Self-initiated Graft Polymerization Research Articles

Enhanced osteogenic and antibacterial properties of polyetheretherketone by ultraviolet-initiated grafting polymerization of a gelatin methacryloyl/epsilon-poly-L-lysine/laponite hydrogel coating.

Polyetheretherketone (PEEK) is a promising material for use in orthopedic implants, but its bio-inert character and lack of antibacterial activity limit its applications in bone repair. In the present study, considering the advantages of PEEK in self-initiated graft polymerization and of hydrogels in bone tissue engineering, we constructed a hydrogel coating (GPL) consisting of Gelatin methacryloyl (GelMA), methacrylamide-modified ε-poly-l-lysine (ε-PLMA) and Laponite on PEEK through UV-initiated crosslinking. The coating improved the hydrophilicity of PEEK, and the coating degraded slowly so that approximately 80% was retained after incubation in PBS for 8 weeks. In vitro studies revealed that as compared to culturing on PEEK, culturing on PEEK-GPL led to enhanced viability and adhesion of cultured human umbilical cord Wharton's jelly-derived mesenchymal stem cells (hWJ-MSCs). Due to the synergistic effect of the micron-scale three-dimensional surface and Laponite, PEEK-GPL exhibited a significantly improved induction of osteogenic differentiation of hWJ-MSCs compared to PEEK, as demonstrated by increased alkaline phosphatase activity, matrix mineralization, and expression of osteogenesis-related genes. Furthermore, PEEK-GPL showed antibacterial activity upon contact with Staphylococcus aureus and Escherichia coli, and this activity would be maintained before complete degradation of the hydrogel because the ε-PLMA was cross-linked covalently into the coating. Thus, PEEK-GPL achieved both osteogenesis and infection prevention in a single simple step, providing a feasible approach for the extensive use of PEEK in bone implants.

Combination of two antithrombogenic methodologies for preventing thrombus formation on a poly(ether ether ketone) substrate

To enhance the total antithrombogenicity of poly(ether ether ketone) (PEEK), we examined a combination of two methodologies for the suppression of activation in both the platelet and coagulation systems. A random copolymer (PMT) composed of a zwitterionic 2-methacryloyloxyethyl phosphorylcholine (MPC) unit and a cationic 2-methacryloyloxyethyl trimethylammonium chloride (TMAEMA) unit was grafted onto the PEEK surface by photoinduced self-initiated graft polymerization of the PEEK substrate (PMTx-g-PEEK). Then, negatively charged heparin was immobilized by ionic binding with TMAEMA units (Hep/PMTx-g-PEEK). The TMAEMA unit composition on grafted PMT altered the surface ζ-potentials of the PEEK substrates. Amounts of immobilized heparin depended on the ζ-potential. The concentration of heparin became constant on the sample surface where the TMAEMA unit composition was 30% or more, and was approximately 2.0 μg/cm2. The Hep/PMTx-g-PEEK with a TMAEMA unit composition of 50% showed not only decreased platelet adhesion, but also a 4-fold extension of the blood coagulation time of the poly(MPC)-g-PEEK substrate. The poly(MPC) layer could inhibit platelet adhesion and activation, resulting in surface antithrombogenic properties. Additionally, heparin released from the Hep/PMTx-g-PEEK prevented activation of the coagulation system in whole blood. Therefore, the combination of these antithrombogenic methodologies was promising for prolonging the blood coagulation period of the materials.

Author Correction: Photoinduced self-initiated graft polymerization of methacrylate monomers on poly(ether ether ketone) substrates and surface parameters for controlling cell adhesion

One of the super engineering plastics, poly(ether ether ketone) (PEEK), was functionalized by photoinduced self-initiated graft polymerization of various methacrylate monomers. Anionic, cationic, zwitterionic, nonionic hydrophilic, and nonionic hydrophobic polymer layers were formed onto PEEK substrates. Physical and chemical surface characterizations of the resultant polymer-grafted PEEK substrates were performed through measurements of their surface free energies and ζ potentials. The values of these parameters varied in the ranges of 39–71 mJ/m2 and −69 to 46 mV, respectively. These parameters reflected the chemical structures of the grafted polymers. To understand the effects of these surface parameters on cell adhesion behavior at the substrate surface, the amount of fibronectin adsorbed on the plasma-contacting surface and the density of fibroblast cells adhered to the surface were determined. The adherent cell density showed a good linear correlation with the amount of fibronectin adsorbed on the plasma-contacting surface. The polymer surface with zero ζ potential showed a lower adsorbed fibronectin density. Both anionic and cationic polymer layers had increased cell adhesion compared with that on the original PEEK substrate, whereas the zwitterionic polymer layers significantly prevented cell adhesion. In conclusion, grafting zwitterionic polymers onto a PEEK substrate is anticipated to be useful in the development of a biomedical PEEK substrate. To obtain functionalization of super-engineering plastic, poly(ether ether ketone) (PEEK) substrate, photoinduced self-initiated graft polymerization of several kinds of functional methacrylate was carried out. Graft polymerization proceeded well, and 50–250 nm in thickness graft polymer layers were generated on the PEEK substrate. Surface characteristics such as surface free energy and surface ζ potential on the polymer-grafted PEEK substrate were corresponded to the chemical structure of the graft polymers. Cell attachment on the polymer-grafted PEEK substrate was examined. The surface ζ potentials of the polymer-grafted PEEK substrates governed the cell adhesion density.

Photoinduced self-initiated graft polymerization of methacrylate monomers on poly(ether ether ketone) substrates and surface parameters for controlling cell adhesion

Photoinduced self-initiated graft polymerization of methacrylate monomers on poly(ether ether ketone) substrates and surface parameters for controlling cell adhesion

Immobilization of polyphosphoesters on poly(ether ether ketone) (PEEK) for facilitating mineral coating

Poly(ether ether ketone) (PEEK) is an alternative material to metals for orthopedic applications. However, the compatibility of PEEK with hard tissues needs to be improved. To address this issue, this study proposes a novel technique for PEEK surface modifications. A polyphosphodiester macromonomer (PEPMA·Na) was synthesized via the demethylation of polyphosphotriester macromonomer obtained via the ring-opening polymerization of cyclic phosphoesters using 2-hydroxypropyl methacrylamide as the initiator. The surface modification of PEEK was performed via photoinduced and self-initiated graft polymerization of PEPMA·Na without using any photoinitiators. The amount of phosphorus due to poly(PEPMA·Na) immobilized on PEEK increased with an increase in the photoirradiation time. The PEEK surface turned hydrophilic due to poly(PEPMA·Na) grafting, with almost similar advancing and receding contact angles, implying that the modified PEEK surface (PEEK-g-poly(PEPMA·Na)) was homogeneous. Specimens were mineral coated by simple static soaking in ×1.5 simulated body fluid (1.5SBF) and by an alternative process that included additional soaking steps in 200 mM CaCl2 aq. and 200 mM K2HPO4 aq. before static soaking in 1.5SBF. Specimens were immersed in 1.5SBF for 28 days in simple static soaking, after which the PEEK-g-poly(PEPMA·Na) surface was completely covered with spherical cauliflower-like mineral deposits that resembled octacalcium phosphate (OCP). Their structural similarities were confirmed via X-ray diffraction (XRD), energy dispersive X-ray spectrometry (EDS), and X-ray fluorescence (XRF) analyses. However, these mineral deposits were not observed on the bare PEEK surface. Due to the additional soaking steps (alternative soaking) undertaken before the static soaking of the specimens in 1.5SBF, the mineral coating on the PEEK-g-poly(PEPMA·Na) was dramatically accelerated and the surface was fully covered with mineral deposits in only one day of soaking. The mineral deposits resulting from both the soaking processes had similar structures. Compared with bare PEEK, osteoblastic MC3T3-E1 cells proliferated more actively on mineral-coated PEEK-g-poly(PEPMA·Na). Thus, the surface immobilization of poly(PEPMA·Na) on a PEEK surface is effective for mineral coating and may be useful to provide hard-tissue compatibility on PEEK.

High-efficiency preparation of poly(2-methacryloyloxyethyl phosphorylcholine) grafting layer on poly(ether ether ketone) by photoinduced and self-initiated graft polymerization in an aqueous solution in the presence of inorganic salt additives

A highly efficient methodology for preparing a poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC) layer on the surface of poly(ether ether ketone) (PEEK) was examined by photoinduced and self-initiated graft polymerization. To enhance the polymerization rate, we demonstrated the effects of inorganic salt additives in the feed monomer solution on thickness of grafted PMPC layer. Photoinduced polymerization occurred and the PMPC graft layer was successfully formed on the PEEK surface, regardless of inorganic salt additives. Moreover, it was clearly observed that the addition of inorganic salt enhanced the grafting thickness of PMPC layer on the surface even when the photoirradiation time was shortened. The addition of inorganic salt additives in the feed monomer solution enhanced the polymerization rate of MPC and resulted in thicker PMPC layers. In particular, we evaluated the effect of NaCl concentration and how this affected the polymerization rate and layer thickness. We considered that this phenomenon was due to the hydration of ions in the feed monomer solution and subsequent apparent increase in the MPC concentration. A PMPC layer with over 100-nm-thick, which was prepared by 5-min photoirradiation in 2.5mol/L inorganic salt aqueous solution, showed good wettability and protein adsorption resistance compared to that of untreated PEEK. Hence, we concluded that the addition of NaCl into the MPC feed solution would be a convenient and efficient method for preparing a graft layer on PEEK. Statement of SignificancePhotoinduced and self-initiated graft polymerization on the PEEK surface is one of the several methodologies available for functionalization. However, in comparison with free-radical polymerization, the efficiency of polymerization at the solid-liquid interface is limited. Enhancement of the polymerization rate for grafting could solve the problem. In this study, we observed the acceleration of the polymerization rate of MPC in an aqueous solution by the addition of inorganic salt. The salt itself did not show any adverse effects on the radical polymerization; however, the apparent concentration of the monomer in feed may be increased due to the hydration of ions attributed to salt additives. We could obtain PMPC-grafted PEEK with sufficient PMPC thickness to obtain good functionality with only 5-min photoirradiation by using 2.5mol/L NaCl in the feed solution.

Surface modification of PEEK for improving osteocompatibility

Event Abstract Back to Event Surface modification of PEEK for improving osteocompatibility Shun Kunomura1* and Yasuhiko Iwasaki2, 3* 1 Kansai university, Graduate School of Science and Engineering, Japan 2 Kansai university, Faculty of Chemistry, Materials and Bioengineering, Japan 3 Kansai university, ORDIST, Japan Introduction: Currently, metallic implants such as titanium alloys and cobalt-chromium alloy are used in cementless total hip arthroplasty. Metallic implants have excellent strength and toughness and are effective as osteocompatibility materials. However, they have been known to cause complications such as transient osteoporosis of the hip results from stress shielding, metal allergy and fatigue fracture. To prevent them, polyetheretherketone (PEEK) is employed, which has excellent mechanical properties and durability. Although bone fixation devices of PEEK showed high performance, osteocompatibility of the surface is not sufficient. In order to apply PEEK for the stem of an artificial hip joint, osteocompatibility should be added. We have clarified that poly (ethylene sodium phosphate) shows the high affinity to calcium deposits generated from osteoblasts [1]. Moreover, Yang et al. reported that functions of osteoblasts were promoted on polyphosphoesters [2]. In this study, we modified the poly (ethylene sodium phosphate) on PEEK surface by self-initiated graft polymerization to improve osteocompatibility of the surface. Materials and Methods: Poly (ethylene sodium phosphate) macromonomers (PEPMA·Na) were synthesized according to a previously described method [1]. PEEK specimens were soaked in PEPMA·Na solution, kept 40°C over night to evaporate the solvent, and irradiated UV-light for several periods. PEPMA·Na immobilized PEEK (PEP-PEEK) was performed by water contact angle measurements and X-ray photoelectron spectroscopy. MC3T3-E1 cells were used to investigate the interaction between cells and the PEP-PEEK. Moreover, the specimens were soaked in the simulated body fluid (SBF) to evaluate apatite-forming ability on the surface [3]. Results: Fig. 1 shows the XPS data for PEP-PEEK surfaces and the phosphorus composition increased with an increase in the UV-irradiation time. The surface wettability of PEEK is also significantly improved by the surface modification. Although the cell adhesion of the PEP-PEEK surface was lower than the original PEEK surface, the proliferation of the adherent cells was observed. The calcium deposition on PEP-PEEK surface was preferentially occurred compare with that on the original PEEK surface as shown in Fig .2. Discussion: The enhancement of surface wettability and phosphorus composition suggests immobilization of PEPMA·Na on PEEK surface. The low cell adhesion of PEP-PEEK surface would be due to the high wettability of PEPMA·Na reduced cell adhesion. The previous literature reported that apatite-forming ability correlated with osseointegration [3]. Therefore, PEP-PEEK surface which induces calcium deposition may have osteocompatibility. Conclusion: PEPMA·Na was synthesized, and modified on the surface of PEEK by UV-irradiation. Although cell adhesion of the PEP-PEEK surface was reduced, proliferation of the adherent cells was observed. And the surface modification could significantly enhance the calcium deposition. Therefore, the PEPMA·Na-immobilization on PEEK would be useful way for improving osteocompatibility. A part of this work was supported by AMED Strategic Promotion of Innovative Research and Development

Reduced platelets and bacteria adhesion on poly(ether ether ketone) by photoinduced and self‐initiated graft polymerization of 2‐methacryloyloxyethyl phosphorylcholine

Aromatic poly(ether ether ketone) (PEEK) is a super engineering plastic, which has good mechanical properties and is resistant to physical and chemical stimuli. We have, therefore, attempted to use PEEK in cardiovascular devices. Synthetic cardiovascular devices require both high hemocompatibility and anti-inflammatory activity in addition to the mechanical properties. We modified the PEEK surface by photoinduced and self-initiated graft polymerization with 2-methacryloyloxyethyl phosphorylcholine (MPC; PMPC-grafted PEEK) for obtaining good antithrombogenicity. Polymerization was carried out on the surface of PEEK under radiation of ultraviolet (UV) light during which we controlled monomer concentrations, temperatures, and UV intensities. The biological performance of the PMPC-grafted PEEK was examined and compared with that of unmodified PEEK. With increase in the thickness of the PMPC layer, the amount of fibrinogen adsorption decreased significantly in comparison to that in the case of unmodified PEEK. When placed in contact with human platelet-rich plasma, surface of the PMPC-grafted PEEK clearly showed inhibition of platelet adhesion and activation. Also, bacterial adhesion was reduced dramatically on the PMPC-grafted PEEK. Thus, the PMPC grafting on PEEK improved the antithrombogenicity.