Poly(etheretherketone) is a rigid semicrystalline thermoplastic that combines excellent mechanical properties, broad chemical resistance, and bone-like stiffness, and is widely used in biomedical fields. However, the hydrophobic bio-inert surface of poly(etheretherketone) tends to hinder its biomedical applications when direct osteointegration between the implants and the host tissue is desired. In this investigation, poly(etheretherketone) surface was functionalized by a method with chemistry analogous to the formation of organosilane self-assembled monolayers on glass or silicon. First, poly(etheretherketone) surface activation with selective carbonyl reduction introduces surface hydroxylation. And then treatment of the hydroxylation-pretreated poly(etheretherketone) samples with a substituted organosilane solution forms the carboxyl (–COOH) functional surface layers. The modified surfaces were characterized using X-ray photoelectron spectroscopy, water contact angle measurements, differential scanning calorimetry, X-ray diffraction, and surface profiler. The effect of cell adhesion, spreading, and proliferation on each specimen was investigated. Pre-osteoblast cells (MC3T3-E1) adhesion, spreading, and proliferation were improved remarkably on surface-carboxylated poly(etheretherketone). Poly(etheretherketone) modified with –COOH on its surface has potential use in orthopedic or dental implants.
KurtzSMDevineJN. PEEK biomaterials in trauma, orthopedic, and spinal implants. Biomaterials2007; 28: 4845–4869.
2.
Abu BakarMSChengMHWTangSM. Tensile properties, tension-tension fatigue and biological response of polyetheretherketone-hydroxyapatite composites for load-bearing orthopedic implants. Biomaterials2003; 24: 2245–2250.
3.
GodaraARaabeDGreenS. The influence of sterilization processes on the micromechanical properties of carbon fiber-reinforced PEEK composites for bone implant applications. Acta Biomater2007; 3: 209–220.
4.
WenzLMerrittKBrownS. In vitro biocompatibility of polyetheretherketone and polysulfone composites. J Biomed Mater Res1990; 24: 207–215.
5.
KatzerAMarquardtHWestendorfJ. Polyetheretherketone—cytotoxicity and mutagenicity in vitro. Biomaterials2002; 23: 1749–1759.
6.
MorrisonCMacnairRMacDonaldC. In vitro biocompatibility testing of polymers for orthopaedic implants using cultured fibroblasts and osteoblasts. Biomaterials1995; 16: 987–992.
7.
AwajaFBaxDVZhangS. Cell Adhesion to PEEK treated by plasma immersion ion implantation and deposition for active medical implants. Plasma Process Polym2012; 9: 355–362.
8.
von WilmowskyCLutzRMeiselU. In vivo evaluation of beta-TCP containing 3D laser sintered poly(ether ether ketone) composites in pigs. J Bioact Compat Pol2009; 24: 169–184.
9.
BoyanBDHummertTWDeanDD. Role of material surfaces in regulating bone and cartilage cell response. Biomaterials1996; 17: 137–146.
10.
HanCMLeeEJKimHE. The electron beam deposition of titanium on polyetheretherketone (PEEK) and the resulting enhanced biological properties. Biomaterials2010; 31: 3465–3470.
11.
RobottiPZappiniG. Thermal plasma spray deposition of titanium and hydroxyapatite on polyaryletheretherketone implants. In: KurtzSM (ed.) PEEK biomaterials handbook. Oxford: William Andrew Publishing, 2012, pp. 119–143.
12.
NoisetOSchneiderYJMarchand-BrynaertJ. Surface modification of poly(aryl ether ether ketone) (PEEK) film by covalent coupling of amines and amino acids through a spacer arm. J Polym Sci Pol Chem1997; 35: 3779–3790.
13.
DawRCandanSBeckA. Plasma copolymer surfaces of acrylic acid/1, 7 octadiene: surface characterisation and the attachment of ROS 17/2.8 osteoblast-like cells. Biomaterials1998; 19: 1717–1725.
ScotchfordCACooperELeggettGJ. Growth of human osteoblast-like cells on alkanethiol on gold self-assembled monolayers: the effect of surface chemistry. J Biomed Mater Res1998; 41: 431–442.
16.
LeeJHParkJWLeeHB. Cell adhesion and growth on polymer surfaces with hydroxyl groups prepared by water vapour plasma treatment. Biomaterials1991; 12: 443–448.
17.
SavojiHHadjizadehAMaireM. Electrospun nanofiber scaffolds and plasma polymerization: a promising combination towards complete, stable endothelial lining for vascular grafts. Macromol Biosci2014; 14: 1084–1095.
18.
LiuWCaiQZhangF. Dose-dependent enhancement of bone marrow stromal cells adhesion, spreading and osteogenic differentiation on atmospheric plasma-treated poly(l-lactic acid) nanofibers. J Bioact Compat Pol2013; 28: 453–467.
19.
ZhaoYWongHMWangW. Cytocompatibility, osseointegration, and bioactivity of three-dimensional porous and nanostructured network on polyetheretherketone. Biomaterials2013; 34: 9264–9277.
20.
ArimaYIwataH. Effect of wettability and surface functional groups on protein adsorption and cell adhesion using well-defined mixed self-assembled monolayers. Biomaterials2007; 28: 3074–3082.
21.
ScotchfordCAGilmoreCPCooperE. Protein adsorption and human osteoblast-like cell attachment and growth on alkylthiol on gold self-assembled monolayers. J Biomed Mater Res2002; 59: 84–99.
22.
FaucheuxNSchweissRLützowK. Self-assembled monolayers with different terminating groups as model substrates for cell adhesion studies. Biomaterials2004; 25: 2721–2730.
23.
NakaokaRYamakoshiYIsamaK. Effects of surface chemistry prepared by self-assembled monolayers on osteoblast behavior. J Biomed Mater Res2010; 94A: 524–532.
24.
ToworfeGBhattacharyyaSCompostoR. Effect of functional end groups of silane self-assembled monolayer surfaces on apatite formation, fibronectin adsorption and osteoblast cell function. J Tissue Eng Regen M2009; 3: 26–36.
25.
GoddardJMHotchkissJH. Polymer surface modification for the attachment of bioactive compounds. Prog Polym Sci2007; 32: 698–725.
26.
ChengJYWeiCWHsuKH. Direct-write laser micromachining and universal surface modification of PMMA for device development. Sensor Actuat B: Chem2004; 99: 186–196.
27.
LongTMPrakashSShannonMA. Water-vapor plasma-based surface activation for trichlorosilane modification of PMMA. Langmuir2006; 22: 4104–4109.
28.
NoisetOHenneuseCSchneiderYJ. Surface reduction of poly(aryl ether ether ketone) film: UV spectrophotometric, H-3 radiochemical, and X-ray photoelectron spectroscopic assays of the hydroxyl functions. Macromolecules1997; 30: 540–548.
29.
BlundellDJOsbornBN. The morphology of poly(aryl-ether-ether-ketone). Polymer1983; 24: 953–958.
30.
NaffakhMGomezMAEllisG. Thermal properties, structure and morphology of PEEK/thermotropic liquid crystalline polymer blends. Polym Int2003; 52: 1876–1886.
31.
LuXZuoYZhaoX. The improved performance of a Mg-rich epoxy coating on AZ91D magnesium alloy by silane pretreatment. Corrosion Sci2012; 60: 165–172.
32.
BriggsDFairleyN. XPS of chemically modified low-density polyethylene surfaces: observations on curve-fitting the C 1s spectrum. Surf Interface Anal2002; 33: 283–290.
33.
ZhengYXiongCZhangL. Formation of bone-like apatite on plasma-carboxylated poly(etheretherketone) surface. Mater Lett2014; 126: 147–150.
34.
ZhangGSunSYangD. The surface analytical characterization of carbon fibers functionalized by H2SO4/HNO3 treatment. Carbon2008; 46: 196–205.
35.
WijenayakaAKColbyCBAtkinsGJ. Biomimetic hydroxyapatite coating on glass coverslips for the assay of osteoclast activity in vitro. J Mater Sci: Mater M2009; 20: 1467–1473.
36.
AnselmeK. Osteoblast adhesion on biomaterials. Biomaterials2000; 21: 667–681.
37.
PonsonnetLReybierKJaffrezicN. Relationship between surface properties (roughness, wettability) of titanium and titanium alloys and cell behaviour. Mat Sci Eng C2003; 23: 551–560.
38.
HaoLLawrenceJChianKS. Osteoblast cell adhesion on a laser modified zirconia based bioceramic. J Mater Sci: Mater M2005; 16: 719–726.
39.
ZhuXLChenJScheidelerL. Effects of topography and composition of titanium surface oxides on osteoblast responses. Biomaterials2004; 25: 4087–4103.
40.
MyungSWKoYMKimBH. Effect of plasma surface functionalization on preosteoblast cells spreading and adhesion on a biomimetic hydroxyapatite layer formed on a titanium surface. Appl Surf Sci2013; 287: 62–68.
41.
ZhangZSunJHuH. Osteoblast-like cell adhesion on porous silicon-incorporated TiO2 coating prepared by micro-arc oxidation. J Biomed Mater Res2011; 97B: 224–234.
