Thoroughly Hydrophilized Electrospun Poly(L-Lactide)/ Poly(ε-Caprolactone) Sponges for Tissue Engineering Application

Biodegradable electrospun sponges are of interest for various applications including tissue engineering, drug release, dental therapy, plant protection, and plant fertilization. Biodegradable electrospun poly(l -lactide)/poly(ε-caprolactone) (PLLA/PCL) blend fiber-based sponge with hierarchical pore structure is inherently hydrophobic, which is disadvantageous for application in tissue engineering, fertilization, and drug delivery. Contact angles and model studies for staining with a hydrophilic dye for untreated, plasma-treated, and surfactant-treated PLLA/PCL sponges are reported. Thorough hydrophilization of PLLA/PCL sponges is found only with surfactant-treated sponges. The MTT assay on the leachates from the sponges does not indicate any cell incompatibility. Furthermore, the cell proliferation and penetration of the hydrophilized sponges are verified by in vitro cell culture studies using MG63 and human fibroblast cells.     

Biodegradable Polymers for Orthopedic Applications: Synthesis and Processability of Poly (l-Lactide) and Poly (Lactide-co-€-Caprolactone)

Abstract

The synthesis of poly(l-lactide) (PLLA), poly(l-lactide-co-e-caprolactone), and poly(DL-lactide-co-e-caprolactone) by ring-opening bulk polymerization was investigated. Polymerization temperature had a significant effect on the PLLA molecular weight. At 184°C a polymer with a molecular weight of only 10 × 10⁴ resulted. This was lower by a factor of 2 than that obtained at 103 and 145°C. The stannous octoate (SnOct) concentration, with a monomer/SnOct molar ratio in the range of 1,000 to 10,000, was not found to have a significant effect on the PLLA molecular weight. A heterogeneous structure in polymerized PLLA was observed. The intrinsic viscosity of poly(lactide-co-€-caprolactone), obtained at 130°C, monomer/SnOct molar ratio 5,000, and polymerization time of 30 hours, decreased with increasing €-caprolactone content within the first 9 wt% and then leveled off. Die-drawing of PLLA cylinders, for the purpose of increasing the polymer's mechanical strength, was unsuccessful due to the brittleness of the polymer. The drawability of poly(l-lactide), however, was greatly improved by copolymerization with €-caprolactone. With only 3 wt% of €-caprolactone, for example, the tensile strength of die-drawn poly(l-lactide-co-e-caprolactone) was increased by a factor of more than 3. Polymer processing temperature was also investigated. The requirement for low processing temperatures in melt manufacture of controlled release matrix devices containing thermal sensitive drugs was accomplished by three methods: through the use of low molecular weight poly(DL-lactide), adding (DL-lactic) acid oligomer to high molecular weight PDLLA, and copolymerizing DLLA with €-caprolactone. The glass transition temperatures of the modified high molecular weight PDLLA decreased significantly. Melt extrusion below 100°C could be performed.     

Preparation of Poly(ε-caprolactone)/Poly(ester amide) Electrospun Membranes for Vascular Repair

With adjustable amphiphilicity and anionic/cationic charge, biodegradability and biocompatibility, amino acid-based poly(ester amide)s(PEAs) have drawn attention in the research of tissue engineered vascular grafts. In this work, L-phenylalanine-based PEAs with or without L-lysine were synthesized through polycondensation, and ultrafine fibrous grafts consisted of PEAs and poly(ε-caprolactone)(PCL) in given mass ratios were further prepared via blend electrospinning. Surface characterizations by Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy confirmed the chemical structure, and the wettability indicated that the prepared PCL/PEAs electrospun membranes exhibited less hydrophobic than PCL. Tensile results showed that the PCL/PEAs membranes possessed suitable mechanical properties, which could meet the requirements of artificial blood vessels. Cell culture and hemolytic tests exhibited that the PCL/PEAs electrospun membranes are biocompatible. In general, the electrospun grafts of PCL/PEAs could be applied for vascular repair.     

Probing the Effects of Antimicrobial-Lysozyme Derivatization on Enzymatic Degradation of Poly(ε-caprolactone) Film and Fiber

Surface derivatization is essential for incorporating unique functionalities into biodegradable polymers. Nonetheless, its precise effects on enzymatic biodegradation still lack comprehensive understanding. In this study, a facile solution-based method is employed to surface derivatize poly(ε-caprolactone) films and electrospun fibers with lysozyme, aiming to impart antimicrobial properties and examine the impact on enzymatic degradation. The derivatized films and fibers have shown high antibacterial efficacy against Escherichia coli and Staphylococcus aureus. Through gravimetric analysis, it is observed that the degradation rate experiences a slight decrease upon lysozyme derivatization. However, this reduction is effectively countered by the inclusion of Tween-20, as affirmed by isothermal titration calorimetry. Comparing films and fibers, the latter undergoes degradation at a more accelerated pace, coupled with a rapid decline in molecular weight. This study provides valuable insights into the factors influencing the degradation of surface-derivatized biopolymers through electrospinning, offering a simple strategy to mitigate biomaterial-associated infections.     

Crystallizability of Poly(ε-caprolactone) Blends with Poly(vinylphenol) under Different Conditions

The intermolecular interaction between poly（vinylphenol） （PVPh） and polycaprolactone （PCL） and the crystallization behavior of PCL in PCL/PVPh blends with different compositions and under different conditions were investigated by Fourier transform infrared spectra （FTIR） and differential scanning calorimetry （DSC）. It has been shown that the PCL in the blends with different blend ratios all exists in crystalline state after solution casting, even though the crystallinity decreases with increasing PVPh content. For the melt crystallized samples, PCL in its 80/20 PCL/PVPh sample can still crystallize. The crystallinity is, however, lower than that of the solution cast sample. For blends containing 50% or 20% PCL, the as-cast samples are semicrystalline and can change to compatible amorphous state after heat treatment process. FTIR analysis shows the existence of hydrogen bonding between PCL and PVPh and the fraction of hydrogen bonds increases remarkably after heat treatment process.     

Polylactones. 13. Transesterification of Poly(L-Lactide) with Poly(Glycoude), Poly(β-Propio-Lactone), and Poly[ε -Caprolactone)

Homogeneous blends of poly(L-lactide) (M _n = 30 000 to 40 000) and poly(β-propiolactone) or poly(ε-caprolactone) were prepared in solution. The solvent-free blends were subjected to transesterification catalyzed by means of methyl triflate, triflic acid, boron trifluoride, or tributyltin methoxide at 100 or 150°C. At 100°C, transesterification was barely detectable even after 96 h. When poly(β-propiolactone) was used as the reactant at 150°C, degradation was faster than transesterification regardless of the catalyst. The same negative result was obtained for heterogeneous blends of poly(L-lactide) and poly(glycolide). In the case of poly(ε-caprolactone), copolyesters with slightly blocky sequences were obtained with tributyltin methoxide as catalyst, whereas the acidic catalysts caused rapid degradation. The copolyesters were characterized by means of ¹H-NMR spectroscopy with regard to their molar composition, by means of ¹³C-NMR spectroscopy with regard to their sequences, and by means of differential scanning calorimetry with regard to crystallinity.     

Investigation of Calcium Carbonates Enhanced Poly(ε-caprolactone) Materials for Biomedical Applications

In this study poly(ε-caprolactone) – calcium-carbonate composites were obtained by melt-mixing. Two crystal-modifications of calcium-carbonate were used, namely calcite and aragonite. Compressive and tensile tests were executed on samples with various compositions to analyze the effect of filler content and particle geometry. Both minerals improved the compressive modulus and strength significantly, however the influence of calcite was superior. The tensile modulus was also highly increased. The elongation at break remained high even at 50 wt% aragonite filling, but decreased with two orders in the case of calcite. Biocompatibility tests were also carried out with human osteoblast cells and the results were promising. The relative cell number increased due to calcium-carbonate. Both filler material is able to enhance the mechanical and biological properties of poly(ε-caprolactone) significantly. Aragonite samples remained more ductile compared to calcite ones, but the calcite filled scaffolds are stiffer, stronger and slightly more biocompatible than aragonite filled materials.     

Recovery of Uniaxially Stretched Amorphous Poly(ethylene terephthalate) Film

Thedeformationandrecoveryofamorphouspolymerwerestudiedinrecentyears'-'.SomeresearcherssuggestedthatthepostyieldingdeformationofamorphouspolymerwasmadeupoftwocomponentsfromDSC--volumeanddimensionrecoveryexperiments'-'.Butunderstandingaboutthisprocesswasincomplete,especiallyaboutthemotionofthechain.Theaimofthisarticlewastoinvestigate,onamacroscopicscale,thedifferentcomponentsoflargescaletensiledeformationbyobservingtherecoveryofuniaxiallystretcheda-PETfilmasafunctionoftime,temperatureanddrawra…     

Dielectric Characterization of Biopolymer/Poly(ϵ-Caprolactone) Hydrogels

The dielectric properties of a series of pure atelocollagen samples and of atelocollagen-based hydrogels long-range cross-linked with bifunctional poly(?-caprolactone) derivative, or further short-range cross-linked by UV irradiation, were discussed in relation to the cross-linking method, composition, and hierarchical assembly. Three main factors with significant influence on the electrical behavior, frequency, temperature, and moisture content, are analyzed in detail.     

Synthesis and Antibacterial Activity of Selenium-functionalized Poly(ε-caprolactone)

A selenium-functionalizedε-caprolactone was synthesized by introducing a phenyl selenide group at the 7-position.A polymer was obtained through the ring-opening polymerization of this monomer in a base/thiourea binary organocatalytic system.A living polymerization process was achieved under mild conditions.The resulting polymers had a controlled molecular weight with a narrow molecular weight distributions and high end-group fidelity.Random copolymers could be obtained by copolymerizing this monomer withε-caprolactone.The thermal degradation temperature of the obtained copolymers decreased with the increasing molar ratio of selenide functionalized monomer in copolymers,while the glass transition temperature increased.In addition,the phenyl selenide side group could be further modified to a polyselenonium salt,which resulted in a polymer with good antibacterial properties.The survival rate of E.coli and S.aureus was only 9%with a polymer concentration of 62.5μg/mL.     

Microwave-assisted Polymerization of ε-Caprolactone with Maleic Acid as Initiator and Drug Release Behavior of Ibuprofen-Poly(ε-caprolactone) System

Poly( ε-caprolactone)(PCL) with weight-average molar mass over 10000g/mol was synthesized by microwave-assisted ring -opening polymerization of ε-caprolactone(ε-CL) with maleic acid(MA) as initiator (2.45GHz,360W,85min),Ibuprofen-PCL controlled release system was prepared directly by the ROP of ε-CL in its mixture with ibuprofen.The release of ibuprofen from the system was sustained and steady.     

Microwave-Assisted Synthesis of Poly(ε-caprolactone)-block-poly(ethylene glycol) and Poly(lactide)-block-poly(ethylene glycol)

Summary: This study reported the preparation and characterization of PCL-b-mPEG (poly(ε-caprolactone)-block-poly(ethylene glycol)) and PLL-b-mPEG (poly(L-lactide)-block-poly(ethylene glycol)) diblock copolymers by microwave heating and comparison of resulted products the ones with prepared by conventional heating. Diblock copolymers were synthesized successfully by the microwave-assisted ROP in the presence of stannous octoate (SnOct₂) as catalyst under nitrogen atmosphere in different monomer ratios. Structural and functional characterization of copolymers were performed by FTIR, ¹H-NMR and DSC. Molecular weight values were determined by GPC and also calculated from ¹H-NMR. According to the results, microwave irradiation allowed to obtain polymers with very narrow size distribution in very short reaction time. Similar polymers prepared by conventional heating were also synthesized for comparison. Molecular weight and conversion of polymers were increased by irradiation time. This change was continued until a certain time point after which no more increase was observed. It was concluded that microwave irradiation is a succesful method to obtain these diblock copolymers in very short reaction time and with a similar conversion obtained by conventional method.     

Enhanced Crystallization Rate of Biodegradable Poly(ε-caprolactone) by Cyanuric Acid as an Efficient Nucleating Agent

The influence of cyanuric acid(CA) as an efficient nucleating agent on the crystallization behavior and morphology of biodegradable poly(ε-caprolactone)(PCL) was extensively studied in this work with several techniques for the first time. The nonisothermal melt crystallization behavior and overall isothermal melt crystallization rate of PCL were significantly enhanced by only a small amount of CA. The addition of CA apparently improved the nonisothermal melt crystallization peak temperature, overall isothermal melt crystallization rate, and nucleation density of PCL spherulites, but did not modify the crystallization mechanism and crystal structure of PCL, indicating that CA was an efficient nucleating agent for the crystallization of PCL. The possible nucleation mechanism of CA on the crystallization of PCL was also discussed on the basis of their crystal structures.     

Electrochemical Properties of Poly (ethyl acrylate-co-lithium methacrylate) Latex Film Solid Electrolyte

Muchattentionhasbeenpaidtothedevelopmentofnewpolymerelectrolytewithspecialmorphology,soastoimprovetheirelectrochemicalpropertiestomeettheneedsoflithium(ion)battery.Inthiswork,PEMlatexwassynthesizedbyemulsion-fi-eepolymerization.ThemicrophotoofPEMlate...     

Flexible Gradient Poly(ether-ester) from the Copolymerization of Epoxides and ε-Caprolactone Mediated by a Hetero-bimetallic Complex

Copolymerization is a commonly employed method for optimizing the properties of polymer materials. Incorporating ether segments into polyesters main chain to obtain polyether-polyester copolymers is an effective strategy to realize the integration of multiple properties of polyester and polyether, and to develop more high-performance, multi-purpose polymer materials. Herein, the synthesis of poly(ether-ester)s is accessible by employing the biphenyl-linked heterodinuclear salen Cr-Al complex in the presence of PPNCl for the copolymerization of epoxides and ε-caprolactone(CL). Monitoring the copolymerization process reveals that catalyst 1 exhibited good performance for the copolymerization of epoxides and CL, affording copolymers with a gradient sequence structure. The dynamic thermomechanical analysis(DMA) study indicates the obtained poly(ether-ester)s possess enhanced flexibility compared with the block copolymers or blend of PPO and PCL homopolymers with the same ratio. This study provides a theoretical basis for the preparation of high-performance polymer materials.     

Effect of Physical Aging on Heterogeneity of Poly(ε-caprolactone) Toughening Poly(lactic acid) Probed by Nanomechanical Mapping

Poly(lactic acid)(PLA) is a promising bio-based environmentally-friendly plastic. Nevertheless, the physical aging-induced brittleness of PLA limits its widespread applications. Blending with immiscible ductile polymer is an effective way to toughen PLA. However, the underlying details of the toughening mechanism and, in particular, the effect of physical aging are not well understood. Herein, atomic force microscopy(AFM) based nanomechanical mapping technology was utilized to visualize the diff...     

Poly(ethylene oxide)-block-poly(α-cinnamyl-ε-caprolactone-co-ε-caprolactone) diblock copolymer nanocarriers for enhanced solubilization of caffeic acid phenethyl ester

We report novel micellar carriers, comprising pendant cinnamyl moieties in the core-forming block, designed to increase the solubilization of caffeic acid phenethyl ester (CAPE) in aqueous media. Amphiphilic poly(ethylene oxide)-block-poly(α-cinnamyl-ε-caprolactone-co-ε-caprolactone) (PEO-b-P(CyCL-co-CL) diblock copolymers were synthesized by ring-opening copolymerization of α-propargyl-ε-caprolactone and ε-caprolactone from a monofunctional PEO macroinitiator and subsequent attachment of cinnamyl groups via click reaction. In addition, a linear PEO-b-PCL diblock copolymer was synthesized and used in this study for comparison. Next, nanosized micelles from PEO-b-P(CyCL-co-CL) and PEO-b-PCL were formed via the solvent evaporation method and then loaded with CAPE. Dynamic and electrophoretic light scattering, and transmission electron microscopy were used to characterize both blank and loaded carriers. The potential of the micelles comprising pendant cinnamyl group to solubilize CAPE in water was evaluated in a comparative fashion to that of nonmodified PEO-b-PCL diblock copolymer.     

Poly(2-vinylpyridine) as a template for the radical polymerization of methacrylic acid—VI. Influence of the solvent

The template polymerization (TP) of methacrylic acid (MAA) along poly(2-vinylpyridine) (P2VP) has been investigated to study effects of solvent polarity upon the kinetics. The solvents were DMSO, DMF and dioxane. In DMSO, there is no rate enhancement due to the presence of the template; this is consistent with the fact that poly(methacrylic acid) (PMAA) and P2VP do not form complexes in this strongly solvating medium. The rate enhancement (template effect) in DMF is primarily due to termination retardation of P2VP-bound PMAA radicals. The largest template effect was found in 1,4-dioxane (about three times that in DMF). The cause may be the faster complexation of PMAA-radicals to the template (ca 10 times that in DMF). The non-steady state conditions for the template radical concentration, which is an essential aspect for the estimation of the various rate coefficients of the proposed kinetic model for TP, could be confirmed with EPR-measurements.