Study on the properties of poly(beta-hydroxybutyrate) grafted with maleic anhydride

The thermal stability, crystallization behavior and biodegradability of poly(beta -hydroxybutyrate) (PHB) grafted with maleic anhydride (MA) were studied by DSC,TGA, optical microscopy and WAXD. The results showed that thermal stability of maleated PHB was obviously improved, comparing with that of pure PHB. The temperature of decomposition was enhanced about 20 degreesC After grafting MA, the crystallization behavior of PHB changed evidently. The rate of spherulite growth decreased, the crystallization temperature from the melt state reduced, and the cold crystallization temperature from the glass state increased. With the increase in graft degree, the banding texture of spherulite became more distinct and orderly. Moreover, the introduction of MA groups promoted the biodegradation of PHB.

Miscibility and crystallization of poly(beta-hydroxybutyrate) and poly(p-vinylphenol) blends

The miscibility and crystallization behavior of poly(beta-hydroxybutyrate) (PHB) and poly(p-vinylphenol) (PVPh) blends were studied by differential scanning calorimetry and optical microscopy (OM). The blends exhibit a single composition-dependent glass transition temperature, characteristic of miscible systems, A depression of the equilibrium melting temperature of PHB is observed. The interaction parameter values obtained from analysis of the melting point depression are of large negative values, which suggests that PHB and PVPh blends are thermodynamically miscible in the melt. Isothermal crystallization kinetics in the miscible blend system PHB/PVPh was examined by OM. The presence of the amorphous PVPh component results in a reduction in the rate of spherulite growth of PHB. The spherulite growth rate is analyzed using the Lauritzen-Hoffman model, The isothermally crystallized blends of PHB/PVPh were examined by wide-angle X-ray diffraction and smell-angle X-ray scattering (SAXS). The long period obtained from SAXS increases with the increase in PVPh component, which implies that the amorphous PVPh is squeezed into the interlamallar region of PHB.

Validação de métodos para determinação do teor de 3-hidroxibutirato e 3-hidroxivalerato em polímero biodegradável

The efficiency of two methods for determining 3-hydroxybutyrate and 3-hydroxyvalerate content in the biopolymer (poly(3-hydroxybutyrate-co-3-hydroxyvalerate) has been evaluated. Both methods are based on (a) the hydrolysis of polymers, (b) the esterification with methyl (method A) and isoamilic alcohol (method B) and (c) analysis of the esters by gas chromatography using flame ionization detection (GC-FID). After optimization of the analytical conditions, the main validation parameters (linearity, quantification limit, detection limit, recovery, sensitivity and precision) were determined showing that both analytical procedures can be applied to control the process of poly(3-hydroxybutyrate) production. However, method B gives better analytical results than method A and has the advantage of not using chlorinated solvents.

Estrutura eletrônica de derivados de Poli(3-Hexiltiofeno) para aplicações em camadas ativas de células solares orgânicas

Pós-graduação em Ciência e Tecnologia de Materiais - FC

Estudo termoanalítico de blendas de poli(tereftalato de etileno) e poli(3-hidroxibutirato)

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Eletrodos nanoestruturados de 'TI' 'O IND.2' aplicados na degradação fotoeletrocatalítica de aminas aromáticas e desenvolvimento de dispositivo fotovoltaico 'TI 'O IND.2' / 'SB IND.2' 'S IND.3' / 'P3' 'HT'

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Biodegradation of films of low density polyethylene (LDPE), poly(hydroxibutyrate-co-valerate) (PHBV), and LDPE/PHBV (70/30) blend with Paecilomyces variotii

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Understanding the mechanical and biodegradation behaviour of poly(hydroxybutyrate)/rubber blends in relation to their morphology

In this work poly(hydroxybutyrate/poly(vinyl butyral)- co-(vinyl alcohol)-co(vinyl acetate) (or ethylene propylene diene monomer rubber) blends were prepared by conventional processing techniques (extrusion and injection moulding). A droplet type morphology was obtained for P(3HB)/PVB blends whereas P(3HB)/EPDM blends presented some extent of co-continuous morphology. In addition, rubbery domains were much smaller in the case of PVB. These differences in morphology are discussed taking into account solubility parameters and rheological behaviours of each component. For both blends, the increase of elastomer ratio led to a decrease of Young's modulus but an increase in elongation at break and impact strength. The latter increased more in the case of P(3HB)/EPDM blends although the rubbery domains were larger. These results are explained in the light of the glass transition of the rubber and the presence of plasticizer in the case of PVB. The addition of elastomer also resulted in an increase of P(3HB) biodegradation rate, especially in the case of EPDM. It is assumed that, in this case, the size and morphology of the rubbery domains induce a geometrical modification of the erosion front which leads to an increase of the interface between P(3HB) phase and the degradation medium and consequently to an apparently faster biodegradation kinetics of PHB/rubber blends. Copyright (C) 2011 Society of Chemical Industry

Elaboration and Characterization of Nano-Biocomposites Based on Plasticized Poly(Hydroxybutyrate-Co-Hydroxyvalerate) with Organo-Modified Montmorillonite

Nano-biocomposites based on a biodegradable bacterial copolyester, poly(hydroxybutyrate-co-hydroxyvalerate), have been elaborated with an organo-modified montmorillonite (OMMT) clay as nanofiller, and acetyl tributyl citrate as plasticizer. The corresponding (nano)structures, thermal and mechanical properties, permeability, and biodegradability have been determined. Polyhydroxyalkanoates are very thermal sensitive then to follow the degradation the corresponding matrices have been analyzed by size exclusion chromatography. The results indicate that the addition of the plasticizer decreases the thermo-mechanical degradation, during the extrusion. These nano-biocomposites show an intercalated/exfoliated structure with good mechanical and barrier properties, and an appropriated biodegradation kinetic. Intending to understand the changes in the thermal properties, the nano-biocomposites were characterized by thermal gravimetric analysis and differential scanning calorimetry. The presence of the OMMT clay did not influence significantly the transition temperatures. However, the filler not only acted as a nucleating agent which enhanced the crystallization, but also as a thermal barrier, improving the thermal stability of the biopolymer. The results indicated that the addition of the plasticizer reduces the glass transition temperature and the crystalline melting temperature. The plasticizer acts as a processing aid and increases the processing temperature range (lower melting temperature).

Proof for a nonproteinaceous calcium-selective channel in Escherichia coli by total synthesis from (R)-3-hydroxybutanoic acid and inorganic polyphosphate

Traditionally, the structure and properties of natural products have been determined by total synthesis and comparison with authentic samples. We have now applied this procedure to the first nonproteinaceous ion channel, isolated from bacterial plasma membranes, and consisting of a complex of poly(3-hydroxybutyrate) and calcium polyphosphate. To this end, we have now synthesized the 128-mer of hydroxybutanoic acid and prepared a complex with inorganic calcium polyphosphate (average 65-mer), which was incorporated into a planar lipid bilayer of synthetic phospholipids. We herewith present data that demonstrate unambiguously that the completely synthetic complex forms channels that are indistinguishable in their voltage-dependent conductance, in their selectivity for divalent cations, and in their blocking behavior (by La3+) from channels isolated from Escherichia coli. The implications of our finding for prebiotic chemistry, biochemistry, and biology are discussed.

Polymer nanocomposites based on P3OT, TPU and SWNT: preparation and characterization

Single walled carbon nanotubes (SWNTs) were incorporated in polymer nanocomposites based on poly(3-octylthiophene) (P3OT), thermoplastic polyurethane (TPU) or a blend of them. Thermogravimetry demonstrated the success of the purification procedure employed in the chemical treatment of SWNTs prior to composite preparation. Stable dispersions of SWNTs in chloroform were obtained by non-covalent interactions with the dissolved polymers. Composites exhibited glass transitions, melting temperatures and heat of fusion which changed in relation to pure polymers. This behavior is discussed as associated to interactions between nanotubes and polymers. The conductivity at room temperature of the blend (TPU-P3OT) with SWNT is higher than the P3OT/SWNT composite.

The stimulation of healing within a rat calvarial defect by mPCL–TCP/collagen scaffolds loaded with rhBMP-2

Bone morphogenetic proteins (BMPs) have been widely investigated for their clinical use in bone repair and it is known that a suitable carrier matrix to deliver them is essential for optimal bone regeneration within a specific defect site. Fused deposited modeling (FDM) allows for the fabrication of medical grade poly 3-caprolactone/tricalcium phosphate (mPCL–TCP) scaffolds with high reproducibility and tailor designed dimensions. Here we loaded FDM fabricated mPCL–TCP/collagen scaffolds with 5 mg recombinant human (rh)BMP-2 and evaluated bone healing within a rat calvarial critical-sized defect. Using a comprehensive approach, this study assessed the newly regenerated bone employing microcomputed tomography (mCT), histology/histomorphometry, and mechanical assessments. By 15 weeks, mPCL–TCP/collagen/rhBMP-2 defects exhibited complete healing of the calvarium whereas the non- BMP-2-loaded scaffolds showed significant less bone ingrowth, as confirmed by mCT. Histomorphometry revealed significantly increased bone healing amongst the rhBMP-2 groups compared to non-treated scaffolds at 4 and 15 weeks, although the % BV/TV did not indicate complete mineralisation of the entire defect site. Hence, our study confirms that it is important to combine microCt and histomorphometry to be able to study bone regeneration comprehensively in 3D. A significant up-regulation of the osteogenic proteins, type I collagen and osteocalcin, was evident at both time points in rhBMP-2 groups. Although mineral apposition rates at 15 weeks were statistically equivalent amongst treatment groups, microcompression and push-out strengths indicated superior bone quality at 15 weeks for defects treated with mPCL–TCP/collagen/rhBMP-2. Consistently over all modalities, the progression of healing was from empty defect < mPCL–TCP/collagen < mPCL–TCP/collagen/rhBMP-2, providing substantiating data to support the hypothesis that the release of rhBMP-2 from FDM-created mPCL–TCP/collagen scaffolds is a clinically relevant approach to repair and regenerate critically-sized craniofacial bone defects. Crown Copyright 2008 Published by Elsevier Ltd. All rights reserved.

Mesoporous bioglass/silk composite scaffolds for bone tissue engineering

In the past 20 years, mesoporous materials have been attracted great attention due to their significant feature of large surface area, ordered mesoporous structure, tunable pore size and volume, and well-defined surface property. They have many potential applications, such as catalysis, adsorption/separation, biomedicine, etc. [1]. Recently, the studies of the applications of mesoporous materials have been expanded into the field of biomaterials science. A new class of bioactive glass, referred to as mesoporous bioactive glass (MBG), was first developed in 2004. This material has a highly ordered mesopore channel structure with a pore size ranging from 5–20 nm [1]. Compared to non-mesopore bioactive glass (BG), MBG possesses a more optimal surface area, pore volume and improved in vitro apatite mineralization in simulated body fluids [1,2]. Vallet-Regí et al. has systematically investigated the in vitro apatite formation of different types of mesoporous materials, and they demonstrated that an apatite-like layer can be formed on the surfaces of Mobil Composition of Matters (MCM)-48, hexagonal mesoporous silica (SBA-15), phosphorous-doped MCM-41, bioglass-containing MCM-41 and ordered mesoporous MBG, allowing their use in biomedical engineering for tissue regeneration [2-4]. Chang et al. has found that MBG particles can be used for a bioactive drug-delivery system [5,6]. Our study has shown that MBG powders, when incorporated into a poly (lactide-co-glycolide) (PLGA) film, significantly enhance the apatite-mineralization ability and cell response of PLGA films. compared to BG [7]. These studies suggest that MBG is a very promising bioactive material with respect to bone regeneration. It is known that for bone defect repair, tissue engineering represents an optional method by creating three-dimensional (3D) porous scaffolds which will have more advantages than powders or granules as 3D scaffolds will provide an interconnected macroporous network to allow cell migration, nutrient delivery, bone ingrowth, and eventually vascularization [8]. For this reason, we try to apply MBG for bone tissue engineering by developing MBG scaffolds. However, one of the main disadvantages of MBG scaffolds is their low mechanical strength and high brittleness; the other issue is that they have very quick degradation, which leads to an unstable surface for bone cell growth limiting their applications. Silk fibroin, as a new family of native biomaterials, has been widely studied for bone and cartilage repair applications in the form of pure silk or its composite scaffolds [9-14]. Compared to traditional synthetic polymer materials, such as PLGA and poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), the chief advantage of silk fibroin is its water-soluble nature, which eliminates the need for organic solvents, that tend to be highly cytotoxic in the process of scaffold preparation [15]. Other advantages of silk scaffolds are their excellent mechanical properties, controllable biodegradability and cytocompatibility [15-17]. However, for the purposes of bone tissue engineering, the osteoconductivity of pure silk scaffolds is suboptimal. It is expected that combining MBG with silk to produce MBG/silk composite scaffolds would greatly improve their physiochemical and osteogenic properties for bone tissue engineering application. Therefore, in this chapter, we will introduce the research development of MBG/silk scaffolds for bone tissue engineering.

High performance additive manufactured scaffolds for bone tissue engineering application

This study demonstrates the feasibility of additive manufactured poly(3-caprolactone)/silanized tricalcium phosphate (PCL/TCP(Si)) scaffolds coated with carbonated hydroxyapatite (CHA)-gelatin composite for bone tissue engineering. In order to reinforce PCL/TCP scaffolds to match the mechanical properties of cancellous bone, TCP has been modified with 3-glycidoxypropyl trimethoxysilane (GPTMS) and incorporated into PCL to synthesize a PCL/TCP(Si) composite. The successful modification is confirmed by X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR) analysis. Additive manufactured PCL/TCP(Si) scaffolds have been fabricated using a screw extrusion system (SES). Compression testing demonstrates that both the compressive modulus and compressive yield strength of the developed PCL/TCP(Si) scaffolds fall within the lower ranges of mechanical properties for cancellous bone, with a compressive modulus and compressive yield strength of 6.0 times and 2.3 times of those of PCL/TCP scaffolds, respectively. To enhance the osteoconductive property of the developed PCL/TCP(Si) scaffolds, a CHA-gelatin composite has been coated onto the scaffolds via a biomimetic co-precipitation process, which is verified by using scanning electron microscopy (SEM) and XPS. Confocal laser microscopy and SEM images reveal a most uniform distribution of porcine bone marrow stromal cells (BMSCs) and cellsheet accumulation on the CHA-gelatin composite coated PCL/TCP(Si) scaffolds. The proliferation rate of BMSCs on the CHA-gelatin composite coated PCL/TCP(Si) scaffolds is 2.0 and 1.4 times higher compared to PCL/TCP(Si) and CHA coated PCL/TCP(Si) scaffolds, respectively, by day 10. Furthermore, the reverse transcription polymerase chain reaction (RT-PCR) and western blot analyses reveal that CHA-gelatin composite coated PCL/TCP(Si) scaffolds stimulate osteogenic differentiation of BMSCs the most compared to the other scaffolds. In vitro results of SEM, confocal microscopy and proliferation rate also show that there is no detrimental effect of GPTMS modification on biocompatibility of the scaffolds.

Design, fabrication and characterization of PCL electrospun scaffolds—a review

The expanding interest in electrospinning fibers for bioengineering includes a significant use of polyesters, including poly(3-caprolactone) (PCL). This review summarizes literature on PCL and selected blends, and provides extensive descriptions of the broad range of parameters used in manufacturing such electrospun fibers. Furthermore the chemical, physical and biological approaches for characterizing the electrospun material are described and opinions offered on important information to include in future publications with this electrospun material.