Preparation and Characterization of Gelatin–Poly(L-lactic) Acid/Poly(hydroxybutyrate-co-hydroxyvalerate) Composite Nanofibrous Scaffolds

Poly(L-lactic) acid (PLLA) scaffolds, prepared by electrospinning technology, have been suggested for use in tissue engineering. They remain a challenge for application in biological fields due to PLLA's slow degradation and hydrophobic nature. We describe PLLA, PLLA/poly(hydroxybutyrate-co-hydroxyvalerate) (PHBV), and PLLA/PHBV/gelatin (Gt) composite nanofiberous scaffolds (Gt–PLLA/PHBV) electrospun by changing the electrospinning technology. The morphologies and hydrophilicity of these fibers were characterized by scanning electron microscopy (SEM) and water contact angle measurement. The results showed that the addition of PHBV and Gt resulted in a decrease in the diameters and their distribution and greatly improved the hydrophilicity. The in-vitro degradation test indicated that GT–PLLA/PHBV composite scaffolds exhibited a faster degradation rate than PLLA and PLLA/PHBV scaffolds. Dermal fibroblasts viabilities on nanofibrous scaffolds were characterized by [3-(4, 5-dimethylthiazol-2-yl)-2, 5-diphenyltetrazolium bromide] (MTT) assay and cell morphologies after 7 days culture. Results indicated that the GT–PLLA/PHBV composite nanofibers showed the highest bioactivity among the three scaffolds and increased with increasing time. The SEM images of cells/scaffolds composite materials showed the GT–PLLA/PHBV composite nanofibers enhanced the dermal fibroblasts's adhesion, proliferation, and spreading. It is suggested that the nanofibrous composite scaffolds of GT–PLLA/PHBV composites would be a promising candidate for tissue engineering scaffolds.     

Preparation and Characterization of Electroactive Anion‐Exchange Acrylic Polymer–Gold Composites

The characteristics and performance of an ionic polymer–metal composite (IPMC), prepared with an anion‐exchange acrylic copolymer, was examined. The acrylic copolymer was synthesized by the radical copolymerization of fluoroalkyl methacrylate and 2‐(dimethyl amino)ethyl methacrylate(AMA). Effects of the AMA repeating unit's content in the copolymer and effects of the anion type present on the actuation of the IPMC were observed. The optimal content of 19.4 wt% AMA in the IPMC copolymer yielded the best actuation. The actuation also improved according to the type of anion present in the composite, in the following order: Br^???4 ^?.     

Synthesis and Characterization of New Organic–Inorganic Hybrid Nanosilica Fillers Prepared by Sol–Gel Reaction

In light of the success of making multicomponent sol–gel glasses, in this study the synthesis of new hybrid nanosilicas with controlled hydrophilic/hydrophobic properties was carried out by incorporating organic based species with appropriate functional groups to inorganic based alkoxides by co-condensation reaction. Furthermore, in this study the acidity and the water content during reaction synthesis was proven to be critical in controlling the structure of the hybrid nanosilicas. These nanosilicas with different hydrophobicity were obtained by using TEOS (tetraethylorthosilicate) and 10 wt% two organic modifiers (tris-hydroxymethylaminomethane — TRIS — and 1,1,1,3,3,3-hexamethyldisilazane-HDMS). The average diameter of the nano-particles ranged between 7 and 10 nm. The addition of the organic modifiers changed the pH of the hybrid nanosilicas, to a different extent depending on the nature of the organic modifier. The hydrophobicity in the hybrid nanosilicas estimated from pH measurements in water and ethanol, and from IR spectroscopy, can be tailored by incorporating different organic modifiers on the network during synthesis. Finally, the measurement of pH of the hybrid nanosilicas by using solvents with different polarity/acidity was a simple and efficient method of assessing the hydrophobicity of the nanosilicas.     

Synthesis of an Organic–Inorganic Hybrid Polymeric Material and Its Adsorption Performance Characterization Toward Acrylamide

An organic–inorganic hybrid functionalized material was successfully synthesized by a surface molecular imprinting technique combined with a nonhydrolytic sol–gel process using acrylamide as the template, methacrylic acid as the functional monomer, methacryloxypropyltrimethoxysilane as the cross-linker, and magnetic chitosan microspheres as the support material. The adsorption ability and selectivity of this material toward acrylamide was characterized. Experimental results showed that the imprinted polymer exhibited better recognition and selective performance toward acrylamide than the nonimprinted polymer. The saturated binding capacity (Q _max) was 104.68 mg/g, and the equilibrium dissociation constant was 263.16 mg/mL. This prepared material also offered fast kinetics for the adsorption and desorption of acrylamide. After shaking for 5 min, an adsorption capacity of 4.71 mg/g was obtained, and it almost reached the adsorption equilibrium within 90 min.     

Preparation and Characterization of Poly(L-lactide-co-glycolide-co-ε-caprolactone) Scaffolds by Thermally Induced Phase Separation

Abstract

The technique of thermally induced phase separation (TIPS) is favorable for the fabrication of a porous scaffold due to a number of advantages. In this work the poly(L-lactide-co-glycolide-co-ε-caprolactone) (PLLGC) terpolymer was synthesized by melt copolymerization and porous scaffolds thereof from its solution in 1,4-dioxane were fabricated by using the TIPS method. The effects of fabrication parameters, including polymer concentration and freezing temperature, on the morphology, pore size and mechanical properties were studied. The results showed that the average pore size of the PLLGC porous scaffold increased with a decrease in PLLGC concentration and the pore size resulting from freezing at 4?°C (about 20–100?μm) was significantly larger than for other samples (20–50?μm) frozen at lower temperatures. The porosity of the scaffolds decreased with increasing PLLGC concentration or decreasing freezing temperature. On the other hand, the compressive strength of the scaffolds increased with the increase of PLLGC concentration or the decrease of freezing temperature, as would be expected. The present results can be applied in design to control the processing parameters of TIPS for a scaffold with desired pore morphology.     

Preparation and Degradation Behaviors of Poly(L-lactide-co-glycolide-co-ε-caprolactone)/1,4-butanediamine Modified Poly(lactic-co-glycolic acid) Blend Film

Abstract

Polymer blending is an attractive method for producing new polymer materials with excellent properties. In this work the blended polymers were prepared from poly(L-lactide-co-glycolide-co-ε-caprolactone) and 1,4-butanediamine modified poly(lactic-co-glycolic acid) (PLLGC/BMPLGA). The hydrophilicity was studied by static water contact angle tests. The in-vitro degradation behaviors of the PLLGC/BMPLGA blended films were investigated during various degradation periods. The results showed that the introduction of the PLLGC reduced the hydrophilicity and degradation rate of the blended polymers while improved the tensile strength and elongation percentage. Therefore, we suggest the blends of the PLLGC and BMPLGA could supply a potential biomaterial for application in the medical field for use as tissue engineering scaffolds or drug delivery.     

Designing and Characterization of Poly(L-Lactide)/Poly(ϵ-Caprolactone) Multiblock Copolymers

A series of poly(L-lactide)/poly(?-caprolactone) (PLA/PCL) biodegradable multiblock copolymers was synthesized by a two-step process and characterized. Ring-opening polymerization was used to prepare a series of HO-PLA-PCL-PLA-OH copolymers initiated by hydroxyl-terminated PCL. Then the triblock copolymers and 1,6-hexamethylene diisocyanate (HDI) were reacted with different copolymer/HDI weight ratios. Consequently, a series of PLA/PCL multiblock copolymers with designed molecular chain structure was obtained. Gel permeation chromatography (GPC), Fourier transform infrared (FTIR) spectroscopy, and ¹H NMR were used to characterize these copolymers and the results showed that the designed PLA/PCL copolymers had been synthesized. Dynamic mechanical analysis (DMA) was applied to characterize their thermal properties. Stress–strain curves showed that a PLA/PCL copolymer with adjustable mechanical properties had been achieved.     

Synthesis and Characterization of CdS/CISe Quantum Dots with Core–Shell Structure

Quantum dots have received great interest due to their excellent optoelectronic properties. However, the surface defects of quantum dots affect the carrier transport and ultimately reduce the photovoltaic efficiency. In this paper, a core–shell quantum dot by hot-injection method is prepared to grow a narrow-band semiconductor layer (CuInSe₂ (CISe) quantumdot) on the surface of a broad-band core material (cadmium sulfide (CdS) nanocrystal). The composition, structure, optical properties, and decay lifetime of CdS/CISe core–shells are investigated in more detail by X-ray diffraction (XRD), transmission electron microscopy (TEM), photoluminescence (PL), UV–vis spectrophotometry, and fluorescence spectroscopy. The CdS/CISe core–shell structure has a broadened absorption range and still shows CISe-related quantum effects. The increased size of the core–shell and the smaller specific surface area of the CISe shell layer lead to a lower carrier complexation chance, which improves the carrier lifetime.     

Preparation and Properties of 2, 4-2-Isocyanic Acid Methyl Ester/Poly(ϵ-caprolactone)/Diethylene Glycol Hydrogels

The hydrophilic polyurethane (PU) hydrogels have become attractive in the biomedical field for drug delivery. In this work 2, 4-2-isocyanic acid methyl ester (TDI), poly(?-caprolactone) (PCL), and poly(ethylene glycol) (PEG) were used to prepare a prepolymer and then diethylene glycol (DEG) was used as a chain extender to prepare a novel hydrophilic polyurethane, TDI/PCL-PEG/DEG. The obtained PU hydrogels were characterized by Fourier transform infrared (FT-IR) spectroscopy and scanning electronic microscopy (SEM). By varying the ratio of PCL to PEG in the copolymer, modulations of hydrophilicity and drug release behavior were observed. FT-IR analysis confirmed the successful synthesis of the TDI/PCL-PEG/DEG hydrogels. The introduction of PEG into the PU hydrogels led to a porous structure. The water contact angle and swelling ratio results confirmed that the hydrophilicity increased with increasing amounts of the PEG segments. The introduction of PEG also increased the release rate of chloramphenicol, used as model drug, from the PU hydrogels.     

Preparation and Characterization of Poly(L-lactide-co-glycolide-co-ε-caprolactone)/Nano-biaoactive Glass-Nano-β-tricalcium Phosphate Composite Scaffolds

Abstract

Polymeric/ceramic composite scaffolds that are biocompatible and biodegradable are widely used for tissue engineering applications. In this work a series of poly(L-lactide-co-glycolide-co-ε-caprolactone)/nano-biaoactive glass-nano-β-tricalcium phosphate composite scaffolds were successfully fabricated and the influences of the inorganic content and freezing temperature on the physical properties were studied. The composite scaffolds with various inorganic contents showed an interconnected pore structure with irregular shapes. The composite scaffolds had a porosity that was reduced with increasing inorganic content and decreasing freezing temperature. The incorporation of inorganic fillers and decreasing freezing temperature improved the mechanical properties of the hybrid scaffolds. By appropriate control of these two factors (10.0?wt% content of NBAG and β-TCP with freezing at ?30?°C) a suitable composite scaffold was prepared as a potential bone tissue engineering implant.     

Polymer–Polymer and Single Polymer Composites Involving Nanofibrillar Poly(vinylidene Fluoride): Manufacturing and Mechanical Properties

Nanofibrillar polymer–polymer composites (NFCs) and single polymer composites (SPCs) were produced using linear low density polyethylene (LLDPE) and poly(vinylidene fluoride) (PVDF). The NFCs were fabricated by means of a microfibrillar composite concept comprising melt blending, cold drawing, and compression molding retaining the highly oriented PVDF reinforcing nanofibrils (diameter of approximately 250 nm) dispersed without any agglomeration in the isotropic LLDPE matrix. The SPC films were prepared by partial surface premelting of neat PVDF nanofibrils (diameter of about 130 nm) using hot compaction at 148°C (about 20°C below the complete melting of PVDF), thus preserving the PVDF nanofibrillar identity. Tensile testing of NFCs based on LLDPE and PVDF showed an increase in the tensile modulus by 135% and in the tensile strength at break by 211%, as compared to those of an isotropic LLDPE film. Furthermore, the PVDF SPCs showed an enhancement of tensile modulus of 30% and strength at break of 305% when compared to those of an isotropic PVDF film.     

Preparation and luminescence of (SBA-15)–Eu2O3 composite materials

In this study, (SBA-15)–Eu₂O₃ host-guest composites have been prepared with SBA-15 mesoporous sieve as host and Eu₂O₃ as guest via the solid-phase ultrasonic method and liquid-phase medium ultrasonic method. The host–guest composite materials showed the properties of luminescence. Four excitation peaks appeared in the excitation spectra of the samples. The excitation peaks are located at 397, 415, 466, 537 nm; 392, 408, 464, 532 nm and 393, 406, 465, 533 nm for the nano-Eu₂O₃, the liquid-phase medium ultrasonic method (LPMUM) and the solid-phase ultrasonic method (SPUM) samples, respectively. SBA-15 has the well-ordered hexagonal arrays of mesopores, which makes centrosymmetry of Eu³⁺ higher in the prepared (SBA-15)–Eu₂O₃ samples. The intensity of ⁵D₀→⁷F₁ transition strengthens, and the intensity of ⁵D₀→⁷F₂ transition weakens.     

Magnetic Resonance of Chromium (V) with 2–Hydroxy–2–Ethylbutyrates

A complex of Cr (V) with 2–hydroxy–2–ethylbutyric acid (EHBA) has been studied experimentally by the method of electron spin resonance (ESR). The tensor components of the g–factor, the dependences of the ESR line widths on the concentration of paramagnetic centers, and the SHF power of saturation are determined. It is shown that the main mechanism of dynamic polarization of nuclei in the EHBACr^V complex in a propanediol solution is the mechanism of dynamic cooling with a burnt hole. It has been established that the ESR spectra of the EHBACr^V solutions in deuterated and ordinary propanediol display practically the same behavior, which is indicative of the good solubility of the complex in deuterated alcohols.     

Characterization of semiconductor detectors of (1–30)-keV monoenergetic and backscattered electrons

Semiconductor detectors of backscattered electrons are basic elements of all modern scanning electron microscopes. Their quality is determined by the properties of planar p-n junctions and the parameters of the protective layer on the detector surface. The main characteristics of semiconductor detectors are considered, their response functions are calculated, and the threshold signal cutoff energies are found both for a monoenergetic electron beam and for detection of the total energy spectrum of backscattered electrons. The experimental results are in good agreement with the computational model data.     

Morphology and Pore Size Distribution of Biocompatible Interconnected Porous Poly(L-lactic acid) Foams with Nanofibrous Structure Prepared by Thermally Induced Liquid–Liquid Phase Separation

Biocompatible, highly interconnected microporous poly(L-lactic acid) (PLLA) foams with nanofibrous structure, containing pores with average diameter below 1 μm and fibers with diameters of 10² nm scale, were prepared through the thermally induced liquid–liquid phase separation (TIPS) method consisting of quenching of the PLLA solution, freeze extraction with ethanol, and vacuum drying. Diverse foam morphologies were obtained by systematically changing parameters involved in the TIPS process, such as polymer concentration, solvent composition, and quenching temperatures. The morphology of different foams was examined by scanning electron microscopy to characterize the pore size and the pore size distribution. The results showed that most porous foams had a nanofibrous structure with interconnected open pores. In the case of using tetrahydrofuran (THF) as solvent, the higher the PLLA concentration, the smaller the average pore diameter and the narrower the pore size distribution. In the case of using the mixed solvents of THF/DOX (1,4-dioxane) with higher than 6/4 volume ratio, there appeared a maximum value of average pore diameter and a widest pore size distribution at 0.09 g/mL PLLA concentration. The average pore diameter of the foams increased with increasing DOX content in the mixed solvent and ranged from 0.2 to 0.9 μm depending on the process parameters. When the DOX content reached 60% by volume, the morphology of the foams contained some large closed pores with diameter ranging from 1 to 10 μm. By decreasing the quenching temperature, the average pore diameter of foams decreased and the pore size distribution became narrower. All the pore size distribution fit F-distribution equations.     

Preparation of poly(vinyl alcohol)–silicone based hybrid membranes for the pervaporation separation of water–acetic acid mixtures

Hybrid membranes were prepared using poly(vinyl alcohol) (PVA) and tetraethylorthosilicate (TEOS) via hydrolysis followed by condensation. The obtained membranes were characterized by Fourier transform infrared spectroscopy, wide-angle x-ray diffraction and differential scanning calorimetry. A remarkable decrease in degree of swelling was observed with increasing TEOS content in membranes and is attributed to the formation of hydrogen bonding and covalent bonds in the membrane matrix. The pervaporation performance of these membranes for the separation of water–acetic acid mixtures was investigated in terms of feed concentration and the content of TEOS used as cross-linking agent. The membrane containing 1 : 2 mass ratio of PVA and TEOS gave the highest separation selectivity of 1116 with a flux of 3.33 × 10^?2kg/m²h at 30°C for 10 mass% of water in the feed. Except for membrane M-1, the observed values of water flux are close to the values of total flux in the investigated composition range, signifying that the developed membranes are highly water selective. From the temperature dependence of diffusion and permeation values, the Arrhenius apparent activation parameters have been estimated. The resulting activation energy values obtained, showing that water permeation is lower than that of acetic acid, suggest that the membranes have higher separation efficiency. The activation energy values calculated for total permeation and water permeation are close to each other for all the membranes except membrane M-1, signifying that coupled-transport is minimal because of the higher selective nature of membranes. The negative heat of sorption values (ΔH _s) for water in all the membranes suggests a Langmuir mode of sorption.     

Micromechanical Behavior and Glass Transition Temperature of Poly(Methyl Methacrylate)–Rubber Blends

Abstract

The microhardness of transparent rubber‐toughened poly(methyl methacrylate) (RTPMMA) was investigated by means of the microindentation technique. Core‐shell particles (CSP) with a rubbery shell were used as reinforcing material for the production of RTPMMA. The increasing volume fraction of CSP within the poly(methyl methacrylate) (PMMA) matrix is shown to soften the material, diminishing the hardness (H) value of RTPMMA of about 40% of the initial value at 35 vol% CSP content. Creep experiments under the indenter are reported. The creep constant is found to increase by adding CSP up to a leveling‐off value. On the other hand, the thermal variation of the creep constant for the blends shows a maximum. Results reveal a good correlation of the glass transition temperature (T _g) value deduced from microindentation, and the values obtained from differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) techniques. Contrary to expectation H is shown to decrease with increasing glass transition temperature. In the case of the drawn materials, the indentation anisotropy is shown to gradually increase with draw ratio and CSP content. This finding is explained on the basis of the higher orientation of the PMMA molecules near the periphery of CSP.     

Synthesis and Characterization of Novel Poly(1‐Naphthylamine)‐Montmorillonite Nanocomposites Intercalated by Emulsion Polymerization

Nanocomposites of montmorillonite (MMT) with poly(1‐naphthylamine) (PNA) is investigated for the first time by emulsion polymerization using three different oxidants. Polymerization of PNA was confirmed by Fourier transformation infrared (FT‐IR) as well as UV‐visible spectra. The in situ intercalative polymerization of PNA within MMT layers was confirmed by FT‐IR, X‐ray diffraction, conductivity; scanning electron microscopy (SEM) as well as transmission electron microscopy studies. X‐ray diffraction revealed intercalated as well as exfoliated structures of PNA/MMT nanocomposites, which were compared with the reported polyaniline‐MMT nanocomposites. It was found that the increase in the concentration of PNA in the interlayer galleries of MMT led to destruction of the layered clay structure resulting in exfoliation of the nanocomposite. Conductivity of the nanocomposites was found to be in the range of 10^?3 to 10^?2 S cm^?1 which was found to be higher than the ones reported for polyaniline‐clay nanocomposites as well as PEOA‐OMMT nanocomposites at similar concentrations of intercalated species. The morphology of PNA/MMT nanocomposites was found to be governed by the nature of the oxidant used.     

Rheology Behavior of Hydrophobically Modified Poly(acrylic acid) with Twin-Tailed Pendant in Water—Ethylene Glycol Mixture

A hydrophobically modified poly(acrylic acid) (HMPA) with twin-tailed hydrophobic pendant side groups was prepared by precipitation polymerization. The rheology behavior of HMPA was examined in mixtures of water and ethylene glycol (EG) of different proportions. It was shown that the solvent had a direct impact on both the steady and dynamic rheology behaviors of the HMPA solutions. The change of hydrophobic interactions in the EG-rich mixtures may be attributed to the observed decrease in polymer coil dimension together with a lower tendency of the hydrophobes to form junctions. As the temperature decreased, the viscosities and numbers of active junctions of HMPA in water–EG mixtures increased.