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1.
ACS Sustain Chem Eng ; 12(13): 5251-5262, 2024 Apr 01.
Artigo em Inglês | MEDLINE | ID: mdl-38577586

RESUMO

Heat-shrinkable films are widely used as disposable secondary packaging but are conventionally made from fossil-based and nonbiodegradable polyvinyl chloride or polyethylene. To lower the environmental impact of such products, this work reports the development of recyclable, biodegradable, and partially biosourced heat-shrinkable biocomposites that are cost-competitive with existing shrink wraps. Poly(butylene adipate-co-terephthalate), a growing biodegradable thermoplastic, was simultaneously reinforced with pulp fibers and partially cross-linked in a single-step reactive melt processing. The designed peroxide-initiated reaction led to a 55 wt % cocontinuous insoluble gel incorporating all the pulp fibers into a cross-linked polymer network. In the solid state, the cross-linked biocomposite shows 60% elongation at break with a 200% increase in Young's modulus, while the only addition of pulp fibers stiffens and embrittles the matrix. Creep tests in the melt state indicated that the cross-linked network induces homogeneous shrinking even during the loading phase, demonstrating the potential use of the biocomposites as heat-shrinkable films. The shrinking also promotes the shape-memory of the biocomposite, which retains its dimensions after four cycles. The circularity of the materials was assessed by mechanical recycling and industrial composting, which have proven feasible end-of-life options for heat-shrinkable biocomposites.

2.
Molecules ; 29(3)2024 Jan 31.
Artigo em Inglês | MEDLINE | ID: mdl-38338411

RESUMO

This review introduces groundbreaking insights in polymer science, specifically spotlighting a novel review of the solid-state modification (SSM) approach of thermoplastic polymers, a method not extensively explored. Unlike traditional melt polymer modification, SSM stands out by incorporating monomers or oligomers into the amorphous phase of polymers through innovative exchange reactions. The background of the study places thermoplastics within the context of their increased use over the past century, highlighting their versatility in various applications and the associated environmental and health concerns due to certain additives. The results section outlines the unique aspects of SSM and its increasing recognition for its potential to enhance material performance in areas such as catalysts and composites. It also discusses the application of SSM in modifying different thermoplastic polymers, highlighting various studies demonstrating the method's effectiveness in altering polymer properties. Finally, this work emphasizes SSM's importance in environmental sustainability and its potential in the recycling and upcycling of plastic materials. It acknowledges the challenges and future perspectives in the field, particularly regarding the scalability of SSM techniques for industrial applications and their role in advancing a circular economy in the polymer industry.

3.
ACS Omega ; 7(41): 36403-36414, 2022 Oct 18.
Artigo em Inglês | MEDLINE | ID: mdl-36278048

RESUMO

During the past years, the synthesis of polymer prodrug structures, based on natural phytochemical compounds with a great range of valuable biological properties, has become a promising solution in cancer prevention, imaging, and detection. Curcumin (Curc) remains one of the most studied natural products, due to the impressive palette of biological properties and the possibility to be easily loaded in various micro- and nanostructures and chemically modified. In this study, pegylated curcumin derivatives were prepared by a direct esterification reaction between poly(ethylene glycol)diacid (PEG of 600 g/mol molar mass, PEG600) and Curc in the presence of N,N'-dicyclohexylcarbodiimide (PEG600-Curc). The successful reaction resulted in a water-soluble stable product that was characterized by infrared spectroscopy (Fourier transform infrared (FT-IR)) and proton (1H) and carbon (13C) NMR. The effect of the pH values of buffer solutions on PEG600-Curc spectral properties (absorption and photoluminescence) was investigated by UV-vis and fluorescence spectrophotometry. Based on the biological tests, it was confirmed that PEG600-Curc exhibits cytotoxic activity against Graffi cell lines, as a function of the Curc concentration in the conjugate and the incubation time. PEG600-Curc antibacterial activity was validated in microbiological tests against pathogenic microorganisms such as Staphylococcus aureus. Most importantly, despite the covalent attachment of Curc to PEG and the slight reduction in the therapeutic index of the conjugate, both the anticancer and antimicrobial activities remain the highest reported, thus opening the gate for further, more clinically oriented studies.

4.
Polymers (Basel) ; 14(6)2022 Mar 16.
Artigo em Inglês | MEDLINE | ID: mdl-35335518

RESUMO

Over the last decades, the global life expectancy of the population has increased, and so, consequently, has the risk of cancer development. Despite the improvement in cancer therapies (e.g., drug delivery systems (DDS) and theranostics), in many cases recurrence continues to be a challenging issue. In this matter, the development of nanotechnology has led to an array of possibilities for cancer treatment. One of the most promising therapies focuses on the assembly of hierarchical structures in the form of nanoclusters, as this approach involves preparing individual building blocks while avoiding handling toxic chemicals in the presence of biomolecules. This review aims at presenting an overview of the major advances made in developing nanoclusters based on polymeric nanoparticles (PNPs) and/or inorganic NPs. The preparation methods and the features of the NPs used in the construction of the nanoclusters were described. Afterwards, the design, fabrication and properties of the two main classes of nanoclusters, namely noble-metal nanoclusters and hybrid (i.e., hetero) nanoclusters and their mode of action in cancer therapy, were summarized.

5.
Molecules ; 26(19)2021 Sep 30.
Artigo em Inglês | MEDLINE | ID: mdl-34641488

RESUMO

The present work highlights the crucial role of the interfacial compatibilization on the design of polylactic acid (PLA)/Magnesium (Mg) composites for bone regeneration applications. In this regard, an amphiphilic poly(ethylene oxide-b-L,L-lactide) diblock copolymer with predefined composition was synthesised and used as a new interface to provide physical interactions between the metallic filler and the biopolymer matrix. This strategy allowed (i) overcoming the PLA/Mg interfacial adhesion weakness and (ii) modulating the composite hydrophilicity, bioactivity and biological behaviour. First, a full study of the influence of the copolymer incorporation on the morphological, wettability, thermal, thermo-mechanical and mechanical properties of PLA/Mg was investigated. Subsequently, the bioactivity was assessed during an in vitro degradation in simulated body fluid (SBF). Finally, biological studies with stem cells were carried out. The results showed an increase of the interfacial adhesion by the formation of a new interphase between the hydrophobic PLA matrix and the hydrophilic Mg filler. This interface stabilization was confirmed by a decrease in the damping factor (tanδ) following the copolymer addition. The latter also proves the beneficial effect of the composite hydrophilicity by selective surface localization of the hydrophilic PEO leading to a significant increase in the protein adsorption. Furthermore, hydroxyapatite was formed in bulk after 8 weeks of immersion in the SBF, suggesting that the bioactivity will be noticeably improved by the addition of the diblock copolymer. This ceramic could react as a natural bonding junction between the designed implant and the fractured bone during osteoregeneration. On the other hand, a slight decrease of the composite mechanical performances was noted.


Assuntos
Materiais Biocompatíveis/química , Magnésio/química , Células-Tronco Mesenquimais/fisiologia , Poliésteres/química , Polímeros/química , Adulto , Adesão Celular/fisiologia , Células Cultivadas , Humanos , Células-Tronco Mesenquimais/citologia
6.
Polymers (Basel) ; 13(15)2021 Aug 03.
Artigo em Inglês | MEDLINE | ID: mdl-34372179

RESUMO

The influence of ultra-short laser modification on the surface morphology and possible chemical alteration of poly-lactic acid (PLA) matrix in respect to the optimization of cellular and antibacterial behavior were investigated in this study. Scanning electron microscopy (SEM) morphological examination of the processed PLA surface showed the formation of diverse hierarchical surface microstructures, generated by irradiation with a range of laser fluences (F) and scanning velocities (V) values. By controlling the laser parameters, diverse surface roughness can be achieved, thus influencing cellular dynamics. This surface feedback can be applied to finely tune and control diverse biomaterial surface properties like wettability, reflectivity, and biomimetics. The triggering of thermal effects, leading to the ejection of material with subsequent solidification and formation of raised rims and 3D-like hollow structures along the processed zones, demonstrated a direct correlation to the wettability of the PLA. A transition from superhydrophobic (θ > 150°) to super hydrophilic (θ < 20°) surfaces can be achieved by the creation of grooves with V = 0.6 mm/s, F = 1.7 J/cm2. The achieved hierarchical architecture affected morphology and thickness of the processed samples which were linked to the nature of ultra-short laser-material interaction effects, namely the precipitation of temperature distribution during material processing can be strongly minimized with ultrashort pulses leading to non-thermal and spatially localized effects that can facilitate volume ablation without collateral thermal damage The obtained modification zones were analyzed employing Fourier transform infrared (FTIR), X-ray photoelectron spectroscopy (XPS), Energy dispersive X-ray analysis (EDX), and optical profilometer. The modification of the PLA surface resulted in an increased roughness value for treatment with lower velocities (V = 0.6 mm/s). Thus, the substrate gains a 3D-like architecture and forms a natural matrix by microprocessing with V = 0.6 mm/s, F = 1.7 J/cm2, and V = 3.8 mm/s, F = 0.8 J/cm2. The tests performed with Mesenchymal stem cells (MSCs) demonstrated that the ultra-short laser surface modification altered the cell orientation and promoted cell growth. The topographical design was tested also for the effectiveness of bacterial attachment concerning chosen parameters for the creation of an array with defined geometrical patterns.

7.
Mar Pollut Bull ; 167: 112295, 2021 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-33799154

RESUMO

The substitution of petrochemical plastics by bio-based and biodegradable plastics are in need of an evaluation for the potential toxic impacts that they can have on marine wildlife. This study aims to assess the toxicological effects of polylactic acid microparticles at two concentrations, 10 and 100 µg/L, during 8 days on the blue mussel, Mytilus edulis. No significant oxidative stress (catalase, glutathione-S-transferase and superoxide dismutase activities), neurotoxicity (acetylcholinesterase), or immunotoxicity (lysosomal membrane stability and acid phosphatase activity) were detectable. The multivariate analysis of metabolomic data allowed us to differentiate the individuals according to the exposure. From the loading plot of OPLS-DA, 48 ions down-regulated in the individuals exposed to microplastics. They were identified based on HRMS data as glycerophospholipids.


Assuntos
Mytilus edulis , Mytilus , Poluentes Químicos da Água , Animais , Catalase , Humanos , Microplásticos , Plásticos , Poluentes Químicos da Água/análise , Poluentes Químicos da Água/toxicidade
8.
Polymers (Basel) ; 13(4)2021 Feb 04.
Artigo em Inglês | MEDLINE | ID: mdl-33557338

RESUMO

One-step reactive melt processing (REx) via radical reactions was evaluated with the aim of improving the rheological properties of poly(ε-caprolactone) (PCL). In particular, a water-assisted REx was designed under the hypothesis of increasing crosslinking efficiency with water as a low viscous medium in comparison with a slower PCL macroradicals diffusion in the melt state. To assess the effect of dry vs. water-assisted REx on PCL, its structural, thermo-mechanical and rheological properties were investigated. Water-assisted REx resulted in increased PCL gel fraction compared to dry REx (from 1-34%), proving the rationale under the formulated hypothesis. From dynamic mechanical analysis and tensile tests, the crosslink did not significantly affect the PCL mechanical performance. Dynamic rheological measurements showed that higher PCL viscosity was reached with increasing branching/crosslinking and the typical PCL Newtonian behavior was shifting towards a progressively more pronounced shear thinning. A complete transition from viscous- to solid-like PCL melt behavior was recorded, demonstrating that higher melt elasticity can be obtained as a function of gel content by controlled REx. Improvement in rheological properties offers the possibility of broadening PCL melt processability without hindering its recycling by melt processing.

9.
Materials (Basel) ; 14(2)2021 Jan 18.
Artigo em Inglês | MEDLINE | ID: mdl-33477447

RESUMO

This work details the scalable and solventless synthesis of a potential fully biobased monobenzoxazine resin derived from tyrosol and furfurylamine. The structure of the monomer was studied by nuclear magnetic resonance (NMR) spectroscopy and Fourier transform infrared (FTIR). The curing of the precursors was characterized by differential scanning calorimetry (DSC), rheological measurements, and thermogravimetric analysis (TGA). The properties of the resulting biobased polybenzoxazine were then determined by thermogravimetric analysis (TGA) and dynamic mechanical thermal analysis (DMA). A thermally stable resin was obtained with 5% and 10% weight-reduction-temperature (T d5 and T d10) values of 349 and 395 °C, respectively, and a char yield of 53%. Moreover, the low melting temperature, low viscosity, and excellent thermomechanical behavior make this fully biobased resin a promising candidate for coating applications.

10.
ACS Appl Bio Mater ; 4(10): 7445-7455, 2021 10 18.
Artigo em Inglês | MEDLINE | ID: mdl-35006713

RESUMO

In this study, a simple method to immobilize chitosan on a poly(lactic acid) (PLA) surface was developed in a fast manner. The immobilization was realized in two steps. First, an atmospheric plasma (MWAP) torch was used to modify the PLA surface in less than 5 min in order to create enough activated sites toward the chitosan adhesion, followed by a direct dip coating to spread and immobilize chitosan on this MWAP-modified PLA surface. The modification of the PLA surface properties was confirmed by X-ray photoelectron spectroscopy (XPS), water contact angle, and atomic force microscopy. It resulted that the activated species derived from the plasma torch, i.e., hydroxyl and carboxylic acid moieties, enabled an increase of the hydrophilicity of the PLA surface. Interestingly, this activated surface allows a good spreading of chitosan solution from dip coating and leads to a homogeneous stable coating. Our XPS results bring us the hypothesis that the stabilization of the chitosan layer is mainly induced by noncovalent interactions such as hydrogen bonding and electrostatic interactions. A first insight into the biological properties of theses surfaces was assessed in terms of the antimicrobial activity of the here-designed surfaces.


Assuntos
Anti-Infecciosos , Quitosana , Anti-Infecciosos/farmacologia , Quitosana/química , Micro-Ondas , Poliésteres
11.
ACS Appl Bio Mater ; 4(4): 3067-3078, 2021 04 19.
Artigo em Inglês | MEDLINE | ID: mdl-35014395

RESUMO

The present study aims to improve the interfacial bonding between hydroxyapatite particles (HAs) and polylactide (PLA) to enhance the mechanical performance and biocompatibility of bone implants based on HA/PLA. For this, one-shot surface functionalization of HA via plasma polymerization is developed. Taking advantage of acetylene plasma chemistry, the hydrophobicity of HA particles was finely tuned prior to their introduction into a PLA matrix via an extrusion process. The effect of the plasma power (20 or 100 W) on the composition of the plasma polymer film (PPF) formed on the HA surface was studied via Fourier transform infrared (FTIR) spectroscopy, time-of-flight secondary-ion mass spectrometry (ToF-SIMS), and X-ray photoelectron spectroscopy (XPS). The amount of PPF formed was evaluated via thermogravimetric analyses (TGA). Cytotoxicity of the modified HA particles was monitored by the WST-1 proliferation assay and lactate dehydrogenase (LDH) release and showed that independent on the studied conditions, cell viability remained above the 70% threshold and LDH accumulation changes were insignificant, suggesting good biocompatibility. Contact angle measurements and morphological and rheological analyses showed that the low working power promoted more hydrophobic surfaces and a better HA/PLA interface. Dynamic mechanical analyses revealed that the storage modulus at 37 °C increased for the composite containing functionalized particles by 1.5 times compared to the neat particle's composites. This work opens a route toward further one-shot development of improved scaffolds for bone tissue engineering.


Assuntos
Regeneração Óssea/efeitos dos fármacos , Materiais Revestidos Biocompatíveis/farmacologia , Osteoblastos/efeitos dos fármacos , Polímeros/farmacologia , Materiais Revestidos Biocompatíveis/síntese química , Materiais Revestidos Biocompatíveis/química , Durapatita/química , Durapatita/farmacologia , Humanos , Teste de Materiais , Estrutura Molecular , Tamanho da Partícula , Poliésteres/química , Poliésteres/farmacologia , Polímeros/química , Engenharia Tecidual , Alicerces Teciduais/química
12.
Polymers (Basel) ; 11(12)2019 Dec 02.
Artigo em Inglês | MEDLINE | ID: mdl-31810223

RESUMO

Reactive extrusion and magnesium (II) N-heterocyclic carbene catalyst are successfully employed in continuous polylactide synthesis. The possibility of using six-membered N-heterocyclic carbene adducts to act as efficient catalysts towards the sustainable synthesis of poly(l-lactide) through ring-opening polymerization of l-lactide (LA) is first investigated in bulk batch reactions. Under optimized solvent-free conditions, polylactide (PLA) of moderate to high molecular weights and excellent optical activities are successfully achieved. These promising results are further applied in the continuous production of PLA in an extruder.

13.
Materials (Basel) ; 13(1)2019 Dec 18.
Artigo em Inglês | MEDLINE | ID: mdl-31861398

RESUMO

In this study, a highly efficient flame-retardant bioplastic poly(lactide) was developed by covalently incorporating flame-retardant DOPO, that is, 9,10-dihydro-oxa-10-phosphaphenanthrene-10-oxide. To that end, a three-step strategy that combines the catalyzed ring-opening polymerization (ROP) of L,L-lactide (L,L-LA) in bulk from a pre-synthesized DOPO-diamine initiator, followed by bulk chain-coupling reaction by reactive extrusion of the so-obtained phosphorylated polylactide (PLA) oligomers (DOPO-PLA) with hexamethylene diisocyanate (HDI), is described. The flame retardancy of the phosphorylated PLA (DOPO-PLA-PU) was investigated by mass loss cone calorimetry and UL-94 tests. As compared with a commercially available PLA matrix, phosphorylated PLA shows superior flame-retardant properties, that is, (i) significant reduction of both the peak of heat release rate (pHRR) and total heat release (THR) by 35% and 36%, respectively, and (ii) V0 classification at UL-94 test. Comparisons between simple physical DOPO-diamine/PLA blends and a DOPO-PLA-PU material were also performed. The results evidenced the superior flame-retardant behavior of phosphorylated PLA obtained by a reactive pathway.

14.
ACS Omega ; 3(1): 1069-1080, 2018 Jan 31.
Artigo em Inglês | MEDLINE | ID: mdl-31457949

RESUMO

All-biobased and biodegradable nanocomposites consisting of poly(l-lactide) (PLLA) and starch nanoplatelets (SNPs) were prepared via a new strategy involving supramolecular chemistry, i.e., stereocomplexation and hydrogen-bonding interactions. For this purpose, a poly(d-lactide)-b-poly(glycidyl methacrylate) block copolymer (PDLA-b-PGMA) was first synthesized via the combination of ring-opening polymerization and atom-transfer radical polymerization. NMR spectroscopy and size-exclusion chromatography analysis confirmed a complete control over the copolymer synthesis. The SNPs were then mixed up with the copolymer for producing a PDLA-b-PGMA/SNPs masterbatch. The masterbatch was processed by solvent casting for which a particular attention was given to the solvent selection to preserve SNPs morphology as evidenced by transmission electron microscopy. Near-infrared spectroscopy was used to highlight the copolymer-SNPs supramolecular interactions mostly via hydrogen bonding. The prepared masterbatch was melt-blended with virgin PLLA and then thin films of PLLA/PDLA-b-PGMA/SNPs nanocomposites (ca. 600 µm) were melt-processed by compression molding. The resulting nanocomposite films were deeply characterized by thermogravimetric analysis and differential scanning calorimetry. Our findings suggest that supramolecular interactions based on stereocomplexation between the PLLA matrix and the PDLA block of the copolymer had a synergetic effect allowing the preservation of SNPs nanoplatelets and their morphology during melt processing. Quartz crystal microbalance and dynamic mechanical thermal analysis suggested a promising potential of the stereocomplex supramolecular approach in tuning PLLA/SNPs water vapor uptake and mechanical properties together with avoiding PLLA/SNPs degradation during melt processing.

15.
RSC Adv ; 8(48): 27119-27130, 2018 Jul 30.
Artigo em Inglês | MEDLINE | ID: mdl-35540004

RESUMO

A novel poly(epsilon-caprolactone) (PCL) supramolecular network exhibiting shape-memory behavior was successfully constructed with pendant UPy units that are highly able to dimerize. The dynamic network was obtained by a simple and versatile strategy consisting of chain-extension reaction between α,ω-dihydroxyoligoPCL and hydroxylated UPy units in the presence of hexamethylene diisocyanate as a coupling agent and further intermolecular dimerization of the UPy along the polyurethane backbone. 1H NMR analyses confirmed the dynamic features of the system, and DMTA in tensile mode was investigated to assess the SMP properties. Recyclability was also assessed by taking advantage of these supramolecular networks. Further addition of cellulose nanocrystals into the polymer network enabled adjustment of the extent of the net-points and therefore the SMP features. As confirmed by dispersion tests in solution and SEM observations, these bio-based nanofillers were homogeneously distributed in the network via supramolecular interaction between the hydroxyl groups present on their surface and UPy moieties along the polyurethane backbone. Thus, the here developed nanomaterials might reveal applicability in areas where a combination of SMP and biocompatibility is needed.

16.
Polymers (Basel) ; 10(1)2017 Dec 22.
Artigo em Inglês | MEDLINE | ID: mdl-30966043

RESUMO

The crystallization and morphology of PLA-mb-PBS copolymers and their corresponding stereocomplexes were studied. The effect of flexible blocks (i.e., polybutylene succinate, PBS) on the crystallization of the copolymers and stereocomplex formation were investigated using polarized light optical microscopy (PLOM), differential scanning calorimetry (DSC), infrared spectroscopy (FTIR), and carbon-13 nuclear magnetic resonance spectroscopy (13C-NMR). The PLA and PBS multiple blocks were miscible in the melt and in the glassy state. When the PLA-mb-PBS copolymers are cooled from the melt, the PLA component crystallizes first creating superstructures, such as spherulites or axialites, which constitute a template within which the PBS component has to crystallize when the sample is further cooled down. The Avrami theory was able to fit the overall crystallization kinetics of both semi-crystalline components, and the n values for both blocks in all the samples had a correspondence with the superstructural morphology observed by PLOM. Solution mixtures of PLLA-mb-PBS and PLDA-mb-PBS copolymers were prepared, as well as copolymer/homopolymer blends with the aim to study the stereocomplexation of PLLA and PDLA chain segments. A lower amount of stereocomplex formation was observed in copolymer mixtures as compared to neat L100/D100 stereocomplexes. The results show that PBS chain segments perturb the formation of stereocomplexes and this perturbation increases with the amount of PBS in the samples. However, when relatively low amounts of PBS in the copolymer blends are present, the rate of stereocomplex formation is enhanced. This effect dissappears when higher amounts of PBS are present. The stereocomplexation was confirmed by FTIR and solid state 13C-NMR analyses.

17.
Polymers (Basel) ; 9(8)2017 Aug 02.
Artigo em Inglês | MEDLINE | ID: mdl-30971007

RESUMO

Two methods, the first physical and the other chemical, were investigated to modify the surface roughness of polydimethylsiloxane (PDMS) films. The physical method consisted of dispersing multi-walled carbon nanotubes (MWCNTs) and magnetic cobalt ferrites (CoFe2O4) prior to thermal cross-linking, and curing the composite system in the presence of a uniform magnetic field H. The chemical method was based on exposing the films to bromine vapours and then UV-irradiating. The characterizing techniques included scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS), Fourier transform infrared (FTIR) spectroscopy, optical microscopy, atomic force microscopy (AFM) and magnetic force microscopy (MFM). The surface roughness was quantitatively analyzed by AFM. In the physical method, the random dispersion of MWCNTs (1% w/w) and magnetic nanoparticles (2% w/w) generated a roughness increase of about 200% (with respect to PDMS films without any treatment), but that change was 400% for films cured in the presence of H perpendicular to the surface. SEM, AFM and MFM showed that the magnetic particles always remained attached to the carbon nanotubes, and the effect on the roughness was interpreted as being due to a rupture of dispersion randomness and a possible induction of structuring in the direction of H. In the chemical method, the increase in roughness was even greater (1000%). Wells were generated with surface areas that were close to 100 µm² and depths of up to 500 nm. The observations of AFM images and FTIR spectra were in agreement with the hypothesis of etching by Br radicals generated by UV on the polymer chains. Both methods induced important changes in the surface roughness (the chemical method generated the greatest changes due to the formation of surface wells), which are of great importance in superficial technological processes.

18.
ACS Appl Mater Interfaces ; 8(30): 19197-201, 2016 Aug 03.
Artigo em Inglês | MEDLINE | ID: mdl-27434018

RESUMO

Smart multiresponsive bionanocomposites with both humidity- and thermally activated shape-memory effects, based on blends of ethylene-vinyl acetate (EVA) and thermoplastic starch (TPS) are designed. Thermo- and humidity-mechanical cyclic experiments are performed in order to demonstrate the humidity- as well as thermally activated shape memory properties of the starch-based materials. In particular, the induced-crystallization is used in order to thermally activate the EVA shape memory response. The shape memory results of both blends and their nanocomposites reflect the excellent ability to both humidity- and thermally activated recover of the initial shape with values higher than 80 and 90%, respectively.

19.
Biomacromolecules ; 17(9): 3048-59, 2016 09 12.
Artigo em Inglês | MEDLINE | ID: mdl-27434410

RESUMO

This article reports on the successful preparation and characterization of cellulose nanocrystals (CNCs) surface-modified with polylactide (PLA) and poly(butylene succinate) (PBS) binary mixed homopolymer brushes. Their synthesis was designed as a three-step procedure combining polyester synthesis and surface-modification of CNCs with simultaneous polyester grafting via a heterogeneous copper(I)-catalyzed azide-alkyne cycloaddition reaction. For comparison, single homopolymer brushes tethered to CNCs (PLLA-g-CNC and PBSBDEMPAM-g-CNC) were obtained applying the same procedure. The hairy nanoparticles were characterized in terms of chemical composition and thermal properties. Spectroscopic analyses suggested "rippled" microphase separation of both immiscible homopolyesters in the mixed brushes, while others showed impeded homopolyester crystallization after surface-grafting. A synergistic relationship between the polyesters and CNCs was also suggested, i.e., the polyester grafting increases the CNC thermal resistance, while CNC presence imparts char formation. The as-obtained binary homopolymer brushes tethered to nanoparticles makes these surface-modified cellulosic nanomaterials attractive as compatibilization/reinforcement agents for PLA/PBS blends.


Assuntos
Celulose/química , Nanopartículas/química , Nanoestruturas/química , Poliésteres/química , Catálise , Temperatura
20.
Mater Sci Eng C Mater Biol Appl ; 41: 119-26, 2014 Aug 01.
Artigo em Inglês | MEDLINE | ID: mdl-24907744

RESUMO

For the first time the preparation of defect-free fibers from immiscible blends of high molar mass poly(lactic acid) (PLA) and poly(butylene succinate) (PBS) in the whole range of the polyester weight ratios is shown. Electrospinning using the solvent-nonsolvent approach proved most appropriate. Moreover, electrospinning revealed crucial for the obtaining of PLA/PBS materials maintaining integrity. DSC and XRD analyses attested for a plasticizing effect and for increased PLA crystallinity at PBS addition to PLA. The mechanical properties of the PLA/PBS mats were controlled by the alignment of the fibers and changed from plastic to brittle materials upon increasing the PBS content. Drug loading and tests against pathogenic microorganisms suggested that the obtained mats can find application as antibacterial fibrous materials.


Assuntos
Butileno Glicóis/química , Ácido Láctico/química , Polímeros/química , Anti-Infecciosos Urinários/química , Anti-Infecciosos Urinários/farmacologia , Materiais Biocompatíveis/química , Materiais Biocompatíveis/metabolismo , Varredura Diferencial de Calorimetria , Cristalização , Portadores de Fármacos/química , Nitroquinolinas/química , Nitroquinolinas/farmacologia , Poliésteres , Staphylococcus aureus/efeitos dos fármacos
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