioactive sources. The energy nonlinearity is calibrated to better than 1%. Intrinsic contaminations of U-238 and Th-232 in the liquid scintillator are below 10 g/g, assuming secular equilibrium. The water Cherenkov detector achieves a muon detection efficiency better than 99.9% for muons traversing the liquid scintillator volume. During the initial science runs, the data acquisition duty cycle exceeded 97.8%, demonstrating the excellent stability and readiness of JUNO for high-precision neutrino physics
Chronostratigraphical ranges of Lower Jurassic larger benthic foraminifera and lithiotid bivalves calibrated by Carbon and Strontium isotope stratigraphy (Southern Alps, Italy)
No full textFollowing the end-Triassic biotic crisis, the first larger benthic foraminifera (LBF) emerged in shallow-water carbonate platforms of the Early Jurassic Tethys, during the Hettangian and Sinemurian. In inner-platform settings, these LBF frequently coexisted with large aberrant bivalves of the Lithiotis Facies, characterized by thick, gregarious accumulations. This study re-assesses the biostratigraphy of LBF and lithiotid bivalve faunas in a c. 200 m-thick Pliensbachian shallow-water sedimentary succession of the Rotzo Formation in the Trento Platform (Southern Alps, Italy). By integrating carbon and strontium isotope stratigraphy, we refine the chronostratigraphical framework for key LBF taxa that are widely used in Lower Jurassic carbonate platform biostratigraphy. Strontium isotope stratigraphy reveals that Orbitopsella primaeva first occurs in the lowermost Pliensbachian Jamesoni Zone, younger than the late Sinemurian age typically cited. Similarly, the last occurrence of Orbitopsella praecursor is in the lowermost upper Pliensbachian (early Margaritatus Zone), later than the traditionally accepted uppermost lower Pliensbachian. This study also constrains the timing of the appearance, development and demise of lithiotid bivalve associations in the Trento Platform. Lithioperna first appears in the lowermost Pliensbachian Jamesoni Zone, followed by Opisoma near the boundary between the Jamesoni and Ibex zones. Higher in the succession, Lithiotis becomes prominent near the Davoei–Margaritatus zone boundary, forming thick accumulations intercalated with brachiopod-rich beds. The final phase of the Lithiotis Facies is marked by Cochlearites–Lithioperna mounds, starting from the Subnodosus Subzone of the Margaritatus Zone. The disappearance of the lithiotid bivalves coincides with the onset of relatively deeper water conditions at the Rotzo Formation–Misone Limestone boundary in the uppermost Pliensbachian Spinatum Zone
Intercultura e comparazione educativa: un’indagine etnografica presso la comunità nigeriana residente nella Provincia di Ravenna
No full textL’oggetto di questa ricerca riguarda l’elaborazione di prassi di educazione inter e transculturali in una cornice teorica che fa riferimento al dibattito sul post-coloniale (Dussel, 1992). Alla luce di ciò, l’ambito entro il quale si è scelto di sviluppare l’indagine è di stampo epistemologico, con il fine di comprendere i processi di costruzione e interpretazione della realtà nell’incontro con la differenza culturale. Attraverso uno approccio comparativo, le testimonianze della cultura Yoruba - etnia diffusa e storicamente radicata nella parte meridionale della Nigeria - ci permettono di esplorare la Conoscenza, indagando le sue trame, in relazione alla cultura di riferimento e alla mitologia che ha ispirato i processi di sintetizzazione ed elaborazione dell’immagine del mondo (Gramigna, 2015), nonché di comparare differenti sistemi di razionalità. Il fine è quello di costruire prassi educative solidali ed inclusive.
Conoscere la conoscenza (Morin, 2007), rappresenta il punto di partenza sia per apprendere ad orientarci in una realtà sempre più complessa, sia per iniziare un’opera di scavo (Foucault, 1999) e di diafanizzazione tanto dei propri stili cognitivi quanto delle epistemologie implicite (Bateson, 2005). Ecco che l’approccio epistemologico ci consente di iniziare una riflessione sui concetti di ‘centro’ e ‘margine’ (Gramigna, Righetti, 2001; Gramigna, 2020; Freire, 2022), di sconvolgerne i confini, avviando pratiche e patiche (Fabbri, 2022) formative metacognitive. In quest’ottica, dare voce e spazio alle culture collocate al margine di chi ha storicamente ‘dominato’ il discorso sulla realtà, ci permette di pensare, immaginare e quindi progettare azioni educative che superino l’Intercultura a favore di una Transcultura che promuova la trasformazione e l’accoglienza della differenza e che ci permetta di ri-conoscenci attraverso lo sguardo dell’Altro (Ricouer, 2005).
Coerentemente con l’epistemologia, la metodologia è di stampo qualitativo, si avvale degli strumenti dell’indagine etnografica e fa dell’ermeneutica la sua tecnologia applicata all’analisi e alla progettazione educativa. Si tratta di una ricerca di carattere etnopedagogico che si identifica nel rigore epistemologico, nella coerenza tra obiettivi, strumenti, metodi, linguaggi e risultati via via raggiunti. Si dà rilievo alla qualità del fenomeno preso in esame, in questo caso la narrazione proposta dai testimoni Yoruba, cercando di identificarne gli elementi significativi, rilevando la relazione con il contesto nel quale si sviluppano. Attraverso un approccio archeologico (Foucault, 1999) si procede con la fase di decodificazione, quindi di interpretazione e comprensione delle trame narrative che orientano e costruiscono la realtà in sistemi di razionalità differenti.
Pertanto, si propone il racconto ispirato ai miti e alla storia del popolo Yoruba come strumento di Pedagogia Narrativa utile per avviare processi metacognitivi e autoermeneutici in una cornice transculturale. Le parole, le metafore, le immagini dei racconti provenienti da lontano evocano nuove relazioni di significato e con esse, nuove emozioni, promuovendo una postura cognitiva permeabile al cambiamento, aperta a nuove narrazioni sulla realtà, accogliente l’‘inconsueto’ e il ‘diverso’ come possibili trame di infiniti mondi possibili. È in questo aspetto che si colloca la cifra decoloniale della proposta, poiché si invita a considerare altri linguaggi, altre forme di razionalità, attraverso la coscientizzazaione delle proprie credenze implicite. La sperimentazione nella scuola di narrazioni metacognitive ad elevato tenore inter e transculturale, la trasferibilità delle azioni progettate, la partecipazione al dibattito scientifico sul tema e la divulgazione dei risultati che ci preponiamo di conseguire ci consentono di ipotizzarne anche l’impatto e le ricadute in senso positivo.The object of this research concerns processing inter and transcultural practices of education in a theoretical frame that refers to the debate about the post-colonial (Dussel, 1992). In the light of this, the investigation has an epistemological character, with the aim of understanding the processes of construction and interpretation of reality in the encounter with cultural difference. Through a comparative approach, the testimonies of Yoruba culture - a widespread and historically rooted ethnic group in the southern part of Nigeria - allow us to explore Knowledge, investigating its plots, in relation to the reference culture and mythology that inspired the processes of synthesis and elaboration of the image of the world (Gramigna, 2015), as well as to compare different systems of rationality. The aim is to build supportive and inclusive educational practices.
Knowing knowledge (Morin, 2007), represents the starting point both for learning to orient ourselves in an increasingly complex reality, and for starting a work of excavation (Foucault, 1999) and diaphanization of both one's own cognitive styles and implicit epistemologies (Bateson, 2005). Here, the epistemological approach allows us to begin a reflection on the concepts of ‘center’ and ‘margin’ (Gramigna, Righetti, 2001; Gramigna, 2020; Freire, 2022), to upset its boundaries, starting educational, emotional (Fabbri, 2022) and metacognitive practices.
In this perspective, giving voice and space to cultures placed on the margin of those who have historically ‘dominated’ the discourse on reality, allows us to think, imagine and therefore design educational actions that overcome the Interculture in favor of a Transculture that promotes the transformation and reception of difference and that allows us to re-know each other through the look of the Other (Ricouer, 2005).
Coherently with epistemology, the investigation refers to a qualitative methodology, it uses ethnographic investigation tools, such as semi-structured interview, self-narration, free narration, observation and makes hermeneutics its technology applied to educational analysis and design. This is an ethno-pedagogical research that is identified in the epistemological rigor, in the coherence between objectives, tools, methods, languages and results gradually achieved. Emphasis is given to the quality of the phenomenon examined, in this case the narrative proposed by the Yoruba witnesses, trying to identify the significant elements, noting the relationship with the context in which they develop. Through an archaeological approach (Foucault, 1999) we proceed with the phase of decoding, therefore of interpretation and understanding of the narrative plots that orient and build reality in different systems of rationality.
In the light of this, the narrative inspired by the myths and history of the Yoruba people is proposed as a tool of Narrative Pedagogy useful for starting metacognitive and auto-hermeneutic processes in a transcultural frame. The words, the metaphors, the images of the stories coming from afar evoke new relationships of meaning and with them, new emotions, promoting a cognitive posture permeable to change, open to new narratives on reality, welcoming the ‘unusual’ and the ’different’ as possible plots of infinite possible worlds. It is in this aspect that the decolonial feature of the proposal is placed, since it invites us to consider other languages, other forms of rationality, through the awareness of our own implicit beliefs.
The experimentation in the school of metacognitive narratives with a high inter and transcultural tenor, the transferability of the actions designed, the participation in the scientific debate on the topic and the dissemination of the results that we aim to achieve, allow us to also hypothesize their impact and repercussions in a positive sense
Built Heritage Adapted Information Management Through AI. The AIM-EBIM Project
No full textThe paper is focused on an ongoing project funded by the Emilia-Romagna region and aimed at the creation of a new workflow finalizing digital data from integrated survey towards an “adaptive” Building Information Modeling (BIM). The project AIM-eBIM—Adapted Information Management for existing Buildings Information Modeling brings together regional research laboratories and companies to pursue industrial research topics towards a greater deployment of digital tools. Digital surveying has triggered huge potential for innovation, but generating new challenges in managing and using large amount of data, often unused. The quantity of surveyed data to document built or Cultural Heritage often does not correspond to the quality or reliability of information. Moreover, parametric modeling of existing heritage through BIM is becoming as pervasive as necessary, considering regula-tory trends. However, these tools can be ineffective from the point of view of users (professionals, companies) who must deal with such complexity. The challenge is to bring discretization (and simplification) processes on source data toward an easier informative integration into BIM models, by facilitating and enhancing interpreta-tion needs. In this direction, Artificial Intelligence (AI) algorithms are part of the process. The adapted informative implementation of parametric models is based on digital source data (laser and photogrammetry) segmentation by AI on specific topics (documentation, analysis, monitoring, conservation, project) and criteria (materials, techniques, components, structures)