126 results on '"Callone E"'
Search Results
52. Antileishmanial activity of euplotin C, the sesquiterpene taxonomic marker from maine ciliate Euplotes crassus
- Author
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Savoia, D., Allice, T., Avanzino, C., Callone, E., and Dini, Fernando
- Published
- 2003
53. New terpenoids from protista cell cultures: towards an understanding of their biogenesis
- Author
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Guella, G., Callone, E., Mancini, I., and Dini, Fernando
- Published
- 2003
54. Relazioni filogenetiche all’interno del genere Euplotes (Ciliata, Hypotrichida)
- Author
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DI GIUSEPPE, Graziano, Erra, Fabrizio, Guella, G, Callone, E, and Dini, Fernando
- Published
- 2003
55. Structure-related behavior of hybrid organic-inorganic materials prepared in different synthesis conditions from Zr-based NBBs and 3-methacryloxypropyl trimethoxysilane
- Author
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Di Maggio, R., primary, Callone, E., additional, Girardi, F., additional, and Dirè, S., additional
- Published
- 2012
- Full Text
- View/download PDF
56. FIRB "SQUARE" PROJECT: NANO-STRUCTURED SENSORS FOR THE DETECTION OF THE POLLUTING IC ENGINE EXHAUST GASES AND FOR INDOOR AIR QUALITY MONITORING
- Author
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MARZORATI, D., primary, MERLONE BORLA, E., additional, LATTORE, M., additional, CARTURAN, G., additional, CALLONE, E., additional, NERI, G., additional, MICALI, G., additional, BONAVITA, A., additional, RONCARI, E., additional, SANSON, A., additional, DI NATALE, C., additional, MARTINELLI, E., additional, PENNAZZA, G., additional, PAOLESSE, R., additional, SICILIANO, P., additional, FORLEO, A., additional, CAPONE, S., additional, TAURINO, A. M., additional, DEBENEDETTI, B., additional, DEORSOLA, F., additional, IANNOTTA, S., additional, TOCCOLI, T., additional, COPPEDÈ, N., additional, LICHERI, R., additional, ORRÙ, R., additional, and CAO, G., additional
- Published
- 2008
- Full Text
- View/download PDF
57. A STUDY OF INDIUM OXIDE SENSORS FOR DIABETES BIOMARKER DETECTION IN THE HUMAN BREATH
- Author
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NERI, G., primary, BONAVITA, A., additional, MICALI, G., additional, IPSALE, S., additional, CALLONE, E., additional, and CARTURAN, G., additional
- Published
- 2008
- Full Text
- View/download PDF
58. Resistive CO gas sensors based on In2O3 and InSnOx nanopowders synthesized via starch-aided sol–gel process for automotive applications
- Author
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Neri, G., primary, Bonavita, A., additional, Micali, G., additional, Rizzo, G., additional, Callone, E., additional, and Carturan, G., additional
- Published
- 2008
- Full Text
- View/download PDF
59. A picoscale catalyst for hydrogen generation from NaBH4 for fuel cells
- Author
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Peña-Alonso, R., primary, Sicurelli, A., additional, Callone, E., additional, Carturan, G., additional, and Raj, R., additional
- Published
- 2007
- Full Text
- View/download PDF
60. A community-built calibration system: The case study of quantification of metabolites in grape juice by qNMR spectroscopy
- Author
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Ales Čamra, John Warren, Taylor David, Dinesh Chalasani, Daniele Ragno, Jan Teipel, Tommaso Di Noia, Aurimas Bieliauskas, Elina Zailer-Hafer, Stefano Todisco, Domenico Acquotti, Lorraine M. Bateman, James Donarski, Piero Mastrorilli, Rosa Ragone, Cristina Airoldi, John S. Harwood, Michael Assfalg, Dolores Molero Vilchez, Francesco Longobardi, Magali Martin-Biran, Elisabetta Schievano, Domenico Mallamace, Elisabetta Torregiani, Biagia Musio, Stefania Pontrelli, Paolo Dambruoso, Marina Veronesi, Livio Stevanato, Augusta Caligiani, Erwann Hamon, Maurizio Triggiani, Davide Bertelli, Flaminia Cesare Marincola, Stefano Mammi, Bernd Diehl, Vito Gallo, Daniela Valensin, Bhavaraju Sitaram, Alessandro Barge, Claudia Di Napoli, Elena Sáez Barajas, Pasquale Scapicchio, Emanuela Callone, Antonino Rizzuti, Panteleimon G. Takis, Fabio Bertocchi, Anna Borioni, Cristiano Zuccaccia, Maria Cecilia Rossi, Mario Latronico, Andrea Kobrlová, Luca Goldoni, Nicola Intini, Freddy Thomas, Roberto Gobetto, Renzo Luisi, Ana M. Gil, Pierluigi Mazzei, Julien Wist, Roberto Consonni, Francesca Benevelli, Algirdas Šačkus, Antonio Randazzo, Salvatore Milone, Archimede Rotondo, Roger J. Mulder, Silvia Davalli, Andrea Mele, Musio, B, Ragone, R, Todisco, S, Rizzuti, A, Latronico, M, Mastrorilli, P, Pontrelli, S, Intini, N, Scapicchio, P, Triggiani, M, Di Noia, T, Acquotti, D, Airoldi, C, Assfalg, M, Barge, A, Bateman, L, Benevelli, F, Bertelli, D, Bertocchi, F, Bieliauskas, A, Borioni, A, Caligiani, A, Callone, E, Čamra, A, Cesare Marincola, F, Chalasani, D, Consonni, R, Dambruoso, P, Davalli, S, David, T, Diehl, B, Donarski, J, Gil, A, Gobetto, R, Goldoni, L, Hamon, E, Harwood, J, Kobrlová, A, Longobardi, F, Luisi, R, Mallamace, D, Mammi, S, Martin-Biran, M, Mazzei, P, Mele, A, Milone, S, Molero Vilchez, D, Mulder, R, Napoli, C, Ragno, D, Randazzo, A, Rossi, M, Rotondo, A, Šačkus, A, Sáez Barajas, E, Schievano, E, Sitaram, B, Stevanato, L, Takis, P, Teipel, J, Thomas, F, Torregiani, E, Valensin, D, Veronesi, M, Warren, J, Wist, J, Zailer-Hafer, E, Zuccaccia, C, Gallo, V, Musio, B., Ragone, R., Todisco, S., Rizzuti, A., Latronico, M., Mastrorilli, P., Pontrelli, S., Intini, N., Scapicchio, P., Triggiani, M., Di Noia, T., Acquotti, D., Airoldi, C., Assfalg, M., Barge, A., Bateman, L., Benevelli, F., Bertelli, D., Bertocchi, F., Bieliauskas, A., Borioni, A., Caligiani, A., Callone, E., Camra, A., Cesare Marincola, F., Chalasani, D., Consonni, R., Dambruoso, P., Davalli, S., David, T., Diehl, B., Donarski, J., Gil, A. M., Gobetto, R., Goldoni, L., Hamon, E., Harwood, J. S., Kobrlova, A., Longobardi, F., Luisi, R., Mallamace, D., Mammi, S., Martin-Biran, M., Mazzei, P., Mele, A., Milone, S., Molero Vilchez, D., Mulder, R. J., Napoli, C., Ragno, D., Randazzo, A., Rossi, M. C., Rotondo, A., Sackus, A., Saez Barajas, E., Schievano, E., Sitaram, B., Stevanato, L., Takis, P. G., Teipel, J., Thomas, F., Torregiani, E., Valensin, D., Veronesi, M., Warren, J., Wist, J., Zailer-Hafer, E., Zuccaccia, C., and Gallo, V.
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Analyte ,Magnetic Resonance Spectroscopy ,Traceability ,qNMR Interlaboratory comparison Calibration Multiple regression Validation Food quality control ,02 engineering and technology ,01 natural sciences ,Analytical Chemistry ,NO ,Food quality control ,Matrix (chemical analysis) ,Interlaboratory comparison ,Validation ,CHIM/06 - CHIMICA ORGANICA ,Calibration ,Calibration, Food quality control, Interlaboratory comparison, Multiple regression, qNMR, Validation ,Vitis ,qNMR ,Multiple regression ,qNMR, Interlaboratory comparison, Calibration, Multiple regression, Validation, Food quality control ,Spectroscopy ,Fruit and Vegetable Juices ,Reproducibility ,Spectrometer ,Chemistry ,010401 analytical chemistry ,Analytical technique ,021001 nanoscience & nanotechnology ,0104 chemical sciences ,qNMR, interlaboratory comparison ,Fruit and Vegetable Juice ,0210 nano-technology ,Biological system - Abstract
Nuclear Magnetic Resonance (NMR) is an analytical technique extensively used in almost every chemical laboratory for structural identification. This technique provides statistically equivalent signals in spite of using spectrometer with different hardware features and is successfully used for the traceability and quantification of analytes in food samples. Nevertheless, to date only a few internationally agreed guidelines have been reported on the use of NMR for quantitative analysis. The main goal of the present study is to provide a methodological pipeline to assess the reproducibility of NMR data produced for a given matrix by spectrometers from different manufacturers, with different magnetic field strengths, age and hardware configurations. The results have been analyzed through a sequence of chemometric tests to generate a community-built calibration system which was used to verify the performance of the spectrometers and the reproducibility of the predicted sample concentrations.
- Published
- 2020
61. A picoscale catalyst for hydrogen generation from NaBH4 for fuel cells
- Author
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Peña-Alonso, R., Sicurelli, A., Callone, E., Carturan, G., and Raj, R.
- Subjects
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FUEL cells , *HYDROGEN production , *CARBON nanotubes , *ELECTROCHEMISTRY - Abstract
Abstract: NaBH4, a safe and high energy density source of H2 for fuel cells, requires a catalyst for reliable hydrogen production. In this paper we show that Pt and Pd atoms, apparently dispersed elementally, on functionalized surfaces of carbon nanotubes (CNT) leads to the highest value for the figure of merit ( [NaBH4]−1) reported so far in the literature. This result was achieved with a 150μm thick CNT paper. Thinner paper produces even higher rates of hydrogen generation. The catalyst is robust, continuing to operate without degradation in performance for more than 20 cycles. The kinetic data are analyzed by a combination of first order and zero order reactions. The analysis provides a framework for predicting the performance of the catalyst for fuel cell applications. [Copyright &y& Elsevier]
- Published
- 2007
- Full Text
- View/download PDF
62. Structure of Starch–Sepiolite Bio-Nanocomposites: Effect of Processing and Matrix–Filler Interactions
- Author
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Daniele Bugnotti, Sara Dalle Vacche, Leandro Hernan Esposito, Emanuela Callone, Sara Fernanda Orsini, Riccardo Ceccato, Massimiliano D’Arienzo, Roberta Bongiovanni, Sandra Dirè, Alessandra Vitale, Bugnotti, D, Dalle Vacche, S, Esposito, L, Callone, E, Orsini, S, Ceccato, R, D’Arienzo, M, Bongiovanni, R, Dirè, S, and Vitale, A
- Subjects
CHIM/03 - CHIMICA GENERALE ED INORGANICA ,Polymers and Plastics ,crystalline structure ,nanocomposite ,plasticized starch ,bio-composite ,sepiolite filler ,yuca starch ,General Chemistry - Abstract
Sepiolite clay is a natural filler particularly suitable to be used with polysaccharide matrices (e.g., in starch-based bio-nanocomposites), increasing their attractiveness for a wide range of applications, such as packaging. Herein, the effect of the processing (i.e., starch gelatinization, addition of glycerol as plasticizer, casting to obtain films) and of the sepiolite filler amount on the microstructure of starch-based nanocomposites was investigated by SS-NMR (solid-state nuclear magnetic resonance), XRD (X-ray diffraction) and FTIR (Fourier-transform infrared) spectroscopy. Morphology, transparency and thermal stability were then assessed by SEM (scanning electron microscope), TGA (thermogravimetric analysis) and UV–visible spectroscopy. It was demonstrated that the processing method allowed to disrupt the rigid lattice structure of semicrystalline starch and thus obtain amorphous flexible films, with high transparency and good thermal resistance. Moreover, the microstructure of the bio-nanocomposites was found to intrinsically depend on complex interactions among sepiolite, glycerol and starch chains, which are also supposed to affect the final properties of the starch–sepiolite composite materials.
- Published
- 2023
63. Structural effects of TiO2 nanoparticles in photocurable ladder-like polysilsesquioxane nanocomposites
- Author
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Sandra Dirè, Emanuela Callone, Riccardo Ceccato, Francesco Parrino, Barbara Di Credico, Silvia Mostoni, Roberto Scotti, Massimiliano D’Arienzo, Dire, S, Callone, E, Ceccato, R, Parrino, F, Di Credico, B, Mostoni, S, Scotti, R, and D'Arienzo, M
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Biomaterials ,Ladder-like polysilsesquioxane ,Structural propertie ,XRD ,Materials Chemistry ,Ceramics and Composites ,TiO2 ,General Chemistry ,Methacrylate group ,Condensed Matter Physics ,NMR ,Electronic, Optical and Magnetic Materials - Abstract
Ladder-like polysilsesquioxanes (LPSQs) are characterized by a double-stranded siloxane backbone, whose chemical and structural properties depend on both the synthesis parameters and the nature of the organic side-chains. In the case of ladder-like (methacryloxypropyl) polysilsesquioxanes (LPMASQ), polymer matrices can be produced by exploiting the presence of photocurable methacrylate groups. Consequently, they can be used to prepare functional nanocomposites (NCs), either by blending with organic polymers such as polybutadiene or exploiting the inorganic fillers’ dispersion. Since the properties of LPMASQ-based NCs are strongly related to their structure, the structural changes of polymerized LPMASQ were investigated upon addition of low loadings of TiO2 nanoparticles (up to 3 wt%) by solid state nuclear magnetic resonance and X-ray diffraction. The filler addition leads to the reduction of the polymerization capacity of the LPMASQ organic side-chains. Moreover, a different organization of ladder chains has been highlighted, ascribable to the increase in fully condensed linear ladder units at the expenses of folded chains and defective structures. The methodological approach here adopted can be extended to other composite systems and may help to describe the properties at the filler-matrix interface, offering valuable hints for a better design of these materials. Graphical Abstract
- Published
- 2023
64. Silica hairy nanoparticles: a promising material for self-assembling processes
- Author
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Luca Giannini, Massimiliano D’Arienzo, Barbara Di Credico, Andreas Meyer, Roberto Scotti, Luciano Tadiello, Emanuela Callone, Simone Mascotto, Laura Tripaldi, Sandra Dirè, Tripaldi, L, Callone, E, D'Arienzo, M, Dirè, S, Giannini, L, Mascotto, S, Meyer, A, Scotti, R, Tadiello, L, and Di Credico, B
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chemistry.chemical_classification ,CHIM/03 - CHIMICA GENERALE ED INORGANICA ,Nanocomposite ,Materials science ,Morphology (linguistics) ,CHIM/07 - FONDAMENTI CHIMICI DELLE TECNOLOGIE ,Nanoparticle ,Nanotechnology ,General Chemistry ,Polymer ,Condensed Matter Physics ,silica, self-assembly, nanoparticles ,Polybutadiene ,chemistry ,Self assembling ,Particle ,Glass transition - Abstract
"Hairy" nanoparticles (HNPs), i.e. inorganic NPs functionalized with polymer chains, are promising building blocks for the synthesis of advanced nanocomposite (NC) materials having several technological applications. Recent evidence shows that HNPs self-organize in a variety of anisotropic structures, resulting in an improvement of the functional properties of the materials, in which are embedded. In this paper, we propose a three-step colloidal synthesis of spherical SiO2-HNPs, with controlled particle morphology and surface chemistry. In detail, the SiO2 core, synthesized by a modified Stöber method, was first functionalized with a short-chain amino-silane, which acts as an anchor, and then covered by maleated polybutadiene (PB), a rubbery polymer having low glass transition temperature, rarely considered until now. An extensive investigation by a multi-technique analysis demonstrates that the synthesis of SiO2-HNPs is simple, scalable, and potentially applicable to different kind of NPs and polymers. Morphological analysis shows the overall distribution of SiO2-HNPs with a certain degree of spatial organization, suggesting that the polymer coating induces a modification of NP-NP interactions. The role of the surface PB brushes in influencing the special arrangement of SiO2-HNPs was observed also in cis-1,4-polybutadiene (cis-PB), since the resulting NC exhibited the particle packing in "string-like" superstructures. This confirms the tendency of SiO2-HNPs to self-assemble and create alternative structures in polymer NCs, which may impart them peculiar functional properties.
- Published
- 2021
65. Decoration of silica and sepiolite surfaces with photoreversible coupling agent: a new route for producing multifunctional hybrid nanoparticles
- Author
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Sara Fernanda Orsini, Roberta Bongiovanni, Emanuela Callone, Laura Cipolla, Barbara Di Credico, Sandra Dirè, Silvia Mostoni, Roberto Nistico, Simona Petroni, Roberto Scotti, Massimiliano D'Arienzo, Orsini, S, Bongiovanni, R, Callone, E, Cipolla, L, DI CREDICO, B, Dirè, S, Mostoni, S, Nistico', R, Petroni, S, Scotti, R, and D'Arienzo, M
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silica ,sepiolite ,nanoparticle ,functionalization ,photoreversible unit - Published
- 2022
66. Synthesis and Characterization of Alkoxysilane-Bearing Photoreversible Cinnamic Side Groups: A Promising Building-Block for the Design of Multifunctional Silica Nanoparticles
- Author
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Sara Fernanda Orsini, Laura Cipolla, Simona Petroni, Sandra Dirè, Riccardo Ceccato, Emanuela Callone, Roberta Bongiovanni, Sara Dalle Vacche, Barbara Di Credico, Silvia Mostoni, Roberto Nisticò, Luisa Raimondo, Roberto Scotti, Massimiliano D’Arienzo, Orsini, S, Cipolla, L, Petroni, S, Dirè, S, Ceccato, R, Callone, E, Bongiovanni, R, Dalle Vacche, S, Di Credico, B, Mostoni, S, Nisticò, R, Raimondo, L, Scotti, R, and D'Arienzo, M
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molecule ,functionalized particles ,CHIM/03 - CHIMICA GENERALE ED INORGANICA ,irradiation ,photocycloaddition ,aromatic compound ,photoreversible crosslinking ,Surfaces and Interfaces ,Condensed Matter Physics ,cinnamic acid ,silica ,sepiolite ,Electrochemistry ,functionalization ,General Materials Science ,Spectroscopy - Abstract
The present study reports on the synthesis of a new alkoxysilane-bearing light-responsive cinnamyl group and its application as a surface functionalization agent for the development of SiO2 nanoparticles (NPs) with photoreversible tails. In detail, cinnamic acid (CINN) was activated with N-hydroxysuccinimide (NHS) to obtain the corresponding NHS-ester (CINN-NHS). Subsequently, the amine group of 3-aminopropyltriethoxysilane (APTES) was acylated with CINN-NHS leading to the generation of a novel organosilane, CINN-APTES, which was then exploited for decorating SiO2 NPs. The covalent bond to the silica surface was confirmed by solid state NMR, whereas thermogravimetric analysis unveiled a functionalization degree much higher compared to that achieved by a conventional double-step post-grafting procedure. In light of these intriguing results, the strategy was successfully extended to naturally occurring sepiolite fibers, widely employed as fillers in technological applications. Finally, a preliminary proof of concept of the photoreversibility of the obtained SiO2@CINN-APTES system has been carried out through UV diffuse reflectance. The overall outcomes prove the consistency and the versatility of the methodological protocol adopted, which appears promising for the design of hybrid NPs to be employed as building blocks for photoresponsive materials with the ability to change their molecular structure and subsequent properties when exposed to different light stimuli.
- Published
- 2022
67. Studying stearic acid interaction with ZnO/SiO2 nanoparticles with tailored morphology and surface features: A benchmark for better designing efficient ZnO-based curing activators
- Author
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Silvia Mostoni, Paola Milana, Massimiliano D'Arienzo, Sandra Dirè, Emanuela Callone, Cinzia Cepek, Silvia Rubini, Ayesha Farooq, Carmen Canevali, Barbara Di Credico, Roberto Scotti, Mostoni, S, Milana, P, D'Arienzo, M, Dirè, S, Callone, E, Cepek, C, Rubini, S, Farooq, A, Canevali, C, Di Credico, B, and Scotti, R
- Subjects
Surface interaction ,Process Chemistry and Technology ,Zinc oxide ,Materials Chemistry ,Ceramics and Composites ,Vulcanization ,Activator ,Surfaces, Coatings and Films ,Electronic, Optical and Magnetic Materials ,Stearic acid - Abstract
The interaction between activators (ZnO) and co-activators (stearic acid, SA) represents a key step in the vulcanization process, to generate Zn(II) intermediate complexes that enhance the reaction kinetic and promote the shortening of sulfur bridges, leading to highly cross-linked materials. To understand the influence of the structural, morphological and surface properties of ZnO in the reactivity with SA, in this work, pure ZnO nanoparticles (NPs) and ZnO NPs anchored on SiO2 (ZnO/SiO2) were prepared through soft chemistry techniques. Tailoring of morphology and surface features was accomplished through a fine control of the synthetic parameters, as demonstrated by the careful characterization of the activators. Then, the interaction of pure ZnO and ZnO/SiO2 activators with SA in the absence of rubber was investigated by using Differential Scanning Calorimetry (DSC). The occurrence of Zn(II)-SA complexes with different thermal stability and structural properties was assessed by a comprehensive thermogravimetric and spectroscopic survey. The generation and the chemical structure of these specific vulcanization intermediates was related to the peculiar characteristics of the ZnO/SiO2 systems and, in turn, to their ability in imparting faster kinetics and higher curing efficiency to isoprene rubber nanocomposites, compared to bare ZnO. These results, besides proposing a valid benchmark for achieving further insights on the interaction of stearic acid with activators, pave the way to provide specific protocols for a better design and implementation of ZnO-based materials able to effectively enhance the rubber vulcanization process, with significant economic and environmental advantages.
- Published
- 2022
68. TiO2 containing hybrid nanocomposites with active–passive oxygen scavenging capability
- Author
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Andreas Meyer, Roberto Scotti, Simone Mascotto, Riccardo Conta, Sandra Dirè, Massimiliano D’Arienzo, Barbara Di Credico, Emanuela Callone, Francesco Parrino, Parrino, F, D'Arienzo, M, Callone, E, Conta, R, Di Credico, B, Mascotto, S, Meyer, A, Scotti, R, and Dire, S
- Subjects
General Chemical Engineering ,Oxygen scavenging ,Infrared spectroscopy ,chemistry.chemical_element ,Photocatalytic energy transfer ,02 engineering and technology ,010402 general chemistry ,Photochemistry ,01 natural sciences ,Oxygen ,Industrial and Manufacturing Engineering ,law.invention ,chemistry.chemical_compound ,Polybutadiene ,law ,TiO ,Environmental Chemistry ,Electron paramagnetic resonance ,Nanocomposite ,Hybrid organic/inorganic material ,Singlet oxygen ,General Chemistry ,Ladder-like silsesquioxane ,021001 nanoscience & nanotechnology ,Fluorescence ,0104 chemical sciences ,chemistry ,Hydroxyl radical ,0210 nano-technology - Abstract
Ladder-like silsesquioxanes (SSQs) and TiO2 have been functionalized with methacryloyloxypropyl chains and embedded in a polybutadiene (PB) matrix giving rise to hybrid (organic–inorganic) nanocomposites (NCs) capable of acting as oxygen scavenging materials. The joint use of infrared spectroscopy, small-angle X-ray scattering, and permittivity measurements highlighted that the presence of TiO2, regardless of its modification, does not significantly alter the structure of the NCs, but just reduces the crosslinking degree and induces a local disorganization of the ladder-like SSQ stacks. The introduction of an optimum amount (0.5 wt%) of modified TiO2 within the polymeric matrix enhanced the oxygen uptake rate of ca. 70% with respect to the sole polymeric material. Moreover, the uptake kinetics changes from the first to second order with respect to the PB amount, clearly indicating different oxidation mechanisms. NCs containing modified TiO2 showed an oxygen uptake rate ranging from 30 to 60% higher than that achievable in the presence of bare TiO2. The superior activity of the materials containing modified TiO2 has been related to mechanistic aspects. Fluorescence and electron spin resonance spectroscopies allowed to underline the role of singlet oxygen within the polymeric matrix, although the known photochemical oxidation of PB and the TiO2 induced hydroxyl radical mediated oxidation cannot be excluded. These results open the route to highly efficient flexible oxygen scavenging materials for the protection of electronic devices such as organic based light emitting diodes, solar cells, and liquid crystal displays, which require high targets of protection from oxygen and water.
- Published
- 2021
69. Design of a Zn Single-Site Curing Activator for a More Sustainable Sulfur Cross-Link Formation in Rubber
- Author
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Barbara Di Credico, Massimiliano D’Arienzo, Roberto Scotti, Marzio Rancan, Sandra Dirè, A Susanna, Lidia Armelao, S Mostoni, Emanuela Callone, Raffaella Donetti, Mostoni, S, D’Arienzo, M, Di Credico, B, Armelao, L, Rancan, M, Dirè, S, Callone, E, Donetti, R, Susanna, A, and Scotti, R
- Subjects
rubber vulcanization ,Materials science ,ZnO, XPS, rubber vulcanization, Zn single-site curing activator, sustainability ,General Chemical Engineering ,rubber ,chemistry.chemical_element ,Zinc ,Zn single-site curing activator ,Industrial and Manufacturing Engineering ,Article ,law.invention ,chemistry.chemical_compound ,Natural rubber ,law ,XPS ,Isoprene ,Curing (chemistry) ,Cross-link ,zinc ,Vulcanization ,technology, industry, and agriculture ,General Chemistry ,sustainability ,Silane ,chemistry ,Chemical engineering ,single site ,visual_art ,ZnO ,visual_art.visual_art_medium ,Leaching (metallurgy) - Abstract
ZnO is a worldwide used activator for a rubber vulcanization process, which promotes fast curing kinetics and high cross-linking densities of rubber nanocomposites (NCs). However, its extended use together with leaching phenomena occurring during the production and life cycle of rubber products, especially tires, entails potential environmental risks, as ecotoxicity toward aquatic organisms. Pushed by this issue, a novel activator was developed, which introduces highly dispersed and active zinc species in the vulcanization process, reducing the amount of employed ZnO and keeping high the curing efficiency. The activator is constituted by Zn(II) single sites, anchored on the surface of SiO2 nanoparticles (NPs) through the coordination with functionalizing amino silane groups. It behaves as a double-function material, acting at the same time as a rubber reinforcing filler and a curing activator. The higher availability and reactivity of the single-site Zn(II) centers toward curative agents impart faster kinetics and higher efficiency to the vulcanization process of silica/isoprene NCs, compared to conventionally used ZnO activators. Moreover, the NCs show a high cross-linking degree and improved dynamic mechanical properties, despite the remarkably lower amount of zinc employed than that normally used for rubber composites in tires. Finally, the structural stability of Zn(II) single sites during the curing reactions and in the final materials may represent a turning point toward the elimination of zinc leaching phenomena.
- Published
- 2021
70. SiO2/Ladder-Like Polysilsesquioxanes Nanocomposite Coatings: Playing with the Hybrid Interface for Tuning Thermal Properties and Wettability
- Author
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Massimiliano D’Arienzo, Giuseppe Trusiano, Sara Orsini, Roberta Maria Bongiovanni, Emanuela Callone, Sara Dalle Vacche, R Scotti, Carlo Antonini, Barbara Di Credico, E Cobani, Sandra Dirè, Francesco Parrino, D'Arienzo, M, Dir(`(e)), S, Cobani, E, Orsini, S, DI CREDICO, B, Antonini, C, Callone, E, Parrino, F, Dalle Vacche, S, Trusiano, G, Bongiovanni, R, and Scotti, R
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Materials science ,Thermal resistance ,engineering.material ,interfaces ,chemistry.chemical_compound ,Coating ,nanocomposites ,hybrid materials ,Materials Chemistry ,Surface roughness ,Hybrid material ,silsesquioxanes ,hydrophobic properties ,coating ,Nanocomposite ,Surfaces and Interfaces ,Hydrophobic propertie ,Interface ,Silsesquioxane ,Surfaces, Coatings and Films ,chemistry ,Chemical engineering ,lcsh:TA1-2040 ,engineering ,Surface modification ,Wetting ,lcsh:Engineering (General). Civil engineering (General) - Abstract
The present study explores the exploitation of ladder-like polysilsesquioxanes (PSQs) bearing reactive functional groups in conjunction with SiO2 nanoparticles (NPs) to produce UV-curable nanocomposite coatings with increased hydrophobicity and good thermal resistance. In detail, a medium degree regular ladder-like structured poly (methacryloxypropyl) silsesquioxane (LPMASQ) and silica NPs, either naked or functionalized with a methacrylsilane (SiO2@TMMS), were blended and then irradiated in the form of a film. Material characterization evidenced significant modifications of the structural organization of the LPMASQ backbone and, in particular, a rearrangement of the silsesquioxane chains at the interface upon introduction of the functionalized silica NPs. This leads to remarkable thermal resistance and enhanced hydrophobic features in the final nanocomposite. The results suggest that the adopted strategy, in comparison with mostly difficult and expensive surface modification and structuring protocols, may provide tailored functional properties without modifying the surface roughness or the functionalities of silsesquioxanes, but simply tuning their interactions at the hybrid interface with silica fillers.
- Published
- 2020
71. Tailoring the Dielectric and Mechanical Properties of Polybutadiene Nanocomposites by Using Designed Ladder-like Polysilsesquioxanes
- Author
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Emanuela Callone, Davide Rovera, Alessandro Pegoretti, Roberto Scotti, Sandra Dirè, Massimiliano D’Arienzo, Veronica Masneri, Barbara Di Credico, Fabio Ziarelli, Simone Mascotto, D’Arienzo, M, Diré, S, Masneri, V, Rovera, D, Di Credico, B, Callone, E, Mascotto, S, Pegoretti, A, Ziarelli, F, and Scotti, R
- Subjects
Materials science ,02 engineering and technology ,Dielectric ,010402 general chemistry ,Methacrylate ,01 natural sciences ,chemistry.chemical_compound ,Polybutadiene ,mechanical propertie ,General Materials Science ,dielectric propertie ,chemistry.chemical_classification ,Nanocomposite ,nanocomposite ,Small-angle X-ray scattering ,hybrid material ,Polymer ,021001 nanoscience & nanotechnology ,Silsesquioxane ,0104 chemical sciences ,silsesquioxanes ,chemistry ,Chemical engineering ,interface ,0210 nano-technology ,Hybrid material - Abstract
In this study, the preparation of polybutadiene/polysilsesquioxane nanocomposites (NCs) having tunable thermomechanical and dielectric properties is reported. This was achieved by using different amounts of a filler consisting of a silsesquioxane with a defined ladder-like molecular structure (LPMASQ) bearing reactive methacrylate functionalities. In detail, solid-state nuclear magnetic resonance (NMR) investigation revealed that an increasing amount of filler leads to a progressive homopolymerization of LPMASQ units resulting in the generation of domains in the composites, which induce a kind of polymer chain confinement in proximity of the hybrid interface. The evolution of the molecular organization of the inorganic nanobuilding blocks as a function of their concentration has been highlighted also by small-angle X-ray scattering (SAXS) experiments. The gradual assembly of LPMASQ units gives rise to peculiar dielectric properties along with enhanced thermal and mechanical stability of the final NCs, thus supplying suitable materials for applications in high performance dielectrics. Furthermore, these outcomes support the idea that a careful control of the molecular architecture and organization of the silsesquioxanes in a polymer matrix allows to simultaneously modulate two or more distinct functional features of polymer NCs
- Published
- 2018
72. Unveiling the hybrid interface in polymer nanocomposites enclosing silsesquioxanes with tunable molecular structure: Spectroscopic, thermal and mechanical properties
- Author
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Massimiliano D’Arienzo, Matteo Redaelli, Alessandro Pegoretti, Emanuela Callone, Evgeny Borovin, Sandra Dirè, Roberto Scotti, Franca Morazzoni, Barbara Di Credico, D'Arienzo, M, Dirè, S, Redaelli, M, Borovin, E, Callone, E, Di Credico, B, Morazzoni, F, Pegoretti, A, and Scotti, R
- Subjects
Materials science ,Polymer nanocomposite ,Surfaces, Coatings and Film ,Nanotechnology ,02 engineering and technology ,010402 general chemistry ,01 natural sciences ,Biomaterials ,chemistry.chemical_compound ,Colloid and Surface Chemistry ,Polybutadiene ,Polymer chemistry ,Hybrid material ,chemistry.chemical_classification ,Nanocomposite ,Silsesquioxane ,Electronic, Optical and Magnetic Material ,Nanobuilding block ,Compatibilization ,Dynamic mechanical analysis ,Polymer ,Interface ,021001 nanoscience & nanotechnology ,Biomaterial ,0104 chemical sciences ,Surfaces, Coatings and Films ,Electronic, Optical and Magnetic Materials ,chemistry ,Siloxane ,0210 nano-technology ,Mechanical propertie - Abstract
Organic–inorganic nanobuilding blocks (NBBs) based on silsesquioxanes (SSQs) have potential applications as nanofillers, thermal stabilizers, and rheological modifiers, which can improve thermomechanical properties of polymer hosts. The possibility to tune both siloxane structure and pendant groups can promote compatibilization and peculiar interactions with a plethora of polymers. However, the control on SSQs molecular architecture and functionalities is usually delicate and requires careful synthetic details. Moreover, investigating the influence of NBBs loading and structure on the hybrid interface and, in turn, on the polymer chains mobility and mechanical properties, may be challenging, especially for low-loaded materials. Herein, we describe the preparation and characterization of polybutadiene (PB) nanocomposites using as innovative fillers thiol-functionalized SSQs nanobuilding blocks (SH-NBBs), with both tailorable functionality and structure. Swelling experiments and, more clearly, solid-state NMR, enlightened a remarkable effect of SH-NBBs on the molecular structure and mobility of the polymeric chains, envisaging the occurrence of chemical interactions at the hybrid interface. Finally, thermal and DMTA analyses revealed that nanocomposites, even containing very low filler loadings (i.e. 1, 3 wt%), exhibited enhanced thermomechanical properties, which seem to be connected not only to the loading, but also to the peculiar cage or ladder-like architecture of SH-NBBs.
- Published
- 2018
73. Resistive CO gas sensors based on In2O3 and InSnO x nanopowders synthesized via starch-aided sol–gel process for automotive applications
- Author
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Neri, G., Bonavita, A., Micali, G., Rizzo, G., Callone, E., and Carturan, G.
- Subjects
- *
THIN films , *CHEMICAL reactions , *POISONOUS gases , *DETECTORS - Abstract
Abstract: Pure and Sn-doped In2O3 nanopowders have been synthesized by a starch-aided sol–gel process. A detailed characterization by means of TEM and HRTEM, TG–MS, XRD and 119Sn solid-state NMR analysis has been carried out. It has shown that the grains of the samples as-synthesized and dried at 120°C are in the nanometer range. Moreover, on the Sn-doped In2O3 sample, the homogeneous distribution of the dopant with no segregation phase effects has been demonstrated. The thermal treatment at 550°C induced an increase of grain size up to about 30nm and of crystallinity. The behaviour of the resistive gas sensors based on the synthesized nanopowders in the monitoring of carbon monoxide for automotive applications has been evaluated. Electrical and sensing tests have been performed on the sensor devices in a thick film configuration depositing pure and Sn-doped In2O3 nanopowders by screen-printing over a ceramic substrate. The results have been discussed in relation to the chemical and microstructural properties of the synthesized nanopowders. The good sensing behaviour of these samples has been associated with their special features such as very small grains and high oxygen vacancies due to the peculiar reductive character of starch pyrolysis. [Copyright &y& Elsevier]
- Published
- 2008
- Full Text
- View/download PDF
74. Size-controlled self-assembly of anisotropic sepiolite fibers in rubber nanocomposites
- Author
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Luciano Tadiello, Franca Morazzoni, Barbara Di Credico, Emanuela Callone, Lucia Conzatti, E Cobani, Sandra Dirè, T Hanel, Davide Cristofori, Luca Giannini, Paola Stagnaro, Massimiliano D’Arienzo, Roberto Scotti, Di Credico, B, Cobani, E, Callone, E, Conzatti, L, Cristofori, D, D'Arienzo, M, Dirã, S, Giannini, L, Hanel, T, Scotti, R, Stagnaro, P, Tadiello, L, and Morazzoni, F
- Subjects
Polymer nanocomposite ,Composite number ,Sepiolite ,020101 civil engineering ,02 engineering and technology ,0201 civil engineering ,Natural rubber ,Geochemistry and Petrology ,Polymer chemistry ,Organoclay ,Composite material ,chemistry.chemical_classification ,Filler networking ,Nanocomposite ,Geology ,Polymer ,Self-assembly ,021001 nanoscience & nanotechnology ,Rubber nanocomposite ,chemistry ,visual_art ,Nanofiber ,visual_art.visual_art_medium ,0210 nano-technology - Abstract
The development of advanced polymer nanocomposites requires a strong filler-polymer interfacial interaction and an optimal filler nanodispersion. The incorporation of the clays into a polymer matrix frequently does not improve the composite mechanical properties, owing to both poor dispersion and macroscopic particle dimensions. In this work, pristine and organically-modified sepiolites (Sep) were structurally modified by an acid treatment, which provides nano-sized sepiolite (NS-Sep) fibers with reduced particle size and increased silanol groups on the surface layer. NS-Sep fibers were used to prepare styrene-butadiene rubber nanocomposites with enhanced mechanical properties. Dynamic-mechanical analysis of clay polymer nanocomposites demonstrated that the NS-Sep fibers provided an excellent balance between reinforcing and hysteretic behavior, compared to the large-sized pristine Sep and isotropic silica. This was related to the enhanced interfacial chemical interaction between NS-Sep and rubber, as well as to the size and self-assembly of anisotropic nanofibers to form filler network structures, as supported by transmission electron microscopy analysis. The preparation of nanocomposites, based on Sep nanofibers obtained by a simple and versatile acid treatment, can thus be considered an alternative approach for the designing of advanced clay polymer nanocomposites.
- Published
- 2018
75. Hybrid SiO2@POSS nanofiller: a promising reinforcing system for rubber nanocomposites
- Author
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Luciano Tadiello, Roberto Scotti, Luca Giannini, Emanuela Callone, Lucia Conzatti, Massimiliano D’Arienzo, Franca Morazzoni, Stefano Polizzi, Ilaria Schizzi, Matteo Redaelli, Sandra Dirè, Barbara Di Credico, D'Arienzo, M, Redaelli, M, Callone, E, Conzatti, L, DI CREDICO, B, Dirè, S, Giannini, L, Polizzi, S, Schizzi, I, Scotti, R, Tadiello, L, and Morazzoni, F
- Subjects
Filler (packaging) ,Materials science ,Hybrid nanocomposites, POSS ,POLYMER NANOCOMPOSITES, SURFACE MODIFICATION, BUTADIENE RUBBER, POSS, NANOPARTICLES, POLYPROPYLENE, METHACRYLATE, MORPHOLOGY, PARTICLES ,POLYMER NANOCOMPOSITES ,METHACRYLATE ,Composite number ,rubber ,Modulus ,02 engineering and technology ,010402 general chemistry ,01 natural sciences ,Nanocages ,Natural rubber ,nanocomposites ,morphology ,NANOPARTICLES ,Materials Chemistry ,PARTICLES ,General Materials Science ,SURFACE MODIFICATION ,Composite material ,POLYPROPYLENE ,Settore CHIM/02 - Chimica Fisica ,POSS ,chemistry.chemical_classification ,reinforcement ,Nanocomposite ,Polymer ,021001 nanoscience & nanotechnology ,Grafting ,0104 chemical sciences ,chemistry ,visual_art ,BUTADIENE RUBBER ,visual_art.visual_art_medium ,0210 nano-technology - Abstract
A novel hybrid nanofiller, SiO2@POSS, where the silica nanoparticles (NPs) and the POSS belong to the same functional structure, has been synthesized by grafting different loadings of OctaMethacrylPOSS onto silanized commercial SiO2, using a surface reaction mediated by dicumylperoxide (DCP). The peroxide, besides anchoring the nanocages onto the silica surface, ensures the presence of methacryl functionalities in the final structure, which are still available for cross-linking reactions with a polymer host. The hybrid SiO2@POSS NPs were used to prepare, by ex situ blending, SBR nanocomposites. The dynamic-mechanical analysis performed on the cured SBR/SiO2@ POSS composites indicated that the presence of POSS induces a remarkable increase of modulus either at low or at high strain, and a considerable decrease of hysteresis. This has been associated with the peculiar hybrid structure of the SiO2@POSS filler, in which silica NP aggregates are partially interconnected and surrounded by a thin shell of POSS nanounits which, thanks to their high number of reactive functionalities, promote the formation of "sticky regions'' among the silica aggregates and, consequently, a tight filler network wherein rubber is immobilized. This grants a relevant reinforcement and increased hysteretic properties, suggesting SiO2@POSS as a promising filler system for decreasing the energy loss under strain and for leading to a potential reduction of filler utilization in rubber composite formulations.
- Published
- 2017
76. ZnO nanoparticles anchored to silica filler. A curing accelerator for isoprene rubber composites
- Author
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Lidia Armelao, Franca Morazzoni, B Di Credico, Emanuela Callone, Roberto Scotti, Luca Giannini, Massimiliano D’Arienzo, Sandra Dirè, A Susanna, T Hanel, Susanna, A, Armelao, L, Callone, E, Dirè, S, D'Arienzo, M, DI CREDICO, B, Giannini, L, Hanel, T, Morazzoni, F, and Scotti, R
- Subjects
Materials science ,General Chemical Engineering ,Nanoparticle ,chemistry.chemical_element ,Zinc ,Sol–gel ,Industrial and Manufacturing Engineering ,law.invention ,chemistry.chemical_compound ,Natural rubber ,law ,Curing accelerator ,Polymer chemistry ,Zinc oxide ,Environmental Chemistry ,Chemical Engineering (all) ,Curing (chemistry) ,Isoprene ,Sol-gel ,Chemistry (all) ,Vulcanization ,General Chemistry ,chemistry ,Chemical engineering ,Rubber nanocomposite ,Silica filler ,Covalent bond ,visual_art ,visual_art.visual_art_medium ,Rubber nanocomposite, Zinc oxide, Silica filler, Sol–gel, Curing accelerator, Vulcanization - Abstract
ZnO nanoparticles (NPs) were anchored to SiO 2 spherical nanoparticles by hydrolysis and condensation of Zn(CH 3 COO) 2 in the presence of SiO 2 . The ZnO/SiO 2 NPs were then blended with isoprene rubber. The immobilization of ZnO NPs on the silica surface, due to covalent Si O Zn bonds provides a homogeneous dispersion of zinc in the rubber matrix and increases the accessibility of the curative reactants to Zn 2+ ions. This improves the efficiency of the rubber curing and reduces the amount of used ZnO.
- Published
- 2015
77. Polymeric Hydrogels for Intervertebral Disc Replacement/Integration: Playing with the Chemical Composition for Tuning Shear Behavior and Hydrophilicity.
- Author
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Maniglio D, Bissoli E, Callone E, Dirè S, and Motta A
- Abstract
Damages to the intervertebral disc (IVD) due to improper loading or degeneration result in back pain, which is a common disease affecting an increasing number of patients. Different strategies for IVD remediation have been developed, from surgical treatment to disc replacement, by using both metallic and non-metallic materials. Hydrogels are very attractive materials due to their ability to simulate the properties of many soft tissues; moreover, their chemical composition can be varied in order to assure performances similar to the natural disc. In particular, for the replacement of the IVD outer ring, namely, the anulus fibrosus , the shear properties are of paramount importance. In this work, we produced hydrogels through the photo-induced crosslinking of different mixtures composed of two hydrophilic monofunctional and difunctional polymers, namely, poly(ethyleneglycol) methyl ether methacrylate (PEGMEMA) and poly(ethyleneglycol) dimethacrylate (PEGDMA), together with a hydrophobic molecule, i.e., tert-butyl acrylate (tBA). By changing the ratio among the precursors, we demonstrated the tunability of both the shear properties and hydrophilicity. The structural properties of hydrogels were studied by solid-state nuclear magnetic resonance (NMR). These experiments provided insights on both the structure and molecular dynamics of polymeric networks and, together with information obtained by differential scanning calorimetry (DSC), allowed for correlating the physical properties of the hydrogels with their chemical composition.
- Published
- 2023
- Full Text
- View/download PDF
78. Ladder-like Poly(methacryloxypropyl) silsesquioxane-Al 2 O 3 -polybutadiene Flexible Nanocomposites with High Thermal Conductivity.
- Author
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Mingarelli P, Romeo C, Callone E, Fredi G, Dorigato A, D'Arienzo M, Parrino F, and Dirè S
- Abstract
Ladder-like poly(methacryloxypropyl)-silsesquioxanes (LPMASQ) are photocurable Si-based gels characterized by a double-stranded structure that ensures superior thermal stability and mechanical properties than common organic polymers. In this work, these attractive features were exploited to produce, in combination with alumina nanoparticles (NPs), both unmodified and functionalized with methacryloxypropyl-trimethoxysilane (MPTMS), LPMASQ/Al
2 O3 composites displaying remarkable thermal conductivity. Additionally, we combined LPMASQ with polybutadiene (PB) to produce hybrid nanocomposites with the addition of functionalized Al2 O3 NPs. The materials underwent thermal stability, structural, and morphological evaluations via thermogravimetric analysis (TGA), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDXS), Fourier transform infrared spectroscopy (FTIR), and solid-state nuclear magnetic resonance (NMR). Both blending PB with LPMASQ and surface functionalization of nanoparticles proved to be effective strategies for incorporating a higher ceramic filler amount in the matrices, resulting in significant increases in thermal conductivity. Specifically, a 113.6% increase in comparison to the bare matrix was achieved at relatively low filler content (11.2 vol%) in the presence of 40 wt% LPMASQ. Results highlight the potential of ladder-like silsesquioxanes in the field of thermally conductive polymers and their applications in heat dissipation for flexible electronic devices.- Published
- 2023
- Full Text
- View/download PDF
79. Amino-Alcohol Organic-Inorganic Hybrid Sol-Gel Materials Based on an Epoxy Bicyclic Silane: Synthesis and Characterization.
- Author
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Sousa RPCL, Figueira RB, Callone E, Dirè S, Costa SPG, and Raposo MMM
- Abstract
Organic-inorganic hybrids (OIHs) are a type of material that can be obtained using the sol-gel process and has the advantages of organic and inorganic moieties in a single material. Polyetheramines have been widely used in the preparation of this type of material, particularly in combination with epoxy-based alkoxysilanes. Nevertheless, epoxyciclohexylethyltrimethoxysilane (ECHETMS) is a promising alkoxysilane with an epoxy terminal group that is quite unexplored. In this work, four novel OIH materials were synthesized using the sol-gel method. The OIHs were based on Jeffamines
® of different molecular weights (D-230, D-400, ED-600, and ED-900), together with ECHETMS. The materials were characterized using multinuclear solid state NMR, FTIR, BET, UV/Vis spectroscopy, EIS, and TGA. The influence of the Jeffamine molecular weight and the suitability of these materials to act as a supporting matrix for heteroaromatic probes were assessed and discussed. The materials show interesting properties in order to be applied in a wide range of sensing applications.- Published
- 2023
- Full Text
- View/download PDF
80. Interplay between coordination sphere engineering and properties of nickel diketonate-diamine complexes as vapor phase precursors for the growth of NiO thin films.
- Author
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Benedet M, Barreca D, Fois E, Seraglia R, Tabacchi G, Roverso M, Pagot G, Invernizzi C, Gasparotto A, Heidecker AA, Pöthig A, Callone E, Dirè S, Bogialli S, Di Noto V, and Maccato C
- Abstract
NiO-based films and nanostructured materials have received increasing attention for a variety of technological applications. Among the possible strategies for their fabrication, atomic layer deposition (ALD) and chemical vapor deposition (CVD), featuring manifold advantages of technological interest, represent appealing molecule-to-material routes for which a rational precursor design is a critical step. In this context, the present study is focused on the coordination sphere engineering of three heteroleptic Ni(II) β-diketonate-diamine adducts of general formula [NiL
2 TMEDA] [L = 1,1,1-trifluoro-2,4-pentanedionate (tfa), 2,2-dimethyl-6,6,7,7,8,8,8-heptafluoro-3,5-octanedionate (fod) or 2,2,6,6-tetramethyl-3,5-heptanedionate (thd), and TMEDA = N , N , N ', N '-tetramethylethylenediamine]. Controlled variations in the diketonate structure are pursued to investigate the influence of steric hindrance and fluorination degree on the chemico-physical characteristics of the compounds. A multi-technique investigation supported by density functional calculations highlights that all complexes are air-insensitive and monomeric and that their thermal properties and fragmentation patterns are directly dependent on functional groups in the diketonate ligands. Preliminary thermal CVD experiments demonstrate the precursors' suitability for the obtainment of NiO films endowed with flat and homogeneous surfaces, paving the way to future implementation for CVD end-uses.- Published
- 2023
- Full Text
- View/download PDF
81. Modeling a Dynamic Printability Window on Polysaccharide Blend Inks for Extrusion Bioprinting.
- Author
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Perin F, Spessot E, Famà A, Bucciarelli A, Callone E, Mota C, Motta A, and Maniglio D
- Subjects
- Hyaluronic Acid, Alginates, Printing, Three-Dimensional, Ink, Bioprinting methods
- Abstract
Extrusion-based bioprinting is one of the most widespread technologies due to its affordability, wide range of processable materials, and ease of use. However, the formulation of new inks for this technique is based on time-consuming trial-and-error processes to establish the optimal ink composition and printing parameters. Here, a dynamic printability window was modeled for the assessment of the printability of polysaccharide blend inks of alginate and hyaluronic acid with the intent to build a versatile predictive tool to speed up the testing procedures. The model considers both the rheological properties of the blends (viscosity, shear thinning behavior, and viscoelasticity) and their printability (in terms of extrudability and the ability of forming a well-defined filament and detailed geometries). By imposing some conditions on the model equations, it was possible to define empirical bands in which the printability is ensured. The predictive capability of the built model was successfully verified on an untested blend of alginate and hyaluronic acid chosen to simultaneously optimize the printability index and minimize the size of the deposited filament.
- Published
- 2023
- Full Text
- View/download PDF
82. Structure of Starch-Sepiolite Bio-Nanocomposites: Effect of Processing and Matrix-Filler Interactions.
- Author
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Bugnotti D, Dalle Vacche S, Esposito LH, Callone E, Orsini SF, Ceccato R, D'Arienzo M, Bongiovanni R, Dirè S, and Vitale A
- Abstract
Sepiolite clay is a natural filler particularly suitable to be used with polysaccharide matrices (e.g., in starch-based bio-nanocomposites), increasing their attractiveness for a wide range of applications, such as packaging. Herein, the effect of the processing (i.e., starch gelatinization, addition of glycerol as plasticizer, casting to obtain films) and of the sepiolite filler amount on the microstructure of starch-based nanocomposites was investigated by SS-NMR (solid-state nuclear magnetic resonance), XRD (X-ray diffraction) and FTIR (Fourier-transform infrared) spectroscopy. Morphology, transparency and thermal stability were then assessed by SEM (scanning electron microscope), TGA (thermogravimetric analysis) and UV-visible spectroscopy. It was demonstrated that the processing method allowed to disrupt the rigid lattice structure of semicrystalline starch and thus obtain amorphous flexible films, with high transparency and good thermal resistance. Moreover, the microstructure of the bio-nanocomposites was found to intrinsically depend on complex interactions among sepiolite, glycerol and starch chains, which are also supposed to affect the final properties of the starch-sepiolite composite materials.
- Published
- 2023
- Full Text
- View/download PDF
83. Synthesis and Characterization of Alkoxysilane-Bearing Photoreversible Cinnamic Side Groups: A Promising Building-Block for the Design of Multifunctional Silica Nanoparticles.
- Author
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Orsini SF, Cipolla L, Petroni S, Dirè S, Ceccato R, Callone E, Bongiovanni R, Dalle Vacche S, Di Credico B, Mostoni S, Nisticò R, Raimondo L, Scotti R, and D'Arienzo M
- Subjects
- Silicon Dioxide chemistry, Propylamines chemistry, Nanoparticles chemistry, Multifunctional Nanoparticles
- Abstract
The present study reports on the synthesis of a new alkoxysilane-bearing light-responsive cinnamyl group and its application as a surface functionalization agent for the development of SiO
2 nanoparticles (NPs) with photoreversible tails. In detail, cinnamic acid (CINN) was activated with N -hydroxysuccinimide (NHS) to obtain the corresponding NHS-ester (CINN-NHS). Subsequently, the amine group of 3-aminopropyltriethoxysilane (APTES) was acylated with CINN-NHS leading to the generation of a novel organosilane, CINN-APTES, which was then exploited for decorating SiO2 NPs. The covalent bond to the silica surface was confirmed by solid state NMR, whereas thermogravimetric analysis unveiled a functionalization degree much higher compared to that achieved by a conventional double-step post-grafting procedure. In light of these intriguing results, the strategy was successfully extended to naturally occurring sepiolite fibers, widely employed as fillers in technological applications. Finally, a preliminary proof of concept of the photoreversibility of the obtained SiO2 @CINN-APTES system has been carried out through UV diffuse reflectance. The overall outcomes prove the consistency and the versatility of the methodological protocol adopted, which appears promising for the design of hybrid NPs to be employed as building blocks for photoresponsive materials with the ability to change their molecular structure and subsequent properties when exposed to different light stimuli.- Published
- 2022
- Full Text
- View/download PDF
84. Barium Titanate Functionalization with Organosilanes: Effect on Particle Compatibility and Permittivity in Nanocomposites.
- Author
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Zamperlin N, Bottacini A, Callone E, Pegoretti A, Fontana M, and Dirè S
- Subjects
- Barium, Dimethylpolysiloxanes, Elastomers, Laurates, Titanium, Nanocomposites, Organosilicon Compounds
- Abstract
Barium titanate (BT) recently gained new interest in the preparation of dielectric and piezoelectric lead-free materials for applications in sensors, electronics, energy harvesting and storage fields. Barium titanate nanocomposites can achieve attractive performance, provided that the compatibility between ceramic particles and polymeric matrices is enhanced to the benefit of the physical properties of the final composite. Tuning the particle-matrix interface through particle functionalization represents a viable solution. In this work, surface functionalization of BT nanoparticles (NPs), obtained by hydrothermal synthesis, with 3-glycidyloxypropyltrimethoxysilane, 2-[(acetoxy(polyethyleneoxy)propyl]triethoxysilane and triethoxysilylpropoxy(polyethyleneoxy)dodecanoate, was performed after optimizing the hydroxylation process of the NPs to improve their surface reactivity and increase the yield of grafting. Solid-state nuclear magnetic resonance and thermogravimetric analysis were used to quantify the molecules grafted onto the ceramic nanoparticles. Both bare and functionalized particles were employed in the realization of epoxy- and polydimethylsiloxane (PDMS)-based nanocomposites. Functionalization was proven to be beneficial for particle dispersibility and effective for particle alignment in the PDMS matrix. Moreover, the dielectric constant measurements revealed the potential of PDMS-based nanocomposites for applications in the field of dielectric elastomers.
- Published
- 2022
- Full Text
- View/download PDF
85. Silica hairy nanoparticles: a promising material for self-assembling processes.
- Author
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Tripaldi L, Callone E, D'Arienzo M, Dirè S, Giannini L, Mascotto S, Meyer A, Scotti R, Tadiello L, and Di Credico B
- Abstract
"Hairy" nanoparticles (HNPs), i.e. inorganic NPs functionalized with polymer chains, are promising building blocks for the synthesis of advanced nanocomposite (NC) materials having several technological applications. Recent evidence shows that HNPs self-organize in a variety of anisotropic structures, resulting in an improvement of the functional properties of the materials, in which are embedded. In this paper, we propose a three-step colloidal synthesis of spherical SiO
2 -HNPs, with controlled particle morphology and surface chemistry. In detail, the SiO2 core, synthesized by a modified Stöber method, was first functionalized with a short-chain amino-silane, which acts as an anchor, and then covered by maleated polybutadiene (PB), a rubbery polymer having low glass transition temperature, rarely considered until now. An extensive investigation by a multi-technique analysis demonstrates that the synthesis of SiO2 -HNPs is simple, scalable, and potentially applicable to different kind of NPs and polymers. Morphological analysis shows the overall distribution of SiO2 -HNPs with a certain degree of spatial organization, suggesting that the polymer coating induces a modification of NP-NP interactions. The role of the surface PB brushes in influencing the special arrangement of SiO2 -HNPs was observed also in cis -1,4-polybutadiene ( cis -PB), since the resulting NC exhibited the particle packing in "string-like" superstructures. This confirms the tendency of SiO2 -HNPs to self-assemble and create alternative structures in polymer NCs, which may impart them peculiar functional properties.- Published
- 2021
- Full Text
- View/download PDF
86. Facile preparation of a cobalt diamine diketonate adduct as a potential vapor phase precursor for Co 3 O 4 films.
- Author
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Klotzsche M, Barreca D, Bigiani L, Seraglia R, Gasparotto A, Vanin L, Jandl C, Pöthig A, Roverso M, Bogialli S, Tabacchi G, Fois E, Callone E, Dirè S, and Maccato C
- Abstract
Co3O4 thin films and nanosystems are implemented in a broad range of functional systems, including gas sensors, (photo)catalysts, and electrochemical devices for energy applications. In this regard, chemical vapor deposition (CVD) is a promising route for the fabrication of high-quality films in which the precursor choice plays a key role in the process development. In this work, a heteroleptic cobalt complex bearing fluorinated diketonate ligands along with a diamine moiety [Co(tfa)2·TMEDA; tfa = 1,1,1-trifluoro-2,4-pentanedionate and TMEDA = N,N,N',N'-tetramethylethylenediamine] is investigated as a potential Co molecular precursor for the CVD of Co3O4 systems. For the first time, the compound is characterized by crystal structure determination and comprehensive analytical studies, focusing also on its thermal properties and fragmentation patterns, important figures of merit for a CVD precursor. The outcomes of this investigation, accompanied by detailed theoretical studies, highlight its very favorable properties for CVD applications. In fact, growth experiments under oxygen atmospheres containing water vapor revealed the suitability of Co(tfa)2·TMEDA for the fabrication of high-quality, phase-pure Co3O4 thin films. The versatility of the proposed strategy in tailoring Co3O4 structural/morphological features highlights its potential to obtain multi-functional films with controllable properties for a variety of eventual technological end-uses.
- Published
- 2021
- Full Text
- View/download PDF
87. A novel and selective silk fibroin fragmentation method.
- Author
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Agostinacchio F, Maniglio D, Callone E, Migliaresi C, Dirè S, and Motta A
- Subjects
- Animals, Protein Structure, Secondary, Silk, Tissue Engineering, Bombyx, Fibroins
- Abstract
In the tissue-engineering field silk fibroin can be tailored to the target applications by modifying its secondary structure and molecular weight, and functionalizing the molecule with specific active groups linked to the amino acid side chains. To better tune the silk fibroin molecular weight and structural properties, we propose the creation of a lower molecular weight fibroin-derived material through a selective and tunable enzymatic attack on the fibroin chain. Cleavage at specific amino acid sites leads to precise silk fibroin fragmentation and, thus, lower molecular weight materials whose length and properties can be tuned with the enzyme concentration. The cleavage increased the presence of free amino groups, hence reactivity, and aqueous solutions of the resulting polymer remained stable for up to seven days. Films of fragmented fibroin were prepared and characterized, demonstrating that the fragmentation did not affect β-sheet formation after methanol treatment, but differences were detected after the water-vapor annealing process, confirmed by structural and thermal analyses. The adopted fragmentation method is fast, controllable and precise, allowing the creation of a silk-derived material class that is stable in water, with a tunable molecular weight and secondary structure rearrangements, and is thus a versatile tool for the further tunability and modulation of bioengineered constructs.
- Published
- 2021
- Full Text
- View/download PDF
88. Design of a Zn Single-Site Curing Activator for a More Sustainable Sulfur Cross-Link Formation in Rubber.
- Author
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Mostoni S, D'Arienzo M, Di Credico B, Armelao L, Rancan M, Dirè S, Callone E, Donetti R, Susanna A, and Scotti R
- Abstract
ZnO is a worldwide used activator for a rubber vulcanization process, which promotes fast curing kinetics and high cross-linking densities of rubber nanocomposites (NCs). However, its extended use together with leaching phenomena occurring during the production and life cycle of rubber products, especially tires, entails potential environmental risks, as ecotoxicity toward aquatic organisms. Pushed by this issue, a novel activator was developed, which introduces highly dispersed and active zinc species in the vulcanization process, reducing the amount of employed ZnO and keeping high the curing efficiency. The activator is constituted by Zn(II) single sites, anchored on the surface of SiO
2 nanoparticles (NPs) through the coordination with functionalizing amino silane groups. It behaves as a double-function material, acting at the same time as a rubber reinforcing filler and a curing activator. The higher availability and reactivity of the single-site Zn(II) centers toward curative agents impart faster kinetics and higher efficiency to the vulcanization process of silica/isoprene NCs, compared to conventionally used ZnO activators. Moreover, the NCs show a high cross-linking degree and improved dynamic mechanical properties, despite the remarkably lower amount of zinc employed than that normally used for rubber composites in tires. Finally, the structural stability of Zn(II) single sites during the curing reactions and in the final materials may represent a turning point toward the elimination of zinc leaching phenomena., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)- Published
- 2021
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89. A Bio-inspired Multifunctionalized Silk Fibroin.
- Author
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Santi S, Mancini I, Dirè S, Callone E, Speranza G, Pugno N, Migliaresi C, and Motta A
- Subjects
- Hydrogels, Laminin, Rheology, Fibroins
- Abstract
A bio-inspired multifunctionalized silk fibroin (BMS) was synthesized in order to mimic the interaction of nidogen with the type IV collagen and laminin of basement membranes. The designed BMS consists of a motif of laminin α-chain-derived, called IK peptide, and type IV collagen covalently bound to the silk fibroin (SF) by using EDC/NHS coupling and a Cu-free click chemistry reaction, respectively. Silk fibroin was chosen as the main component of the BMS because it is versatile and biocompatible, induces an in vivo favorable bioresponse, and moreover can be functionalized with different methods. The chemical structure of BMS was analyzed by using X-ray photoelectron spectroscopy, attenuated total reflection-Fourier transform infrared, cross-polarization magic angle spinning nuclear magnetic resonance techniques, and colorimetric assay. The SF and BMS solutions were cross-linked by sonication to form hydrogels or casted to make films in order to evaluate and compare the early adhesion and viability of MRC5 cells. BMS hydrogels were also characterized by rheological and thermal analyses.
- Published
- 2021
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90. A community-built calibration system: The case study of quantification of metabolites in grape juice by qNMR spectroscopy.
- Author
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Musio B, Ragone R, Todisco S, Rizzuti A, Latronico M, Mastrorilli P, Pontrelli S, Intini N, Scapicchio P, Triggiani M, Di Noia T, Acquotti D, Airoldi C, Assfalg M, Barge A, Bateman L, Benevelli F, Bertelli D, Bertocchi F, Bieliauskas A, Borioni A, Caligiani A, Callone E, Čamra A, Cesare Marincola F, Chalasani D, Consonni R, Dambruoso P, Davalli S, David T, Diehl B, Donarski J, Gil AM, Gobetto R, Goldoni L, Hamon E, Harwood JS, Kobrlová A, Longobardi F, Luisi R, Mallamace D, Mammi S, Martin-Biran M, Mazzei P, Mele A, Milone S, Molero Vilchez D, Mulder RJ, Napoli C, Ragno D, Randazzo A, Rossi MC, Rotondo A, Šačkus A, Sáez Barajas E, Schievano E, Sitaram B, Stevanato L, Takis PG, Teipel J, Thomas F, Torregiani E, Valensin D, Veronesi M, Warren J, Wist J, Zailer-Hafer E, Zuccaccia C, and Gallo V
- Subjects
- Calibration, Magnetic Resonance Spectroscopy, Fruit and Vegetable Juices analysis, Vitis chemistry
- Abstract
Nuclear Magnetic Resonance (NMR) is an analytical technique extensively used in almost every chemical laboratory for structural identification. This technique provides statistically equivalent signals in spite of using spectrometer with different hardware features and is successfully used for the traceability and quantification of analytes in food samples. Nevertheless, to date only a few internationally agreed guidelines have been reported on the use of NMR for quantitative analysis. The main goal of the present study is to provide a methodological pipeline to assess the reproducibility of NMR data produced for a given matrix by spectrometers from different manufacturers, with different magnetic field strengths, age and hardware configurations. The results have been analyzed through a sequence of chemometric tests to generate a community-built calibration system which was used to verify the performance of the spectrometers and the reproducibility of the predicted sample concentrations., (Copyright © 2020 Elsevier B.V. All rights reserved.)
- Published
- 2020
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91. Effect of the Organic Functional Group on the Grafting Ability of Trialkoxysilanes onto Graphene Oxide: A Combined NMR, XRD, and ESR Study.
- Author
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Calovi M, Callone E, Ceccato R, Deflorian F, Rossi S, and Dirè S
- Abstract
The functional properties displayed by graphene oxide (GO)-polymer nanocomposites are strongly affected by the dispersion ability of GO sheets in the polymeric matrix, which can be largely improved by functionalization with organosilanes. The grafting to GO of organosilanes with the general formula RSi(OCH
3 )3 is generally explained by the condensation reactions of silanols with GO reactive groups. In this study, the influence of the organic group on the RSi(OCH3 )3 grafting ability was analyzed in depth, taking into account the interactions of the R end chain group with GO oxidized groups. Model systems composed of commercial graphene oxide reacted with 3-aminopropyltrimethoxysilane (APTMS), 3-mercaptopropyltrimethoxysilane (MPTMS), and 3-methacryloxypropyltrimethoxysilane, (MaPTMS), respectively, were characterized by natural abundance13 C,15 N and29 Si solid state nuclear magnetic resonance (NMR), x-ray diffraction (XRD), and electron spin resonance (ESR). The silane organic tail significantly impacts the grafting, both in terms of the degree of functionalization and direct interaction with GO reactive sites. Both the NMR and XRD proved that this is particularly relevant for APTMS and to a lower extent for MPTMS. Moreover, the epoxy functional groups on the GO sheets appeared to be the preferential anchoring sites for the silane condensation reaction. The characterization approach was applied to the GO samples prepared by the nitric acid etching of graphene and functionalized with the same organosilanes, which were used as a filler in acrylic coatings obtained by cataphoresis, making it possible to correlate the structural properties and the corrosion protection ability of the layers., Competing Interests: The authors declare no conflicts of interest.- Published
- 2019
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92. Docosane-Organosilica Microcapsules for Structural Composites with Thermal Energy Storage/Release Capability.
- Author
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Fredi G, Dirè S, Callone E, Ceccato R, Mondadori F, and Pegoretti A
- Abstract
Organic phase change materials (PCMs) represent an effective solution to manage intermittent energy sources as the solar thermal energy. This work aims at encapsulating docosane in organosilica shells and at dispersing the produced capsules in epoxy/carbon laminates to manufacture multifunctional structural composites for thermal energy storage (TES). Microcapsules of different sizes were prepared by hydrolysis-condensation of methyltriethoxysilane (MTES) in an oil-in-water emulsion. X-ray diffraction (XRD) highlighted the difference in the crystalline structure of pristine and microencapsulated docosane, and
13 C solid-state nuclear magnetic resonance (NMR) evidenced the influence of microcapsules size on the shifts of the representative docosane signals, as a consequence of confinement effects, i.e., reduced chain mobility and interaction with the inner shell walls. A phase change enthalpy up to 143 J/g was determined via differential scanning calorimetry (DSC) on microcapsules, and tests at low scanning speed emphasized the differences in the crystallization behavior and allowed the calculation of the phase change activation energy of docosane, which increased upon encapsulation. Then, the possibility of embedding the microcapsules in an epoxy resin and in an epoxy/carbon laminate to produce a structural TES composite was investigated. The presence of microcapsules agglomerates and the poor capsule-epoxy adhesion, both evidenced by scanning electron microscopy (SEM), led to a decrease in the mechanical properties, as confirmed by three-point bending tests. Dynamic mechanical analysis (DMA) highlighted that the storage modulus decreased by 15% after docosane melting and that the glass transition temperature of the epoxy resin was not influenced by the PCM. The heat storage/release properties of the obtained laminates were proved through DSC and thermal camera imaging tests.- Published
- 2019
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93. Silk Fibroin Porous Scaffolds Loaded with a Slow-Releasing Hydrogen Sulfide Agent (GYY4137) for Applications of Tissue Engineering.
- Author
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Raggio R, Bonani W, Callone E, Dirè S, Gambari L, Grassi F, and Motta A
- Abstract
Hydrogen sulfide (H
2 S) is a physiological gasotransmitter known to possess a regulatory role in several tissues, including bone. The exogenous administration by injection of solutions of H2 S-releasing compounds (e.g., GYY4137) has been previously investigated as a novel therapeutic approach for the treatment of bone diseases. Here, GYY4137 was embedded into fibroin sponges, previously shown to be suitable as scaffolds for bone, thanks to their biocompatibility, scalable porous structure, and biodegradability rate. Fibroin porous scaffolds were produced by solvent casting and the particulate leaching method, and GYY4137 was successively incorporated by using dimethyl sulfoxide (DMSO) as vehicle. The process used to produce GYY4137-loaded scaffolds allowed the incorporation of different controlled amounts of GYY4137 into fibroin matrices. The loading process preserved the properties of the system components in the final products, as assessed by SEM, FT-IR, NMR, and different thermal analyses techniques. Release of H2 S from GYY4137 incorporated into the scaffolds was monitored upon incubation in saline solution at physiological pH: H2 S-release kinetic was found to be dependent on the amount of GYY4137. To ensure biocompatibility, mouse fibroblasts and human primary bone marrow stromal cells were seeded onto scaffolds, and short-term viability assays were performed. Results showed that the GYY4137-loaded scaffold did not induce cytotoxicity in any of the cell type tested. Our findings demonstrate that embedding an H2 S-releasing donor in silk fibroin scaffold is a suitable strategy to achieve a long-lasting release of H2 S that preserves cell viability and allows local delivery at sites of tissue injury.- Published
- 2018
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94. Unveiling the hybrid interface in polymer nanocomposites enclosing silsesquioxanes with tunable molecular structure: Spectroscopic, thermal and mechanical properties.
- Author
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D'Arienzo M, Diré S, Redaelli M, Borovin E, Callone E, Di Credico B, Morazzoni F, Pegoretti A, and Scotti R
- Abstract
Organic-inorganic nanobuilding blocks (NBBs) based on silsesquioxanes (SSQs) have potential applications as nanofillers, thermal stabilizers, and rheological modifiers, which can improve thermomechanical properties of polymer hosts. The possibility to tune both siloxane structure and pendant groups can promote compatibilization and peculiar interactions with a plethora of polymers. However, the control on SSQs molecular architecture and functionalities is usually delicate and requires careful synthetic details. Moreover, investigating the influence of NBBs loading and structure on the hybrid interface and, in turn, on the polymer chains mobility and mechanical properties, may be challenging, especially for low-loaded materials. Herein, we describe the preparation and characterization of polybutadiene (PB) nanocomposites using as innovative fillers thiol-functionalized SSQs nanobuilding blocks (SH-NBBs), with both tailorable functionality and structure. Swelling experiments and, more clearly, solid-state NMR, enlightened a remarkable effect of SH-NBBs on the molecular structure and mobility of the polymeric chains, envisaging the occurrence of chemical interactions at the hybrid interface. Finally, thermal and DMTA analyses revealed that nanocomposites, even containing very low filler loadings (i.e. 1, 3 wt%), exhibited enhanced thermomechanical properties, which seem to be connected not only to the loading, but also to the peculiar cage or ladder-like architecture of SH-NBBs., (Copyright © 2017 Elsevier Inc. All rights reserved.)
- Published
- 2018
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95. Hydrophobic Coatings by Thiol-Ene Click Functionalization of Silsesquioxanes with Tunable Architecture.
- Author
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Dirè S, Bottone D, Callone E, Maniglio D, Génois I, and Ribot F
- Abstract
The hydrolysis-condensation of trialkoxysilanes under strictly controlled conditions allows the production of silsesquioxanes (SSQs) with tunable size and architecture ranging from ladder to cage-like structures. These nano-objects can serve as building blocks for the preparation of hybrid organic/inorganic materials with selected properties. The SSQs growth can be tuned by simply controlling the reaction duration in the in situ water production route (ISWP), where the kinetics of the esterification reaction between carboxylic acids and alcohols rules out the extent of organosilane hydrolysis-condensation. Tunable SSQs with thiol functionalities (SH-NBBs) are suitable for further modification by exploiting the simple thiol-ene click reaction, thus allowing for modifying the wettability properties of derived coatings. In this paper, coatings were prepared from SH-NBBs with different architecture onto cotton fabrics and paper, and further functionalized with long alkyl chains by means of initiator-free UV-induced thiol-ene coupling with 1-decene (C10) and 1-tetradecene (C14). The coatings appeared to homogeneously cover the natural fibers and imparted a multi-scale roughness that was not affected by the click functionalization step. The two-step functionalization of cotton and paper warrants a stable highly hydrophobic character to the surface of natural materials that, in perspective, suggests a possible application in filtration devices for oil-water separation. Furthermore, the purification of SH-NBBs from ISWP by-products was possible during the coating process, and this step allowed for the fast, initiator-free, click-coupling of purified NBBs with C10 and C14 in solution with a nearly quantitative yield. Therefore, this approach is an alternative route to get sol-gel-derived, ladder-like, and cage-like SSQs functionalized with long alkyl chains., Competing Interests: The authors declare no conflict of interest.
- Published
- 2017
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96. Hybrid Coatings Enriched with Tetraethoxysilane for Corrosion Mitigation of Hot-Dip Galvanized Steel in Chloride Contaminated Simulated Concrete Pore Solutions.
- Author
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Figueira RB, Callone E, Silva CJR, Pereira EV, and Dirè S
- Abstract
Hybrid sol-gel coatings, named U(X):TEOS, based on ureasilicate matrices (U(X)) enriched with tetraethoxysilane (TEOS), were synthesized. The influence of TEOS addition was studied on both the structure of the hybrid sol-gel films as well as on the electrochemical properties. The effect of TEOS on the structure of the hybrid sol-gel films was investigated by solid state Nuclear Magnetic Resonance. The dielectric properties of the different materials were investigated by electrochemical impedance spectroscopy. The corrosion behavior of the hybrid coatings on HDGS was studied in chloride-contaminated simulated concrete pore solutions (SCPS) by polarization resistance measurements. The roughness of the HDGS coated with hybrids was also characterized by atomic force microscopy. The structural characterization of the hybrid materials proved the effective reaction between Jeffamine
® and 3-isocyanate propyltriethoxysilane (ICPTES) and indicated that the addition of TEOS does not seem to affect the organic structure or to increase the degree of condensation of the hybrid materials. Despite the apparent lack of influence on the hybrids architecture, the polarization resistance measurements confirmed that TEOS addition improves the corrosion resistance of the hybrid coatings (U(X):TEOS) in chloride-contaminated SCPS when compared to samples prepared without any TEOS (U(X)). This behavior could be related to the decrease in roughness of the hybrid coatings (due TEOS addition) and to the different metal coating interaction resulting from the increase of the inorganic component in the hybrid matrix.- Published
- 2017
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97. Synthesis and characterization of strontium-substituted hydroxyapatite nanoparticles for bone regeneration.
- Author
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Frasnelli M, Cristofaro F, Sglavo VM, Dirè S, Callone E, Ceccato R, Bruni G, Cornaglia AI, and Visai L
- Subjects
- Animals, Apoptosis drug effects, Cattle, Cell Line, Tumor, Cell Proliferation drug effects, Cell Survival drug effects, Humans, Bone Regeneration drug effects, Durapatite chemical synthesis, Durapatite chemistry, Durapatite pharmacology, Nanoparticles chemistry, Strontium chemistry, Strontium pharmacology
- Abstract
The production of stable suspensions of strontium-substituted hydroxyapatite (Sr-HA) nanopowders, as Sr ions vector for bone tissue regeneration, was carried out in the present work. Sr-HA nanopowders were synthesized via aqueous precipitation methods using Sr
2+ amount from 0 to 100mol% and were characterized by several complementary techniques such as solid-state Nuclear Magnetic Resonance spectroscopy, X-ray diffraction, Infrared spectroscopy, N2 physisorption and Transmission Electron Microscopy. The substitution of Ca2+ with Sr2+ in HA is always isomorphic with gradual evolution between the two limit compositions (containing 100% Ca and 100% Sr), this pointing out the homogeneity of the synthesized nanopowders and the complete solubility of strontium in HA lattice. Strontium addition is responsible for an increasing c/a ratio in the triclinic unit cell. A significant variation of the nanopowders shape and dimension is also observed, a preferential growth along the c-axis direction being evident at higher strontium loads. Modifications in the local chemical environment of phosphate and hydroxyl groups in the apatite lattice are also observed. Stable suspensions were produced by dispersing the synthesized nanopowders in bovine serum albumin. Characterization by Dynamic Light Scattering and ζ-potential determination allowed to show that Ca2+ →Sr2+ substitution influences the hydrodynamic diameter, which is always twice the particles size determined by TEM, the nanoparticles being always negatively charged as a result from the albumin rearrangement upon the interaction with nanoparticles surface. The biocompatibility of the suspensions was studied in terms of cell viability, apoptosis, proliferation and morphology, using osteosarcoma cell line SAOS-2. The data pointed out an increased cell proliferation for HA nanoparticles containing larger Sr2+ load, the cells morphology remaining essentially unaffected., (Copyright © 2016 Elsevier B.V. All rights reserved.)- Published
- 2017
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98. Processing Influence on Molecular Assembling and Structural Conformations in Silk Fibroin: Elucidation by Solid-State NMR.
- Author
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Callone E, Dirè S, Hu X, and Motta A
- Abstract
This study is devoted to the deep evaluation of processing-induced protein conformation changes by using silk fibroin fibers and their cast films stabilized by different methods as a model. The control of the hierarchical assembling of silk fibroin is the key for finely tuning the biological functions and physical-chemical properties of the final materials for applications in biomedical fields. However, previous methods usually only focused on the change of beta-sheet crystallinity in silk materials, which can not explain a lot of their specific prosperities generated from different processing methods. By using complementary solid-state NMR, together with FTIR and DSC techniques, we for the first time established the correlations between processing conditions and silk fibroin molecular configurations, and experimentally assess the presence and quantify the percentage of the asymmetric 3-fold helical conformation (Silk III) in silk materials, together with their well-known Silk I-like helix/coil dominated and Silk II beta-sheet dominated configurations. This work provides a roadmap for researchers to quantify the percentage of different silk structures by solid NMR, and further understand how silk molecular conformations (Silk I-like, II, III) can impact the properties and functions of different silk materials, that are broadly used today for different biomedical applications.
- Published
- 2016
- Full Text
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99. Smart and Covalently Cross-Linked: Hybrid Shape Memory Materials Reinforced through Covalent Bonds by Zirconium Oxoclusters.
- Author
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Gibin G, Lorenzetti A, Callone E, Dirè S, Dolcet P, Venzo A, Causin V, Marigo A, Modesti M, and Gross S
- Abstract
The first examples of organic-inorganic hybrid materials reinforced by transition-metal oxoclusters that exhibit shape memory properties, based on the covalent incorporation of zirconium-based inorganic building blocks, are reported. Methacrylate-functionalized zirconium oxoclusters Zr
4 O2 (OMc)12 and [Zr6 O4 (OH)4 (OOCCH2 CH3 )3 {OOCC(CH3 )=CH2 }9 ]2 , with the covalent incorporation in a butyl acrylate (BA)/polycaprolactone dimethacrylate (PCLDMA) copolymer and the noncovalent incorporation of [Zr6 O4 (OH)4 (OOCCH2 CH3 )12 ]2 are focused upon herein. Shape recovery and fixity rates are studied to observe if the shape memory properties are preserved upon going from a simple copolymer to noncovalent or covalent-based hybrids. These rates display values higher than 90 %, which provides evidence that the oxocluster does not hinder the shape memory properties in the hybrid materials. The introduction of an inorganic phase and the progressively more stable interactions between organic and inorganic parts lead to an enhancement of the thermomechanical properties. The materials are characterized through FTIR spectroscopy, thermogravimetric analysis, differential scanning calorimetry, and swelling tests. Dynamic-mechanical analyses are used to investigate whether the hybrid materials display thermally activated shape memory properties. The stability of the hybrid materials are evaluated by a combined spectroscopic approach based on FTIR, solid-state NMR, and X-ray absorption spectroscopy., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)- Published
- 2016
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100. Influence of Sol-Gel Conditions on the Growth of Thiol-Functionalized Silsesquioxanes Prepared by In Situ Water Production.
- Author
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Borovin E, Callone E, Papendorf B, Guella G, and Diré S
- Subjects
- Chromatography, Gel, Magnetic Resonance Spectroscopy, Organosilicon Compounds, Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization, Spectroscopy, Fourier Transform Infrared, Water, Gels, Silanes chemistry, Sulfhydryl Compounds chemistry
- Abstract
Thiol-functionalized oligosilsesquioxanes have been synthesized by sol-gel chemistry via the in-situ water production (ISWP) approach, exploiting the esterification reaction of chloro-acetic acid and 1-propanol. The extent of hydrolysis-condensation of 3-Mercaptopropyltrimethoxysilane (McPTMS) has been studied by FT-IR and NMR spectroscopy, gel permeation chromatography (GPC) and MALDI-TOF techniques. The esterification reaction plays a key role in ruling out the oligomer structural development. In this work, we have investigated the influence of the theoretical amount of water available for the organosilane hydrolysis, defined by the ratio of chloro-acetic acid to McPTMS in the reaction mixture, and the role of different catalysts like trifluoroacetic acid (TFA) and dibutyldilauryltin (DBTL). The behavior of the catalyst is complex since, according to its nature, it may improve the kinetics of the sol-gel reactions and the esterification reaction as well. Comparing the reactions carried out with under-stoichiometric water content, the degree of condensation of the silsesquioxanes is higher if the reaction is catalyzed by TFA than by DBTL, because TFA may improve the kinetics of both hydrolysis-condensation and esterification reactions. The use of DBTL in under-stoichiometric and stoichiometric hydrolytic conditions raises the yield in ladder-like structures. The degree of condensation generally increases increasing the hydrolysis ratio as well as the yield in cage-like structures. However, when an over-stoichiometric amount of water is provided for the sol-gel reaction, condensation degree and ratio among cages and ladder-like structures appear unaffected by the employed catalyst.
- Published
- 2016
- Full Text
- View/download PDF
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