Biocompatibility of Modified Bionanocellulose and Porous Poly(ϵ-caprolactone) Biomaterials

Biocompatibility of modified bionanocellulose (BC) and porous poly(? caprolactone) (PCL) were compared to UHMWPE. For all the materials lack of cytotoxic effect to mouse fibroblasts was observed in vitro. In vivo study, subcutaneous implantations in Wistar rats, lasted for seven, 14, and 30 days. Subsequently the composition of surrounding tissue and explants surface changes was evaluated. No symptoms of acute inflammation were observed. Surrounding tissue thickness, the number of granulocytes, lymphocytes, macrophages, and blood vessels differed in time and revealed regular healing process. It is concluded that investigated PCL and BC are the materials with superior biocompatibility with high application potential.     

Effects of Poly(ϵ-caprolactone) on Structure and Properties of Poly(lactic acid)/Poly(ϵ-caprolactone) Meltblown Nonwoven

To obtain flexile poly(lactic acid)-based melt-blown nonwoven filtration material, poly(lactic acid)/poly(?-caprolactone) melt-blown nonwoven with various components were melt-spun by melt-blown processing in the Melt-blown Experiment Line. The 3 wt.% tributyl citrate to poly(?-caprolactone) was added in the composites as compatibilizer. The effect of poly(?-caprolactone) on the structure, morphology, mechanical and filtration properties of poly(lactic acid)/poly(?-caprolactone) melt-blown nonwoven was reported. Scanning electron microscopy micrographs revealed good dispersion of the additive in the fiber webs. The crystallinity of melt-blown webs with poly(?-caprolactone) was more than that of poly(lactic acid) alone. The tensile strength, ductility and air permeability of poly(lactic acid) melt-blown nonwovens were enhanced significantly. The input of poly(?-caprolactone) increased the diameter of fibers and decreased the filtration efficiency of poly(lactic acid)/poly(?-caprolactone) melt-blown nonwoven.     

Fabrication and In Vitro Bioactivity of Poly (ϵ-caprolactone) Composites Filled with Silane-Modified Nano-Apatite Particles

Silane coupling agents were firstly employed to modify the surfaces of nano-apatite (n-HA) particles, and then thin films of the silanized n-HA/PCL composites were successfully developed by incorporating solvent dispersion and thermal co-blending with hot-pressing methods. In vitro studies were conducted using the 2-time simulated body fluid (2SBF). Composite specimens were soaked in 2SBF from 3 to 14. Results showed that a layer of bone-like apatite was formed within 7 days on the surfaces of all composites, after its immersion in 2SBF, demonstrating moderate in vitro bioactivity of these composites.     

Scale of Homogeneous Mixing in Miscible Blends of Organosolv Lignin Esters with Poly(ϵ-caprolactone)

Abstract

Organosolv lignin (OSL) esters (side-chain carbon number, n = 3, 4, and 5) have been demonstrated to be miscible with poly(?-caprolactone) (PCL) on a scale (20–30 nm) for detecting glass transition temperature (T _g) by differential scanning calorimetry (Polym. J. 2009, 41(3), 219–227). Further precise quantification of homogeneity was conducted for the OSL propionate (OSL-Pr, n = 3)/PCL and OSL butyrate (OSL-Bu, n = 4)/PCL blends by means of dynamic mechanical analysis (DMA) and solid-state nuclear magnetic resonance (NMR). DMA revealed a composition-dependent T _g for these blend samples, which implies the attainment of an intimate mixing of the ingredients on a scale of ≤15 nm. From the measurements of proton spin-lattice relaxation times (T _1ρ ^H) using solid-state NMR, the blends were estimated to be substantially homogeneous on a scale of ～6 nm. But the equalization of the T _1ρ ^H for the components of OSL-Pr/PCL was not remarkable; that is, the constituents of OSL-Pr/PCL were relatively imperfectly miscible with each other.     

Surface Modification of Nanoporous Poly(ϵ-caprolactone) Membrane with Poly(ethylene glycol) to Prevent Biofouling: Part II. Effects of Graft Density and Chain Length

Biofouling is a common problem in wastewater treatments and medical devices. It is important to find a strategy to prevent biofouling and surface modification. This study presents a novel approach to modifying the surface of nanoporous poly(?-caprolactone) membrane with poly(ethylene glycol) (PEG) to prevent biofouling problems. Oxygen plasma and poly(ethylene glycol)-monoacrylates (PEGMAs) were utilized in the surface modification process. Mouse embryonic fibroblast was used as a model biofoulant. The effects of the density and length of PEG chains on surface properties and cell adhesion were investigated. Contact angle measurements and attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectra illustrated that PEG can be successfully immobilized on the membrane surface. Membranes which were pre-treated with higher PEG concentrations can lead to higher grafting density and greater resistance against cell adhesion. The resistance against cell adhesion cannot be enhanced while the PEG concentration is higher than a certain point, i.e., 0.1 M. For different chain lengths, PEG(400)MA can provide higher resistance to cell adhesion than PEG(200)MA and PEG(1000)MA.     

Surface Modification of Nanoporous Poly(ϵ-caprolactone) Membrane with Poly(ethylene glycol) to Prevent Biofouling: Part I. Effects of Plasma Power and Treatment Time

Biofouling, a result of protein adsorption and cell adhesion on a surface, is detrimental to membrane performance. The objective of this study is to modify the polycaprolactone (PCL) membrane surface with poly(ethylene glycol) (PEG) to prevent fibroblast adhesion. To achieve this goal, oxygen plasma and PEG(400)-monoacrylate were used to graft the PEG onto the membrane surface through covalent bonding. Various plasma treatment conditions were investigated to optimize the PEG-grafting quality and to achieve minimum fibroblast adhesion. After the treatment, the water contact angle decreased significantly. Attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR) spectra indicated that PEG was successfully grafted onto the PCL membrane with the appearance of the PEG characteristic peaks. X-ray photoelectron spectroscopy (XPS) revealed that different plasma powers and treatment times changed the surface composition of membranes. To evaluate the applicability of this new strategy for the prevention of biofouling, NIH 3T3 fibroblast was used as a model biofoulant. Cell adhesion and morphology studies indicate that either lower plasma power or shorter treatment time is able to improve resistance to the cell adhesion. This simple and efficient method can be applied to inhibit biofouling on the membrane surface.     

Crystallisation of nanohybrids of poly(ϵ-caprolactone) and hydrotalcites containing antimicrobial species

Abstract

New composites of poly(?-caprolactone) containing Zn/Al hydrotalcites [layer double hydroxide (LDH)] and ‘active’ antimicrobial anions (benzoate, dichlorobenzoate, o-hydroxybenzoate and p-hydroxybenzoate) prepared with two different techniques have been characterised through differential scanning calorimetry and dynamic mechanical analysis. The method of preparation of the samples has a strong influence on the dispersion of the nanolayers within the polymeric matrix, and, in turn, on the crystallisation kinetics: in fact, the samples prepared by high energy ball milling crystallise much faster than those prepared by casting. The different ‘active’ anions strongly affect the value of the LDH interlamellar distance, which, in turn, affects their capacity of dispersion in the polymer. As a consequence of the different kinds of dispersion, the sample containing benzoate LDH or dichlorobenzoate LDH crystallises faster than that containing p-hydroxybenzoate LDH. Such results are of great importance in the definition of processing and use conditions of such materials of potential interest in food ‘active’ packaging.     

Poly(ε-caprolactone) diol functionalized with a cinnamoyl group and its UV-triggered in-plane alignment

Stimuli-sensitive biomaterials can present variable and tailored functions under specific external stimuli, thus showing potential for application in various biosciences. Significant efforts have focused on the utilization of light as a stimulus in biomedical applications because of its unique advantages, especially the precise control over its position, movement, and non-contact irradiation. This article highlights the preparation of a photo-reactive oligomer composed of biodegradable moieties and its UV-triggered in-plane molecular orientation, implicating its surface as a potential molecular alignment layer. We focus especially on the alignment of nematic liquid crystalline (LC) molecules on the biodegradable layer with molecular orientation, because they are promising candidates for sensing and interfacial applications.     

Hyperbranched poly (amine-ester)-poly(ε-caprolactone) copolymer and their nanoparticles as camptothecin delivery system

A new amphiphilic hyperbranched poly (amine-ester)-poly(ε-caprolactone) copolymer (HPAE-co-PCL) was synthesized by ring-opening polymerization of ε-caprolactone and branched poly (amine-ester) (HPAE-OHs) with Sn(Oct)₂ as catalyst. The chemical structures of copolymers were determined by FT-IR, ¹H-NMR (¹³C-NMR), thermo gravimetric analysis apparatus (TGA) and differential scanning calorimetry (DSC). Camptothecin (CPT)-loaded copolymer nanoparticles were prepared by the oil-in water (o/w) emulsion technique method. Their physicochemical characteristics, e.g. morphology and nanoparticles size distribution were then evaluated by means of fluorescence spectroscopy, environmental scanning electron microscopy (ESEM), and dynamic light scattering (DLS). CPT-loaded nanoparticles assumed a spherical shape and have unimodal size distribution. It was found that the chemical composition of the nanoparticles was a key factor in controlling nanoparticles size, drug-loading content, and drug release behavior. As the molar ratio of ε-caprolactone to HPAE increased, the nanoparticles size and drug-loading content increased, and the drug release rate decreased. The antitumor activity of the CPT-loaded HPAE-co-PCL nanoparticles against human hepatoma HEPG2 cells was evaluated by 3-(4, 5-Dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide (MTT) method. The CPT-loaded HPAE-co-PCL nanoparticles showed comparable anticancer efficacy with the free drug.     

Poly(ε-caprolactone)-based additives: Plasticization efficacy and migration resistance

A family of poly(caprolactone) (PCL)-based oligomeric additives was evaluated as plasticizers for poly(vinyl chloride) (PVC). We found that the entire family of additives, which consist of a PCL core, diester linker, and alkyl chain cap, were effective plasticizers that improve migration resistance. The elongation at break and tensile strength of the blends made with the PCL-based additives were comparable to blends prepared with diisononyl phthalate (DINP), a plasticizer typically used industrially, and diheptyl succinate (DHPS), an alternative biodegradable plasticizer. Increasing concentration was found to decrease glass transition temperature (T_g) and increase elongation at break, confirming their role as functional plasticizers. We found that all of the PCL-based plasticizers exhibited significantly reduced leaching into hexanes compared to DINP and DHPS. The PCL-based plasticizers with shorter carbon chain lengths reduced leaching more than those with longer carbon chain lengths.     

Enhancing the grafting amount of Poly(ε-caprolactone) on MgO nanoparticles by modifying with ethylene glycol for improving mechanical properties of Poly(ε-caprolactone)

A new surface modification method to improve the graft polymerization of ε-caprolactone (CL) on MgO surface was developed. The MgO nanoparticles were first modified with ethylene glycol (EG), and then used for initiating graft polymerization of CL. The modified MgO nanoparticles were attested by fourier transform infrared spectroscopy, thermal gravimetric analysis and dispersion stability test. The results showed that EG was successfully grafted onto the MgO surface, the hydroxyl group of the grafted EG initiated the graft polymerization of CL onto the MgO surface in the presence of stannous octanoate. The PCL grafting amount (11.13%) on MgO modified with EG (MgO-EG) is much higher than that of unmodified MgO (3.95%). MgO-EG-PCL with 11.13 wt% of grafted PCL exhibited the most excellent dispersibility in chloroform. The MgO-EG-PCL/PCL composites exhibited the most significant improvement, tensile strength and the elongation at break of PCL increased from 15.64 to 19.58 MPa and from 272.34% to 420.73%, respectively.     

Temperature-Responsive Poly(?-caprolactone) Cell Culture Platform with Dynamically Tunable Nano-Roughness and Elasticity for Control of Myoblast Morphology

We developed a dynamic cell culture platform with dynamically tunable nano-roughness and elasticity. Temperature-responsive poly(ɛ-caprolactone) (PCL) films were successfully prepared by crosslinking linear and tetra-branched PCL macromonomers. By optimizing the mixing ratios, the crystal-amorphous transition temperature (T_m) of the crosslinked film was adjusted to the biological relevant temperature (~33 °C). While the crosslinked films are relatively stiff (50 MPa) below the T_m, they suddenly become soft (1 MPa) above the T_m. Correspondingly, roughness of the surface was decreased from 63.4–12.4 nm. It is noted that the surface wettability was independent of temperature. To investigate the role of dynamic surface roughness and elasticity on cell adhesion, cells were seeded on PCL films at 32 °C. Interestingly, spread myoblasts on the film became rounded when temperature was suddenly increased to 37 °C, while significant changes in cell morphology were not observed for fibroblasts. These results indicate that cells can sense dynamic changes in the surrounding environment but the sensitivity depends on cell types.     

Surface Morphology and Properties of Rigid Poly(γ-benzyl L-glutamate) Membrane Modified by Flexible Poly(Vinyl Chloride)

Rigid poly(γ-benzyl L-glutamate)/flexible poly(vinyl chloride) (PBLG/PVC) blend membranes were prepared by casting the polymer blend solution in dichloroethane. Structure and morphologies of the PBLG/PVC blend membranes were investigated by Fourier transform infrared spectroscopy (FT-IR), atomic force microscopy (AFM), and scanning electron microscopy (SEM). Thermal, mechanical, and chemical properties of PBLG/PVC blend membranes were studied by differential scanning calorimetry (DSC), tensile tests, and other physical methods. It was found that the introduction of PVC could exert marked effects on the morphology and the properties of PBLG membrane.     

Multiarm star with poly(ethyleneimine) core and poly(ε-caprolactone) arms as modifiers of diglycidylether of bisphenol A thermosets cured by 1-methylimidazole

Well-defined multiarm star copolymers, with hyperbranched poly(ethyleneimine) (PEI) as the core and poly(ε-caprolactone) (PCL) arms with different degree of polymerization were synthesized by cationic ring-opening polymerization of ε-caprolactone from a hyperbranched poly(ethyleneimine) core and used to modify diglycidylether of bisphenol A formulations cured with 1-methylimidazole as anionic initiator. The curing process was studied by dynamic scanning calorimetry (DSC) and FTIR. By rheometry the complex viscosity of the multiarm stars synthesized and the influence of their addition to the reactive mixture was analyzed in detail. The resulting materials were characterized by thermal and mechanical tests. The addition of the multiarm star to the formulation led to homogeneous materials with a slightly toughened fracture in comparison to neat DGEBA thermosets without compromising thermal characteristics.     

Kinetic investigation and regularities during the synthesis of Poly(ε-caprolactam-co-ε-caprolactone) and Poly(ε-caprolactam-co-δ-valerolactone) biodegradable copolymers

Summary Large diversity of tailor-made poly[(ε-caprolactam)-co-(ε-caprolactone)] P[(CLA)-co-(CLO)] and poly[(ε-caprolactam)-co-(δ-valerolactone)] P[(CLA)-co-(VLO)] copolymers have been obtained via activated anionic polymerization of ε-caprolactam (CLA) with sodium caprolactam (NaCL) as a basic initiator. In the present study several poly(ε-caprolactones) (PCLOs) and poly(δ-valerolactone) polyols were employed as effective bifunctional polymeric activators (PACs) and suitable comonomers of CLA. The obtained poly(esteramides) PEAS were isolated and their structure was confirmed by the ¹H NMR and FTIR spectroscopy. The influence of the molecular weight and type of the PACs, the CLA/PAC ratio and polymerization conditions on the conversion, intrinsic viscosity and polymerization kinetic was explored. The results demonstrated that the use of the PACs reduces the polymerization time to several minutes and polymerization process proceeds without induction period at low energy of activation and high yield of copolymers. Evaluation of the PACs activity and the activation energy confirmed that the PACs are highly active compounds efficient to CLA features modification.     

Bulk Synthesis of Monodisperse and Highly Biocompatible Poly(ɛ-caprolactone)-diol by Transesterification Side-Reactions

Ring-opening polymerization of ε-caprolactone was performed at 130°C, under partial vacuum in the presence of stannous octoate as the catalyst and 1,4-butanediol as the initiator. After the termination of polymerization by deionized water, a hydroxyl group formed at the end of the polymer chains. Structure of the synthetic poly(ε-caprolactone)-diols (PCL-diol), molecular weight, polydispersity index, and Cell viability were evaluated. Very narrow distribution in the molecular weight obtained for PCL-diols is due to a new method for synthesis. It was shown that by the increase in PCL-diols, the compatibility of human mesenchymal stem cells grew up.     

Development and Assessment of Electrospun Poly(ε-caprolactone)–Poly(vinylalcohol) Blend Nanofibers for Pest Control in Stored Products

l-Carvone is a constituent of essential oil consisting of monoterpene ketone that possesses various medicinal properties. In this context, the present study focuses on the fabrication and assessment of electrospun poly(ε-caprolactone)–poly(vinylalcohol blend nanofibers imbibed with l-Carvone (5%, w/v) that served as a suitable polymeric carrier to preserve the antimicrobial and antioxidant activities of l-Carvone for a longer period of time. The fumigant potential of l-Carvone and C-PP fibers were assessed toward saw-toothed beetle, a major pest found in stored products. The prepared fragrant C-PP fibers displayed a promising potential formulation for the control of stored product pest such as saw-toothed beetle.     

Enhancement of Poly(Vinyl Alcohol)–Poly(Vinyl Pyrrolidone) Blend Properties using Modified Copper (II) Oxide and Ultrasonic Irradiation

Copper (II) oxide nanoparticles supported within poly(vinyl alcohol)/poly(vinyl pyrrolidone) films have been successfully prepared through ultrasonication method. It is discernible that before the preparation of blends, the surface of copper (II) oxide nanoparticles was modified with citric acid and vitamin C as biosafe capping agents. X-ray diffraction scans illustrated the semicrystalline nature of the obtained pure blend and exhibited a good combination between the blend and the modified copper (II) oxide nanoparticles. Also, thermal stability of blends was improved in comparison to the pure polymer blend with increasing modified copper (II) oxide nanoparticles.     

Physical characterization and rheological behavior of polyurethane/poly(ϵ-caprolactone) blends,prepared by solution blending using dimethylacetamide

Blending effects of thermoplastic polyurethane based on polycaprolactone diol, PU (PCL diol), and poly (ϵ-caprolactone) (PCL) on the rheological properties and morphological behavior of the solvent-cast blends were investigated by parallel plate rheometer. The amount of PCL was varied from 20 to 50% by weight. Fourier transform infrared (FTIR) results showed existence of hydrogen bonding in PU/PCL blends. From FTIR, we also found the increase of PCL composition tends to reduction of intermolecular hydrogen bonding and enhancing of microphase separation in blends. Differential scanning calorimetry (DSC) indicated that these blend systems are partially miscible. Based on rheological characterization, decrease can be seen in the moduli, zero shear viscosity and plateau modulus of blends, as compared with net PU. Using Cole-Cole plots and composition dependencies of η₀ and the other viscoelastic functions expressed variation of morphology of blends due to increase of PCL content. Frequency sweep tests on PU/PCL (80/20) at five temperatures showed validity of time-temperature superposition in this blend. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Mechanical and Physical properties of chitosan and whey blended with poly(ε-caprolactone)

Properties important for packaging were studied on blends of 0-15 wt% poly( l caprolactone) and chitosan and a whey-protein-isolate. The blends were obtained by solution mixing, and films were produced by solvent casting. Transparency was measured by UV/VIS spectroscopy and the printability was qualitatively estimted by using a red ethanol dye. Mechanical properties of solid films and seals were assessed by tensile tests. Stiffness and folding endurence were also measured. The blend morphology was characterized by scanning electron microscopy. It was found that all the blends were transparent. The whey-protein-isolate had the best printability properties and printability remained in the poly( l -caprolactone)-blends. Film stiffness decreased and strain at break increased strongly when the pure chitosan and the pure whey-protein-isolate were wetted. The addition of poly( l -caprolactone) to chitosan and whey-protein-isolate had only a moderate effect on the toughness properties but a strong effect on the modulus which could be predicted by the Halpin-Tsai model. The modulus of the whey-protein-isolate increased and the modulus of the chitosan decreased with the addiion of poly( l -caprolactone). It was found that it was impossible to seal chitosan with a standard heat-pulse sealing technique. The whey-protein-isolate was sealable but the strength of the seals was lower than the intrinsic strength of the pure whey-protein-isolate. The folding endurance properties of chitosan and its blends were far better than those of the whey-protein-isolate and its blends.