Construction of functional aliphatic polycarbonates for biomedical applications

Aliphatic polycarbonates are one important kind of biodegradable polymers and have been commonly used as integral components of engineered tissues, medical devices and drug delivery systems. As far as the biomedical application is concerned, traditional aliphatic polycarbonates usually suffer from the strong hydrophobicity, deficient functionality, and insufficient compatibility with cell/organs. Consequently, the application is quite limited in scope. Due to the imparted appealing properties, aliphatic polycarbonates bearing specifically designed functional/reactive groups attract great interest from researchers in the recent years. The present review outlines the development up to date concerning the design and biomedical application of functional aliphatic polycarbonates, with an emphasis on their ring-opening (co)polymerization preparation.     

Silicate-based polymer-nanocomposite membranes for polymer electrolyte membrane fuel cells

Proton-exchange membrane fuel cells have emerged as a promising emission free technology to fulfill the existing power requirements of the 21st century. Nafion^® is the most widely accepted and commercialized membrane to date and possesses excellent electrochemical properties below 80 °C, under highly humidified conditions. However, a decrease in the proton conductivity of Nafion^® above 80 °C and lower humidity along with high membrane cost has prompted the development of new membranes and techniques. Addition of inorganic fillers, especially silicate-based nanomaterials, to the polymer membrane was utilized to partially overcome the aforementioned limitations. This is because of the lower cost, easy availability, high hydrophilicity and higher thermal stability of the inorganic silicates. Addition of silicates to the polymer membrane has also improved the mechanical, thermal and barrier properties, along with water uptake of the composite membranes, resulting in superior performance at higher temperature compared to that of the virgin membrane. However, the degrees of dispersion and interaction between the organic polymer and inorganic silicates play vital roles in improving the key properties of the membranes. Hence, different techniques and solvent media were used to improve the degrees of nanofiller dispersion and the physico-chemical properties of the membranes. This review focuses mainly on the techniques of silicate-based nanocomposite fabrication and the resulting impact on the membrane properties.     

Orthogonal ligation to spherical polymeric microparticles: Modular approaches for surface tailoring

Modular ligation strategies for the functionalization of polymeric microspheres provide new perspectives for their applications in material science. In the current trend article we highlight variable synthetic procedures for generating functional microspheres via orthogonal modular conjugation chemistries. An overview of the different surface chemistries available is provided, followed by surface-sensitive characterization techniques relevant for the microparticles. Finally, we explore future trends in modular orthogonal modification approaches on microparticles and provide an outlook on the perspectives that the field of surface-modification of polymeric microparticles holds.     

Synthesis and functionalization of nanoengineered materials using click chemistry

The synthesis of nanoengineered materials with precise control over material composition, architecture and functionality is integral to advances in diverse fields, including biomedicine. Over the last 10 years, click chemistry has emerged as a prominent and versatile approach to engineer materials with specific properties. Herein, we highlight the application of click chemistry for the synthesis of nanoengineered materials, ranging from ultrathin films to delivery systems such as polymersomes, dendrimers and capsules. In addition, we discuss the use of click chemistry for functionalizing such materials, focusing on modifications aimed at biomedical applications.     

Interpolymer radical coupling: A toolbox complementary to controlled radical polymerization

The current review focuses on the relevance and practical benefit of interpolymer radical coupling methods. The latter are developing rapidly and constitute a perfectly complementary macromolecular engineering toolbox to the controlled radical polymerization techniques (CRP). Indeed, all structures formed by CRP are likely to be prone to radical coupling reactions, which multiply the available synthetic possibilities. Basically, the coupling systems can be divided in two main categories. The first one, including the atom transfer radical coupling (ATRC), silane radical atom abstraction (SRAA) and cobalt-mediated radical coupling (CMRC), relies on the recombination of macroradicals produced from a dormant species. The second one, including atom transfer nitroxide radical coupling (ATNRC), single electron transfer nitroxide radical coupling (SETNRC), enhanced spin capturing polymerization (ESCP) and nitrone/nitroso mediated radical coupling (NMRC), makes use of a radical scavenger in order to promote the conjugation of the polymer chains. More than a compilation of macromolecular engineering achievements, the present review additionally aims to emphasize the particularities, synthetic potential and present limitations of each system.     

Degradability Enhancement of Poly(Lactic Acid) by Stearate-Zn(3)Al LDH Nanolayers

Recent environmental problems and societal concerns associated with the disposal of petroleum based plastics throughout the world have triggered renewed efforts to develop new biodegradable products compatible with our environment. This article describes the preparation, characterization and biodegradation study of poly(lactic acid)/layered double hydroxide (PLA/LDH) nanocomposites from PLA and stearate-Zn₃Al LDH. A solution casting method was used to prepare PLA/stearate-Zn₃Al LDH nanocomposites. The anionic clay Zn₃Al LDH was firstly prepared by co-precipitation method from a nitrate salt solution at pH 7.0 and then modified by stearate anions through an ion exchange reaction. This modification increased the basal spacing of the synthetic clay from 8.83 Å to 40.10 Å. The morphology and properties of the prepared PLA/stearate-Zn₃Al LDH nanocomposites were studied by X-ray diffraction (XRD), transmission electron microscope (TEM), scanning electron microscope (SEM), thermogravimetric analysis (TGA), tensile tests as well as biodegradation studies. From the XRD analysis and TEM observation, the stearate-Zn₃Al LDH lost its ordered stacking-structure and was greatly exfoliated in the PLA matrix. Tensile test results of PLA/stearate-Zn₃Al LDH nanocomposites showed that the presence of around 1.0–3.0 wt % of the stearate-Zn₃Al LDH in the PLA drastically improved its elongation at break. The biodegradation studies demonstrated a significant biodegradation rate improvement of PLA in the presence of stearate-Zn₃Al LDH nanolayers. This effect can be caused by the catalytic role of the stearate groups in the biodegradation mechanism leading to much faster disintegration of nanocomposites than pure PLA.     

梳状两亲型SMA衍生物的制备及其表面活性

通过C16～18脂肪醇聚氧乙烯醚对苯乙烯-马来酸酐共聚物(SMA)进行酯化接枝改性,制备了5个梳状两亲型SMA衍生物,即SMA-g-O-3、SMA-g-O-6、SMA-g-O-10、SMA-g-O-15和SMA-g-O-20。通过测定反应体系中原料SMA和酯化产物的酸值的变化可确定酯化反应率,其酯化率都在90%以上,且随脂肪醇聚氧乙烯醚中EO加合数的减少,酯化率相应增加,最高可达95.62%;对酯化物的水溶性及其水溶液的表面活性的研究结果表明,SMA-g-O-20的水溶性较好;25℃时,SMA钠盐水溶液降低表面张力能力有限,表面张力曲线上没有出现拐点,而改性后的SMA衍生物表面活性有较大提高,其中SMA-g-O-15水溶液的表面活性最好,其水溶液的CMC值为0.078 g/L,γCMC为26.74 mN/m。     

超支化聚酰胺酯复合改性混合稀土氧化物的研究

通过AB2单体（由二乙醇胺和丁二酸酐室温反应获得）原位溶液缩聚生成超支化聚酰胺酯(HBPAE)对混合稀土氧化物（RE2O3, RE为La、Ce、Pr、Nd等）实施复合改性,获得了一系列HBPAE/RE2O3复合材料。采用红外光谱、元素分析、X射线光电子能谱、扫描电子显微镜、X射线粉末衍射、热重分析和分散性实验等方法,表征了复合改性前后RE2O3的结构与性能,分析了复合界面的作用特征,探讨了改性后HBPAE对RE2O3性能的影响。结果表明,AB2单体原位缩聚成均匀包裹RE2O3粒子的HBPAE,HBPAE与RE2O3在界面上有4.71 %的配位键接;复合改性仅在RE2O3的表面发生,而不会影响RE2O3的深层晶相结构;调整HBPAE 和 RE2O3的复合比例,可使HBPAE/RE2O3复合材料具有可调的热稳定性;HBPAE的复合改性还提高了RE2O3在有机溶剂中的分散稳定性。     

MBS接枝共聚物对PMMA树脂的增韧研究

采用乳液聚合法在聚丁二烯（PB）乳胶粒子上接枝苯乙烯（St）和甲基丙烯酸甲酯(MMA),合成了一系列的MBS接枝共聚物（简称MBS）,将其与聚甲基丙烯酸甲酯（PMMA）进行熔融共混制备PMMA/MBS共混物,研究了PB及相对分子质量调节剂叔十二烷基硫醇（TDDM）含量对共混物力学性能和微观形态结构的影响。结果表明,随着MBS中PB所占比例的增加,共混物的冲击强度表现出先增大后减小的趋势,当PB所占比例为50 %（质量分数,下同）时,共混物的冲击强度达到200 J/m,而拉伸强度表现出上升的趋势;随着TDDM用量的增加,MBS的接枝率和接枝效率降低,导致共混物的冲击强度先增加后减小;随着MBS中PB所占比例的增加,接枝率的逐渐降低,MBS在PMMA基体中分散程度逐渐变差。     

聚（3，4-乙撑二氧噻吩）/樟脑磺酸复合材料的合成及其电化学性能

以樟脑磺酸(HCSA)为掺杂剂,FeCl3为氧化剂,通过化学氧化聚合合成了聚(3,4-乙撑二氧噻吩)/樟脑磺酸(PEDOT/HCSA)复合材料;采用FTIR和SEM对其结构和形貌进行了表征;探讨了掺杂剂与单体摩尔比、氧化剂用量和反应时间对产品导电性能的影响;分析了产品的电化学性能。结果表明,当n〔3,4-乙撑二氧噻吩(EDOT)〕:n(樟脑磺酸):n(氯化铁)=2:1:40,反应时间41 h时,复合材料具有良好的导电性能和电化学性能,电导率为10.4 S/cm,经150次充放电老化后比容量可保持在140 F/g左右,是一种潜在的超级电容器电极材料。