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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.
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.
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.
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.
Biopolymers are gaining increasing importance as substitutes for plastics derived from fossil fuels, especially for packaging applications. In particular, furanoate-based polyesters appear as the most credible alternative due to their intriguing physic/mechanical and gas barrier properties. In this study, block copolyesters containing 2,5-furan and trans-1,4-cyclohexane moieties were synthesized by reactive blending, starting from the two parent homopolymers: poly(propylene furanoate) (PPF) and poly(propylene cyclohexanedicarboxylate) (PPCE). The whole range of molecular architectures, from long block to random copolymer with a fixed molar composition (1:1 of the two repeating units) was considered. Molecular, thermal, tensile, and gas barrier properties of the prepared materials were investigated and correlated to the copolymer structure. A strict dependence of the functional properties on the copolymers' block length was found. In particular, short block copolymers, thanks to the introduction of more flexible cyclohexane-containing co-units, displayed high elongation at break and low elastic modulus, thus overcoming PPF's intrinsic rigidity. Furthermore, the exceptionally low gas permeabilities of PPF were further improved due to the concomitant action of the two rings, both capable of acting as mesogenic groups in the presence of flexible aliphatic units, and thus responsible for the formation of 1D/2D ordered domains, which in turn impart outstanding barrier properties.
Giulia Guidotti; Laura Genovese; Michelina Soccio; Matteo Gigli; Andrea Munari; Valentina Siracusa; Nadia Lotti. Block Copolyesters Containing 2,5-Furan and trans-1,4-Cyclohexane Subunits with Outstanding Gas Barrier Properties. International Journal of Molecular Sciences 2019, 20, 2187 .
AMA StyleGiulia Guidotti, Laura Genovese, Michelina Soccio, Matteo Gigli, Andrea Munari, Valentina Siracusa, Nadia Lotti. Block Copolyesters Containing 2,5-Furan and trans-1,4-Cyclohexane Subunits with Outstanding Gas Barrier Properties. International Journal of Molecular Sciences. 2019; 20 (9):2187.
Chicago/Turabian StyleGiulia Guidotti; Laura Genovese; Michelina Soccio; Matteo Gigli; Andrea Munari; Valentina Siracusa; Nadia Lotti. 2019. "Block Copolyesters Containing 2,5-Furan and trans-1,4-Cyclohexane Subunits with Outstanding Gas Barrier Properties." International Journal of Molecular Sciences 20, no. 9: 2187.
The present paper describes the synthesis of novel bio-based poly(butylene 1,4-cyclohexane dicarboxylate)-containing random copolymers for sustainable and flexible packaging applications. On one side, the linear butylene moiety has been substituted by glycol subunits with alkyl pendant groups of different length. On the other side, copolymers with different cis/trans isomer ratio of cyclohexane rings have been synthesized. The prepared samples were subjected to molecular, thermal, diffractometric, and mechanical characterization. The barrier performances to O2, CO2, and N2 gases were also evaluated. The presence of side alkyl groups did not alter the thermal stability, whereas it significantly influences the formation of ordered phases that deeply affect the functional properties, mainly in terms of mechanical response and barrier performance. In particular, the final materials present higher flexibility and significantly improved barrier properties with respect to the homopolymer and most polymers widely employed for flexible packaging. The improvement due to copolymerization was more pronounced in the case of higher co-unit-containing copolymers and for the samples with cyclohexane rings in the trans conformation.
Giulia Guidotti; Michelina Soccio; Valentina Siracusa; Massimo Gazzano; Andrea Munari; Nadia Lotti. Novel Random Copolymers of Poly(butylene 1,4-cyclohexane dicarboxylate) with Outstanding Barrier Properties for Green and Sustainable Packaging: Content and Length of Aliphatic Side Chains as Efficient Tools to Tailor the Material’s Final Performance. Polymers 2018, 10, 866 .
AMA StyleGiulia Guidotti, Michelina Soccio, Valentina Siracusa, Massimo Gazzano, Andrea Munari, Nadia Lotti. Novel Random Copolymers of Poly(butylene 1,4-cyclohexane dicarboxylate) with Outstanding Barrier Properties for Green and Sustainable Packaging: Content and Length of Aliphatic Side Chains as Efficient Tools to Tailor the Material’s Final Performance. Polymers. 2018; 10 (8):866.
Chicago/Turabian StyleGiulia Guidotti; Michelina Soccio; Valentina Siracusa; Massimo Gazzano; Andrea Munari; Nadia Lotti. 2018. "Novel Random Copolymers of Poly(butylene 1,4-cyclohexane dicarboxylate) with Outstanding Barrier Properties for Green and Sustainable Packaging: Content and Length of Aliphatic Side Chains as Efficient Tools to Tailor the Material’s Final Performance." Polymers 10, no. 8: 866.
Both academia and industry are currently devoting many efforts to develop high gas barrier bioplastics as substitutes of traditional fossil-based polymers. In this view, this contribution presents a new biobased aromatic polyester, i.e., poly(propylene 2,5-thiophenedicarboxylate) (PPTF), which has been compared with the furan-based counterpart (PPF). Both biopolyesters have been characterized from the molecular, thermo-mechanical and structural points of view. Gas permeability behavior has been evaluated with respect to 100% oxygen, carbon dioxide and nitrogen at 23 °C. In case of CO2 gas test, gas transmission rate has been also measured at different temperatures. The permeability behavior at different relative humidity has been investigated for both biopolyesters, the thiophen-containing sample demonstrating to be better than the furan-containing counterpart. PPF’s permeability behavior became worse than PPTF’s with increasing RH, due to the more polar nature of the furan ring. Both biopolyesters under study are characterized by superior gas barrier performances with respect to PEF and PET. With the simple synthetic strategy adopted, the exceptional barrier properties render these new biobased polyesters interesting alternatives in the world of green and sustainable packaging materials. The different polarity and stability of heterocyclic rings was revealed to be an efficient tool to tailor the ability of crystallization, which in turn affects mechanical and barrier performances.
Giulia Guidotti; Michelina Soccio; Nadia Lotti; Massimo Gazzano; Valentina Siracusa; Andrea Munari. Poly(propylene 2,5-thiophenedicarboxylate) vs. Poly(propylene 2,5-furandicarboxylate): Two Examples of High Gas Barrier Bio-Based Polyesters. Polymers 2018, 10, 785 .
AMA StyleGiulia Guidotti, Michelina Soccio, Nadia Lotti, Massimo Gazzano, Valentina Siracusa, Andrea Munari. Poly(propylene 2,5-thiophenedicarboxylate) vs. Poly(propylene 2,5-furandicarboxylate): Two Examples of High Gas Barrier Bio-Based Polyesters. Polymers. 2018; 10 (7):785.
Chicago/Turabian StyleGiulia Guidotti; Michelina Soccio; Nadia Lotti; Massimo Gazzano; Valentina Siracusa; Andrea Munari. 2018. "Poly(propylene 2,5-thiophenedicarboxylate) vs. Poly(propylene 2,5-furandicarboxylate): Two Examples of High Gas Barrier Bio-Based Polyesters." Polymers 10, no. 7: 785.
Many efforts are currently devoted to the design and development of high performance bioplastics to replace traditional fossil-based polymers. In response, this contribution presents a new biobased aromatic polyester, i.e., poly(butylene 2,5-thiophenedicarboxylate) (PBTF). Here, PBTF is characterized from the molecular, thermo-mechanical and structural point of view. Gas permeability is evaluated at different temperatures, in the range below and above glass transition, providing a full insight into the performances of this material under different operating conditions, and demonstrating the superior gas barrier behavior of PBTF with respect to other polyesters, such as PEF and PET. The combination of calorimetric and diffractometric studies allows for a deep understanding of the structure of PBTF, revealing the presence of a not-induced 2D-ordered phase (meso-phase), responsible for its outstanding gas permeability behavior. The simple synthetic strategy adopted, the exceptional barrier properties, combined with the interesting mechanical characteristics of PBTF open up new scenarios in the world of green and sustainable packaging materials.
Giulia Guidotti; Matteo Gigli; Michelina Soccio; Nadia Lotti; Massimo Gazzano; Valentina Siracusa; Andrea Munari. Poly(butylene 2,5-thiophenedicarboxylate): An Added Value to the Class of High Gas Barrier Biopolyesters. Polymers 2018, 10, 167 .
AMA StyleGiulia Guidotti, Matteo Gigli, Michelina Soccio, Nadia Lotti, Massimo Gazzano, Valentina Siracusa, Andrea Munari. Poly(butylene 2,5-thiophenedicarboxylate): An Added Value to the Class of High Gas Barrier Biopolyesters. Polymers. 2018; 10 (2):167.
Chicago/Turabian StyleGiulia Guidotti; Matteo Gigli; Michelina Soccio; Nadia Lotti; Massimo Gazzano; Valentina Siracusa; Andrea Munari. 2018. "Poly(butylene 2,5-thiophenedicarboxylate): An Added Value to the Class of High Gas Barrier Biopolyesters." Polymers 10, no. 2: 167.
In the last decade, there has been an increased interest from the food packaging industry toward the development and application of biodegradable and biobased plastics, to contribute to the sustainable economy and to reduce the huge environmental problem afflicting the planet. In this framework, the present paper describes the synthesis of novel PBS (poly(butylene succinate))-based random copolymers with different composition containing glycol sub-units characterized by alkyl pendant groups of different length. The prepared samples were subjected to molecular, thermal, diffractometric and mechanical characterization. The barrier performances to O₂, CO₂ and N₂ gases were also evaluated, envisioning for these new materials an application in food packaging. The presence of the side alkyl groups did not alter the thermal stability, whereas it significantly reduced the sample crystallinity degree, making these materials more flexible. The barrier properties were found to be worse than PBS; however, some of them were comparable to, or even better than, those of Low Density Polyethylene (LDPE), widely employed for flexible food packaging. The entity of variations in the final properties due to copolymerization were more modest in the case of the co-unit with short side methyl groups, which, when included in the PBS crystal lattice, causes a more modest decrement of crystallinity degree.
Giulia Guidotti; Michelina Soccio; Valentina Siracusa; Massimo Gazzano; Elisabetta Salatelli; Andrea Munari; Nadia Lotti. Novel Random PBS-Based Copolymers Containing Aliphatic Side Chains for Sustainable Flexible Food Packaging. Polymers 2017, 9, 724 .
AMA StyleGiulia Guidotti, Michelina Soccio, Valentina Siracusa, Massimo Gazzano, Elisabetta Salatelli, Andrea Munari, Nadia Lotti. Novel Random PBS-Based Copolymers Containing Aliphatic Side Chains for Sustainable Flexible Food Packaging. Polymers. 2017; 9 (12):724.
Chicago/Turabian StyleGiulia Guidotti; Michelina Soccio; Valentina Siracusa; Massimo Gazzano; Elisabetta Salatelli; Andrea Munari; Nadia Lotti. 2017. "Novel Random PBS-Based Copolymers Containing Aliphatic Side Chains for Sustainable Flexible Food Packaging." Polymers 9, no. 12: 724.