Immobilization of Bovine Serum Albumin on Poly(ether ether ketone)for Surface Biocompatibility Improvement

UV-induced graft polymerization of acrylic acid(AA)on poly(ether ether ketone)(PEEK)films was carried out to introduce-COOH for the subsequent immobilization of bovine serum albumin(BSA).BSA was introd...     

聚醚醚酮表面的亲水改性和胶原蛋白固定化

采用紫外光接枝法对聚醚醚酮(PEEK)表面进行化学修饰和生物分子固定化.首先向PEEK表面引入亲水性的丙烯酰胺,并以此为反应位点通过戊二醛将胶原和胶原蛋白固定在PEEK表面.用接触角测定仪、扫描电镜、荧光标记和X射线光电子能谱等对改性薄膜进行了表征.结果表明,PEEK上丙烯酰胺的接枝密度高达50.9μg/cm~2;改性薄膜表面浸润性显著提高,水接触角最低降至(22±3)°.荧光标记胶原固定的PEEK薄膜荧光发射光谱强度最高,并在X射线光电子能谱中检测到N元素,表明胶原已固定化,固定胶原蛋白的浓度为10.2μg/cm~2.     

UV-induced Self-initiated Graft Polymerization of Acrylamide onto Poly(ether ether ketone)

Photo-grafting of hydrophilic monomer was used to enhance the hydrophilicity of poly(ether ether ketone) (PEEK) with the aim of extending its applications to biological fields. PEEK sheets were surface modified by grafting of acrylamide(AAm) with ultraviolet(UV) irradiation in the presence or absence of benzophenone(BP). The effects of BP, irradiation time and monomer concentration on the surface wettability of PEEK were investigated. Characterization of modified PEEK using scanning electron microscopy(SEM), energy-disperse spectrometer(EDS) and water contact angle measurements shows that AAm was successfully grafted on PEEK surface both in presence and absence of BP. With the increase in irradiation time and monomer concentration, contact angles decrease to as low as 30°, demonstrating a significant improvement of surface hydrophilicity. In agreement with the decrease in contact angle, under identical conditions, the nitrogen concentration increases, suggesting the increase in grafting degree of the grafting polymerization. This investigation demonstrates a self-initiation of PEEK due to its BP-like structure in the backbone of the polymer. Though the graft polymerization proceeds more readily in the presence of BP, the self-initiated graft polymerization is clearly observed.     

气相色谱法探究聚醚醚酮的热降解及热氧化降解（英文）

Poly(ether ether ketone)(PEEK)was synthesized via polycondensation of hydroquinone with 4,4′-difluorobenzophenone at 320℃for 5 h.Thermal and thermo-oxidative degradation of PEEK was studied over a wide range of temperatures.In an inert medium,decomposition of the polymer occurred in one stage,with the formation of a coke residue accounting for approximately 50%of the original polymer mass.In air,the mass loss curve exhibited two distinct stages.The first stage involved breakdown of the main polymer chain,the speed of which indicated a radical chain failure mechanism.In the second stage,the rate of mass loss clearly decreased,indicating a transition from the radical chain failure mechanism to simple combustion reactions(wherein the polymer combusted completely).To further investigate the nature of the processes occurring during the pyrolysis of PEEK,the investigations were carried out using gas chromatograph under isothermal conditions.It was concluded that during thermal degradation,the decomposition of the polymer starts with the rupture of ketone and ether bonds and proceeds to destruction of the benzene ring at higher temperatures,which is accompanied by the formation of H2O and CH4.Above 500℃,the polymer degradation further involved thermohydrolysis.The thermo-oxidation of PEEK,which was accompanied mainly by the formation ofH2,was noticeable beginning at 325℃.The total yield of the latter indicated oxidation of fragments of the benzene ring.     

不同磺化及碱处理聚醚醚酮的表面化学组成及体外生物活性评价

提出一种酸碱结合改性聚醚醚酮（PEEK）方法,并评价其对PEEK表面类骨磷灰石形成的影响.结果表明,通过磺化处理引入-SO₃H,显著改善了样品的亲水性,且磺化程度与H₂SO₄浓度和磺化反应时间成正比,并影响样品的表面形貌.质量分数为85% H₂SO₄处理30 min的PEEK-S具有较好的改性效果.将PEEK-S进一步用NaOH处理,可继续引入Na元素并提高样品的亲水性,但会受处理时间的影响.模拟体液（SBF）浸泡的生物活性评价结果表明,磺化后碱处理24 h的PEEK-Na具有快速的类骨磷灰石沉积能力,浸泡3 d的样品表面即可完全被沉积的类骨磷灰石覆盖,表现出较佳的生物活性.此酸碱双重改性方法操作简单,可大幅度提升PEEK的生物活性,具有较好的应用前景.     

不饱和糖功能单体接枝聚氨酯膜的制备及其血液相容性

通过葡萄糖、丙烯酸羟乙酯和丁二胺反应,制备了含不饱和双键的糖基功能单体。 采用傅里叶红外光谱和核磁共振氢谱对合成的产物进行结构表征确定。 采用紫外光引发接枝聚合技术,将制备的不饱和糖单体接枝聚合到聚氨酯膜的表面,以衰减全反射模式下傅里叶红外光谱对表面接枝反应进行了确认。 通过静态水接触角实验和血小板黏附实验,分别对改性聚氨酯膜表面的亲水性和血液相容性进行了研究,结果表明,改性聚氨酯膜表面的接触角从86°降低到45°,血小板的粘附量由14.36×10³ cells/mm²减少到2.57×10³ cells/mm²,亲水性明显增强,血液相容性显著改善。     

耦联剂辅助吸附法制备CuInS2量子点敏化太阳电池

分别以CuI 和InAc3 作为铜源和铟源, 十二硫醇(DDT)作为硫源, 采用直接加热法合成不同尺寸的CuInS₂ (CIS)量子点. 运用X射线衍射(XRD), 拉曼光谱(Raman), 高分辨率透射电镜(HRTEM), 紫外-可见(UVVis)吸收光谱表征其相结构、形貌及光学性能. 结果表明: 制备的CIS量子点为黄铜矿结构, 且随着时间的延长, 量子点逐渐长大, 吸收光谱的激子吸收峰逐渐红移, 表现出量子尺寸效应. 采用巯基乙酸为双功能耦联剂辅助吸附法制备CIS敏化的TiO₂薄膜. 通过衰减全反射红外光谱(ATR-FTIR)分析得出, 巯基乙酸上的羧基与TiO₂表面羟基连接, 另一端上的巯基代替长链的DDT与CIS 耦联, 将CIS 成功锚定在TiO₂表面. 该方法不仅操作简单, 而且容易实现CIS在TiO₂表面的吸附. 太阳电池光电性能测试表明, 粒径大小约为3.6 nm的CIS量子点表现出最优的吸附能力以及光电转换性能. 进一步采用连续离子吸附层法对CIS敏化的TiO₂薄膜进行CdS包覆, 光电转换性能大大提高, 其效率达到2.83%, 这主要源于CdS的包覆钝化了CIS 的表面缺陷, 有效地降低了电子复合.     

Enhanced adhesion of copper plating to polyether ether ketone based on active oxygen species generated under ultraviolet irradiation

Polyether ether ketone (PEEK) is a substrate for metal plating to overcome insulation defects and satisfy the increased demands of mechanically robust electronic circuit boards. However, pristine PEEK is hydrophobic; hence, the adhesion between the metal film and PEEK substrate is poor. Therefore, the PEEK surface should be modified to improve hydrophobicity. We have proposed the active oxygen (AOS) treatment under ultraviolet (UV) light as an alternative to a conventional plasma treatment method. Characteristics of the PEEK surfaces obtained by these methods are compared. We explore the effects of reactive-oxygen and UV light exposure time on the PEEK surface modification. The contact angle of water drop on PEEK after the AOS treatment is lower than that of untreated PEEK. Furthermore, COO groups are observed on the PEEK surface after the treatment. Although plasma treatment has the effect of roughening the surface, it is desirable not to roughen the surface for use in electronic circuit boards. Moreover, we have reported the adhesion strength between PEEK and copper plating without surface roughening.     

Novel thin-film composite membranes with improved water flux from sulfonated cardo poly(arylene ether sulfone) bearing pendant amino groups

A new class of polymeric amine, namely, sulfonated cardo poly(arylene ether sulfone) (SPES-NH₂) was synthesized and used for the preparation of thin-film composite membrane. The TFC membranes were prepared on a polysulfone supporting film through interfacial polymerization with trimesoyl chloride (TMC) solutions and amine solutions containing SPES-NH₂ and m-phenylenediamine (MPDA). The resultant membranes were characterized with water permeation performance, chemical structure, hydrophilicity of active layer and membrane morphology including top surface and cross-section. The membrane prepared under the optimum condition showed the salt rejection and water flux reached 97.3% and 51.2 L/m² h, respectively. The high salt rejection and water flux was attributed to the rigid polymer backbone and the presence of strong hydrophilic sulfonic groups.     

基于MWCNT/TiO2对电极和硫醇盐/二硫化物非碘氧化还原电对的染料敏化太阳能电池性能

采用水热法合成出多壁纳米碳管/二氧化钛(MWCNT/TiO₂)复合物, 并作为染料敏化太阳能电池(DSSC)中对电极材料并组装成电池. 通过场发射扫描电子显微镜(FE-SEM)、傅里叶变换红外(FTIR)光谱、X射线粉末衍射(XRD)、同步热重-差示扫描量热(TGA-DSC)、拉曼(Raman)光谱和光电子能谱(XPS)等方法对其形貌、组成和结构进行表征. 结果表明, 酸化MWCNT表面―COOH与水热生长出的锐钛矿TiO₂表面―OH之间, 通过形成类似于O＝C―O―Ti 或者C―O―Ti 的结构, 能有效地增强复合物薄膜层与导电玻璃基底之间的相互作用. 通过循环伏安(CV)、电化学阻抗谱(EIS)、塔菲尔曲线(Tafel)和电池的伏安特性曲线等方法研究了该类对电极对硫醇盐/二硫化物(T-/T₂)非碘氧化还原电对的光电化学特性. 结果表明: 当MWCNT与TiO₂质量比为3:1时, 基于该复合物对电极与T-/T₂非碘氧化还原电对所组装DSSC的开路电压为0.63 V, 短路电流为15.81 mA·cm^-2, 填充因子为0.65, 光电转换效率达到6.47%.     

合成气一步法制备二甲醚核壳结构催化剂的制备及其反应性能

以生物质(葡萄糖、蔗糖、淀粉)为模板剂,通过水热合成法制备具有核壳结构的CuO-ZnO-Al₂O₃@Al₂O₃复合催化剂,该催化剂以甲醇合成催化剂CuO-ZnO-Al₂O₃为核,甲醇脱水催化剂Al₂O₃为壳.SEM-EDS对催化剂核壳结构的表征发现,通过改变水热合成温度和合成时间可以调变催化剂中Al₂O₃壳层的厚度.将该复合催化剂用于合成气直接制备二甲醚的反应,在空速1 500 mL/(h·g_cat)、温度260 ℃、压力5.0 MPa的条件下,CO转化率和二甲醚选择性分别达到35.2%和61.1%.     

聚醚醚酮/聚醚醚酮酮共混体系的熔融和等温结晶行为

采用熔融共混方法制备了聚醚醚酮和聚醚醚酮酮的共混物,用DSC对共混物的熔融行为和等温结晶行为进行了研究.结果表明,共混物熔点随聚醚醚酮含量增加而降低,但与聚醚醚酮酮有相同的平衡熔点,二者共混没有改变其结晶的成核与生长机制.     

Analysis of Solvent Effect on Mechanical Properties of Poly(ether ether ketone) Using Nano-indentation

Poly (ether ether ketone)(PEEK) is a high-performance semi-crystalline thermoplastic polymer.Exposure of the polymeric surface to solvents can have a strong effect like softening/swelling of polymeric network or dissolution.In this study, nano-indentation analysis was performed to study the effect of acetone on the surface mechanical properties of PEEK using different exposure time.The experiments were performed with a constant loading rate (10 nm/s) to a maximum indentation displacement (1000 nm).A 30-second hold segment was included at the maximum load to account for any creep effects followed by an unloading segment to 80% unloading.The indentation hardness and the elastic modulus were computed as a continuous function of the penetration displacement in the continuous stiffness mode (CSM) indentation.The experimental data showed that the peak load decreased from ~5.2 mN to ~1.7 mN as exposure time in solvent environment increased from 0 to 18 days.The elastic modulus and the hardness of PEEK samples also displayed a decreasing trend as a function of exposure time in the solvent environment.Two empirical models were used to fit the experimental data of hardness as a function of exposure time which showed a good agreement with the experimental values.     

Effect of Antioxidants on the Stability of Poly(ether ether ketone) and the Investigation on the Effect Mechanism of the Antioxidants to Poly(ether ether ketone)

Two types of antioxidants (a phenolic antioxidant and a phosphorous antioxidant) were used to improve the stability of poly (ether ether ketone) (PEEK). To evaluate the effect of the antioxidants on the properties of PEEK and the stabilization mechanism, some characterization methods were carried out, such as rheometer, TGA, and electron spin resonance (ESR). The results indicated that the efficiency of the phosphorous antioxidant (DS) in improving the stability of PEEK was better than that of the phenolic antioxidant (DN) and the thermal stability of PEEK sample containing 0.07 wt% DS was the best among all samples due to the decrease of the free radicals density, as proven by ESR measurement. The possible stabilization mechanism of the antioxidants to PEEK was proposed to reveal the reason that caused the different performances of the two types of antioxidants to PEEK.     

可逆加成-断裂链转移自由基聚合法合成梳型磺化聚醚醚酮

以带双硫酯取代基聚醚醚酮为大分子链转移剂, 采用可逆加成-断裂链转移自由基聚合(RAFT)法合成不同接枝率的磺化聚醚醚酮(g-SPEEK), 并对其结构进行表征. 在单体/链转移剂/引发剂的投料比(摩尔比)为50:4:1, 温度为70 ℃, 反应24 h, 得到聚合物膜的离子交换容量和吸水率分别为1.312 mmol/g和43.51%, 其溶胀率为5.05%, 低于Nafion膜的11.50%. 热重分析(TGA)结果表明该梳型g-SPEEK具有较好的热力学稳定性, 且该聚合物膜具有与Nafion膜相当的抗氧化性. 在相同的离子交换容量下, 梳型g-SPEEK比主链型SPEEK具有更好的H⁺离子透过性能.     

Evaluation of Stabilization Performances of Antioxidants in Poly(ether ether ketone)

Two types of antioxidants(a primary antioxidant and a secondary antioxidant) were used to improve the stability of poly(ether ether ketone)(PEEK). The effects of the antioxidants on the properties of PEEK and the stabilization mechanism were investigated by some characterization methods, such as rheometer, thermogravimetric ana- lysis(TGA), universal tester and electron spin resonance(ESR). The results indicate that the efficiency of the phosphorous antioxidant(DS) in improving the stability of PEEK was better than that of the phenolic antioxidant(DN) in both melting stability and thermal stability, and the thermal stability of PEEK sample containing 0.07%(mass fraction) DS was the best among all the samples due to the decrease of the free radicals density, as proven by ESR measurement. Additionally, no obvious changes could be observed in mechanical properties of PEEK containing antioxidants compared to those of virgin PEEK.     

Poly(ether ether ketone)‐bischromenes: Synthesis,characterization, and influence on thermal,mechanical, and thermo mechanical properties of epoxy resin

Poly(ether ether ketone) s with terminal propargyl groups (PEEK‐PR) were synthesized from hydroxyl terminated PEEK (PEEKTOH) and characterized. The heat‐triggered polymerization of PEEK‐PR to poly bischromenes having PEEK backbone was confirmed by Fourier transform infrared spectroscopy and differential scanning calorimetric studies. PEEK‐PR was blended with a bisphenol based epoxy resin‐diamino diphenylsulphone system in different proportions and cured to form PEEK‐bischromene‐interpenetrated‐epoxy‐amine networks. Tensile strength and elongation of the cured blends increased up to 10‐phr loading of PEEK‐PR and then declined. Tensile moduli of all formulations were comparable. Fracture toughness increased by a maximum of 33%, and the fractured surface morphology showed a ductile fracture. The blends exhibited slightly lower glass transition temperature to that of the neat epoxy‐amine system. A reference sample of epoxy‐amine was processed with the optimum loading of the precursor polymer, PEEKTOH, and compared its properties with the PEEK‐PR incorporated epoxy systems. In this way, it is found that the incorporation of addition curable propargylated PEEK increases the strength characteristics with adequate thermal stability and fracture toughness for high‐performance structural applications.     

自交联型磺化聚醚醚酮质子交换膜的合成

以含3,3'-二烯丙基双酚 A 结构单元的聚醚醚酮为基膜材料, 通过自由基加成反应在取代基上引入磺酸基团, 合成侧链型磺化聚醚醚酮(SPEEK)质子交换膜. 用傅里叶变换红外(FTIR)光谱、 核磁共振氢谱(¹H NMR)、 热重分析(TG)和扫描电子显微镜(SEM)等方法对 SPEEK 的结构进行表征. 实验结果表明, 巯基丙磺酸被接枝在聚醚醚酮侧基上, SPEEK 膜具有明显的亲水疏水微相分离形貌, 磺酸基团相互聚集形成离子通道. SPEEK 膜离子交换容量为 2.12 mmol/g, 钒离子渗透率为 1.54×10^-6 cm²/min, 低于Nafion117 膜的钒离子渗透率, 阻钒能力优于 Nafion117 膜. 以 SPEEK-4 膜组装电池的自放电时间约为130 h, 长于 Nafion117 膜的 66 h. 电池充放电循环 50 次, SPEEK-4 膜的库仑效率、 电压效率和能量效率没有明显降低, 显示出良好的稳定性.     

A comparison of the strength of autohesion of plasma treated amorphous and semi‐crystalline PEEK films

Polyether ether ketone (PEEK) is a promising material for the encapsulation of electronic components for medical implants but a strong and hermetic joining technology is required. Autohesion is a self‐bonding method that avoids the need for adhesives. The strengths of autohesive joins using amorphous and semi‐crystalline PEEK films after surface activation using RF plasma were compared. Both types of PEEK films showed successful autohesion after activation with the bond strength of the amorphous sample being twice as high as the bond strength of the semi‐crystalline sample. Plasma treatment increased the autohesion strength of PEEK with no observed change in surface roughness (as measured by profilometer). The water contact angle was reduced by the treatment. X‐ray photoelectron spectroscopy (XPS) was carried out to determine surface chemistry. In the case of the semi‐crystalline surface, plasma treatment increased the relative percentage of C? O functional groups compared to the untreated surface. For treated surfaces nitrogen concentration correlated positively with bond strength while oxygen concentration correlated negatively with the semi‐crystalline PEEK samples and positively with the amorphous PEEK samples. The oxygen groups most likely are formed after the treatment by ambient oxidation are not conducive to bond formation, possibly because of the quenching of radicals that would otherwise form links. Copyright © 2010 John Wiley & Sons, Ltd.     

卤素离子对TiO2薄膜光致亲水性的影响

将卤化钾盐KX(X＝I、Br、Cl、F)分别引入至TiO₂溶胶中, 利用提拉法在载玻片上制得含有卤素离子的TiO₂-X薄膜样片, 通过测试样片紫外光照下水滴接触角的变化, 考察了不同浓度的KI以及不同卤素离子对TiO₂薄膜光致亲水性能的影响, 并通过测试光照后的亲水薄膜样片暗处放置不同时间后接触角的变化, 比较了含TiO₂-I和TiO₂-F薄膜样片亲水性能的持久性. 结果表明, 适量的KI有助于提高TiO2薄膜的光致亲水性, 当TiO₂溶胶中KI浓度为1.0×10^-5 mol•L^-1时, 其所制得TiO₂薄膜的光致亲水性最好, 继续增大KI浓度时, 薄膜的光致亲水性逐步下降, 当KI浓度达1.0×10^-2 mol•L^-1时, 其光致亲水性较纯TiO₂薄膜差；同时, 适量的KBr、KCl加入也有助于提高TiO₂薄膜的光致亲水性, 且随KI＞KBr＞KCl的顺序逐渐减弱, 但KF的加入降低了薄膜的光致亲水性；另外, 卤素离子的加入还有助于提高TiO₂薄膜亲水性能的持久性, 且KF＞KI. 分析认为, 卤素离子对TiO₂薄膜光致亲水性的影响与其给电子或捕获光致电子作用有关, 并提出了其作用模型, 而卤素离子与亲水基团(羟基)的氢键作用是使KX-TiO₂薄膜能够延长亲水性时间的原因.