Archivio istituzionale della ricerca - Università dell'Insubria
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Bis(phenolate)–Titanium(IV) Catalysts for Efficient and Sustainable Direct Amide Bond Formation
No full textAmides are fundamental and hugely widespread functional groups in key bioactive and industrially relevant molecules. However, conventional methods for amide bond formation, particularly in peptide synthesis, are challenging in terms of environmental impact, waste, and production costs. The most commonly used method for amide bond formation involves activating carboxylic acids with excess coupling agents, heavily affecting the atom economy of the process. Despite the need for more sustainable alternatives, research on catalytic methodologies to minimize such drawbacks remains limited. In this study, we explored the use of titanium alkoxides of general formula Ti(OAr)2(OiPr)2, as efficient and environmentally friendly catalysts for amide bond formation. Our results indicated that the replacement of isopropoxide ligands with the less basic phenolates 2,4-dimethylphenolate and 2,6-dimethylphenolate significantly improved the reactivity of the Ti-center. Indeed, by using 5% mol of titanium bis(2,6-dimethylphenoxy)diisopropoxy (Ti2), or 10% mol of titanium bis(2,4-dimethylphenoxy)diisopropoxy (Ti1), we achieved efficient direct amidation between benzylamine and various carboxylic acids, including N-protected amino acids for which limited data are available in the literature. This work highlights the potential of titanium-based catalysis as a sustainable and effective solution for amide bond formation, particularly in peptide synthesis
Sinonasal Sarcomas Management: An International Consensus Statement
No full textIntroduction Sinonasal sarcomas are exceedingly rare entities, constituting less than 7% of head and neck sarcomas. Their complex histology needs specialized treatment, which is often based on multimodal approaches including surgery, radiation therapy, and/or chemotherapy. This manuscript aims to gather expert opinions to establish common management principles for sinonasal sarcomas.Methods This international consensus followed a modified Delphi method in seven steps, including statements definition by the core group, expert panel recruitment, and a two-round survey. Sixty-two statements on sinonasal sarcoma management were developed. Experts from multiple continents participated, and results were anonymized and analyzed between March and May 2025.Results A total of 44 invited experts were recruited, 43.2% otorhinolaryngologists/head and neck surgeons, 31.8% medical oncologists, and 25% radiation oncologists. Participants varied in age and experience, representing Europe (70.5%), North America (18.2%), South America (6.8%), and Asia (4.5%). Among all histologies, biphenotypic sarcoma, chondrosarcoma, leiomyosarcoma, and myofibrosarcoma are principally treated with an upfront surgical management, differently from Ewing sarcoma and rhabdomyosarcoma in which chemotherapy, eventually associated with radiotherapy, is often chosen. In the remaining histologies (angiosarcoma, liposarcoma, malignant peripheral nerve sheath tumor [MPNST], osteosarcoma, and synovial sarcoma), a precise multimodal treatment is less standardized and needs to be discussed on a case-by-case basis.Conclusion Sinonasal sarcomas require a histology-driven approach to determine upfront treatment, whether surgical, medical, or multimodal. Despite this structured strategy, prognosis remains highly variable across subtypes. Multidisciplinary evaluation and individualized management in referral centers are crucial to address the biological diversity and anatomical complexity of these rare malignancies
Transformer-driven monocular high-resolution DTM generation on mars via multimodal integration of CaSSIS imagery and MOLA altimetry
No full textThe global extent of the grassland biome and implications for the terrestrial carbon sink
No full textEffects of intraoperative higher versus lower positive end-expiratory pressure during one-lung ventilation for thoracic surgery on postoperative pulmonary complications (PROTHOR): a multicentre, international, randomised, controlled, phase 3 trial
No full textBackground: The effect of higher positive end-expiratory pressure (PEEP) and recruitment manoeuvres aimed at lung expansion as compared with lower PEEP without recruitment manoeuvres aimed at permissive atelectasis on postoperative pulmonary complications (PPCs) in patients undergoing one-lung ventilation (OLV) during thoracic surgery is unclear. We aimed to determine the contribution of an intraoperative lung expansion strategy to preventing PPCs. Methods: In this multicentre, randomised, controlled, international phase 3 trial (PROTHOR) conducted at 74 sites in 28 countries, we enrolled adult patients (aged ≥18 years) with a BMI of less than 35 kg/m2 who were scheduled for open thoracic or video-assisted thoracoscopic surgery under general anaesthesia requiring one-lung ventilation with a double-lumen tube, with a planned operative time of more than 60 min, and an expected duration of one-lung ventilation longer than that of two-lung ventilation. Patients were randomly assigned (1:1), using permuted blocks of random size (4, 6, and 8) and stratified by study site, to receive one-lung ventilation with either a higher PEEP of 10 cm H2O and periodic lung recruitment manoeuvres (high PEEP group) or a lower PEEP of 5 cm H2O without routine recruitment manoeuvres (low PEEP group). All patients received protective tidal volumes of 5 mL/kg predicted body weight during one-lung ventilation and 7 mL/kg predicted body weight during two-lung ventilation. Postoperative assessors were masked to treatment allocation. The primary outcome was a composite of PPCs during the first 5 postoperative days, including aspiration pneumonia, moderate or severe respiratory failure, acute respiratory distress syndrome (ARDS), pulmonary infection, atelectasis, cardiopulmonary oedema, pleural effusion, non-operative pneumothorax, pulmonary infiltrates, prolonged air leak, purulent pleuritis, pulmonary embolism, and pulmonary haemorrhage. A modified intention-to-treat analysis was performed, with patients analysed according to their assigned treatment group, except in cases of withdrawal of informed consent, cancellation of surgery, and or loss to follow-up. This trial is registered with ClinicalTrials.gov (NCT02963025) and is completed. Findings: Between Jan 3, 2017, and Feb 12, 2024, 2200 patients were randomly allocated: 1099 to the high PEEP group and 1101 to the low PEEP group. 43 patients in the high PEEP group and 33 in the low PEEP group were excluded from the modified intention-to-treat analysis after randomisation. The primary outcome occurred in 555 (53·6%) of 1036 patients in the high PEEP group and 592 (56·4%) of 1049 patients in the low PEEP group (absolute risk difference –2·68 percentage points [95% CI –6·36 to 1·01]; p=0·155). Intraoperative complications occurred in 484 (49·8%) of 972 patients in the high PEEP group and in 305 (31·3%) of 974 patients in the low PEEP group (absolute risk difference 18·09 percentage points [95% CI 14·41–21·77]), among which hypotension (360 [37·3%] of 966 patients in the high PEEP group vs 140 [14·3%] of 978 in the low PEEP group) and new arrhythmias (89 [9·9%] of 899 vs 37 [3·9%] of 956) were more frequent in the high PEEP group, while hypoxaemia rescue manoeuvres were more frequent in the low PEEP group (29 [3·3%] of 888 vs 86 [8·8%] of 982). The proportions of patients with extrapulmonary postoperative complications (110 [10·6%] of 1036 vs 107 [10·2%] of 1049 patients), and the numbers of adverse events (209 vs 204 events), did not differ between groups. Interpretation: In patients with a BMI of less than 35 kg/m2 undergoing thoracic surgery, one-lung ventilation using higher PEEP with recruitment manoeuvres, compared with lower PEEP without recruitment manoeuvres, did not reduce PPCs. The choice for intraoperative lung expansion or permissive atelectasis should take the individual gas-exchange and haemodynamic conditions into account, which might vary during the intraoperative period. Funding: Clinical Trials Network of the European Society of Anaesthesiology and Intensive Care; Department of Anaesthesiology and Intensive Care, University Hospital Carl Gustav Carus, Technische Universität Dresden (Dresden, Germany); Conselho Nacional de Desenvolvimento Científico e Tecnológico (Brasília, Brazil); and the Association of Anaesthetists of GB and Ireland
Intraoral Vestibular Pressure: Quantification and Implications on Gum Trophism
No full textIntroduction: This pioneering study delves into the dynamics of intraoral pressure, examining its consistency across different subjects and conditions. The null hypothesis is a different pressure at rest between the intraoral zone and the atmospheric pressure. Materials and Methods: Utilizing a novel apparatus and method, based on the concept of communicating vessels, the research aimed to measure resting intraoral pressure at the vestibular level. Results: The findings revealed no significant variations in intraoral pressure across different individuals or under varying sectors of analysis or wakefulness versus sleep state. The average resting pressure in the oral vestibule was identified to be −1.25 mmHg, suggesting a residual relative negative pressure post-swallowing that could aid in various physiological functions. Discussion: The values found align with previous studies on swallowing and with studies that have attempted to measure the intraoral pressure exerted by the muscles of cheeks and lips. The study further supports existing theories on peri-implant tissue maturation and the role of oral vacuum in promoting gingival growth. Specifically, it suggests a potential impact of the negative pressure gradient on gingival microcirculation as an explanation for the volumetric growth of gingival tissue. Conclusion: Within the limitation of the present sample size, this research confirms the hypothesis related to intraoral pressure in understanding various physiological processes within the oral cavity, paving the way for further exploration in this domain with implications for dental and oral health practices
Bonding Mechanisms Underpinning Structural and Electronic Properties of Halide Perovskites
No full textHalide perovskites have emerged as a versatile class of optoelectronic materials, exhibiting outstanding performance across a broad spectrum of applications, including photovoltaics, light-emitting devices, non-classical light sources, and radiation detectors. On the fundamental side, the nature of chemical bonding in halide perovskites plays a crucial role in determining their structural and (opto)electronic properties, chemical stability, and formability. For instance, their electronic bandgap is highly sensitive to octahedral tilting as well as to lattice expansion or contraction, due to changes in the orbital overlap. In fact, one of the most intriguing features of halide perovskites is their dynamic structural behavior rooted in the flexibility of the BX6 octahedra framework, which underpins complex interactions between charge carriers and the lattice. These materials exhibit pronounced structural softness and anharmonicity, as indicated by their low thermal conductivity and high thermal expansion coefficients. These features significantly influence charge transport and thermolectric properties, making halide perovskites promising candidates for various applications. In this context, this review aims to provide readers with a comprehensive overview of recent advances in the detailed atomic-scale characterization of halide perovskites, combining experimental structural chemistry and computational techniques, an essential step toward the rational design of novel materials with tailored optoelectronic properties for next-generation technologies. It examines the atomic structure and dynamics of these materials, emphasizing how chemical bonding within the inorganic framework and interactions with organic moieties in hybrid and layered systems govern their structural behavior, ultimately influencing their optoelectronic performance
The Impact of Non-Radical Hysterectomy on Urinary Functions: Evaluation of Symptoms—A Systematic Review and Meta-Analysis
No full textBackground Simple hysterectomy is one of the most common gynaecological surgical procedures worldwide; however, its association as a possible aetiological factor for urinary dysfunction remains controversial. Objective To evaluate the clinical impact of different types of non-radical hysterectomy on lower urinary tract symptoms (LUTS). Search Strategy A structured search was conducted across scientific sources through December 1989 to March 2025, using terms including: 'urodynamics', 'urinary incontinence', 'stress incontinence', 'urge incontinence', 'urinary urgency', 'urinary frequency', 'urinary nocturia' and 'urinary retention', 'lower urinary tract symptoms', 'hysterectomy'. Selection Criteria Randomised controlled trials and prospective observational studies assessing patients undergoing simple hysterectomy with pre- and post-operative evaluation by validated questionnaires. Exclusion criteria included case reports, reviews, editorials, short communications, radical hysterectomy, post-operative assessment only, non-English publications and studies on pelvic organ prolapse surgery. Data Collection and Analysis Ten studies, encompassing 1769 patients, were included in the analysis. Five outcomes were selected: changes in urinary frequency; occurrence of stress urinary incontinence; occurrence of urge urinary incontinence; changes in nocturia; changes in incomplete bladder emptying. Main Results Changes from baseline to last follow-up available in urinary frequency (OR 0.48, 95% CI 0.36-0.66; p < 0.00001); stress urinary incontinence (OR = 0.54, 95% CI 0.44-0.68; p < 0.00001); urge urinary incontinence (OR = 0.76, 95% CI 0.72-0.94; p = 0.01); nocturia (OR 0.55, 95% CI 0.36-0.84; p = 0.005); incomplete bladder (OR = 0.95, 95% CI 0.66-1.36; p = 0.77). Conclusion The present meta-analysis suggests that simple hysterectomy is associated with a reduction in the prevalence of urinary symptoms postoperatively. Trial Registration PROSPERO: CRD4202457557
Tyre-derived ecotoxicity: Differentiating the effects from particles and chemical leachates on the blue mussel Mytilus edulis
Full text linkTyre particles contain complex chemical additives that can leach out into the aquatic environment, posing potential risks to marine organisms. Despite growing evidence of adverse effects, the relative importance of particle-driven versus chemically mediated toxicity remains poorly explored, especially under environmentally relevant exposure scenarios. This study used the blue mussel ( Mytilus edulis ) as a model to differentiate these effects by exposing individuals to cryomilled tyre particles (TP), their leachates (L) and pre-leached particles (TPL) over 36 days at the environmentally relevant concentration of 0.1 g/L. Chemical analysis confirmed uptake of key organic additives such as poly(1,2-dihydro-2,2,4-trimethylquinoline) (TMQ), N-(1,3-dimethylbutyl)- N ′-phenyl- p -phenylenediamine (6PPD), and 6PPD-quinone (6PPDQ), with certain compounds persisting after depuration. Particle-exposed mussels accumulated higher additive concentrations than those exposed to only leachates, indicating enhanced chemical release from particles. Biomarker responses revealed signs of oxidative stress and neurotoxicity in exposed mussels across all treatments, with earlier responses in leachate exposure and delayed responses during particle exposures. These results demonstrate that chemical additives are key toxicity drivers alongside physical particles, highlighting the importance of considering both pathways in environmental risk assessments. To our knowledge, this study is among the first to experimentally separate particle and leachate specific effects in mussels by using tyre particles before and after leaching to create contrasting chemical loads, thereby providing novel insights into their distinct and combined impacts on marine biota
Collaborative evaluation of in silico predictions for high throughput toxicokinetics
No full textHigh throughput toxicokinetic (HTTK) methods address chemical risk assessment data gaps but require chemicalspecific values that can be obtained by in vitro measurements or in silico models. In this study, seven quantitative structure property relationship (QSPR) models were used to estimate intrinsic hepatic clearance (Clint), fraction of chemical unbound in plasma (fup), and/or TK elimination half-life (t1/2). Performance of the QSPR models was evaluated using literature time-course in vivo TK data, mainly from rats. Simulations of the in vivo data were made with a high throughput physiologically based TK (HT-PBTK) model using the different QSPR model predictions as inputs. We estimate that using rat in vivo data to evaluate QSPR models trained on human in vitro measured data might inflate error estimates by as much as root mean squared log10 error (RMSLE) 0.8. A sensitivity analysis showed that Clint and fup parameters inform predictions of area under the curve (AUC) and steady-state concentration (Css). We estimate that AUC can be predicted by HTTK with RMSLE 0.9 using in vitro measurements and 0.6-0.8 using QSPR model values. We anticipate that, for some novel compounds, QSPRs for HTTK input parameters will give predictions of TK similar to those based on in vitro measurements