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Among the several actions contributing to the development of a sustainable society, there is the eco-design of new plastic materials with zero environmental impact but that are possibly characterized by properties comparable to those of the traditional fossil-based plastics. This action is particularly urgent for food packaging sector, which involves large volumes of plastic products that quickly become waste. This work aims to contribute to the achievement of this important goal, proposing new bio-based cycloaliphatic polymers based on trans-1,4-cyclohexanedicarboxylic acid and containing different amount of camphoric acid (from 0 to 15 mol %), a cheap and bio-based building block. Such chemical modification was conducted in the melt by avoiding the use of solvents. The so-obtained polymers were processed in the form of films by compression molding. Afterwards, the new and successfully synthesized random copolymers were characterized by molecular (NMR spectroscopy and GPC analysis), thermal (DSC and TGA analyses), diffractometric (wide angle X-ray scattering), mechanical (through tensile tests), and O2 and CO2 barrier point of view together with the parent homopolymer. The article aims to relate the results obtained with the amount of camphoric moiety introduced and to present, the different microstructure in the copolymers in more detail; indeed, in these samples, a different crystalline form developed (the so-called β-PBCE). This latter form was the kinetically favored and less packed one, as proven by the lower equilibrium melting temperature determined for the first time by Baur’s equation.
Giulia Guidotti; Gianfranco Burzotta; Michelina Soccio; Massimo Gazzano; Valentina Siracusa; Andrea Munari; Nadia Lotti. Chemical Modification of Poly(butylene trans-1,4-cyclohexanedicarboxylate) by Camphor: A New Example of Bio-Based Polyesters for Sustainable Food Packaging. Polymers 2021, 13, 2707 .
AMA StyleGiulia Guidotti, Gianfranco Burzotta, Michelina Soccio, Massimo Gazzano, Valentina Siracusa, Andrea Munari, Nadia Lotti. Chemical Modification of Poly(butylene trans-1,4-cyclohexanedicarboxylate) by Camphor: A New Example of Bio-Based Polyesters for Sustainable Food Packaging. Polymers. 2021; 13 (16):2707.
Chicago/Turabian StyleGiulia Guidotti; Gianfranco Burzotta; Michelina Soccio; Massimo Gazzano; Valentina Siracusa; Andrea Munari; Nadia Lotti. 2021. "Chemical Modification of Poly(butylene trans-1,4-cyclohexanedicarboxylate) by Camphor: A New Example of Bio-Based Polyesters for Sustainable Food Packaging." Polymers 13, no. 16: 2707.
In recent years there has been a growing interest in the use of proteins as biocompatible and environmentally friendly biomolecules for the design of wound healing and drug delivery systems. Keratin is a fascinating protein, obtainable from several keratinous biomasses such as wool, hair or nails, with intrinsic bioactive properties including stimulatory effects on wound repair and excellent carrier capability. In this work keratin/poly(butylene succinate) blend solutions with functional properties tunable by manipulating the polymer blending ratios were prepared by using 1,1,1,3,3,3-hexafluoroisopropanol as common solvent. Afterwards, these solutions doped with rhodamine B (RhB), were electrospun into blend mats and the drug release mechanism and kinetics as a function of blend composition was studied, in order to understand the potential of such membranes as drug delivery systems. The electrophoresis analysis carried out on keratin revealed that the solvent used does not degrade the protein. Moreover, all the blend solutions showed a non-Newtonian behavior, among which the Keratin/PBS 70/30 and 30/70 ones showed an amplified orientation ability of the polymer chains when subjected to a shear stress. Therefore, the resulting nanofibers showed thinner mean diameters and narrower diameter distributions compared to the Keratin/PBS 50/50 blend solution. The thermal stability and the mechanical properties of the blend electrospun mats improved by increasing the PBS content. Finally, the RhB release rate increased by increasing the keratin content of the mats and the drug diffused as drug-protein complex.
Giulia Guidotti; Michelina Soccio; Edoardo Bondi; Tamara Posati; Giovanna Sotgiu; Roberto Zamboni; Armida Torreggiani; Franco Corticelli; Nadia Lotti; Annalisa Aluigi. Effects of the Blending Ratio on the Design of Keratin/Poly(butylene succinate) Nanofibers for Drug Delivery Applications. Biomolecules 2021, 11, 1194 .
AMA StyleGiulia Guidotti, Michelina Soccio, Edoardo Bondi, Tamara Posati, Giovanna Sotgiu, Roberto Zamboni, Armida Torreggiani, Franco Corticelli, Nadia Lotti, Annalisa Aluigi. Effects of the Blending Ratio on the Design of Keratin/Poly(butylene succinate) Nanofibers for Drug Delivery Applications. Biomolecules. 2021; 11 (8):1194.
Chicago/Turabian StyleGiulia Guidotti; Michelina Soccio; Edoardo Bondi; Tamara Posati; Giovanna Sotgiu; Roberto Zamboni; Armida Torreggiani; Franco Corticelli; Nadia Lotti; Annalisa Aluigi. 2021. "Effects of the Blending Ratio on the Design of Keratin/Poly(butylene succinate) Nanofibers for Drug Delivery Applications." Biomolecules 11, no. 8: 1194.
In the present study, 100% bio-based polyesters of 2,5-thiophenedicarboxylic acid were synthesized via two-stage melt polycondensation using glycols containing 3 to 6 methylene groups. The so-prepared samples were characterised from the molecular point of view and processed into free-standing thin films. Afterward, both the purified powders and the films were subjected to structural and thermal characterisation. In the case of thin films, mechanical response and barrier properties to O2 and CO2 were also evaluated. From the results obtained, it emerged that the length of glycolic sub-units is an effective tool to modulate the chain mobility and, in turn, the kind and amount of ordered phases developed in the samples. In addition to the usual amorphous and 3D crystalline phases, in all the samples investigated it was possible to evidence a further phase characterised by a lower degree of order (mesophase) than the crystalline one, whose amount is strictly related to the glycol sub-unit length. The relative fraction of all these phases is responsible for the different mechanical and barrier performances. Last, but not least, a comparison between thiophene-based homopolymers and their furan-based homologues was carried out.
Giulia Guidotti; Michelina Soccio; Massimo Gazzano; Valentina Siracusa; Nadia Lotti. Poly(Alkylene 2,5-Thiophenedicarboxylate) Polyesters: A New Class of Bio-Based High-Performance Polymers for Sustainable Packaging. Polymers 2021, 13, 2460 .
AMA StyleGiulia Guidotti, Michelina Soccio, Massimo Gazzano, Valentina Siracusa, Nadia Lotti. Poly(Alkylene 2,5-Thiophenedicarboxylate) Polyesters: A New Class of Bio-Based High-Performance Polymers for Sustainable Packaging. Polymers. 2021; 13 (15):2460.
Chicago/Turabian StyleGiulia Guidotti; Michelina Soccio; Massimo Gazzano; Valentina Siracusa; Nadia Lotti. 2021. "Poly(Alkylene 2,5-Thiophenedicarboxylate) Polyesters: A New Class of Bio-Based High-Performance Polymers for Sustainable Packaging." Polymers 13, no. 15: 2460.
A new high molecular weight aliphatic copolyester of PLLA characterized by a ABA triblock architecture was successfully synthesized by ring opening polymerization, using as initiator a low molecular weight hydroxyl terminated random copolymer of PBS, poly(butylene/triethylene succinate). To increase the final polymer molecular weight, thus ensuring both good processability and mechanical properties, chain extension reaction has been performed with hexamethylene diisocyanate (HDI) as chain extender. All the synthetic steps have been carried out in solvent-free conditions. Specifically, the A block consists of LLA sequences, whereas the B one is an aliphatic biodegradable and biocompatible random copolyester of poly(butylene succinate) containing “PEG-like” moiety. The so-obtained material was first characterized by the molecular point of view and then, prior to further characterization, subjected to two different annealing treatments. Annealing revealed to be an efficient tool to control the kind and amount of crystalline phase developed by the material, as confirmed by WAXS structural analysis, and to tailor the mechanical properties, typical of thermoplastic elastomers. Thermal treatment was found to affect also the mechanism of polymer degradation under physiological conditions. Last, but not least, in order to explore the possible use of such new PLLA-based copolymer in vascular tissue engineering, preliminary biocompatibility tests, using endothelial cells, were carried out.
G. Guidotti; M. Soccio; M. Gazzano; L. Fusaro; F. Boccafoschi; A. Munari; N. Lotti. New thermoplastic elastomer triblock copolymer of PLLA for cardiovascular tissue engineering: Annealing as efficient tool to tailor the solid-state properties. Polymer 2020, 213, 123336 .
AMA StyleG. Guidotti, M. Soccio, M. Gazzano, L. Fusaro, F. Boccafoschi, A. Munari, N. Lotti. New thermoplastic elastomer triblock copolymer of PLLA for cardiovascular tissue engineering: Annealing as efficient tool to tailor the solid-state properties. Polymer. 2020; 213 ():123336.
Chicago/Turabian StyleG. Guidotti; M. Soccio; M. Gazzano; L. Fusaro; F. Boccafoschi; A. Munari; N. Lotti. 2020. "New thermoplastic elastomer triblock copolymer of PLLA for cardiovascular tissue engineering: Annealing as efficient tool to tailor the solid-state properties." Polymer 213, no. : 123336.
Herein, we present poly(butylene 1,4-cyclohexanedicarboxylate) (PBCE) films characterized by an unpatterned microstructure and a specific hydrophobicity, capable of boosting a drastic cytoskeleton architecture remodeling, culminating with the neuronal-like differentiation of human bone marrow-mesenchymal stem cells (hBM-MSCs). We have used two different filming procedures to prepare the films, solvent casting (PBCE) and compression-moulding (PBCE*). PBCE film had a rough and porous surface with spherulite-like aggregations (Ø = 10–20 μm) and was characterized by a water contact angle = 100°. PBCE* showed a smooth and continuous surface without voids and visible spherulite-like aggregations and was more hydrophobic (WCA = 110°). Both surface characteristics were modulated through the copolymerization of different amounts of ether-oxygen-containing co-units into PBCE chemical structure. We showed that only the surface characteristics of PBCE-solvent-casted films steered hBM-MSCs toward a neuronal-like differentiation. hBM-MSCs lost their canonical mesenchymal morphology, acquired a neuronal polarized shape with a long cell protrusion (≥150 μm), expressed neuron-specific class III β-tubulin and microtubule-associated protein 2 neuronal markers, while nestin, a marker of uncommitted stem cells, was drastically silenced. These events were observed as early as 2-days after cell seeding. Of note, the phenomenon was totally absent on PBCE* film, as hBM-MSCs maintained the mesenchymal shape and behavior and did not express neuronal/glial markers.
Francesco Morena; Chiara Argentati; Michelina Soccio; Ilaria Bicchi; Francesca Luzi; Luigi Torre; Andrea Munari; Carla Emiliani; Matteo Gigli; Nadia Lotti; Ilaria Armentano; Sabata Martino. Unpatterned Bioactive Poly(Butylene 1,4-Cyclohexanedicarboxylate)-Based Film Fast Induced Neuronal-Like Differentiation of Human Bone Marrow-Mesenchymal Stem Cells. International Journal of Molecular Sciences 2020, 21, 9274 .
AMA StyleFrancesco Morena, Chiara Argentati, Michelina Soccio, Ilaria Bicchi, Francesca Luzi, Luigi Torre, Andrea Munari, Carla Emiliani, Matteo Gigli, Nadia Lotti, Ilaria Armentano, Sabata Martino. Unpatterned Bioactive Poly(Butylene 1,4-Cyclohexanedicarboxylate)-Based Film Fast Induced Neuronal-Like Differentiation of Human Bone Marrow-Mesenchymal Stem Cells. International Journal of Molecular Sciences. 2020; 21 (23):9274.
Chicago/Turabian StyleFrancesco Morena; Chiara Argentati; Michelina Soccio; Ilaria Bicchi; Francesca Luzi; Luigi Torre; Andrea Munari; Carla Emiliani; Matteo Gigli; Nadia Lotti; Ilaria Armentano; Sabata Martino. 2020. "Unpatterned Bioactive Poly(Butylene 1,4-Cyclohexanedicarboxylate)-Based Film Fast Induced Neuronal-Like Differentiation of Human Bone Marrow-Mesenchymal Stem Cells." International Journal of Molecular Sciences 21, no. 23: 9274.
In the field of artificial prostheses for damaged vessel replacement, polymeric scaffolds showing the right combination of mechanical performance, biocompatibility, and biodegradability are still demanded. In the present work, poly(butylene-co-triethylene trans-1,4-cyclohexanedicarboxylate), a biodegradable random aliphatic copolyester, has been synthesized and electrospun in form of aligned and random fibers properly designed for vascular applications. The obtained materials were analyzed through tensile and dynamic-mechanical tests, the latter performed under conditions simulating the mechanical contraction of vascular tissue. Furthermore, the in vitro biological characterization, in terms of hemocompatibility and cytocompatibility in static and dynamic conditions, was also carried out. The mechanical properties of the investigated scaffolds fit within the range of physiological properties for medium- and small-caliber blood vessels, and the aligned scaffolds displayed a strain-stiffening behavior typical of the blood vessels. Furthermore, all the produced scaffolds showed constant storage and loss moduli in the investigated timeframe (24 h), demonstrating the stability of the scaffolds under the applied conditions of mechanical deformation. The biological characterization highlighted that the mats showed high hemocompatibility and low probability of thrombus formation; finally, the cytocompatibility tests demonstrated that cyclic stretch of electrospun fibers increased endothelial cell activity and proliferation, in particular on aligned scaffolds.
Luca Fusaro; Chiara Gualandi; Diego Antonioli; Michelina Soccio; Anna Liguori; Michele Laus; Nadia Lotti; Francesca Boccafoschi; Maria Letizia Focarete. Elastomeric Electrospun Scaffolds of a Biodegradable Aliphatic Copolyester Containing PEG-like Sequences for Dynamic Culture of Human Endothelial Cells. Biomolecules 2020, 10, 1620 .
AMA StyleLuca Fusaro, Chiara Gualandi, Diego Antonioli, Michelina Soccio, Anna Liguori, Michele Laus, Nadia Lotti, Francesca Boccafoschi, Maria Letizia Focarete. Elastomeric Electrospun Scaffolds of a Biodegradable Aliphatic Copolyester Containing PEG-like Sequences for Dynamic Culture of Human Endothelial Cells. Biomolecules. 2020; 10 (12):1620.
Chicago/Turabian StyleLuca Fusaro; Chiara Gualandi; Diego Antonioli; Michelina Soccio; Anna Liguori; Michele Laus; Nadia Lotti; Francesca Boccafoschi; Maria Letizia Focarete. 2020. "Elastomeric Electrospun Scaffolds of a Biodegradable Aliphatic Copolyester Containing PEG-like Sequences for Dynamic Culture of Human Endothelial Cells." Biomolecules 10, no. 12: 1620.
We report on the molecular origin of poly(pentamethylene 2,5-furanoate)’s particular physical properties. From the structural point of view, we found that this polymer can develop crystallinity when stored under room conditions for months. On the other hand, we used broadband dielectric spectroscopy measurements to analyze in great detail the local and segmental molecular dynamics of the material subjected to several thermal treatments. In this way, we evidenced that the molecular dynamics are sensitive to thermal history over a broad temperature range. This behavior has been attributed to possible interchain interactions detected via infrared spectroscopy and rheology measurements in the noncrystallized polymer.
Daniel E. Martínez-Tong; Michelina Soccio; Beatriz Robles-Hernández; Giulia Guidotti; Massimo Gazzano; Nadia Lotti; Angel Alegria. Evidence of Nanostructure Development from the Molecular Dynamics of Poly(pentamethylene 2,5-furanoate). Macromolecules 2020, 53, 10526 -10537.
AMA StyleDaniel E. Martínez-Tong, Michelina Soccio, Beatriz Robles-Hernández, Giulia Guidotti, Massimo Gazzano, Nadia Lotti, Angel Alegria. Evidence of Nanostructure Development from the Molecular Dynamics of Poly(pentamethylene 2,5-furanoate). Macromolecules. 2020; 53 (23):10526-10537.
Chicago/Turabian StyleDaniel E. Martínez-Tong; Michelina Soccio; Beatriz Robles-Hernández; Giulia Guidotti; Massimo Gazzano; Nadia Lotti; Angel Alegria. 2020. "Evidence of Nanostructure Development from the Molecular Dynamics of Poly(pentamethylene 2,5-furanoate)." Macromolecules 53, no. 23: 10526-10537.
We report on the molecular origin of poly(pentamethylene 2,5-furanoate) particular physical properties. From the structural point of view we found this polymer can develop crystallinity when stored at room conditions for months. On the other hand, we used broadband dielectric spectroscopy (BDS) measurements, to analyze in very detail the local and segmental molecular dynamics of the material subjected to several thermal treatments. In this way we evidenced that the molecular dynamics are sensitive to thermal history over a broad temperature range. This behavior has been attributed to possible inter-chain interactions detected via infrared spectroscopy and rheology measurements in the non-crystallized polymer.
Daniel E Martínez-Tong; Michelina Soccio; Beatriz Robles-Hernández; Giulia Guidotti; Massimo Gazzano; Nadia Lotti; Angel Alegria. Evidence of Nanostructure Development from the Molecular Dynamics of Poly(pentamethylene 2,5- Furanoate). 2020, 1 .
AMA StyleDaniel E Martínez-Tong, Michelina Soccio, Beatriz Robles-Hernández, Giulia Guidotti, Massimo Gazzano, Nadia Lotti, Angel Alegria. Evidence of Nanostructure Development from the Molecular Dynamics of Poly(pentamethylene 2,5- Furanoate). . 2020; ():1.
Chicago/Turabian StyleDaniel E Martínez-Tong; Michelina Soccio; Beatriz Robles-Hernández; Giulia Guidotti; Massimo Gazzano; Nadia Lotti; Angel Alegria. 2020. "Evidence of Nanostructure Development from the Molecular Dynamics of Poly(pentamethylene 2,5- Furanoate)." , no. : 1.
We report on the molecular origin of poly(pentamethylene 2,5-furanoate) particular physical properties. From the structural point of view we found this polymer can develop crystallinity when stored at room conditions for months. On the other hand, we used broadband dielectric spectroscopy (BDS) measurements, to analyze in very detail the local and segmental molecular dynamics of the material subjected to several thermal treatments. In this way we evidenced that the molecular dynamics are sensitive to thermal history over a broad temperature range. This behavior has been attributed to possible inter-chain interactions detected via infrared spectroscopy and rheology measurements in the non-crystallized polymer.
Daniel E Martínez-Tong; Michelina Soccio; Beatriz Robles-Hernández; Giulia Guidotti; Massimo Gazzano; Nadia Lotti; Angel Alegria. Evidence of Nanostructure Development from the Molecular Dynamics of Poly(pentamethylene 2,5- Furanoate). 2020, 1 .
AMA StyleDaniel E Martínez-Tong, Michelina Soccio, Beatriz Robles-Hernández, Giulia Guidotti, Massimo Gazzano, Nadia Lotti, Angel Alegria. Evidence of Nanostructure Development from the Molecular Dynamics of Poly(pentamethylene 2,5- Furanoate). . 2020; ():1.
Chicago/Turabian StyleDaniel E Martínez-Tong; Michelina Soccio; Beatriz Robles-Hernández; Giulia Guidotti; Massimo Gazzano; Nadia Lotti; Angel Alegria. 2020. "Evidence of Nanostructure Development from the Molecular Dynamics of Poly(pentamethylene 2,5- Furanoate)." , no. : 1.
The peculiar reactivity of catechol carbonate (CC) with amines and polyamines in both solvent and catalyst free conditions is herein described. In all the tests performed at room temperature, CC conversion reached 100% in few seconds leading to the selective formation of the corresponding 2-hydroxyphenylcarbamate. This compound is furtherly rapidly converted to the di-substituted urea by the consecutive nucleophilic attack of another amine. Noteworthy, the application of this approach can be successfully extended to the one-pot bio-amine based synthesis of polyurea as herein proposed for the first time in literature. The reaction is of general purpose for primary amines and catechol can be easily recovered by sublimation as pure crystals ready to be recycled for the synthesis of new CC. An exception is related to the reactivity of secondary amine, which leads anyway to the selective formation of substituted phenolic carbamates (e.g. 2-hydroxyphenyl diethylcarbamate), suitable as intermediates in medicinal chemistry.
Michelina Soccio; Rita Mazzoni; Carlo Lucarelli; Silvia Quattrosoldi; Andrea Cingolani; Maurizio Fiorini; Nadia Lotti; Tommaso Tabanelli. Urea and Polyurea Production: An Innovative Solvent- and Catalyst-Free Approach through Catechol Carbonate. ACS Sustainable Chemistry & Engineering 2020, 8, 15640 -15650.
AMA StyleMichelina Soccio, Rita Mazzoni, Carlo Lucarelli, Silvia Quattrosoldi, Andrea Cingolani, Maurizio Fiorini, Nadia Lotti, Tommaso Tabanelli. Urea and Polyurea Production: An Innovative Solvent- and Catalyst-Free Approach through Catechol Carbonate. ACS Sustainable Chemistry & Engineering. 2020; 8 (41):15640-15650.
Chicago/Turabian StyleMichelina Soccio; Rita Mazzoni; Carlo Lucarelli; Silvia Quattrosoldi; Andrea Cingolani; Maurizio Fiorini; Nadia Lotti; Tommaso Tabanelli. 2020. "Urea and Polyurea Production: An Innovative Solvent- and Catalyst-Free Approach through Catechol Carbonate." ACS Sustainable Chemistry & Engineering 8, no. 41: 15640-15650.
Novel A-B-A triblock copolymers based on poly(l-lactic acid) (PLLA) were designed with an ad hoc chemical structure to prepare micro- and nanoparticles for controlled drug delivery. A block is formed by PLLA, while central B block is a copolymeric system based on poly(butylene succinate) and poly(triethylene succinate): more specifically, two copolymers with fix composition (50:50 mol:mol) and different molecular architecture were synthesized. One of them is characterized by a block architecture, i.e. long butylene succinate and triethylene succinate sequences form the macromolecular chains, the other being on the contrary a random copolymer with short sequences. The so-obtained materials were characterized from the molecular and thermal point of view. Moreover, to investigate the effect of both chemical structure and molecular architecture of the polymers synthesized on drug release kinetics, Dexamethasone-encapsulated micro- and nanoparticles were prepared by oil-in-water miniemulsion technique. These particles were subjected to thermal and morphological characterization. After that, drug release studies were carried out, and the effect of chemical composition, sequence distribution and particle size on release profile was evaluated.
Giulia Guidotti; Michelina Soccio; Massimo Gazzano; Elisabetta Salatelli; Nadia Lotti; Andrea Munari. Micro/nanoparticles fabricated with triblock PLLA-based copolymers containing PEG-like subunit for controlled drug release: Effect of chemical structure and molecular architecture on drug release profile. Polymer Degradation and Stability 2020, 180, 109306 .
AMA StyleGiulia Guidotti, Michelina Soccio, Massimo Gazzano, Elisabetta Salatelli, Nadia Lotti, Andrea Munari. Micro/nanoparticles fabricated with triblock PLLA-based copolymers containing PEG-like subunit for controlled drug release: Effect of chemical structure and molecular architecture on drug release profile. Polymer Degradation and Stability. 2020; 180 ():109306.
Chicago/Turabian StyleGiulia Guidotti; Michelina Soccio; Massimo Gazzano; Elisabetta Salatelli; Nadia Lotti; Andrea Munari. 2020. "Micro/nanoparticles fabricated with triblock PLLA-based copolymers containing PEG-like subunit for controlled drug release: Effect of chemical structure and molecular architecture on drug release profile." Polymer Degradation and Stability 180, no. : 109306.
Keratin (Ker) protein regenerated from readily available and low-cost wastes (e.g. raw wool, feathers and textile by-products) is a promising natural polymer for tissue engineering and drug delivery. Nevertheless, while showing good bioactivity and great drug carrier properties, keratin lacks of suitable mechanical characteristics. To overcome this drawback, keratin was blended with poly(butylene succinate) (PBS), a biodegradable and biocompatible polyester able to confer mechanical integrity to the keratin based materials. Despite the poor compatibility at the molecular level between keratin and PBS, their 50-50 blends were successfully electrospun into manageable mats, made of randomly oriented nanofibers with mean diameter of 290 nm. Along with mechanical properties, PBS improves also the thermal stability of the keratin based nanofibrous mats. On the other hand, compared to PBS-only electrospun mats, the presence of keratin improves both swelling ability and biodegradability and amplifies the capacity of drug release as well as fibroblast proliferation of the blend mat.
G. Guidotti; M. Soccio; T. Posati; G. Sotgiu; M. Tiboni; M. Barbalinardo; F. Valle; L. Casettari; R. Zamboni; N. Lotti; A. Aluigi. Regenerated wool keratin-polybutylene succinate nanofibrous mats for drug delivery and cells culture. Polymer Degradation and Stability 2020, 179, 109272 .
AMA StyleG. Guidotti, M. Soccio, T. Posati, G. Sotgiu, M. Tiboni, M. Barbalinardo, F. Valle, L. Casettari, R. Zamboni, N. Lotti, A. Aluigi. Regenerated wool keratin-polybutylene succinate nanofibrous mats for drug delivery and cells culture. Polymer Degradation and Stability. 2020; 179 ():109272.
Chicago/Turabian StyleG. Guidotti; M. Soccio; T. Posati; G. Sotgiu; M. Tiboni; M. Barbalinardo; F. Valle; L. Casettari; R. Zamboni; N. Lotti; A. Aluigi. 2020. "Regenerated wool keratin-polybutylene succinate nanofibrous mats for drug delivery and cells culture." Polymer Degradation and Stability 179, no. : 109272.
Considering the current context of researches aiming at proposing new bioplastics with low costs and properties similar to fossil-based commodities currently on the market, in the present work, a hybrid blend containing a prevalent amount of a cheap inedible cereal flour (70% wt.) and poly (butylene succinate) (PBS) (30% wt.) has been prepared by using a simple, eco-friendly and low cost processing methodology. In order to improve the interfacial tension and enhance the adhesion between the different phases at the solid state, with consequent improvement in microstructure uniformity and in material mechanical and adhesive performance, the PBS fraction in the blend was replaced by variable amount (0-25 % wt.) of a PBS-based green copolymer, which exerted the function of compatibilizer. The copolymer is characterized by an ad hoc chemical structure, containing six-carbon aliphatic rings, also present in the flour starch structure. The two synthetic polyesters obtained through two-stage melt polycondensation have been deeply characterized from the molecular, thermal, and mechanical point of view. Copolymerization deeply impacts on the polymer final properties, the crystallizing ability and stiffness of PBS homopolymer being reduced. Also, the prepared ternary blends were deeply investigated in terms of microstructure, thermal and mechanical properties. Lastly, both pure blend components and ternary blends were subjected to disintegration experiments under composting conditions. The results obtained proved how effective was the compatibilizer action of the copolymer, as evidenced by the investigation conducted on morphology and mechanical properties. Specifically, the mixtures with 15% wt. and 20% wt. of Co appeared to be characterized by the best mechanical performance, showing a progressive increase of deformation, while preserving good values of elastic modulus and stress. The disintegration rate in compost was found higher, the lower the amount of copolymer in the ternary blend. However, after 90 days of incubation, the blend richest in copolymer content lost 62% of weight.
Michelina Soccio; Franco Dominici; Silvia Quattrosoldi; Francesca Luzi; Andrea Munari; Luigi Torre; Nadia Lotti; Debora Puglia. PBS-Based Green Copolymer as an Efficient Compatibilizer in Thermoplastic Inedible Wheat Flour/Poly(butylene succinate) Blends. Biomacromolecules 2020, 21, 3254 -3269.
AMA StyleMichelina Soccio, Franco Dominici, Silvia Quattrosoldi, Francesca Luzi, Andrea Munari, Luigi Torre, Nadia Lotti, Debora Puglia. PBS-Based Green Copolymer as an Efficient Compatibilizer in Thermoplastic Inedible Wheat Flour/Poly(butylene succinate) Blends. Biomacromolecules. 2020; 21 (8):3254-3269.
Chicago/Turabian StyleMichelina Soccio; Franco Dominici; Silvia Quattrosoldi; Francesca Luzi; Andrea Munari; Luigi Torre; Nadia Lotti; Debora Puglia. 2020. "PBS-Based Green Copolymer as an Efficient Compatibilizer in Thermoplastic Inedible Wheat Flour/Poly(butylene succinate) Blends." Biomacromolecules 21, no. 8: 3254-3269.
Poly(2,5-alkylene furanoate)s are bio-based, smart, and innovative polymers that are considered the most promising materials to replace oil-based plastics. These polymers can be synthesized using ecofriendly approaches, starting from renewable sources, and result into final products with properties comparable and even better than those presented by their terephthalic counterparts. In this work, we present the molecular dynamics of four 100% bio-based poly(alkylene 2,5-furanoate)s, using broadband dielectric spectroscopy measurements that covered a wide temperature and frequency range. We unveiled complex local relaxations, characterized by the simultaneous presence of two components, which were dependent on thermal treatment. The segmental relaxation showed relaxation times and strengths depending on the glycolic subunit length, which were furthermore confirmed by high-frequency experiments in the molten region of the polymers. Our results allowed determining structure–property relations that are able to provide further understanding about the excellent barrier properties of poly(alkylene 2,5-furanoate)s. In addition, we provide results of high industrial interest during polymer processing for possible industrial applications of poly(alkylene furanoate)s.
Michelina Soccio; Daniel E. Martínez-Tong; Giulia Guidotti; Beatriz Robles-Hernández; Andrea Munari; Nadia Lotti; Angel Alegria. Broadband Dielectric Spectroscopy Study of Biobased Poly(alkylene 2,5-furanoate)s’ Molecular Dynamics. Polymers 2020, 12, 1355 .
AMA StyleMichelina Soccio, Daniel E. Martínez-Tong, Giulia Guidotti, Beatriz Robles-Hernández, Andrea Munari, Nadia Lotti, Angel Alegria. Broadband Dielectric Spectroscopy Study of Biobased Poly(alkylene 2,5-furanoate)s’ Molecular Dynamics. Polymers. 2020; 12 (6):1355.
Chicago/Turabian StyleMichelina Soccio; Daniel E. Martínez-Tong; Giulia Guidotti; Beatriz Robles-Hernández; Andrea Munari; Nadia Lotti; Angel Alegria. 2020. "Broadband Dielectric Spectroscopy Study of Biobased Poly(alkylene 2,5-furanoate)s’ Molecular Dynamics." Polymers 12, no. 6: 1355.
Fully biobased blends of thermoplastic starch and a poly(butylene cyclohexanedicarboxylate)-based random copolyester containing 25 % of adipic acid co-units (PBCEA) are prepared by melt blending and direct extrusion film casting. The obtained films are characterized from the physicochemical and mechanical point of view and their fragmentation under composting conditions is evaluated. The results demonstrate that the introduction of adipic acid co-units in the PBCE macromolecular chains permits to decrease the blending temperature, thus avoiding unwanted starch degradation reactions. Moreover, the presence of small amounts of citric acid as compatibilizer further improves the interfacial adhesion between the two components and promotes the formation of micro-porosities within the films. The synergistic combination of these factors leads to the development of materials showing an elastomeric behavior, i.e. no evident yield and elongation at break higher than 450 %, good moisture resistance and fast fragmentation in compost.
Franco Dominici; Matteo Gigli; Ilaria Armentano; Laura Genovese; Francesca Luzi; Luigi Torre; Andrea Munari; Nadia Lotti. Improving the flexibility and compostability of starch/poly(butylene cyclohexanedicarboxylate)-based blends. Carbohydrate Polymers 2020, 246, 116631 .
AMA StyleFranco Dominici, Matteo Gigli, Ilaria Armentano, Laura Genovese, Francesca Luzi, Luigi Torre, Andrea Munari, Nadia Lotti. Improving the flexibility and compostability of starch/poly(butylene cyclohexanedicarboxylate)-based blends. Carbohydrate Polymers. 2020; 246 ():116631.
Chicago/Turabian StyleFranco Dominici; Matteo Gigli; Ilaria Armentano; Laura Genovese; Francesca Luzi; Luigi Torre; Andrea Munari; Nadia Lotti. 2020. "Improving the flexibility and compostability of starch/poly(butylene cyclohexanedicarboxylate)-based blends." Carbohydrate Polymers 246, no. : 116631.
In the present paper, four fully biobased homopolyesters of 2,5-furandicarboxylic acid (2,5-FDCA) with high molecular weight have been successfully synthesized by two-stage melt polycondensation, starting from dimethyl ester of 2,5-FDCA and glycols of different length (the number of methylene groups ranged from 3 to 6). The synthesized polyesters have been firstly subjected to an accurate molecular characterization by NMR and GPC. Afterwards, the samples have been successfully processed into free-standing thin films (thickness comprised between 150 to 180 m) by compression molding. Such films have been characterized from the structural (by WAXS and SAXS), thermal (by DSC and TGA), mechanical (by tensile test) and gas barrier (by permeability measurements) point of view. Glycol subunit length revealed to be the key parameter in determining the kind and fraction of ordered phases developed by the sample during compression molding and subsequent cooling. After storage at room temperature for one month, only the homopolymers containing glycol subunit with an even number of -CH2- groups (poly(butylene 2,5-furanoate) (PBF) and poly(hexamethylene 2,5-furanoate) (PHF)) were able to develop a 3D-ordered crystalline phase in addition to the amorphous one, the other two appearing completely amorphous (poly(propylene 2,5-furanoate (PPF) and poly(pentamethylene 2,5-furanoate) (PPeF)). From X-ray scattering experiments using synchrotron radiation, it was possible to evidence a third phase characterized by a lower degree of order (1D or 2D), called mesophase, in all the samples under study, its fraction being strictly related to the glycol subunit length: PPeF was found to be the sample with the highest fraction of mesophase followed by PHF. Such mesophase, together with the amorphous and the eventually present crystalline phase, impacted significantly on the mechanical and barrier properties, these last being particularly outstanding for PPeF, the polyester with the highest fraction of mesophase among those synthesized in the present work.
Giulia Guidotti; Michelina Soccio; Mari Cruz García-Gutiérrez; Tiberio A. Ezquerra; Valentina Siracusa; Edgar Gutiérrez-Fernández; Andrea Munari; Nadia Lotti. Fully Biobased Superpolymers of 2,5-Furandicarboxylic Acid with Different Functional Properties: From Rigid to Flexible, High Performant Packaging Materials. ACS Sustainable Chemistry & Engineering 2020, 8, 9558 -9568.
AMA StyleGiulia Guidotti, Michelina Soccio, Mari Cruz García-Gutiérrez, Tiberio A. Ezquerra, Valentina Siracusa, Edgar Gutiérrez-Fernández, Andrea Munari, Nadia Lotti. Fully Biobased Superpolymers of 2,5-Furandicarboxylic Acid with Different Functional Properties: From Rigid to Flexible, High Performant Packaging Materials. ACS Sustainable Chemistry & Engineering. 2020; 8 (25):9558-9568.
Chicago/Turabian StyleGiulia Guidotti; Michelina Soccio; Mari Cruz García-Gutiérrez; Tiberio A. Ezquerra; Valentina Siracusa; Edgar Gutiérrez-Fernández; Andrea Munari; Nadia Lotti. 2020. "Fully Biobased Superpolymers of 2,5-Furandicarboxylic Acid with Different Functional Properties: From Rigid to Flexible, High Performant Packaging Materials." ACS Sustainable Chemistry & Engineering 8, no. 25: 9558-9568.
Poly(alkylene 2,5-furanoate)s are considered as the most attractive and interesting alternatives to replace oil-based terephthalic polymers. These furan-based polyesters can be synthesized using fully bio-based synthetic strategies, allowing to reduce the environmental impact of plastics. At the same time, these polymers have shown outstanding thermal, mechanical and gas-barrier properties. All these results envisage their industrial use in the near future. Now, considering the downscaling of the products’ size towards the nanometer scale, we present a study of the morphology and nanomechanical properties of poly(alkylene 2,5-furanoate) thin films. Using Atomic Force Microscopy, we report the development of nanostructures upon crystallization, following different thermal treatments, for thin films with thicknesses below 200 nm. Moreover, we studied the impact of crystal growth in the nanomechanical properties of these materials. We found that the polymer thin films preserve their excellent mechanical response even in the confined geometry, as proved by the Young’s moduli values close to the GPa, accompanied by high surface stiffness, and low indentation depths. The poly(alkylene 2,5-furanoate) thin films were found to have nanomechanical properties comparable to those of the oil-based poly(ethylene terephthalate), a further evidence that in the future they could replace traditional polymers in several applications.
Beatriz Robles-Hernández; Michelina Soccio; Iker Castrillo; Giulia Guidotti; Nadia Lotti; Angel Alegria; Daniel E Martínez-Tong. Poly(alkylene 2,5-Furanoate)s Thin Films: Morphology, Crystallinity and Nanomechanical Properties. 2020, 1 .
AMA StyleBeatriz Robles-Hernández, Michelina Soccio, Iker Castrillo, Giulia Guidotti, Nadia Lotti, Angel Alegria, Daniel E Martínez-Tong. Poly(alkylene 2,5-Furanoate)s Thin Films: Morphology, Crystallinity and Nanomechanical Properties. . 2020; ():1.
Chicago/Turabian StyleBeatriz Robles-Hernández; Michelina Soccio; Iker Castrillo; Giulia Guidotti; Nadia Lotti; Angel Alegria; Daniel E Martínez-Tong. 2020. "Poly(alkylene 2,5-Furanoate)s Thin Films: Morphology, Crystallinity and Nanomechanical Properties." , no. : 1.
Poly(alkylene 2,5-furanoate)s are considered as the most attractive and interesting alternatives to replace oil-based terephthalic polymers. These furan-based polyesters can be synthesized using fully bio-based synthetic strategies, allowing to reduce the environmental impact of plastics. At the same time, these polymers have shown outstanding thermal, mechanical and gas-barrier properties. All these results envisage their industrial use in the near future. Now, considering the downscaling of the products’ size towards the nanometer scale, we present a study of the morphology and nanomechanical properties of poly(alkylene 2,5-furanoate) thin films. Using Atomic Force Microscopy, we report the development of nanostructures upon crystallization, following different thermal treatments, for thin films with thicknesses below 200 nm. Moreover, we studied the impact of crystal growth in the nanomechanical properties of these materials. We found that the polymer thin films preserve their excellent mechanical response even in the confined geometry, as proved by the Young’s moduli values close to the GPa, accompanied by high surface stiffness, and low indentation depths. The poly(alkylene 2,5-furanoate) thin films were found to have nanomechanical properties comparable to those of the oil-based poly(ethylene terephthalate), a further evidence that in the future they could replace traditional polymers in several applications.
Beatriz Robles-Hernández; Michelina Soccio; Iker Castrillo; Giulia Guidotti; Nadia Lotti; Angel Alegria; Daniel E Martínez-Tong. Poly(alkylene 2,5-Furanoate)s Thin Films: Morphology, Crystallinity and Nanomechanical Properties. 2020, 1 .
AMA StyleBeatriz Robles-Hernández, Michelina Soccio, Iker Castrillo, Giulia Guidotti, Nadia Lotti, Angel Alegria, Daniel E Martínez-Tong. Poly(alkylene 2,5-Furanoate)s Thin Films: Morphology, Crystallinity and Nanomechanical Properties. . 2020; ():1.
Chicago/Turabian StyleBeatriz Robles-Hernández; Michelina Soccio; Iker Castrillo; Giulia Guidotti; Nadia Lotti; Angel Alegria; Daniel E Martínez-Tong. 2020. "Poly(alkylene 2,5-Furanoate)s Thin Films: Morphology, Crystallinity and Nanomechanical Properties." , no. : 1.
Tammann’s two-stage crystal-nuclei-development method is applied for analysis of the thermal stability of homogenously formed crystal nuclei of poly(butylene isophthalate) (PBI) as well as their possible reorganization on transferring them to the growth temperature, using fast scanning chip calorimetry. Crystal nuclei were formed at 50 °C, that is, at a temperature only slightly higher than the glass transition temperature, and developed to crystals within a pre-defined time at the growth temperature of 85 °C. The number of nuclei, overcritical at the growth temperature, was detected as a function of the transfer-conditions (maximum temperature, heating rate) by evaluation of the developed crystal fraction. For different size-distributions of crystal nuclei, as controlled by the nucleation time, there is detected distinct reduction of the nuclei number on heating to maximum temperatures higher than about 90 to 110 °C, with the latter value holding for longer nucleation time. Longer nucleation allows for both increasing the absolute nuclei number and generation of an increased fraction of larger nuclei. Heating at 1000 K/s to 140–150 °C causes “melting” of even the most stable nuclei. While direct transfer of crystal nuclei from the nucleation temperature (50 °C) to the growth temperature (85 °C) reveals negligible effect of the transfer-heating rate, in-between heating to higher temperatures is connected with distinct nuclei-reorganization above 85 °C on heating slower than 1000–10.000 K/s. The performed study not only provides specific valuable information about the thermal characteristics of crystal nuclei of PBI but also highlights the importance of proper design of Tammann’s nuclei development experiment for analysis of nuclei numbers. With the evaluation of critical rates of temperature-change for suppression of non-isothermal formation of both nuclei and crystals, the kinetics of crystallization of the slow crystallizing PBI is further quantified.
Silvia Quattrosoldi; Nadia Lotti; Michelina Soccio; Christoph Schick; René Androsch. Stability of Crystal Nuclei of Poly (butylene isophthalate) Formed Near the Glass Transition Temperature. Polymers 2020, 12, 1099 .
AMA StyleSilvia Quattrosoldi, Nadia Lotti, Michelina Soccio, Christoph Schick, René Androsch. Stability of Crystal Nuclei of Poly (butylene isophthalate) Formed Near the Glass Transition Temperature. Polymers. 2020; 12 (5):1099.
Chicago/Turabian StyleSilvia Quattrosoldi; Nadia Lotti; Michelina Soccio; Christoph Schick; René Androsch. 2020. "Stability of Crystal Nuclei of Poly (butylene isophthalate) Formed Near the Glass Transition Temperature." Polymers 12, no. 5: 1099.
Fully biobased random copolymers of poly(butylene succinate) (PBS) containing different amount of Pripol 1009 moieties were synthesized by melt polycondensation. Molecular characterization confirmed the chemical structure and the random distribution of counts (NMR) and indicated that high molecular weight samples were obtained (GPC). All the polymers under study were semicrystalline, developing the typical α-PBS crystalline phase, the melting temperature and the crystallinity degree regularly decreasing with the increase of Pripol content. Pripol moieties determined also an improvement of polymer chain flexibility, as proved by the glass transition temperature decreasing, and of thermal stability. Polymer mechanical response was nicely tuned by changing copolymer composition, the copolymer with the highest Pripol content showing the typical behavior of thermoplastic elastomers despite its random nature. Lastly, biodegradation rate in compost also increased with the content of Pripol due to the parallel decrease of sample crystallinity degree. Surprisingly, microorganisms present in the compost preferentially attack BS comonomeric units despite their semicrystalline nature.
Silvia Quattrosoldi; Michelina Soccio; Massimo Gazzano; Nadia Lotti; Andrea Munari. Fully biobased, elastomeric and compostable random copolyesters of poly(butylene succinate) containing Pripol 1009 moieties: Structure-property relationship. Polymer Degradation and Stability 2020, 178, 109189 .
AMA StyleSilvia Quattrosoldi, Michelina Soccio, Massimo Gazzano, Nadia Lotti, Andrea Munari. Fully biobased, elastomeric and compostable random copolyesters of poly(butylene succinate) containing Pripol 1009 moieties: Structure-property relationship. Polymer Degradation and Stability. 2020; 178 ():109189.
Chicago/Turabian StyleSilvia Quattrosoldi; Michelina Soccio; Massimo Gazzano; Nadia Lotti; Andrea Munari. 2020. "Fully biobased, elastomeric and compostable random copolyesters of poly(butylene succinate) containing Pripol 1009 moieties: Structure-property relationship." Polymer Degradation and Stability 178, no. : 109189.