Deposition of calcium hydroxyapatite on negatively charged polyphosphazene surfaces

A number of polyphosphazenes with negatively charged β‐alanine (β‐Ala) and γ‐amino butyric acid (GABA) side groups were synthesized and studied for their ability to initiate the growth of hydroxyapatite (HAp) during exposure to simulated body fluid (SBF). All the polymers were hydrolytically sensitive, with the final hydrolysis rate dependent on the specific active side groups (GABA > β‐Ala). These systems also underwent extensive mineralization, with calcium phosphate deposited across their entire surface during exposure to SBF (up to 115 wt % gain after 4 weeks). This degree of deposition is a major advance over previously reported polyphosphazene systems, which underwent a maximum of 27 wt % gain after immersion in SBF for 4 weeks. The extent of mineralization over the surface was monitored using environmental scanning electron microscopy (ESEM) coupled with energy dispersive X‐ray spectroscopy (EDS). In addition, X‐ray diffraction (XRD) was used to determine the identity of the mineralized material. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41741.     

Crystallinity,reversibility, and injectability of physically crosslinked poly(vinyl alcohol) and poly(ethylene glycol) hydrogels

Crystallite regions within a hydrogel network contribute to its mechanical strength, which is crucial for use in load-bearing applications. However, high amounts of crystallinity can negatively impact the ability for hydrogels to be injected, an attractive property that could replace the need for highly invasive surgical procedures. The reversibility of crystallinity and its lasting impact on the injectability of poly(vinyl alcohol) and poly(ethylene glycol) hydrogels was evaluated in this paper. The relative percent crystallinity in hydrogels was evaluated after storage and autoclaving in syringes in weekly intervals using X-ray diffraction. Results indicate that crystallinity increased over time and significantly decreased after autoclaving for all samples, where postautoclaved samples contained comparable crystallinity percentages to freshly made gels (p > 0.05). Injectability was evaluated using calculated viscosity. Aged samples were able to be injected after autoclaving, yet there was no determination established between viscosity and storage times based on the data. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48706.     

Fabrication of polymer/drug‐loaded hydroxyapatite particle composite fibers for drug sustained release

The aim of this study is to fabricate polymer/hydroxyapatite (HA) particle composite fibers for drug encapsulation and sustained release. Firstly, drug‐loaded hydroxyapatite particles are synthesized in one step, then by electrospinning of the blends of drug‐loaded hydroxyapatite particles and polymer solution the drug‐loaded polymer/hydroxyapatite particle composite fibers are successfully prepared. Effect of loading ratio of drug‐loaded hydroxyapatite particles in the fibers and pH value of the release medium on the drug release kinetics are both investigated, and the results demonstrate that, as compared with the polymer/drug electrospun fibers, the drug in the polymer/drug‐loaded hydroxyapatite particle composite fibers shows a sustained release manner, and the drug release rate can be regulated by both the loading ratio of drug‐loaded hydroxyapatite particles in the composite fibers and pH value of the buffer solution. The results indicate that the developed drug‐loaded polymer/hydroxyapatite particle composite fibers show great potential in bone regeneration and other related biomedical fields. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42871.     

Hybrid biomimetic electrospun fibrous mats derived from poly(ε‐caprolactone) and silk fibroin protein for wound dressing application

To achieve excellent biofunctionality of Bombyx mori silk fibroin (SF), we explored a novel hybridization method to combine the unique properties of SF with poly(ε‐caprolactone) (PCL) electrospun fibers. The hybrid electrospun fibers demonstrate excellent hydrophilicity and biocompatibility that are important to tissue engineering applications. The biomimetic fibrous structure was fabricated by conventional electrospinning of PCL. The individual surfaces of PCL electrospun fibers were coated with silk fibroin protein using a lyophilization technique. The SF coating layers were durable which were further developed by surface modification with fibronectin to improve their biological function. The hybrid electrospun fibers show excellent support for normal human dermal fibroblast (NHDF) cells adhesion and proliferation than neat PCL fibers, while the surface‐modified hybrid electrospun fibers show significantly enhanced proliferation of NHDF cells on their surface. This study indicates the new opportunity of fabrication technique that can construct a biomimetic fibrous structure while the original function as a biomaterial remained existing. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41653.     

Glass microparticle- versus microsphere-filled experimental dental adhesives

This study aimed to formulate antibacterial dental adhesives. Phosphate-substituted methacrylate adhesives were modified with 0–20 wt % copper-doped glass microparticles. Two shapes of microparticles were used: regular shaped (microspheres) and irregular shaped (microparticles). The morphology/composition, roughness, monomer conversion (DC%), thermogravimetric analysis, and antibacterial action against S. mutans and P. aeruginosa and ion release were investigated. The results showed that microspheres produced adhesives with a relatively smoother surface than microparticles did. The DC% of adhesives increased with increasing glass filler content. Filled adhesives showed polymer decomposition at ~315 °C and glass melting at 600–1000 °C. The weight loss percent of adhesives decreased with increasing weight percent of fillers. Glass microparticles at 0–20 wt % significantly increased the antibacterial action of adhesives against both bacteria. Glass microspheres at 0–5 wt % significantly increased the antibacterial action of adhesives against both bacteria. Only 20 wt % microparticle-filled adhesive showed an inhibition zone similar to tobramycin (positive control). Microparticle-filled adhesives (with >5 wt % filler) significantly reduced S. mutans more than their microsphere counterparts. Microsphere-filled adhesives (with ≤5 wt % filler) significantly reduced P. aeruginosa more than their microparticle counterparts. Microsphere-filled adhesives showed higher Cu release than their microparticle counterparts. Accordingly, phosphate-substituted methacrylate filled with glass could be used as an antibacterial adhesive. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47832.     

Developing antibacterial surgical adhesives: An enhancement of cyanoacrylate polymers

Surgical site infections (SSIs) and traumatic wounds have a significant risk of becoming contaminated by microbial pathogens of both endogenous and nosocomial origins, including Staphylococcus aureus and Enterococci sp.. One preventative approach is to protect wounds from infection by using a rapidly curing adhesive to seal the wound and prevent further contamination. Here, we demonstrate the covalent incorporation of an antimicrobial, quaternary ammonium chloride monomer (quat) into a 2-octyl cyanoacrylate (2oc) polymer adhesive. Copolymerization was confirmed via nuclear magnetic resonance spectroscopy. Cytotoxicity of the copolymer was assessed against: S. epidermidis and E. coli, and 3T3 mouse fibroblasts. The CA-Quat polymer was found to exhibit dose-dependent bacteriostatic and bactericidal effects against both E. coli and S. epidermidis, importantly without showing any demonstrable toxicity against mammalian 3T3 fibroblast cells. The described experiments provide promising data to suggest successful copolymerization, effective antibacterial properties, and remarkably low cytotoxic effects of the copolymer on mammalian cells.     

Reliable surface modification of dental plastic substrates to reduce biofouling with a photoreactive phospholipid polymer

Plastic substrates have been widely applied in clinical settings for dental treatments. These substrates should be strong enough for long‐term implantation in the oral cavity and should be resistant to biofouling. We developed a new photoreactive phospholipid polymer to reduce biofouling on dental plastics via a photochemical reaction. Poly(methyl methacrylate) (PMMA) and poly(ether ether ketone) (PEEK) were used as dental plastics. To determine the antibiofouling properties on the polymer surface, the phospholipid polymer was covalently immobilized on the substrates by UV irradiation. We evaluated the antibiofouling properties by observing the protein adsorption and cell and bacterial adhesion. Significant protein adsorption and cell adhesion appeared on the bare PMMA and PEEK substrates but decreased dramatically after surface modification with the phospholipid polymer. Thus, this photoreactive polymer shows potential for conferring dental plastics with antibiofouling properties. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46512.     

Herbally derived polymeric nanofibrous scaffolds for bone tissue regeneration

Hydroxyapatite (HA), the bone mineral and Cissus quadrangularis (CQ), a medicinal plant with osteogenic activity, are attaining increasing interest as a potential therapeutic agent for enhanced bone tissue regeneration. In the present study a synergistic effect of these two agents were analyzed by fabricating PCL‐CQ‐HA nanofibrous scaffolds by electrospinning and compared with PCL‐CQ and PCL (control) nanofibrous scaffolds. Morphology, composition, hydrophilicity, and mechanical properties of the electrospun PCL, PCL‐CQ, PCL‐CQ‐HA nanofibrous scaffolds were examined by Field emission scanning electron microscopy (FESEM), Fourier transform infrared spectroscopy (FTIR), Contact angle and Tensile tests, respectively. The response of human foetal osteoblast cells on these scaffolds were evaluated using MTS assay, alkaline phosphatase activity, alizarin red staining, and osteocalcin expression for bone tissue regeneration. While the observed cellular response to both groups of scaffolds was better than for the control PCL scaffold, the PCL‐CQ‐HA nanofibrous scaffolds provided the most favorable substrate for cell proliferation and mineralization. The results showed that PCL‐CQ‐HA nanofibrous scaffolds had appropriate surface roughness for the osteoblast adhesion, proliferation, and mineralization comparing with other scaffolds. The observed investigation of physicochemical and biological properties suggests that the CQ‐HA loaded PCL nanofibrous scaffolds serve as a potential biocomposite material for bone tissue engineering. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39835.     

Rapid polymer fiber airbrushing: Impact of a device design on the fiber fabrication and matrix quality

Polymer fiber matrixes can be used in a variety of applications, including electronics, tissue engineering, or coatings. Polymer airbrushing (air‐blast spinning) has the potential to overcome some of the limitations of electrospinning and has the advantage of depositing nanofibers directly on various materials. The airbrushing technique has yet to be better evaluated and optimized to achieve a higher fiber reproducibility and bulk material quality. In this study, a gravity‐fed brush (commercial airbrush) and syringe‐pump‐operated brush [custom‐built airbrush (CBA)] were compared to determine the effect of the coaxial brush design on the efficacy of fiber fabrication. At comparable fiber deposition rates, gas pressures, and polymer concentrations, the CBA produced smaller and more uniform fibers with a lower average size of polymer beads. The obtained data suggest that capillary pinching was the dominant mechanism responsible for fiber formation when we used the CBA. The estimated pinching energy was lower for the CBA at the compared polymer concentrations and at a high gas pressure. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42813.     

3D printing-assisted combinatorial approach for designing mechanically-tunable and vascular supportive nanofibrous membranes to repair perforated eardrum

Perforation of eardrum or tympanic membrane (TM) is a common clinical condition, which occurs due to infection or injury of the eardrum, and could results in varying degrees of conductive hearing loss among all ages. In this study, the authors report the combinatorial approach of designing mechanically-tunable and vascular supportive nanofibrous membranes by 3D printing-assisted electrospinning (e-spin) using polycaprolactone (PCL) and gelatin with different mass ratios suitable to repair a perforated eardrum. The physicochemical, mechanical, and biological properties of the membranes were characterized. The results show that the membrane has nanofibrous morphology with fibers are of varying size (400–600 nm in diameter) depending on processing conditions. The wettability and mechanical properties of the membrane can be tuned by regulating the gelatin content. Moreover, a biomimetic repair strategy inspired by chicken eggshell membrane, often used in wound dressings, was also presented for study and results show that the suture retention strength of the fabricated membrane can meet clinical translational requirements to promote TM healing. The vascular cell responsiveness of PCL/gelatin nanofibrous membrane was evaluated using human umbilical vein endothelial cells (HUVECs) and the results showed satisfactory biocompatibility, vascular cell responsiveness, and cell proliferation. The findings of this study demonstrate that the combinatorically engineered PCL/gelatin nanofibrous membrane has great potential for repairing perforated eardrum.     

Influence of hydroxyapatite and BMP‐2 on bioactivity and bone tissue formation ability of electrospun PLLA nanofibers

An excellent bioactive scaffold material which could induce and promote new bone formation is essential in the bone repair field. In this study, the bioactive material hydroxyapatite (HA) and the bone morphogenetic protein‐2 (BMP‐2) were added to poly‐l‐lactic acid (PLLA) using the electrospinning method. Scanning electron microscopy investigations performed on four different fiber scaffolds, PLLA, PLLA/HA, PLLA/BMP‐2 and PLLA/HA/BMP‐2, revealed that the fibers of all scaffolds are closely interwoven, and the presence of large interconnected voids between the fibers, resulting in a three‐dimensional porous network structure that was similar to the structure of the extracellular matrix of healthy bones. In the MG63 cell culture growth experiments, the composite scaffold material PLLA/HA/BMP‐2 showed a higher bioactivity than the other three scaffold materials. The four scaffold materials were implanted in rabbits’ tibia for 30 and 90 days. The results of the animal experiments indicate that the capability of the PLLA/HA/BMP‐2 composite to induce and promote bone tissue formation was better compared with PLLA/HA or PLLA/BMP‐2, suggesting that PLLA combined with HA/BMP‐2 is a promising material for bone tissue repair. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42249.     

Hemocompatibility of polymers for use in vascular endoluminal implants

Implanted polymers for cardiovascular applications may function as structural supports, barriers, or provide a means for local drug delivery. Several thermoplastic biodegradable drug delivery polymers are potential candidates for blood-contacting implant applications. For intravascular applications specifically, a criterion for material selection is the intrinsic hemocompatibility of the baseline polymer. As an initial screening approach for selection of polymers for in vivo use, thin films of polyesters: poly(ɛ-caprolactone) (PCL), poly(lactic acid) (PLA), poly(lactic-co-glycolic acid) (PLGA); polyanhydrides: poly(fatty acid dimer-co-sebacic acid) (PFAD:SA) and poly(biscarboxyphenoxypropane-co-sebacic acid) (PCPP:SA); and poly(ethylene glycol) (PEG)-ylated polyesters: PLA:PEG, PCL:PEG and PCL:PLA:PEG polymers were spin-cast on glass cover slips and placed in an in vitro flow system exposing them at a controlled shear to overflowing human whole blood. Platelet adherence, aggregate formation, and thrombus formation, as well as leukocyte adherence were assessed following 5 min of flow. At 5 min of flow the rank order of materials, in terms of least to most thrombogenic was: PCL < PFAD:SA < PCPP:SA < PLGA < PLA. All PEGylated materials, in general, had less thrombus formation than baseline unmodified materials.     

Binary phase solid‐state photopolymerization behavior of acrylate cryogels under different light sources

Two types of cryogels were obtained using 2‐hydroxyethyl acrylate (HEA) and 2‐hydroxyethyl methacrylate (HEMA) by homogeneous mixing with poly(ethylene glycol) diacrylate (PEGDA) as crosslinker at subzero temperature followed by photopolymerization with two different light initiation sources (high‐pressure Hg arc lamp and UV‐LED).The solution was frozen unidirectionally at ?60 °C before polymerization and finally photopolymerized at the same temperature. The cryogels were characterized using photo‐DSC, UV–vis and Fourier transform infrared spectroscopy, and scanning electron microscopy techniques. The cryogels cured with an LED light showed a higher polymerization rate and better morphological characteristics than ones cured with a high‐pressure Hg arc. The water intake ratio of HEA/PEGDA was higher than HEMA/PEGDA for both curing sources. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46686.     

Bioprinting a cell-laden matrix for bone regeneration: A focused review

Although many efforts have been made to regenerate the bone lesions, existing challenges can be mitigated through the development of tissue engineering scaffolds. However, the weak control on the microstructure of constructs, limitation in preparation of patient-specific and multilayered scaffolds, restriction in the fabrication of cell-laden matrixes, and challenges in preserving the drug/growth factors' efficacy in conventional methods have led to the development of bioprinting technology for regeneration of bone defects. So in this review, conventional 3D printers are classified, then the priority of the different types of bioprinting technologies for the preparation of the cell/growth factor-laden matrixes are focused. Besides, the bio-ink compositions, including polymeric/hybrid hydrogels and cell-based bio-inks are classified according to fundamental and recent studies. Herein, different effective parameters, such as viscosity, rheological properties, cross-linking methods, biodegradation biocompatibility, are considered. Finally, different types of cells and growth factors that can encapsulate in the bio-inks to promote bone repair are discussed, and both in vitro and in vivo achievement are considered. This review provides current and future perspectives of cell-laden bioprinting technologies. The restrictions and challenges are identified, and proper strategies for the development of cell-laden matrixes and high-performance printable bio-inks are proposed.     

Reactive red 120 and NI(II) derived poly(2‐hydroxyethyl methacrylate) nanoparticles for urease adsorption

Non‐porous poly(2‐hydroxyethyl methacrylate) [p(HEMA)] nanoparticles were prepared by surfactant free emulsion polymerization. The p(HEMA) nanoparticles was about 200 nm diameter, spherical form, and non‐porous. Reactive Red 120 (RR 120) was covalently attached to the p(HEMA) nanoparticles and Ni(II) ions were incorporated to attach dye molecules. Urease was immobilized onto RR120‐Ni(II) attached p(HEMA) nanoparticles via adsorption. The maximum urease adsorption capacity of RR120‐Ni(II) attached p(HEMA) nanoparticles was 480.01 mg g^?1 nanoparticles at pH 7.0 in phosphate buffer. It was observed that urease could be repeatedly adsorbed and desorbed without significant loss in adsorption amount. K_m values were 21.50 and 34.06 mM for the free and adsorbed enzyme. The V_max values were 4 U for the free enzyme and 3.3 U for the adsorbed enzyme. The optimum pH was 25 mM pH 7 phosphate buffer for free and adsorbed enzyme. The optimum temperature was determined at 35°C and 55°C for the free and adsorbed enzyme, respectively. These findings show considerable promise for this material as an adsorption matrix in biotechnological applications. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39757.     

Characterization of polyetheretherketone particle suspensions for electrophoretic deposition

Suspensions of polyetheretherketone (PEEK) using mixture of ethanol and isopropanol as solvent were prepared to carry out PEEK electrophoretic deposition (EPD). The rheological behavior and suspension structure of PEEK particles dispersed in co‐solvents were investigated over a range of pH values (1–10) and shear rates (γ = 10¹?3 × 10² s^?1). These PEEK suspensions generally exhibited a pseudoplastic flow behavior, indicating the occurrence of particle aggregation in the liquid medium. The maximum solids fraction (?_m) showed an estimated value of  ?_m = 2.9 wt %. Using a suspension with 3 wt % PEEK concentration, PEEK coatings on stainless steel substrates were obtained by EPD at constant voltage condition. The influence of the electrolyte conductivity on PEEK EPD from ethanol–isopropanol suspensions was studied. Experimental results showed that high‐conductivity ethanol‐based suspensions yield non‐uniform deposits, while low‐conductivity suspensions resulted in uniform coatings. The difference in the deposition behavior is due to the different pH of the suspensions and the relationship of pH with suspension conductivity. pH = 8 was the optimal value for this system in terms of deposition results. The surfaces of EPD PEEK coatings were homogenous and a qualitatively good adhesion between the PEEK deposits and the substrate was confirmed. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40953.     

Fabrication and characterization of novel nanofibers from cress seed mucilage for food applications

Cress seed mucilage (CSM) as a new source of biomacromolecule has gained attraction in food science due to its biodegradability and biocompatibility. In this research CSM–poly(vinyl alcohol) (PVA) nanofibers were produced under different conditions by electrospinning technique. Viscosity and electrical conductivity of the produced biopolymers were analyzed. The effect of CSM to PVA volume ratio and applied electrical field were evaluated on nanofiber morphology by scanning electron spectroscopy. The optimum nanofibers showed smooth and uniform surfaces with diameter size range of 95–278 nm. The results of Fourier transform infrared spectroscopy of CSM–PVA nanofiber with volume ratio of 60:40 showed characteristic peaks of CSM and PVA. X‐ray diffractometer data clearly revealed the amorphous structure of the electrospun nanofibers. Thermogravimetric and derivative thermogravimetric analysis indicated that thermal stability of electrospun nanofibers increased in comparison to CSM and PVA. The results of this study indicated that CSM can be applied as a new source of biopolymer for production of nanofibers that could be used for different applications such as delivery systems and packaging film fabrication. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45811.     

Preparation and optimization of calcium pectate beads for cell encapsulation

A variety of natural polymers are considered suitable for cell entrapment. Pectin, a natural polysaccharide found in the cell walls of all higher terrestrial plants, presents great potential for cell encapsulation because of its ability to form gels. In this study, we investigated the influences of intrinsic and extrinsic factors on the formation and properties of calcium pectate (CP). Beads of CP prepared with 30–35% methyl esterification presented improved gel properties. The molecular weight (M_w), calcium content, and gel time did not significantly affect the gel properties. The gelling properties, sphericity factor (SF), and swelling ratio were significantly influenced by the degree of methyl esterification (DE) and pectin concentration. The DE (<40%), M_w, and calcium concentration had negative effects on the SFs of CP beads. Moreover, increases in the DE (<40%) and pectin concentration increased the swelling ratio. The C3A cells encapsulated in optimized CP beads maintained good viability and proliferation for up to 2 weeks. In conclusion, CP beads are a potential encapsulation material for cell immobilization and application in related fields. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45685.     

Chitosan/silk fibroin composite scaffolds for wound dressing

Three‐dimensional (3D) chitosan/silk fibroin (CS/SF) porous composite scaffolds have been prepared by simply coating a thin layer of CS onto spunlaced SF scaffolds via hydrogen‐bonding assembly technique, and they were characterized by Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), X‐ray diffraction (XRD), and mechanical property measurements. The results show that porous scaffolds have a pore diameter around 50–200 μm, and improved mechanical property compared with SF, resulting from strong intermolecular hydrogen bonding interactions between CS and SF, together with the maintained β‐sheet structure of SF. The medical and biological properties of the composite scaffolds were further evaluated. The results demonstrate that they possess good biocompatibility and a broad spectrum of antimicrobial properties. The in vivo animal experiments show that the composite scaffolds promote skin regeneration of rats without any teratogenic effect and inflection, thus they are very promising in the application of wound dressings. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42503.     

Biocompatible scaffolds composed of chemically crosslinked chitosan and gelatin for tissue engineering

Chitosan‐based scaffolds are widely studied in tissue regeneration because of their biocompatibility and biodegradability. Scaffolds are obtained by different techniques and can be modified with other polymers allowing controlling their properties. This article discusses the assembling of three‐dimensional chitosan porous scaffolds blended with gelatin. Gelatin was used to enhance cells attachment due to the presence of cell adhesion motifs, while improving mechanical strength. 2,5‐dimethoxy‐2,5‐dihydrofurane (DHF) was used as the crosslinking agent, because it allowed to control the reaction kinetics through temperature, time and DHF concentration. The results indicate that scaffolds morphology, pore sizes and distribution, compressive moduli and biodegradation in vitro with lysozyme, can be customized with variations of gelatin content and crosslinking degree. Scaffolds were neither cytotoxic nor genotoxic for human keratinocytes, exhibiting cell–substrate interactions. Our findings demonstrated that chitosan–gelatin scaffolds crosslinked with DHF, as a new crosslinking agent, are suitable in tissue engineering applications. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43814.