Effect of competitive interactions on the structure and properties of blends prepared from an industrial lignosulfonate polymer.

To explore the possibility of applying lignin in practice, an industrial lignosulfonate (0-50 vol%) was blended with four ionomers. The concentrations of carboxyl and carboxylate groups were systematically varied in the ethylene-acrylic acid copolymers to study the competition of hydrogen and ionic bonds forming between the components. The mechanical properties of the blends were determined by tensile testing. The structure was investigated by scanning electron microscopy, while deformation and failure processes were studied by acoustic emission measurements and microscopy. Interfacial interactions were quantitatively characterized by analyzing local deformation processes and by evaluating the composition dependence of the tensile strength using appropriate models. Molecular dynamics simulations indicated that carboxylate groups preferably form clusters in the ionomer phase, consequently, the increasing degree of neutralization results in ionomers with more and more self-interactions of components deteriorating ionomer-lignin interactions. The novel combination of experiments, modeling, and simulation was done for the first time on such materials, and it pointed out that the role of hydrogen bonds is more critical in determining blend properties. Blends can be prepared for practical applications with a good combination of stiffness (0.8 GPa), tensile strength (22 MPa), and elongation-at-break (25 %) at 30 vol% lignosulfonate content and 33 % neutralization.

Interactions, Structure and Properties of PLA/lignin/PBAT Hybrid Blends.

Poly(butylene adipate-co-terephthalate) (PBAT) was added to poly(lactic acid) (PLA)/lignin blends to decrease the considerable stiffness and brittleness of the blends. Two- and three-component blends were prepared in a wide composition range through homogenization in an internal mixer followed by compression molding. Interactions among the components were estimated by comparing the solubility parameters of the materials used and through thermal analysis. Mechanical properties were characterized by tensile testing. The structure of the blends was studied using scanning electron (SEM) and digital optical (DOM) microscopy. The results showed that the interactions between PBAT and lignin are somewhat stronger than those between PLA and the other two components. The maleic anhydride grafted PLA added as a coupling agent proved completely ineffective; it does not modify the interactions. The structural analysis confirmed the immiscibility of the components; the structure of the blends was heterogeneous at each composition. A dispersed structure formed when the concentration of one of the components was small, while, depending on lignin content, an interpenetrating network-like structure developed and phase inversion took place in the range of 30-60 vol% PBAT content. Lignin was located mainly in the PBAT phase. Properties were determined by the relative amount of PBAT and PLA; the addition of lignin deteriorated properties, mainly the deformability of the blends. Other means, such as reactive processing, must be used to improve compatibility and blend properties. The results contribute considerably to a better understanding of structure-property correlations in lignin-based hybrid blends.

Levocetirizine-Loaded Electrospun Fibers from Water-Soluble Polymers: Encapsulation and Drug Release.

Electrospun fibers containing levocetirizine, a BCS III drug, were prepared from three water-soluble polymers, hydroxypropyl methylcellulose (HPMC), polyvinylpyrrolidone (PVP) and polyvinyl alcohol (PVA). Fiber-spinning technology was optimized for each polymer separately. The polymers contained 10 wt% of the active component. An amorphous drug was homogeneously distributed within the fibers. The solubility of the drug in the polymers used was limited, with a maximum of 2.0 wt%, but it was very large in most of the solvents used for fiber spinning and in the dissolution media. The thickness of the fibers was uniform and the presence of the drug basically did not influence it at all. The fiber diameters were in the same range, although somewhat thinner fibers could be prepared from PVA than from the other two polymers. The results showed that the drug was amorphous in the fibers. Most of the drug was located within the fibers, probably as a separate phase; the encapsulation efficiency proved to be 80-90%. The kinetics of the drug release were evaluated quantitatively by the Noyes-Whitney model. The released drug was approximately the same for all the polymers under all conditions (pH), and it changed somewhere between 80 and 100%. The release rate depended both on the type of polymer and pH and varied between 0.1 and 0.9 min-1. Consequently, the selection of the carrier polymer allowed for the adjustment of the release rate according to the requirements, thus justifying the use of electrospun fibers as carrier materials for levocetirizine.

Processing Stabilization of Polyethylene with Grape Peel Extract: Effect of Extraction Technology and Composition.

Dry grape peel powder was extracted by three different techniques, stirred tank reactor, Soxhlet and ultrasound extraction. The composition, physical and chemical structure and inherent stability of the extracts were characterized by various methods. The extracts and reference compounds were added to polyethylene and their stabilization efficiency was determined in multiple extrusion experiments. The composition of the extracts was quite similar. Ten main compounds were identified in the extracts, which contained a considerable number of polyphenols, but only small amounts of quercetin and trans-resveratrol. The extracts proved to be more efficient processing stabilizers than trans-resveratrol and the commercial stabilizer, Irganox 1010, irrespective of the extraction technology used. In spite of their good processing stabilization effect, polymers containing the extracts had poor residual stability. The differences in processing and long-term stabilization must be related to the different structures of the polyphenols contained by the extracts and the reference compounds. The results clearly prove that the IC50 value determined by the DPPH assay is not suitable for the estimation of the efficiency of a compound as a stabilizer for polymers.

Preparation of Biocomposites with Natural Reinforcements: The Effect of Native Starch and Sugarcane Bagasse Fibers.

Biocomposites were prepared from poly(lactic acid) and two natural reinforcements, a native starch and sugarcane bagasse fibers. The strength of interfacial adhesion was estimated by model calculations, and local deformation processes were followed by acoustic emission testing. The results showed that the two additives influence properties differently. The strength of interfacial adhesion and thus the extent of reinforcement are similar because of similarities in chemical structure, the large number of OH groups in both reinforcements. Relatively strong interfacial adhesion develops between the components, which renders coupling inefficient. Dissimilar particle characteristics influence local deformation processes considerably. The smaller particle size of starch results in larger debonding stress and thus larger composite strength. The fracture of the bagasse fibers leads to larger energy consumption and to increased impact resistance. Although the environmental benefit of the prepared biocomposites is similar, the overall performance of the bagasse fiber reinforced PLA composites is better than that offered by the PLA/starch composites.

Quantitative analysis of factors determining the enzymatic degradation of poly(lactic acid).

The enzymatic degradation of poly(lactic acid) was catalyzed with Proteinase K and the effect of various factors on the rate of degradation was analyzed quantitatively with the help of appropriate kinetic models. The Michaelis-Menten model was modified for the purpose by considering the heterogeneous nature of the reaction and the denaturation of the enzyme. The results proved that Proteinase K degrades the polymer very efficiently. The rate of degradation increases considerably up to 0.1 mg/ml enzyme concentration, but remains constant at larger values. Temperature has an optimum at around 50 °C that is somewhat higher than the 37 °C extensively used in the literature as the most advantageous temperature. If degradation occurs in the same medium throughout the process, the formation of lactic acid results in the rapid decrease of pH and finally in the denaturation of the enzyme. The dropping of pH below 5 slows down and finally stops degradation completely. The daily change of the medium results in degradation with a constant rate and the entire amount of the polymer can be decomposed mainly into monomer or smaller oligomer fragments. Degradation rate decreases slightly with increasing molecular weight and increasing d-lactide content. The use of appropriate kinetic models allows quantitative analysis and the prediction of the rate of enzymatic degradation of PLA.

Stabilization of PE with Pomegranate Extract: Contradictions and Possible Mechanisms.

Dry pomegranate peel was extracted with acetone and the extract was added to a Phillips type polyethylene. The concentration of the extract was changed from 0 to 1000 ppm in six steps and stabilization efficiency was checked by the multiple extrusion of the polymer followed by the characterization of chemical structure, processing, and residual stability. The results confirmed the excellent processing stabilization efficiency of the extract, but also the poor long-term stability of PE containing it in accordance with previously published results. The extract is amorphous and its solubility is relatively large in the polymer; thus, these factors cannot be the reason for the poor stabilization efficiency in an oxygen-rich environment. Chemical factors like the self-interaction of the polyphenol molecules, the stability of the radicals forming after hydrogen abstraction, and the lack of hydrogens with the necessary reactivity must be considered during the evaluation of the efficiency of the extract. These factors as well as the insufficient number of active hydrogens hinder the reaction of the additive molecules with oxygen-centered radicals, thus leading to inferior long-term stability. The extract can be used for the processing stabilization of polymers, but for applications requiring long-term stability, it must be combined with other natural antioxidants like flavonoids or Vitamin E.

Deformation and Failure Mechanism of Particulate Filled and Short Fiber Reinforced Thermoplastics: Detection and Analysis by Acoustic Emission Testing.

Acoustic emission, the detection of signals during deformation, is a frequently used method for the study of local deformation processes occurring in heterogeneous polymer systems. Most of these processes result in the evolution of elastic waves which can be detected by appropriate sensors. The analysis of several parameters characterizing the waves offers valuable information about the possible deformation mechanism. The acoustic emission testing of composites may yield very different number of signals from a few hundred to more than 100,000. This latter was proved to be affected mainly by particle size, interfacial adhesion and composition, but other factors, such as matrix modulus and specimen size, also influence it. Local deformation processes are claimed to have a strong effect on macroscopic properties. Indeed, a close correlation was found between the initiation stress of the dominating particle related process derived from acoustic emission testing and the tensile strength in both polypropylene (PP) and poly(lactic acid) (PLA) composites. However, in polyamide (PA)-based heterogeneous polymer systems, deformations related to the matrix dominated composite properties. Besides forecasting failure, the method makes possible the determination of the inherent strength of lignocellulosic fibers being around 40 MPa as well as the quantitative estimation of adhesion strength for composites in which interactions are created by mechanisms other than secondary forces. The proposed approach based on acoustic emission testing proved that in PP/CaCO3 composites, the strength of adhesion can be increased by ten times from about 100 mJ/m2 to almost 1000 mJ/m2 in the presence of a functionalized polymer.

Poly-ε-Caprolactone/Halloysite Nanotube Composites for Resorbable Scaffolds: Effect of Processing Technology on Homogeneity and Electrospinning.

Polycaprolactone (PCL)/halloysite composites were prepared to compare the effect of homogenization technology on the structure and properties of the composites. Halloysite content changed from 0 to 10 vol% in six steps and homogeneity was characterized by various direct and indirect methods. The results showed that the extent of aggregation depends on technology and on halloysite content; the size and number of aggregates increase with increasing halloysite content. Melt mixing results in more homogeneous composites than the simple compression of the component powders or homogenization in solution and film casting. Homogeneity and the extent of aggregation determines all properties, including functionality. The mechanical properties of the polymer deteriorate with increasing aggregation; even stiffness depends on homogeneity. Strength and deformability decreases drastically as the number and size of aggregates increase. Not only dispersed structure, but also the physical state and crystalline structure of the polymer influence homogeneity and properties. The presence of the filler affects the preparation of electrospun fiber scaffolds as well. A part of the filler is excluded from the fibers while another part forms aggregates that complicates fiber spinning and deteriorates properties. The results indicate that spinning is easier and the quality of the fibers is better if a material homogenized previously by melt mixing is used for the production of the fibers.

Physical-Chemical Aspects of the Preparation and Drug Release of Electrospun Scaffolds.

Fibers were spun from a mixture of dichloromethane (DCM) and dimethyl sulfoxide (DMSO) solution of poly(lactic acid)(PLA) containing various amounts of amoxicillin (Amox) as the active component. Composition changes during spinning, structure, solubility, and the location of the drug were considered during the evaluation of drug release and microbial activity. The results showed that the composition of the material changes during the preparation procedure. The solubility of the drug in the components and that of the components in each other is limited, which results in the formation of several phases and the precipitation of the drug. The technology used results in the partitioning of the drug; some is located inside, while the rest is among the fibers. The wetting of the fibers or disks by the water-based dissolution media is poor, the penetration of the liquid into and the diffusion of the active component out of the device takes considerable time. Drug release takes place in one, burst-like step, only Amox located among the fibers dissolve and diffuse into the surrounding medium. The slow second stage of release claimed in the literature is less probable because the size of the Amox molecule is considerably larger than the holes creating the free volume of the polymer. The prepared device has antimicrobial activity, inhibits the growth of the two bacterial strains studied. The time scale of activity is short and corresponds to that of the release experiments and the burst-like behavior of the device. The results clearly prove that physical-chemical factors play a determining role in the effect and efficiency of medical devices prepared from electrospun fibers containing an active component.

Improved Release of a Drug with Poor Water Solubility by Using Electrospun Water-Soluble Polymers as Carriers.

In an attempt to improve the solubility of valsartan, a BCS II drug, fibers containing the drug were prepared from three water-soluble polymers, hydroxypropyl-methyl-cellulose (HPMC), polyvinyl-pyrrolidone (PVP), and polyvinyl-alcohol (PVA). Fiber spinning technology was optimized for each polymer separately. The polymers contained 20 wt% of the active component. The drug was homogenously distributed within the fibers in the amorphous form. The presence of the drug interfered with the spinning process only slightly, the diameters of the fibers were in the same range as without the drug for the HPMC and the PVA fibers, while it doubled in PVP. The incorporation of the drug into the fibers increased its solubility in all cases compared to that of the neat drug. The solubility of the drug itself depends very much on pH and this sensitivity remained the same in the HPMC and PVP fibers; the release of the drug is dominated by the dissolution behavior of valsartan itself. On the other hand, solubility and the rate of release were practically independent of pH in the PVA fibers. The different behavior is explained by the rate of the dissolution of the respective polymer, which is larger for HPMC and PVP, and smaller for PVA than the dissolution rate of the drug. The larger extent of release compared to neat valsartan can be explained by the lack of crystallinity of the drug, its better dispersion, and the larger surface area of the fibers. Considering all facts, the preparation of electrospun devices from valsartan and water-soluble polymers is beneficial, and the use of PVA is more advantageous than that of the other two polymers.

Quantitative determination of release kinetics from fibrous poly(3-hydroxybutyrate) scaffolds.

A fibrous scaffold was prepared from poly(3-hudroxybutirate) (PHB) by wet spinning from chloroform solution. The fibers were precipitated into excess ethanol and they had a regular, cylindrical shape. The diameter of the fibers was regulated by the rate of spinning. A model drug, quercetin, was dissolved in the fiber in various amounts. The rate of drug release could be controlled by the adjustment of fiber diameter. A novel approach is proposed in the paper for the quantitative analysis of release kinetics. The model is based on Fick's laws, and does not use any simplification or introduce empirical constants. The prediction of the new model agreed well with experimental results and proved that the approach offers an exact description of experimental data. Although the method allows the estimation of the diffusion coefficient as well, the value obtained is biased because of the large surface to volume ratio of the scaffold. The comparison of the proposed model to empirical or semi-empirical approaches published earlier showed that the latter are less accurate and predict false results at various stages of the release study. The proposed method of fiber preparation and the model makes possible the prediction and control of the release rate of a drug from fibrous scaffolds.

Synthesis and Applications of Cinchona Squaramide-Modified Poly(Glycidyl Methacrylate) Microspheres as Recyclable Polymer-Grafted Enantioselective Organocatalysts.

This work presents the immobilization of cinchona squaramide organocatalysts on poly(glycidyl methacrylate) solid supports. Preparation of the well-defined monodisperse polymer microspheres was facilitated by comprehensive parameter optimization. By exploiting the reactive epoxy groups of the polymer support, three amino-functionalized cinchona derivatives were immobilized on this carrier. To explore the effect of the amino linker, these structurally varied precatalysts were synthesized by modifying the cinchona skeleton at different positions. The catalytic activities of the immobilized organocatalysts were tested in the Michael addition of pentane-2,4-dione and trans-ß-nitrostyrene with excellent yields (up to 98 %) and enantioselectivities (up to 96 % ee). Finally, the catalysts were easily recovered five times by centrifugation without loss of activity.

Electrospun PLA Fibers Containing Metronidazole for Periodontal Disease.

PURPOSE: Electrospun PLA fiber devices were investigated in the form of fiber mats and disks. Metronidazole was used as an active agent; its concentration was 12.2 and 25.7 wt% in the devices. METHODS: The structure was studied by X-ray diffraction and scanning electron microscopy, drug release by dissolution measurements, while the antimicrobial efficiency was tested on five bacterial strains. RESULTS: The XRD study showed that the polymer was partially crystalline in both devices, but a part of metronidazole precipitated and was in the form of crystals among and within the fibers. Liquid penetration and dissolution were different in the two devices, they were faster in disks and slower in fiber mats, due to the morphology of the device and the action of capillary forces. Disks released the drug much faster than fiber mats. Although the release study indicated fast drug dissolution, the concentration achieved a plateau value in 24 hrs for the disks; the inhibition effect lasted much longer, 13 days for bacteria sensitive to metronidazole. The longer inhibition period could be explained by the slower diffusion of metronidazole located inside the fibers of the device. CONCLUSION: The results suggest that the devices may be effective in the treatment of periodontitis.

Controlled degradation of poly-ε-caprolactone for resorbable scaffolds.

A lipase from Burkholderia cepacia was successfully adsorbed on the surface of halloysite nanotubes and the coated tubes were incorporated into poly-ε-caprolactone (PCL). The efficiency of the halloysite in the adsorption of the enzyme was characterized by the total protein content determined with the Bradford method. The activity of the adsorbed enzyme was estimated by the kinetic resolution of racemic 1-phenylethanol. The immobilized enzyme was mixed with the polymer and compression molded films were prepared at 70 °C. Activity measurements proved that the enzyme remains active even after adsorption; in fact, larger activities were measured for the immobilized enzyme than for the neat enzyme preparation. The supported enzyme degraded PCL efficiently, the rate of degradation depended on the amount of enzyme adsorbed. The kinetics of degradation was described quantitatively with an appropriate model accounting for two of the three steps of the process, i.e. degradation and the denaturation of the enzyme. The determination of time constants allows the adjustment of degradation rate. This is the first time that the enzyme, which catalyzes degradation, is incorporated into the polymer, and not into the degradation medium, thus allowing the preparation of resorbable scaffolds with controlled lifetime.

Poly(lactic acid)/cellulose nanocrystal composites via the Pickering emulsion approach: Rheological, thermal and mechanical properties.

The use of nanocellulose is an attractive method to improve the characteristics of biodegradable polymers, but its effects are often affected by uneven dispersion. In this work, cellulose nanocrystals (CNCs) were evenly dispersed into poly(lactic acid) (PLA) via the Pickering emulsion approach. The PLA/CNC composites prepared were studied by rheological, thermal as well as mechanical measurements. Changes in the rheological characteristics of the composites showed that CNC promoted the transition of the composites from fluid to solid-like behavior at high temperatures. The introduction of 5 wt% CNC improved the crystallinity of PLA considerably and increased the onset temperature of crystallization by about 10 °C. The storage modulus of the composites increased throughout the entire temperature range of testing. Flexural modulus was improved considerably. All the results indicated that the Pickering emulsion approach improved the dispersion of CNC in the PLA matrix and CNC improved efficiently most properties of PLA.

The role of enzyme adsorption in the enzymatic degradation of an aliphatic polyester.

The enzyme catalyzed degradation of poly(3-hydroxybutyrate) (PHB) is a two-step process consisting of the adsorption of the enzyme on the surface of a PHB substrate and the cleavage of ester bonds. A deactivated enzyme was prepared by point mutagenesis to separate the two steps from each other. Measurements carried out with active and inactive enzymes on PHB particles proved that mutagenesis was successful and the modified enzyme did not catalyze degradation. Based on the Michaelis-Menten approach a kinetic model was proposed which could describe the processes quantitatively, the agreement between prediction and the measured data was excellent. The separation of the two processes allowed the determination of the adsorption kinetics of the enzyme; the rate constants of the adsorption and desorption process were determined for the first time. Comparison of these constants to reaction rates showed that adsorption is not instantaneous and can be the rate-determining step. The area occupied by an enzyme molecule was also determined (13.1 nm2) and it was found to be smaller than the value published in the literature (17 ± 8 nm2). The separation of the two steps makes possible the prediction and control of the degradation process.

Enzymatic degradation of poly-[(R)-3-hydroxybutyrate]: Mechanism, kinetics, consequences.

Poly-[(R)-3-hydroxybutyrate] (PHB) films prepared by compression molding and solvent casting, respectively, were degraded with the intracellular depolymerase enzyme natively synthetized by the strain Bacillus megaterium. Quantitative analysis proved that practically only (R)-3-hydroxybutyric acid (3-HBA) forms in the enzyme catalyzed reaction, the amount of other metabolites or side products is negligible. The purity of the product was verified by several methods (UV-VIS spectroscopy, liquid chromatography, mass spectroscopy). Degradation was followed as a function of time to determine the rate of enzymatic degradation. Based on the Michaelis-Menten equation a completely new kinetic model has been derived which takes into consideration the heterogeneous nature of the enzymatic reaction. Degradation proceeds in two steps, the adsorption of the enzyme onto the surface of the PHB film and the subsequent degradation reaction. The rate of both steps depend on the preparation method of the samples, degradation proceed almost twice as fast in compression molded films than in solvent cast samples. The model can describe and predict the formation of the reaction product as a function of time. The approach can be used even for the commercial production of 3-HBA, the chemical synthesis of which is complicated and expensive.

Hydrogen bonding interactions in poly(ethylene-co-vinyl alcohol)/lignin blends.

Blends were prepared from lignin and ethylene-vinyl alcohol (EVOH) copolymers to study the effect of hydrogen bonding interactions on compatibility and structure. The vinyl alcohol (VOH) content of the copolymers changed between 52 and 76 mol%, while the lignin content of the blends varied between 0 and 60 vol%. Low density polyethylene with 0 mol% VOH content was used as reference. The components were homogenized in an internal mixer and they were characterized by various methods including Fourier transform infrared spectroscopy (FTIR), dynamic mechanical analysis, differential scanning calorimetry and scanning electron microscopy. The results of the experiments proved that strong hydrogen bonds form between the two components shown by FTIR spectroscopy, a shift in the relaxation temperatures of the matrix polymer and by the decrease of crystallite size and crystallinity with increasing lignin content. In spite of the strong interactions, heterogeneous structure forms in the studied blends since self-interactions within the neat components are also very strong. The size of dispersed lignin particles is determined by competitive interactions in the blends; stronger EVOH/lignin interactions result in smaller particle size. Although hydrogen bonds are strong, miscible polymer/lignin blends can be prepared only by applying other approaches like plasticization or chemical modification.

The novel technique of vapor pressure analysis to monitor the enzymatic degradation of PHB by HPLC chromatography.

A novel method was introduced for the quantitative determination of substances in aqueous solutions by using the evaporative light scattering (ELS) detector of a high performance liquid chromatograph (HPLC). The principle of the measurement is the different equilibrium vapor pressure of the solvent and the analyte resulting in decreasing evaporation rate, larger droplets and stronger signal with increasing concentration. The new technique based on vapor pressure analysis was validated with traditional UV-Vis detection carried out with a diode array detector (DAD). The new technique was used for monitoring the concentration of solutions obtained during the enzymatic degradation of poly(3-hydroxybutyrate) yielding the 3-hydroxybutyrate monomer as the product. The accuracy of the measurement allowed the determination of degradation kinetics as well. The results obtained with the two techniques showed excellent agreement at small concentrations. Deviations at larger concentrations were explained with the non-linear correlation between analyte concentration and detector signal and the linear regression used for calibration. Mathematical analysis of the method made possible the determination of the evaporation enthalpy of the analyte as well. The new approach is especially suitable for the quantitative analysis of compounds, which do not absorb in the detection range of the DAD detector or if their characteristic absorbance is close to the lower end of its wavelength range.