University of Modena and Reggio Emilia
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Multiple Dimerization Modes in Thiocarboxylate Paddlewheel Complexes: a Comprehensive View of Energy Landscapes from DFT Calculations and Statistics
No full textThiocarboxylate paddlewheels (PWs) [MTr(SOCR)4L] (M = Pt, Pd; Tr = first-row transition metal; L = Tr-coordinated axial ligand) form a variety of dimeric structures via M⋅⋅⋅M’ and M⋅⋅⋅S’ contacts. We found that [PtVO(SOCPh)4] (1), a molecular spin qubit, yields three crystalline toluene (tol) solvates, namely 1⋅0.875tol and two polymorphic 1⋅0.5tol phases. The crystals contain either staggered quasi-coaxial dimers with short Pt⋅⋅⋅Pt’ distances (3.17-3.23 Å) or heavily bent noncoaxial molecular pairs supported by Pt⋅⋅⋅S’ contacts (3.34-3.38 Å). By contrast, in the known solvatomorphs 1⋅CH2Cl2 and 1⋅0.5hex (hex = n-hexane), two collinear molecules compose a “square” dimer via a pair of reciprocating Pt⋅⋅⋅S’ contacts (3.13-3.16 Å). According to gas-phase DFT calculations (PBE0/def2-TZVPP/D3BJ), dimerization is energetically favored by 15–20 kcal mol−1 and is guided by a shallow potential energy surface, with staggered dimers as ground configurations but eclipsed and square dimers well within energetic reach. Inspection of the local energy minima also disclosed a previously unrecognized eclipsed arrangement with ∼45◦ twisting of both PWs relative to the metal plane, whose existence was confirmed by statistical analysis of PW structures in the Cambridge Structural Database. Our results led to a new classification scheme for these PW dimers relevant to molecular magnetism and quantum technologies
Taxon-specific responses to temperature, landscape, and local management challenge common strategies for pest control in vineyards
No full textGrape is among the most pesticide treated crops in Europe. To reduce pesticide use, it is increasingly important to enhance pest control by natural enemies. However, the provision of biological control in vineyards is highly context- and taxa-dependent. Here, we selected 60 vineyards across Italy in order to explicitly explore the effect of vineyard management, temperature and landscape composition on arthropod predators, grapevine pests, dummy caterpillar predation, and seed predation. We found that plant cover in the inter-row was lower in dry-warm climates, and it positively affected only the abundance of hoverflies, while the abundance of carabids, ladybugs, harvest spiders and spiders was affected by temperature and the surrounding landscape. Organic management did not affect predators but supported more abundant populations of the pest Erasmoneura vulnerata. Overall, most leafhopper pests showed species specific responses to local management, temperature and the landscape. The abundance of two leafhopper species decreased with increasing semi-natural areas. By contrast, pest control rate and grape damage did not respond to any of the selected drivers. In conclusion, our findings suggest that local vineyard management significantly influences biocontrol and pests, but the effects are taxon specific and shaped by the surrounding landscape and by the temperature, challenging universal strategies. Therefore, we advocate for developing regional strategies for grape protection accounting for local climate and multiple taxa responses
Organisationen und Recht im 21. Jahrhundert – Zwischen Interessenabwägung und Risikobewältigung
No full textDalla Pandemia ai Plastificanti: Determinanti ambientali e sociali di salute con approccio "life-course"
No full textQuesta tesi article-based ha esaminato come i determinanti ambientali, sociali e politici influenzino la salute nel corso della vita, con particolare attenzione alla pandemia di COVID-19, alla nutrizione sostenibile e all'esposizione a contaminanti ambientali. Integrando approcci di sanità pubblica, epidemiologia ambientale e salute pediatrica, la tesi descrive le interconnessioni tra salute umana e planetaria. Comprende otto articoli peer-reviewed raggruppati in tre capitoli tematici: (1) Affrontare la pandemia di COVID-19; (2) Bambini più sani per un pianeta più sano; (3) Bambini e ftalati: stiamo facendo abbastanza?
Il Capitolo 1 indaga i determinanti multifattoriali della pandemia di COVID-19 in Italia attraverso analisi ecologiche e di popolazione, valutando come fattori ambientali, climatici, demografici e socio-economici abbiano modellato tassi di infezione, ospedalizzazioni e mortalità, nonché l'efficacia dei programmi vaccinali. I risultati dimostrano come la diffusione pandemica sia stata strutturata da disuguaglianze spaziali, vulnerabilità ambientali e differenze nell'implementazione di interventi non farmaceutici. I contributi metodologici includono modelli multipli e framework analitici integrati per valutare domini complessi di rischio sanitario, fornendo evidenze per risposte pandemiche geograficamente e socialmente calibrate.
I Capitoli 2 e 3 si concentrano sulla popolazione pediatrica, connettendo epidemiologia ambientale e promozione della salute infantile.
Il Capitolo 2 esamina le abitudini alimentari di bambini italiani tra 6 mesi e 14 anni, valutandone adeguatezza nutrizionale e sostenibilità ambientale. Gli studi evidenziano un consumo eccessivo di alimenti di origine animale e processati, con diete non allineate alle raccomandazioni sanitarie e agli obiettivi di sostenibilità planetaria. Emerge inoltre scarsa consapevolezza genitoriale delle implicazioni ambientali della dieta e limitato coinvolgimento di scuole e pediatri nella promozione di pattern alimentari sostenibili. Il capitolo sottolinea come interventi precoci possano generare benefici sinergici per la salute infantile e planetaria.
Il Capitolo 3 affronta l'esposizione pediatrica agli ftalati, interferenti endocrini presenti in numerosi prodotti di consumo. Attraverso dati empirici e sintesi della letteratura, identifica le principali vie di esposizione, sintetizza le evidenze del biomonitoraggio e valuta le misure regolamentari attuali. Nonostante i progressi restrittivi, i bambini rimangono esposti per caratteristiche comportamentali e vulnerabilità fisiologica. Il capitolo richiede regolamentazione rafforzata, sorveglianza potenziata e integrazione della tossicologia ambientale nell'assistenza pediatrica e nelle politiche sanitarie.
Complessivamente, la tesi fornisce una descrizione dell'interazione tra fattori ambientali e sociali nella determinazione della salute a livello di popolazione generale e pediatrica, sottolineando il valore di approcci interdisciplinari basati sui dati nell'identificazione di determinanti modificabili di malattia e disuguaglianza. Sul piano concettuale, colloca la salute nel contesto della sostenibilità planetaria, sottolineando che tutelare la salute umana richiede affrontare i sistemi ambientali da cui essa dipende.This article-based dissertation examined how environmental, social, and policy determinants influence health across the life course, with a specific focus on the COVID-19 pandemic, sustainable nutrition, and exposure to environmental contaminants. By integrating approaches from public health, environmental epidemiology, and pediatric health, the dissertation aims to describe the interconnections between human and planetary health. It comprises eight peer-reviewed articles grouped into three thematic chapters: (1) Tackling the COVID-19 Pandemic; (2) Healthier Children for a Healthier Planet; and (3) Children and Phthalates, Are We Doing Enough?
Chapter 1 focuses on the general population investigating the multifactorial determinants of the COVID-19 pandemic in Italy. Through ecological and population-based analyses, the studies assessed how environmental, climatic, demographic, and socio-economic factors shaped infection rates, hospitalizations, and mortality. The research also evaluated the effectiveness of vaccination programs in preventing severe outcomes. The findings showed how the pandemic’s spread and impact were not random but structured by spatial inequities, environmental vulnerabilities, and differences in the implementation of non-pharmaceutical interventions. Methodological contributions included the development of multivariable spatial models and integrated analytical frameworks to assess complex public health risk domains. Together, these studies provided evidence supporting geographically and socially tailored pandemic responses.
Chapters 2 and 3 concentrated on the pediatric population, a population dear to the candidate, and aims to connect environmental epidemiology within child health promotion.
Chapter 2 examines dietary habits among Italian children aged 6 months to 14 years, evaluating their nutritional adequacy and environmental sustainability. The studies demonstrated excessive consumption of animal-based and processed foods, resulting in diets misaligned with both health recommendations and planetary sustainability targets. Additional analyses identified low parental awareness of the environmental implications of diet and limited engagement of schools and pediatricians in promoting healthier, more sustainable eating patterns. By connecting dietary epidemiology with environmental indicators, this chapter emphasized that early-life interventions fostering sustainable diets can produce synergistic benefits for both child and planetary health.
Chapter 3 addresses children’s exposure to phthalates, endocrine-disrupting chemicals present in a variety of consumer products. Drawing on empirical data and literature synthesis, the research identified primary exposure pathways, summarized biomonitoring evidence, and evaluated current policy and regulatory measures. Despite progress in restrictions, findings indicated that children remain exposed due to behavioral characteristics and physiological vulnerability. The chapter calls for enhanced regulation, surveillance, and integration of environmental toxicology into pediatric care and public health policy.
Overall, the dissertation provides a comprehensive understanding of how environmental and societal factors interact to affect health at both population and pediatric levels. It demonstrates the value of interdisciplinary, data-driven approaches in identifying modifiable determinants of disease and inequity. Conceptually, it advanced an overall framework that situates health within the broader context of planetary sustainability, underscoring that safeguarding human health requires addressing the environmental systems upon which it depends
Management of asymptomatic bacterial STIs and doxycycline postexposure prophylaxis: consensus statement of the Italian Society of Infectious and Tropical Diseases
No full textBiomateriali Naturali e Tecniche di Formulazione Avanzate per la Produzione di Nanomedicine
No full textIl crescente interesse verso la sicurezza, l’efficacia e la sostenibilità in ambito sanitario ha accelerato l’impiego di biomateriali naturali nelle applicazioni cliniche. Sostanze naturali come lipidi e proteine offrono spesso biocompatibilità e biodegradabilità, che le rendono materiali ottimali per lo sviluppo di nanosistemi per la veicolazione ed il direzionamento di farmaci. Tuttavia, per trasferire un prodotto farmaceutico a livello industriale e clinico, sono necessari sia materiali efficaci sia processi produttivi scalabili e sostenibili. In risposta a questa esigenza, sono stati individuati o sviluppati metodi innovativi, come l’autoasseblaggio e la microfluidica, che permettono di avere controllo sulle proprietà dei nanosistemi, elevata riproducibilità e compatibilità con l’automazione. Tali approcci riducono anche l’impiego di solventi tossici, semplificano la produzione e agevolano la conformità da un punto di vista regolatorio. L'utilizzo combinato di biomateriali e tecniche avanzate sta promuovendo lo sviluppo e l’applicazione terapeutica delle nanomedicine.
In questo contesto, la prima sezione di questa tesi presenta lo sviluppo di nanoparticelle (NP) autoassemblanti a base di lattoferrina (LF). La denaturazione termica della proteina ha indotto transizioni conformazionali che hanno facilitato l’autoassemblaggio di NP (dimensione ~60 nm, indice di polidispersione ~0,15, potenziale Z +30 mV) con elevata resa (74%). Progettate per applicazione in terapia genica, queste NP hanno mostrato un’elevata capacità di complessare e proteggere un siRNA modello, con un’efficienza di complessazione >98% ai rapporti molari LF:siRNA di 10:1 e 20:1. Test di protezione da RNasi hanno evidenziato una maggiore stabilità del siRNA al rapporto 10:1, con una protezione massima superiore al 60%, mentre il siRNA libero veniva completamente degradato. Tali NP, sia congelate che liofilizzate, hanno mostrato stabilità colloidale e mantenuta capacità di complessazione durante la conservazione in assenza di crioprotettori o stabilizzanti. Studi in vitro in corso su cellule di glioblastoma T98G mirano a valutare uptake cellulare ed efficacia di silenziamento genico per confermare il potenziale terapeutico.
Nella seconda sezione viene descritta l’ottimizzazione di una nuova classe di NP interamente a base di colesterolo (Chol) per la veicolazione di Chol al cervello nella malattia di Huntington (HD). Partendo dalla tecnica della nanoprecipitazione, sono state prodotte NP (dimensione ~230 nm, indice di polidispersione ~0,2 e potenziale Z –20 mV) che sono state poi funzionalizzate con acido butirrico (BUT) per l’attraversamento della barriera emato-encefalica (BEE). Analisi di superficie (ToF-SIMS) hanno confermato la presenza del ligando e studi in vivo hanno mostrato un aumento dell’accumulo nel cervello (corteccia e striato) dopo somministrazione endovenosa. Immagini TEM hanno rivelato la presenza delle NP negli astrociti, confermando l’attraversamento della BEE. È stata inoltre testata una variante di BUT coniugata al glucosio (BUT-Glu), che però non ha mostrato vantaggi significativi rispetto al BUT. Per favorire la scalabilità, il processo produttivo delle NP-Chol-BUT è stato ottimizzato tramite microfluidica e sono state ottenute con ottima riproducibilità NP aventi dimensione ~200 nm, indice di polidispersione <0,15 e stabilità alla liofilizzazione (con saccarosio come crioprotettore). Attualmente sono in corso analisi morfologiche e di superficie delle NP ottenute tramite microfluidica e studi di efficacia in vivo in modelli HD. In futuro si prevede l’espansione di questa piattaforma per la veicolazione simultanea di Chol e siRNA con l’obiettivo di colpire sia i difetti metabolici che genetici della HD.The growing focus on safety, efficacy, and sustainability in healthcare has accelerated interest in natural biomaterials for clinical applications. Natural substances like lipids and proteins often offer biocompatibility and biodegradability, making them optimal materials for drug delivery nanocarriers aimed at improving pharmacokinetics, enabling targeted delivery, and reducing off-target toxicity. However, successful industrial and clinical translation requires not only effective materials but also scalable and sustainable production processes. In response to this need, significant advances have been made to develop innovative fabrication techniques, such as self-assembly methods and microfluidic technologies, that offer precise control over nanocarrier properties, high reproducibility, and compatibility with automation. These approaches also reduce the use of hazardous solvents, simplify production, and facilitate regulatory compliance. By combining natural biomaterials with such advanced fabrication techniques, the field is moving toward clinically viable nanomedicine solutions.
In this context, the first section of this thesis presents the development of lactoferrin (LF)-based nanoparticles (NPs) via a heat-induced, solvent-free self-assembly method. Thermal protein denaturation triggered conformational transitions, facilitating NP formation (size ~60 nm, polydispersity index ~0.15, Z-potential +30 mV) with high assembly efficiency (up to 74%). Designed and optimized for gene delivery applications, these NPs efficiently complexed and protected a model small interfering RNA (siRNA), achieving >98% siRNA complexation efficiency at LF:siRNA molar ratios of 10:1 and 20:1. RNase protection assays indicated enhanced siRNA stability at a 10:1 LF:siRNA molar ratio, with a maximum protection efficiency slightly over 60%, whereas naked siRNA was completely degraded. Notably, both frozen and lyophilized LF NPs retained their size, colloidal stability, and siRNA complexation capacity during storage, without the need for cryoprotectants or stabilizers. Ongoing in vitro studies in T98G glioblastoma cells aim to assess NP uptake, intracellular trafficking, and gene silencing efficacy to further validate their therapeutic potential.
In the second section, we describe the design and optimization of a novel class of fully cholesterol (Chol)-based NPs for brain-targeted delivery in Huntington’s disease (HD). Starting from a conventional nanoprecipitation method, we produced monocomponent Chol-based NPs exhibiting size ~230 nm, polydispersity index ~0.2, and Z-potential –20 mV. These NPs were functionalized with butyric acid (BUT) as a blood-brain barrier (BBB)-targeting ligand to yield NPs-Chol-BUT. Surface analysis (ToF-SIMS) confirmed ligand presentation, and in vivo studies showed enhanced BBB penetration and accumulation in the cortex and striatum following intravenous administration. TEM imaging revealed NPs within astrocytic end-feet, confirming effective BBB crossing. A glucose-conjugated BUT variant (BUT-Glu) was also explored for BBB crossing but did not show significant advantages over native BUT. To facilitate scalability and industrial translation, we optimized the production process of NPs-Chol-BUT via microfluidics, obtaining NPs with size ~200 nm, polydispersity index <0.15, improved batch-to-batch reproducibility, and storage stability under freeze-drying conditions (with sucrose as cryoprotectant). Ongoing work includes morphological and surface characterization of microfluidic-produced NPs and in vivo efficacy studies in HD models. Future directions aim to expand this platform for dual delivery of Chol and therapeutic nucleic acids (e.g., siRNA), targeting both metabolic and genetic defects of HD
The Forgotten Airway: Central Airway Pathology in the ICU.
No full textCentral airway diseases, though infrequent, represent a critical yet underrecognized cause of respiratory failure in the intensive care unit
(ICU). These disorders encompass a wide range of pathologies—including central airway obstruction (CAO), tracheal stenosis,
tracheomalacia, tracheomegaly, tracheoesophageal fistulas, and post-intubation lacerations—which can significantly complicate ventilation,
extubation, and weaning. This narrative review explores the complex anatomical and physiological properties of the trachea and main
bronchi, highlighting the profound impact of their even partial occlusion on airway resistance and work of breathing. We present the
pathophysiological bases, diagnostic strategies, and up-to-date management options for both benign and malignant CAO, with particular
attention to the ICU setting where urgent interventions are often required. The review also addresses iatrogenic airway injuries related to
mechanical ventilation and airway equipment, analyzing both conservative and interventional therapeutic approaches, including endoscopic
techniques and airway stenting. Special focus is given to the implications of central airway pathology in weaning failure, emphasizing the
importance of early recognition to avoid unnecessary reintubations. Overall, this work aims to raise awareness among intensivists and
pulmonologists of the pivotal role that central airway diseases may play in respiratory deterioration, and to advocate for a structured, multidisciplinary approach to their prompt diagnosis and treatment
