Maltodextrin-Based Cross-Linked Electrospun Mats as Sustainable Sorbents for the Removal of Atenolol from Water.

Maltodextrins are products of starch hydrolysis that can be processed into dry fibres through electrospinning and subsequently cured via mild thermal treatment to obtain nonwoven cross-linked polysaccharide-based mats. The sustainability of the process and the bioderived nature make this class of materials suitable candidates to be studied as renewable sorbents for the removal of contaminants from water. In this work, electrospinning of water solutions containing 50% wt. of commercial maltodextrin (Glucidex 2®) and 16.6% wt. of citric acid was carried out at 1.2 mL/h flow and 30 kV applied voltage, followed by thermal curing at 180 °C of the dry fibres produced to obtain cross-linked mats. Well-defined fibres with a mean diameter of 1.64 ± 0.35 µm were successfully obtained and characterised by scanning electron microscopy, thermogravimetric analysis, and attenuated total reflectance Fourier transform infrared spectroscopy. Afterwards, a series of sorption tests were conducted to evaluate the effectiveness of the mats in removing atenolol from water. The results of the batch tests followed by HPLC-UV/Vis showed high sorption rates, with over 90% of the atenolol removed, and a maximum removal capacity of 7 mg/g. Furthermore, continuous fixed-bed sorption tests proved the positive interaction between the polymers and atenolol.

Pluvial flood risk assessment for 2021-2050 under climate change scenarios in the Metropolitan City of Venice.

Pluvial flood is a natural hazard occurring from extreme rainfall events that affect millions of people around the world, causing damages to their properties and lives. The magnitude of projected climate risks indicates the urgency of putting in place actions to increase climate resilience. Through this study, we develop a Machine Learning (ML) model to predict pluvial flood risk under Representative Concentration Pathways (RCP) 4.5 and 8.5 for future scenarios of precipitation for the period 2021-2050, considering different triggering factors and precipitation patterns. The analysis is focused on the case study area of the Metropolitan City of Venice (MCV) and considers 212 historical pluvial flood events occurred in the timeframe 1995-2020. The methodology developed implements spatio-temporal constraints in the ML model to improve pluvial flood risk prediction under future scenarios of climate change. Accordingly, a cross-validation approach was applied to frame a model able to predict pluvial flood at any time and space. This was complemented with historical pluvial flood data and the selection of nine triggering factors representative of territorial features that contribute to pluvial flood events. Logistic Regression was the most reliable model, with the highest AUC score, providing robust result both in the validation and test set. Maximum cumulative rainfall of 14 days was the most important feature contributing to pluvial flood occurrence. The final output is represented by a suite of risk maps of the flood-prone areas in the MCV for each quarter of the year for the period 1995-2020 based on historical data, and risk maps for each quarter of the period 2021-2050 under RCP4.5 and 8.5 of future precipitation scenarios. Overall, the results underline a consistent increase in extreme events (i.e., very high and extremely high risk of pluvial flooding) under the more catastrophic scenario RCP8.5 for future decades compared to the baseline.

Sensitivity analysis for a participatory approach to enhance the climate resilience of Venice, Italy.

Increases in the magnitudes and frequencies of climate-related extreme events are redistributing risk across coastal systems, including their environmental, economic, and social components. Consequently, stakeholders (SHs) are faced with long-term challenges and complex information when managing assets, services, and uses of the coast. In this context, SH engagement is a key step for risk management and in the preparation of resilience plans to respond and adapt to climate change. This paper develops a participatory method to identify and prioritize a set of risk measures, combining multi-criteria analysis with sensitivity analysis. The process involved local and regional authorities of the Veneto region testing the method, including national, regional, and local government, catchment officers, research organizations, natural parks managers and Non-Governmental Organizations (NGOs). SHs identified and ranked a range of adaptation measures to increase climate resilience, with a focus on coastal risk in the Venice lagoon. Results demonstrate that the sensitivity analysis provides useful information on how different sectors of expertise can influence the ranking of the identified risk management measures, highlighting the value of investigating the preferences or priorities of different SH groups within the definition of adaptation plans.

Dextrin-Based Adsorbents Synthesized via a Sustainable Approach for the Removal of Salicylic Acid from Water.

Pharmaceuticals such as salicylic acid are commonly detected in wastewater and surface waters, increasing concern for possible harmful effects on humans and the environment. Their difficult removal via conventional treatments raised the need for improved strategies, among which the development of bioderived adsorbents gained interest because of their sustainability and circularity. In this work, biobased cross-linked adsorbents, synthesized via a sustainable approach from starch derivatives, namely beta-cyclodextrins and maltodextrins, were at first characterized via FTIR-ATR, TGA, SEM, and elemental analysis, showing hydrophilic granular morphologies endowed with specific interaction sites and thermal stabilities higher than 300 °C. Subsequently, adsorption tests were carried out, aiming to assess the capabilities of such polymers on the removal of salicylic acid, as a case study, from water. Batch tests showed rapid kinetics of adsorption with a removal of salicylic acid higher than 90% and a maximum adsorption capacity of 17 mg/g. Accordingly, continuous fixed bed adsorption tests confirmed the good interaction between the polymers and salicylic acid, while the recycling of the adsorbents was successfully performed up to four cycles of use.

Improving Sustainability through Covalent Adaptable Networks in the Recycling of Polyurethane Plastics.

The global plastic waste problem has created an urgent need for the development of more sustainable materials and recycling processes. Polyurethane (PU) plastics, which represent 5.5% of globally produced plastics, are particularly challenging to recycle owing to their crosslinked structure. Covalent adaptable networks (CANs) based on dynamic covalent bonds have emerged as a promising solution for recycling PU waste. CANs enable the production of thermoset polymers that can be recycled using methods that are traditionally reserved for thermoplastic polymers. Reprocessing using hot-pressing techniques, in particular, proved to be more suited for the class of polyurethanes, allowing for the efficient recycling of PU materials. This Review paper explores the potential of CANs for improving the sustainability of PU recycling processes by examining different types of PU-CANs, bond types, and fillers that can be used to optimise the recycling efficiency. The paper concludes that further research is needed to develop more cost-effective and industrial-friendly techniques for recycling PU-CANs, as they can significantly contribute to sustainable development by creating recyclable thermoset polymers.

Interdisciplinary consensus statements on imaging of DRUJ instability and TFCC injuries.

OBJECTIVES: The purpose of this agreement was to establish evidence-based consensus statements on imaging of distal radioulnar joint (DRUJ) instability and triangular fibrocartilage complex (TFCC) injuries by an expert group using the Delphi technique. METHODS: Nineteen hand surgeons developed a preliminary list of questions on DRUJ instability and TFCC injuries. Radiologists created statements based on the literature and the authors' clinical experience. Questions and statements were revised during three iterative Delphi rounds. Delphi panelists consisted of twenty-seven musculoskeletal radiologists. The panelists scored their degree of agreement to each statement on an 11-item numeric scale. Scores of "0," "5," and "10" reflected complete disagreement, indeterminate agreement, and complete agreement, respectively. Group consensus was defined as a score of "8" or higher for 80% or more of the panelists. RESULTS: Three of fourteen statements achieved group consensus in the first Delphi round and ten statements achieved group consensus in the second Delphi round. The third and final Delphi round was limited to the one question that did not achieve group consensus in the previous rounds. CONCLUSIONS: Delphi-based agreements suggest that CT with static axial slices in neutral rotation, pronation, and supination is the most useful and accurate imaging technique for the work-up of DRUJ instability. MRI is the most valuable technique in the diagnosis of TFCC lesions. The main indication for MR arthrography and CT arthrography are Palmer 1B foveal lesions of the TFCC. CLINICAL RELEVANCE STATEMENT: MRI is the method of choice for assessing TFCC lesions, with higher accuracy for central than peripheral abnormalities. The main indication for MR arthrography is the evaluation of TFCC foveal insertion lesions and peripheral non-Palmer injuries. KEY POINTS: • Conventional radiography should be the initial imaging technique in the assessment of DRUJ instability. CT with static axial slices in neutral rotation, pronation, and supination is the most accurate method for evaluating DRUJ instability. • MRI is the most useful technique in diagnosing soft-tissue injuries causing DRUJ instability, especially TFCC lesions. • The main indications for MR arthrography and CT arthrography are foveal lesions of the TFCC.

Learning new physics efficiently with nonparametric methods.

We present a machine learning approach for model-independent new physics searches. The corresponding algorithm is powered by recent large-scale implementations of kernel methods, nonparametric learning algorithms that can approximate any continuous function given enough data. Based on the original proposal by D'Agnolo and Wulzer (Phys Rev D 99(1):015014, 2019, arXiv:1806.02350 [hep-ph]), the model evaluates the compatibility between experimental data and a reference model, by implementing a hypothesis testing procedure based on the likelihood ratio. Model-independence is enforced by avoiding any prior assumption about the presence or shape of new physics components in the measurements. We show that our approach has dramatic advantages compared to neural network implementations in terms of training times and computational resources, while maintaining comparable performances. In particular, we conduct our tests on higher dimensional datasets, a step forward with respect to previous studies.

Learning new physics from an imperfect machine.

We show how to deal with uncertainties on the Standard Model predictions in an agnostic new physics search strategy that exploits artificial neural networks. Our approach builds directly on the specific Maximum Likelihood ratio treatment of uncertainties as nuisance parameters for hypothesis testing that is routinely employed in high-energy physics. After presenting the conceptual foundations of our method, we first illustrate all aspects of its implementation and extensively study its performances on a toy one-dimensional problem. We then show how to implement it in a multivariate setup by studying the impact of two typical sources of experimental uncertainties in two-body final states at the LHC.

Presurgical Perspective and Postsurgical Evaluation of Morton's Neuroma and Other Nerve Lesions.

Magnetic resonance imaging (MRI) is a robust method used for both preoperative and postoperative evaluation of Morton's neuroma and other neural lesions. MRI is used to confirm the diagnosis and for precise localization, estimation of outcome, and differential diagnoses. The differential diagnoses include mechanically induced plantar plate ruptures with associated Morton's neuroma-like tumors in the intermetatarsal/interdigital spaces; mechanical fibrosis cushion formations and pseudo bursae in the plantar foot adipose tissue; rheumatologic affections, such as rheumatoid nodules, gouty nodules, and intermetatarsal bursitis; and lastly the tenosynovial giant cell tumor (formerly called pigmented villonodular synovitis). In the postoperative evaluation after resection of Morton's neuroma, the same differential diagnoses must be considered as in the preoperative evaluation. Similarly, a high prevalence (up to 25%) of asymptomatic Morton's neuroma-like findings in the intermetatarsal and interdigital spaces should be kept in mind when interpreting postoperative recurrent forefoot pain after Morton's neuroma resection.

Sustainable mechanochemical synthesis of ß-cyclodextrin polymers by twin screw extrusion.

Cyclodextrin nanosponges (CD-NS) are cross-linked cyclodextrin polymers characterized by a nanostructured three-dimensional network. CD-NSs in the last years found many different applications in the pharmaceutical field for the controlled release of drugs and for the absorption of undesired substances from physiological media, food, and wastewater. Most of CD-NS syntheses involve the solubilization of the chosen CD in closed batch, using a suitable organic polar aprotic liquid, which may affect potential environmental or biomedical applications. Since the research is now moving towards more sustainable approaches, new and greener syntheses of CD-NS are now being developed. Here, it is reported a new eco-friendly and efficient synthesis of nanosponges through mechanochemistry. Mechanochemistry involves the application of mechanical forces to drive and control chemical reactions by transferring energy to chemical bonds. The mechanochemical approach involves the use of a twin-screw extruder (TSE) as a chemical reactor: TSE are capable of fine temperature control and, furthermore, TS Extrusion is a continuous process and not a batch process. Among the many available CD-NS syntheses, we tested our solvent-free approach on a ß-CD/citric acid (CA) system. Moreover, using TSE, the same polymer was obtained in a considerably shorter time. The so obtained NSs were used for the adsorption and removal of probe molecules, in comparison with NSs prepared by cross-linking ß-CD with CA in batch.

Interdisciplinary consensus statements on imaging of scapholunate joint instability.

OBJECTIVES: The purpose of this agreement was to establish evidence-based consensus statements on imaging of scapholunate joint (SLJ) instability by an expert group using the Delphi technique. METHODS: Nineteen hand surgeons developed a preliminary list of questions on SLJ instability. Radiologists created statements based on the literature and the authors' clinical experience. Questions and statements were revised during three iterative Delphi rounds. Delphi panellists consisted of twenty-seven musculoskeletal radiologists. The panellists scored their degree of agreement to each statement on an eleven-item numeric scale. Scores of '0', '5' and '10' reflected complete disagreement, indeterminate agreement and complete agreement, respectively. Group consensus was defined as a score of '8' or higher for 80% or more of the panellists. RESULTS: Ten of fifteen statements achieved group consensus in the second Delphi round. The remaining five statements achieved group consensus in the third Delphi round. It was agreed that dorsopalmar and lateral radiographs should be acquired as routine imaging work-up in patients with suspected SLJ instability. Radiographic stress views and dynamic fluoroscopy allow accurate diagnosis of dynamic SLJ instability. MR arthrography and CT arthrography are accurate for detecting scapholunate interosseous ligament tears and articular cartilage defects. Ultrasonography and MRI can delineate most extrinsic carpal ligaments, although validated scientific evidence on accurate differentiation between partially or completely torn or incompetent ligaments is not available. CONCLUSIONS: Delphi-based agreements suggest that standardized radiographs, radiographic stress views, dynamic fluoroscopy, MR arthrography and CT arthrography are the most useful and accurate imaging techniques for the work-up of SLJ instability. KEY POINTS: • Dorsopalmar and lateral wrist radiographs remain the basic imaging modality for routine imaging work-up in patients with suspected scapholunate joint instability. • Radiographic stress views and dynamic fluoroscopy of the wrist allow accurate diagnosis of dynamic scapholunate joint instability. • Wrist MR arthrography and CT arthrography are accurate for determination of scapholunate interosseous ligament tears and cartilage defects.

Nanosized SnO2 Prepared by Electrospinning: Influence of the Polymer on Both Morphology and Microstructure.

An electrospinning (ES) procedure of polymeric solutions containing metal oxide precursors, followed by thermal treatments, was exploited to obtain SnO2 nanofibers. Attention was focused on the effect of different templating polymers (polyvinyl pyrrolidone (PVP), polyethylene oxide (PEO) and polyvinyl acetate (PVAc)) on the morphologies and particle size distributions of SnO2. We demonstrated that with different polymers, the final oxide's morphology and crystallite size change. Defined fibers, with homogeneous diameter, were obtained with each polymer, but, after calcination, the morphology of the oxide changes, leading to fibers, "flakes" or "sphere-shaped" particles when PVP, PEO or PVAc were used, respectively, as evidenced by SEM images. Data from HR-TEM and XRD measurements confirm that SnO2 samples consist of crystalline cassiterite, with small mean particle dimensions calculated by Debye-Scherrer equation, i.e., 30, 11 and 25 nm with PVP, PEO and PVAc, respectively. TEM measurements put in evidence lower average particle sizes and for SnO2 obtained with PEO average size of 8.5 nm with a standard deviation of ±4.9 nm was evidenced. By applying different calcination temperatures on fiber mat obtained by the same polymer, i.e., PEO, the influence of polymer not only on the final shape of the oxide particles but also on the crystallite size was definitively demonstrated.

Low density polyethylene degradation by filamentous fungi.

Polyethylene (PE) is the most abundant non-degradable plastic waste, posing a constant and serious threat to the whole ecosystem. In the present study, the fungal community of plastic wastes contaminating a landfill soil has been studied. After 6 months of enrichment, 95 fungi were isolated, mostly belonging to the Ascomycota phylum. They were screened under in vitro condition: most of fungi (97%) were capable of growing in the presence of PE powder (5-10 g L-1) as sole carbon source. Fusarium strains better tolerated high concentration of PE. Up to 13 strains were chosen for further degradation trails, where the process was monitored by respirometry tests and by observing changes in PE chemical and physical structure by FTIR analysis and SEM images. Major results were observed for Fusarium oxysporum, Fusarium falciforme and Purpureocillum lilacinum, as they caused strong oxidation phenomena and changes in the PE film morphology. Results suggested that the initial oxidation mechanisms targeted first the methyl terminal groups. Changes in the infrared spectra were strongly strain-dependent, denoting the activation of different degradation pathways. Through the SEM analysis, the actual damages provoked by fungi were observed, including swellings, pits and furrows, bumps and partial exfoliations. Considering the rising concern about plastic disposal worldwide, the ability of these fungi to colonize PE and utilize it as carbon source is of great interest, as no pretreatments and pro-oxidant stimulants were needed.

Sustainable production of curable maltodextrin-based electrospun microfibers.

Maltodextrins are inexpensive, water-soluble starch hydrolysis products composed of high molecular weight polysaccharide molecules. This feature allows their water solutions to be processed by electrospinning to produce bio-based microfibrous mats. Also, the presence of hydroxyl functions along the maltodextrin's backbone enables cross-linking reactions to be performed, necessary to overcome the intrinsic solubility of the starting material, by exploiting suitable functional molecules. In this work, the electrospinning process to obtain fibre deposition from water solutions of five different commercial maltodextrins was firstly optimized. Well-defined fibres with diameters ranging between 1.1 µm and 1.5 µm were successfully obtained using water as the unique solvent. Subsequently, the same maltodextrin-containing water solutions with citric acid added were then processed again. The presence of citric acid did not hinder the spinnability of the studied systems, while the possibility to achieve a one-step thermal curing of the obtained fibres was proved via solubility tests, TGA, and FTIR-ATR analyses. Eventually, bio-based cross-linked mats with fibre diameters ranging from 0.7 µm to 1.4 µm were obtained from the electrospinning of commercial maltodextrins and citric acid, employing water as the unique solvent and environmentally friendly curing processes. This approach enables the reported mats to be further studied for environmental, pharmaceutical, and medical applications.

Thermosetting Polyurethane Resins as Low-Cost, Easily Scalable, and Effective Oxygen and Moisture Barriers for Perovskite Solar Cells.

Long-term stability of perovskite solar cells (PSCs) is one of the main issues to be solved for forthcoming commercialization of this technology. In this work, thermosetting polyurethane (PU)-based resins are proposed as effective encapsulants for perovskite solar cells to prevent degradation caused by both moisture and oxygen. Application consists of drop-casting the precursor mixture directly over the devices followed by in situ polymerization, avoiding the use of other adhesives. PUs are cost-effective, lightweight, thermal, and light-stable materials whose mechanical, chemical, and physical properties can be easily tuned by thoughtful choice of their precursor. Encapsulated PSCs show extremely good stability when stored under ambient light (maximum, 1000 lux), controlled humidity (28-65%), and temperature (18-30 °C) by retaining 94% of the initial power conversion efficiency after 2500 h (4 months), whereas control devices lose 90% of their performance after 500 h (T80 = 37 h); once stored according to ISOS-D-1, PU-protected devices showed T80 > 1200 h. Encapsulated devices are stable even when immersed in pure water. The demonstration of PUs as promising solution-processed encapsulant materials for PSCs can pave the way for these to become a cost-effective encapsulation route alternative for future industrialization of this technology.

Preparation of Microspheres and Monolithic Microporous Carbons from the Pyrolysis of Template-Free Hyper-Crosslinked Oligosaccharides Polymer.

Carbon-based materials with different morphologies have special properties suitable for application in adsorption, catalysis, energy storage, and so on. Carbon spheres and carbon monoliths are also nanostructured materials showing promising results. However, the preparation of these materials often require the use of a template, which aggravates their costs, making the operations for their removal complex. In this work, hollow carbon microspheres and carbon monolith were successfully prepared via carbonization of hyper-crosslinked polymer based on either cyclodextrins or amylose, in a template-free way. The carbons obtained are of the microporous type, showing a surface area up to 610 m2/g, and a narrow pore distribution, typically between 5 and 15 Å.

Mechanochemical green synthesis of hyper-crosslinked cyclodextrin polymers.

Cyclodextrin nanosponges (CD-NS) are nanostructured crosslinked polymers made up of cyclodextrins. The reactive hydroxy groups of CDs allow them to act as multifunctional monomers capable of crosslinking to bi- or multifunctional chemicals. The most common NS synthetic pathway consists in dissolving the chosen CD and an appropriate crosslinker in organic polar aprotic liquids (e.g., N,N-dimethylformamide or dimethyl sulfoxide), which affect the final result, especially for potential biomedical applications. This article describes a new, green synthetic pathway through mechanochemistry, in particular via ball milling and using 1,1-carbonyldiimidazole as the crosslinker. The polymer obtained exhibited the same characteristics as a CD-based carbonate NS synthesized in a solvent. Moreover, after the synthesis, the polymer was easily functionalized through the reaction of the nucleophilic carboxylic group with three different organic dyes (fluorescein, methyl red, and rhodamine B) and the still reactive imidazoyl carbonyl group of the NS.

New Poly(ß-Cyclodextrin)/Poly(Vinyl Alcohol) Electrospun Sub-Micrometric Fibers and their Potential Application for Wastewater Treatments.

Cyclodextrin (CD)-based polymers are known to efficiently form molecular inclusion complexes with various organic and inorganic guest compounds. In addition, they also have a great potential as metal complexes because deprotonated hydroxyls can strongly bind metal ions under alkaline conditions. The range of environmental conditions for polycyclodextrin/metal ion complexation can be extended by the polymerization of CDs with polyacids. This article describes the preparation and characterization of a new type of poly(ß-cyclodextrin) (Poly-ßCD) sub-micrometric fibers and explores their potential as metal ion sorbents. A water-soluble hyper-branched ß-cyclodextrin polymer was blended with poly(vinyl alcohol) (PVA) and here used to improve the mechanical and morphological features of the fibers. Solutions with a different Poly-ßCD/PVA ratio were electrospun, and the fibers were cross-linked by a post-spinning thermal treatment at 160 °C to ensure non-solubility in water. The fiber morphology was analyzed by scanning electron microscopy (SEM) before and after the curing process, and physical-chemical properties were studied by Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The capability of the insoluble cyclodextrin-based fibers to remove heavy metals from wastewaters was investigated by testing the adsorption of Cu2+ and Cd2+ using inductively coupled plasma-optical emission spectroscopy (ICP-OES). The results suggest that the poly(ß-cyclodextrin)/poly(vinyl alcohol) sub-micrometric fibers can complex metal ions and are especially effective Cu2+ sorbents, thus opening new perspectives to the development of fibers and membranes capable of removing both metal ions and organic pollutants.