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1.
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.

2.
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
3.
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
4.
Langmuir ; 30(1): 358-68, 2014 Jan 14.
Artigo em Inglês | MEDLINE | ID: mdl-24328504

RESUMO

The improvement of the (bio)adhesive properties of elastomeric polydimethylsiloxane (PDMS) coatings is reported. This is achieved by a surface modification consisting of the incorporation of block copolymers containing a PDMS block and a poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) block in a PDMS matrix, followed by matrix cross-linking and immersion of the obtained materials in water. Contact angle measurements (CA), X-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM) showed the presence of the PDMAEMA block at the surface, drastic morphology changes, and improved adhesion properties after immersion in water. Finally, underwater bioadhesion tests show that mussels adhere only to block copolymer-filled coatings and after immersion in water, i.e., when the PDMAEMA blocks have been brought to the coating surface. These observations highlight the significant role of hydrophilic groups in the surface modification of silicone coatings.


Assuntos
Dimetilpolisiloxanos/química , Silicones/química , Adsorção , Animais , Bivalves , Dimetilpolisiloxanos/síntese química , Teste de Materiais , Estrutura Molecular , Tamanho da Partícula , Propriedades de Superfície
5.
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.

6.
ACS Sustain Chem Eng ; 12(29): 10727-10738, 2024 Jul 22.
Artigo em Inglês | MEDLINE | ID: mdl-39055864

RESUMO

Ethylene brassylate is a renewable macrolactone from castor oil that can be polymerized via ring-opening polymerization (ROP) to obtain a fully biosourced biodegradable polyester. ROP mediated by organometallic catalysts leads to high molar mass poly(ethylene brassylate) (PEB). However, the use of metal-free organocatalysis has several advantages, such as the reduction of toxic and expensive metals. In this work, a novel cellulose nanofibril (CNF)/PEB nanocomposite fabrication process by organocatalysis and reactive extrusion (REx) is disclosed. Here, ROP was carried out via solvent-free REx in the presence of CNFs using organic 1,5,7-triazabicyclo[4.4.0]dec-5-ene as a catalyst. Neat or lactate-esterified CNFs (LACNF) were used as initiators to investigate the effect of surface topochemistry on the in situ polymerization and the properties of the nanocomposites. A molar mass of 9 kDa was achieved in the presence of both unmodified and LACNFs with high monomer conversion (>98%) after 30 min reaction in a microcompounder at 130 °C. Tensile analysis showed that both nanofibril types reinforce the matrix and increase its elasticity due to the efficient dispersion obtained through the grafting from polymerization achieved during the REx. Mechanical recycling of the neat polymer and the nanocomposites was proven as a circular solution for the materials' end-of-life and showed that lactate moieties induced some degradation.

7.
Mar Pollut Bull ; 205: 116625, 2024 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-38925025

RESUMO

Quantifying microplastics (MPs) in marine environments is challenging due to the complexities of differentiation from other materials. This study aims to distinguish petro-sourced plastic microfilaments from organic ones in environmental samples using scanning electron microscope coupled with energy dispersive X-ray (SEM-EDX) analysis. Therefore, 38 particles resembling MPs (PRMPs) from sediments and organisms in Madagascar were analyzed. MPs identification thresholds were determined from SEM-EDX analysis of macroplastics and seaweed, the primary sources of microfilaments. SEM-EDX results of the 38 PRMPs were compared with identification/misidentification made by five MPs observation experts. Results indicated that a carbon/oxygen (C/O) ratio >1 distinguished macroplastics and MPs from other sources (seaweed and organic microfilaments). SEM-EDX analysis identified 81.58% of PRMPs as MPs. The average error made by one observer was 36.32%. These findings highlight the need for a method to assess identification error in MPs quantification and recommend SEM-EDX analysis of microfilaments to gauge observer error.


Assuntos
Monitoramento Ambiental , Microscopia Eletrônica de Varredura , Plásticos , Monitoramento Ambiental/métodos , Plásticos/análise , Poluentes Químicos da Água/análise , Microplásticos/análise , Madagáscar , Espectrometria por Raios X , Sedimentos Geológicos/química , Alga Marinha
8.
Biomacromolecules ; 14(3): 890-9, 2013 Mar 11.
Artigo em Inglês | MEDLINE | ID: mdl-23369072

RESUMO

Environmentally friendly poly(butylenesuccinate-co-butyleneazelate) (P(BS-co-BAz)s) aliphatic copolyesters with composition-dependent thermomechanical properties were synthesized from succinic acid (SuA), 1,4-butanediol (BDO), and dimethylazelate (DMAz) through a two-step polycondensation reaction. The molar SuA/AzA ratio was varied from 4:1 to 1:4, and the chemical structure and molecular characteristics of resulting (co)polyesters were characterized by NMR and SEC, whereas thermal properties and crystallinity were studied by differential scanning calorimetry (DSC), dynamic mechanical thermal analyses (DMTA), and X-ray diffraction (XRD). A good agreement between theoretical and experimental SuA/AzA molar ratios in the copolyesters was achieved, together with the recovery of semicrystalline random copolymers of uniform composition along the chains. NMR, DSC, DMTA, and XRD results show that depending on their composition the P(BS-co-BAz) copolyesters might find applications from elastomers to high-impact thermoplastics.


Assuntos
Materiais Biocompatíveis/síntese química , Butileno Glicóis/química , Poliésteres/síntese química , Polímeros/química , Varredura Diferencial de Calorimetria , Espectroscopia de Ressonância Magnética , Difração de Raios X
9.
Biomacromolecules ; 13(9): 2973-81, 2012 Sep 10.
Artigo em Inglês | MEDLINE | ID: mdl-22830993

RESUMO

Novel potentially biobased aliphatic-aromatic copolyesters poly(butylene succinate-co-butylene furandicarboxylate) (PBSFs) in full composition range were successfully synthesized from 2,5-furandicarboxylic acid (FA), succinic acid (SA), and 1,4-butanediol (BDO) via an esterification and polycondensation process using tetrabutyl titanate (TBT) or TBT/La(acac)(3) as catalyst. The copolyesters were characterized by size exclusion chromatography (SEC), Fourier transform infrared (FTIR), (1)H NMR, differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA), and their tensile properties were also evaluated. The weight average molecular weight (M(w)) ranges from 39,000 to 89,000 g/mol. The copolyesters are random copolymers whose composition is well controlled by the feed ratio of the diacid monomers. PBSFs have excellent thermal stability. The glass transition temperature (T(g)) increases continuously with φ(BF) and agrees well with the Fox equation. The crystallizability and T(m) decrease with increasing butylene furandicarboxylate (BF) unit content (φ(BF)) from 0 to 40 mol %, but rise again at φ(BF) of 50-100 mol %. Consequently, the tensile modulus and strength decrease, and the elongation at break increases with φ(BF) in the range of 0-40 mol %. At higher φ(BF), the modulus and strength increase and the ultimate elongation decreases. Thus, depending on φ(BF), the structure and properties of PBSFs can be tuned ranging from crystalline polymers possessing good tensile modulus (360-1800 MPa) and strength (20-35 MPa) to nearly amorphous polymer of low T(g) and high elongation (~600%), and therefore they may find applications in thermoplastics as well as elastomers or impact modifiers.


Assuntos
Materiais Biocompatíveis/síntese química , Butileno Glicóis/química , Ácidos Dicarboxílicos/química , Furanos/química , Poliésteres/síntese química , Ácido Succínico/química , Varredura Diferencial de Calorimetria , Cromatografia em Gel , Cristalização , Temperatura Alta , Espectroscopia de Ressonância Magnética , Peso Molecular , Espectroscopia de Infravermelho com Transformada de Fourier , Resistência à Tração , Termogravimetria , Titânio/química
10.
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.

11.
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.

12.
Macromol Rapid Commun ; 32(24): 1960-4, 2011 Dec 15.
Artigo em Inglês | MEDLINE | ID: mdl-22105987

RESUMO

New polyesters incorporating a variable quantity of imidazolium rings along the backbone are synthesized by Huisgen 1,3-dipolar cycloaddition ("click" reaction). Subsequently, the imidazolium-grafted copolymers reveal an efficient dispersing ability toward the carbon nanotubes (CNTs) through supramolecular interactions in organic media. Interestingly, these compounds offer a simple and reliable strategy to control the quantity of dispersed CNTs as a function of imidazolium content. This approach is particularly suitable for the elaboration of biosourced and biodegradable materials based on poly(butylene succinate) with high-performance properties.


Assuntos
Butileno Glicóis/química , Butileno Glicóis/síntese química , Química Click/métodos , Imidazóis/química , Nanotubos de Carbono/química , Polímeros/química , Polímeros/síntese química
13.
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.

14.
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.

15.
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.

16.
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
17.
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
18.
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
19.
Biomacromolecules ; 11(2): 521-32, 2010 Feb 08.
Artigo em Inglês | MEDLINE | ID: mdl-20058911

RESUMO

Poly(L-lactide) (PLLA) and poly(L-lactide)/poly(ethylene glycol) (PLLA/PEG) electrospun fibrous materials coated with a polyelectrolyte complex (PEC) were prepared. This was achieved by consecutive deposition of a layer of N-carboxyethylchitosan (CECh) and a layer of a double hydrophilic block copolymer, poly(ethylene oxide)-b-quaternized poly[2-(dimethylamino)ethyl methacrylate] (PEO-b-PDMAEMAQ100), resulting in PEC formation between the two polyelectrolytes on the surface. Noteworthy, to improve the water wettability of the electrospun PLLA fibrous materials, that is, to enable more uniform deposition of the polyelectrolyte partners, water/ethanol mixed solvent was used for preparation of CECh and PEO-b-PDMAEMAQ100 solutions. The formation of PEC-based coating was demonstrated by means of scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). The PEC formation allows targeted modification of the biological behavior of the electrospun materials as evidenced by the performed tests in respect to blood cells and pathogenic microorganisms. In contrast to the pristine mats, the novel PEC-coated mats exhibit hemostatic properties and reduce the adhesion of pathogenic microorganisms.


Assuntos
Poliésteres/química , Polietilenoglicóis/química , Materiais Revestidos Biocompatíveis/química , Materiais Revestidos Biocompatíveis/metabolismo , Humanos , Microscopia Eletrônica de Varredura/métodos , Espectroscopia Fotoeletrônica/métodos , Poliésteres/metabolismo , Polietilenoglicóis/metabolismo , Propriedades de Superfície
20.
Biomacromolecules ; 11(1): 151-9, 2010 Jan 11.
Artigo em Inglês | MEDLINE | ID: mdl-19947641

RESUMO

Novel fibrous materials of stereocomplex between high-molecular-weight poly(d- or l-)lactide (HMPDLA or HMPLLA) and diblock copolymers consisting of poly(l- or d-)lactide and poly(N,N-dimethylamino-2-ethyl methacrylate) blocks, respectively (PLLA-block-PDMAEMA or PDLA-block-PDMAEMA), were prepared by solution electrospinning. Fibers with mean diameters ranging from 1400 to 1700 nm were obtained. The stereocomplex formation was evidenced by differential scanning calorimetry (DSC) and X-ray diffraction (XRD) analyses. Annealing at 100 degrees C for 8 h resulted in the appearance of crystalline peaks at 2theta values of 12, 21, and 24 degrees for PLA stereocomplex. X-ray photoelectron spectroscopy (XPS) analyses revealed the gradient composition of the fibers with a surface enriched in tertiary amino groups from PDMAEMA blocks. The availability of tertiary amino groups imparts hemostatic and antibacterial properties to the stereocomplex fibrous materials, as indicated by the performed tests on blood cells and on pathogenic microorganisms.


Assuntos
Materiais Biocompatíveis/farmacologia , Adesão Celular/efeitos dos fármacos , Técnicas Eletroquímicas , Metacrilatos/química , Poliésteres/química , Polímeros/química , Polímeros/síntese química , Materiais Biocompatíveis/síntese química , Materiais Biocompatíveis/química , Plaquetas/efeitos dos fármacos , Plaquetas/metabolismo , Eritrócitos/efeitos dos fármacos , Eritrócitos/metabolismo , Escherichia coli/efeitos dos fármacos , Escherichia coli/metabolismo , Humanos , Espectroscopia Fotoeletrônica , Polímeros/farmacologia , Staphylococcus aureus/efeitos dos fármacos , Staphylococcus aureus/metabolismo , Estereoisomerismo , Propriedades de Superfície , Difração de Raios X
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