高生物活性聚醚醚酮化学改性研究进展

由于聚醚醚酮（PEEK）表面疏水及生物惰性，用作骨科材料难以与周围细胞、骨组织结合。通过化学改性在PEEK分子链中引入具有生物活性的功能化基团是提高其表面细胞黏附、增殖和成骨分化能力最有效的方式。基于功能化基团引入位置的不同，本文将PEEK化学改性分为苯环位改性、酮基位改性和共聚改性等三种，并且重点综述了这些不同化学改性方法的原理和特性及其对PEEK材料生物活性的影响。苯环位改性主要是通过强酸处理引入羧基等官能团，但会残留含硫或含硝化合物，对细胞有一定的毒害作用；酮基位改性是通过胺类、硼氢化钠等试剂与酮基反应，进一步接枝引入功能化基团，但是会破坏PEEK主链上的醚酮比，影响物理性能和热性能。通过亲电、亲核及卤代改性等共聚方式在PEEK侧链引入功能化基团，能保持聚合物主链醚酮比基本不变，同时提升材料生物活性，具有良好的应用前景。在化学改性的基础上，研究多种功能基团的协同作用，进一步引入物理改性，优化面向不同场景的综合性能，是拓宽其在医疗领域应用的发展趋势。     

聚醚醚酮复合材料的改性研究及应用进展

分别从化学改性、填充改性及纤维增强、混合型改性及表面改性等方面综述了聚醚醚酮(PEEK)及其复合材料的改性方法,尤其是对摩擦学性能的改性方法,阐述了PEEK复合材料在各个领域的应用情况,指出了PEEK复合材料摩擦学改性研究的未来发展方向。     

医用聚醚醚酮表面功能化的构建及抗菌性能研究进展

聚醚醚酮(PEEK)表面的生物堕性,限制了其表面与相邻骨组织的良好融合,在实际临床应用中受到限制.通过PEEK表面功能化负载抗菌性和生物活性组分,可有效提升PEEK骨科植入材料的抗菌性能和生物活性,有望拓展其临床应用领域.综述了PEEK表面功能化掺杂抗菌性组分的研究进展,包括PEEK负载抗菌药物、负载金属离子、负载抗菌...     

小分子表面活化改性PEEK骨植入物的研究进展

介绍了常见小分子,如酸类、胺类等改性聚醚醚酮(PEEK)材料用于骨植入物的研究。综述了近年利用小分子通过化学改性及复合改性的方式改善PEEK表面惰性的方法及用于骨修复材料的改性效果。最后对小分子改性PEEK需要注意的工艺问题及其临床应用提出展望。     

PEEK的表面改性和表征

简要介绍了聚醚醚酮(PEEK)的一些特性及应用。综述了近年来用于PEEK薄膜表面改性的几种方法,包括等离子体处理、紫外辐照及湿化学法等。此外,简要概括了改性PEEK表面的表征方法,如扫描电子显微镜、X射线光电子能谱仪和原子力显微镜等。     

硼化钽增强聚醚醚酮复合涂层的制备及性能评价

采用阴极电泳沉积技术在纯钛基板表面沉积聚醚醚酮（PEEK）/硼化钽（TaB₂）复合涂层。采用透射电子显微镜、扫描电子显微镜、X射线衍射仪和摩擦磨损试验机等方式对电泳沉积液分散性、PEEK/TaB₂复合涂层表面形貌、微观结构、结晶行为、摩擦学性能和生物学性能进行表征。结果表明，通过调节电泳沉积参数可以制备形貌均匀、具有一定厚度的PEEK/TaB₂复合涂层，在390 ℃热处理后，涂层均匀致密无孔隙；热处理可以提高PEEK/TaB₂涂层的结晶性能，TaB₂颗粒的加入使PEEK涂层获得更高的结晶度；添加较低含量的TaB₂颗粒时，复合涂层在小牛血清（fetal bovine serum，FBS）介质中表现出良好的摩擦学性能，与纯PEEK涂层相比，磨损率分别下降了48.1 %，69.1 %；但过量TaB₂颗粒在PEEK基质中出现明显的团聚现象， 摩擦系数和磨损率呈现上升趋势；细胞实验表明，TaB₂良好的生物活性促进了样品表面细胞增殖。     

聚醚醚酮耐磨改性研究进展

综述了聚醚醚酮(PEEK)耐磨改性技术的研究进展,包括纤维及晶须增强、纳米粒子填充及共混等技术,并提出了PEEK耐磨改性的发展方向。     

聚醚醚酮的表面改性及在生物医学领域的研究进展

简要介绍了聚醚醚酮（PEEK）的一些特性和应用。从等离子体处理、激光处理、紫外辐照以及湿化学法4个方面对近几年PEEK的表面改性方法以及研究进展进行了综述。     

Research progress of surface modification of biomedical magnesium

由于镁具有优异的生物相容性、可生物降解性及适宜的力学性能而成为潜在的生物医用材料。本文对镁作为生物材料的优缺点进行了综合的评价,分类综述了用不同的表面改性技术在镁及其合金表面制备不同的涂层,包括电化学沉积法及阴极沉积法、离子注入及离子电镀法、阳极氧化及微弧氧化法以及化学转化法,评述了这些涂层对镁的腐蚀性能与生物活性的影响,并对镁作为一种新型可降解的硬组织植入材料的应用前景进行了展望。     

碳纤维界面改性的研究

简介了碳纤维的界面特征及相关的界面理论,综述了冷等离子体接枝法、γ射线辐射处理技术、表面电聚合涂层技术、超声连续改性处理技术等碳纤维表面改性技术的现状与发展趋势,并对每一种不同表面改性技术的优劣进行了比较。     

Current Strategies to Improve the Bioactivity of PEEK

The synthetic thermoplastic polymer polyetheretherketone (PEEK) is becoming a popular component of clinical orthopedic and spinal applications, but its practical use suffers from several limitations. Although PEEK is biocompatible, chemically stable, radiolucent and has an elastic modulus similar to that of normal human bone, it is biologically inert, preventing good integration with adjacent bone tissues upon implantation. Recent efforts have focused on increasing the bioactivity of PEEK to improve the bone-implant interface. Two main strategies have been used to overcome the inert character of PEEK. One approach is surface modification to activate PEEK through surface treatment alone or in combination with a surface coating. Another strategy is to prepare bioactive PEEK composites by impregnating bioactive materials into PEEK substrate. Researchers believe that modified bioactive PEEK will have a wide range of orthopedic applications.     

Chitosan/gelatin-based bioactive and antibacterial coatings deposited via electrophoretic deposition

The fabrication of biocompatible and antibacterial coatings on metallic implants remains a significant challenge for load-bearing orthopedic implants. This study focuses on the electrophoretic deposition of chitosan/gelatin/Ag-Mn doped mesoporous bioactive glass nanoparticles (Ag-Mn MBGNs) composite on the PEEK/bioactive glass layer (called as multi-structured coatings), which had been deposited electrophoretically on 316L stainless steel. The EPD parameters for the deposition of the chitosan/gelatin/Ag-Mn MBGNs coatings were optimized via Taguchi design of experiment approach. Scanning electron microscopy images confirmed that the chitosan/gelatin/Ag-Mn MBGNS layer was deposited on the PEEK/BG layer. The addition of biologically active metallic ions (Mn and Ag) and molecules (chitosan) showed a strong effect on the growth of bacteria. Moreover, the inclusion of Mn and Ag showed a negligible toxic effect on the bioactivity (the ability of the coating to form a bond with the natural bone) of the coatings. Furthermore, the multi-structured coatings presented appropriate wettability and surface roughness for orthopedic applications. Overall, this study provides a direct solution to improve the bioactivity, antibacterial activity, and surface properties of deposited chitosan/gelatin coatings on orthopedic implants that are more manufacturable and translational from research to an industrial scale.     

Effect of doping in hydroxyapatite as coating material on biomedical implants by plasma spraying method: A review

Hydroxyapatite (HAp) is still one of the most widely used bioactive coating material to metallic implant in orthopedic fields because of its good biocompatibility, chemical and structural resemblance to natural bone, osteo-conductivity, coupled with quicker implant fixation and strong bonding between living bone with implants. Many techniques are used to deposit HAp as coating material on metallic implants among which plasma spray coating stands out as this process is cost effective, reliable, and protects surface of metal from wear and corrosion. Although, HAp is a smart choice as implant coating material, however, its medical application has been restricted because of the unfavorable mechanical properties like brittleness, weak fracture toughness and poor tensile strength. Further, HAp coated implants suffer from longer time period for remodeling, slow osseointegration rate and lack of antimicrobial effects/properties. Different methodologies have been adopted as surface modification techniques to increase mechanical as well as biological properties of HAp. Among those approaches use of dopants in HAp is a very efficient way for modification of properties. Therefore, aim of this review paper is to assemble information related to HAp coating by plasma spray technique on implants and discuss their advantages and limitations. The article also reports how addition of various doping ions into HAp can overcome these limitations by effecting structural, compositional, mechanical properties of HAp. Finally, it reports how the single, binary and multi ion dopants incorporation in the HAp structure can affect the properties which ultimately affect implant functionality when coated by plasma spraying method.     

等离子体喷涂生物陶瓷涂层

综合介绍了文献及中国科学院上海硅酸盐研究所在等离子体喷涂生物涂层方面的近期研究进展。羟基磷灰石涂层已在临床上获得应用,但使用效果仍然受其较低的结合强度和结晶度所制约。通过优化喷涂工艺和制备羟基磷灰石基复合涂层,可有效提高羟基磷灰石涂层的结合强度和结晶度。此外,为了获得综合性能优良的植入体材料,制备了多种新型的生物活性陶瓷涂层。纳米氧化钛涂层经合适工艺的后处理可具有良好的生物活性,由于其与钛合金基体有较高的结合强度,在体液环境下具有高稳定性和生物相容性,使纳米氧化钛涂层成为一种具有发展前景的植入体涂层候选材料。新型生物活性硅酸钙涂层具有良好的生物活性,与骨组织能形成有效结合。此外,对这些新型涂层的生物活性机制也做了必要的描述。     

Effect of Extreme Ultraviolet (EUV) Radiation and EUV Induced,N2 and O2 Based Plasmas on a PEEK Surface’s Physico-Chemical Properties and MG63 Cell Adhesion

Polyetheretherketone (PEEK), due to its excellent mechanical and physico-chemical parameters, is an attractive substitute for hard tissues in orthopedic applications. However, PEEK is hydrophobic and lacks surface-active functional groups promoting cell adhesion. Therefore, the PEEK surface must be modified in order to improve its cytocompatibility. In this work, extreme ultraviolet (EUV) radiation and two low-temperature, EUV induced, oxygen and nitrogen plasmas were used for surface modification of polyetheretherketone. Polymer samples were irradiated with 100, 150, and 200 pulses at a 10 Hz repetition rate. The physical and chemical properties of EUV and plasma modified PEEK surfaces, such as changes of the surface topography, chemical composition, and wettability, were examined using atomic force microscopy (AFM), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and goniometry. The human osteoblast-like MG63 cells were used for the analysis of cell viability and cell adhesion on all modified PEEK surfaces. EUV radiation and two types of plasma treatment led to significant changes in surface topography of PEEK, increasing surface roughness and formation of conical structures. Additionally, significant changes in the chemical composition were found and were manifested with the appearance of new functional groups, incorporation of nitrogen atoms up to ~12.3 at.% (when modified in the presence of nitrogen), and doubling the oxygen content up to ~25.7 at.% (when modified in the presence of oxygen), compared to non-modified PEEK. All chemically and physically changed surfaces demonstrated cyto-compatible and non-cytotoxic properties, an enhancement of MG63 cell adhesion was also observed.     

Chitosan graft copolymers‐HA/DBM biocomposites: Preparation,characterization, and in vitro evaluation

The combination of biopolymer with a bioactive component takes advantage of the osteoconductivity and osteoinductivity properties. The studies on composites containing hydroxyapatite (HA), demineralized bone matrix (DBM) fillers and chitosan biopolymer are still conducted. In the present study, the bioactive fillers were loaded onto p(HEMA‐MMA) grafted chitosan copolymer to produce a novel biocomposites having osteoinductive and osteoconductive properties. The produced composites were assessed by TGA, XRD, FTIR, and SEM techniques to prove the interaction between both matrices. In vitro behavior of these composites was performed in SBF to verify the formation of apatite layer onto their surfaces and its enhancement. The results confirmed the formation of thick apatite layer containing carbonate ions onto the surface of biocomposites especially these containing HA‐DBM mixture and pMMA having bone cement formation in their structure. These a novel biocomposites have unique bioactivity properties can be applied in bone implants and tissue engineering applications as scaffolds in future. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Novel full-ceramic monoblock acetabular cup with a bioactive trabecular coating: design,fabrication and characterization

Over the last 25 years, the philosophy behind an optimal fixation of orthopaedic implants to hard tissues progressively evolved towards “bone-conservative” solutions in order to minimize bone resection/loss and maximize tissue-implant integration. Hence, the researchers׳ attention moved from “traditional” fixation of the prosthesis to host bone by using screws or acrylic cement to new strategies based on physico-chemical bonding and surface modification of the implant. This research work explores the feasibility of a novel bioceramic monoblock acetabular cup for hip joint prosthesis that can be fixed to the patient׳s bone by means of a bone-like trabecular coating able to promote implant osteointegration. Sponge replica method was properly adapted and optimized to produce hemispherical foam-like bioactive glass-ceramic coatings that were joined to Al₂O₃/ZrO₂ composite cups by the interposition of a glass-ceramic interlayer. Morphological analyses by scanning electron microscopy (SEM) and micro-computed tomography revealed the good quality of joining at the different interfaces. Preliminary investigation of the mechanical properties was carried out to evaluate the suitability of the device for biomedical use. In vitro bioactive behaviour was assessed by immersion studies in simulated body fluid and evaluating the apatite formation on the struts of the trabecular coating. The concepts and findings reported in the present work can have a significant impact in the field of implantable devices, suggesting a valuable alternative to currently-applied but often suboptimal techniques for bone-prosthesis fixation.     

Production and sulfonation of bioactive polyetheretherketone foam for bone substitute applications

Abstract

In this study, highly porous polyetheretherketone (PEEK) foams were produced by space holder-powder sintering method for bone substitute material and load-bearing orthopaedic hard tissue (knee, hip or spinal) implant applications. NaCl and carbamide powders were used as a space holder (pore former). PEEK has good chemical resistance, radiolucency, sterilization resistance, and mechanical properties close to bone. However, chemical and biological inertness and hydrophobic surface nature of the PEEK limits the bone attachment. Open pores can provide channels for the bone attachment and body fluid transmission, which is beneficial for implant fixation. In addition, sulfonation surface treatment was carried out in sulfuric acid to enhance the bioactivity. Wettability (contact angle) of the samples was investigated by using optical tensiometer. Wetting behaviour of the samples was increased with sulfonation. Apatite-forming ability (bioactivity) of the sulfonated samples was evaluated in simulated body fluid. Sulfonated foams were exhibited improved bioactivity due to the micro-porous surface structure and hydrophilic SO₃H functional groups. Mechanical properties of the foams were also studied.     

SiO2-CaO-P2O5体系生物活性材料的制备研究

化程度的提高会使生物活性有所下降.另外陈化时间应以2 d为宜.