Synthesis of Hydroxy-Functional PMMA Macromonomers by Anionic Polymerization

Living anionic polymerization has been utilized to synthesize hydroxy end-functionalized PMMA macromonomers with styryl or allyl functionalities as the polymerizable end-groups. Protected hydroxy-functionalized alkyl lithium initiators have been used to initiate anionic polymerization of MMA. Subsequently the living chains with protected hydroxyl function have been terminated using 4-vinylbenzyl chloride (4-VBC) or allyl methacrylate (ALMA) to form α-hydroxy-ω-styryl and α-hydroxy-ω-allyl PMMA, respectively. These protected hydroxy-functionalized PMMA macromonomers have been characterized by GPC and ¹H-NMR. Termination using 4-VBC led to 50% functionalization, whereas that using allyl methacrylate led to 100% functionalization of the hydroxy-PMMA.     

Synthesis and Electron-Beam Polymerization of 1-Propenyl Ether Functional Siloxanes

Abstract

A novel synthesis of 1-propenyl ether functionalized siloxanes has been achieved by the controlled, rhodium-catalyzed, chemoselective hydrosilation of 1-allyloxy-4(1-propenoxy)butane (APB) with various H-functional siloxanes. Chemoselective hydrosilation using a variety of Si—H functional siloxanes proceeds exclusively at the allyl ether group of the APB without participation at the 1-propenyl ether group. The electron-beam-induced cationic polymerization of these monomers in the presence of a diaryliodonium salt was studied and found to take place very rapidly and at very low radiation doses.     

两种功能化纳米金粒子固酶电极的催化性能

以合成的4-巯基苯甲酸功能化纳米金粒子和聚乙烯基吡啶包覆纳米金粒子分别作为固酶载体, 制备了2种新型固酶电极, 在此基础上组装了2种酶燃料电池。采用电化学方法结合紫外可见分光光度法、透射电镜技术等手段研究了固酶载体的形貌, 酶-载体间相互作用对电极表面固定酶分子的光谱学性质, 酶-电极间直接电子迁移能力和催化底物反应性能的影响, 进一步评估和比较了两种酶燃料电池的能量输出性能。实验结果表明:4-巯基苯甲酸功能化纳米金粒子固酶基电极可以实现酶-电极间的直接电子迁移而且对葡萄糖和氧气具有良好的催化性能(催化反应起始电位分别为-0.03和0.96 V, 底物转化频率分别是1.3和0.5 s^-1), 其催化性能的重现性、长期使用性能、酸碱耐受性和热稳定性良好, 随着自组装固酶层数的增加, 催化性能随之增强直至达到极限催化电流;电池性能测试结果表明4-巯基苯甲酸功能化纳米金粒子固酶基燃料电池的开路电压为0.88 V, 最大输出能量密度:864.0 μW·cm^-2, 长期使用性能优异(储存3 周后仍可达到最佳能量输出的80%以上)。     

A convenient synthesis of coumarins using reusable ionic liquid as catalyst

Abstract

An efficient and convenient method has been developed for the synthesis of substituted coumarin derivatives using a Brønsted acidic ionic liquid as catalyst under solvent-free conditions. The catalyst can be reused for six consecutive runs without significant loss of activity.     

Two highly stable and selective solid phase microextraction fibers coated with crown ether functionalized ionic liquids by different sol–gel reaction approaches

In this work, two novel crown ether functionalized ionic liquid (FIL)-based solid phase microextraction (SPME) fibers were prepared by sol–gel technology using the synthesized 1-(trimethoxysily)propyl 3-(6′-oxo-benzo-15-crown-5 hexyl) imidazolium bis(trifluoromethanesulphonyl)imide ([TMSP(Benzo15C5)HIM][N(SO₂CF₃)₂]) and 1-allyl-3-(6′-oxo-benzo-15-crown-5 hexyl) imidazolium bis(trifluoromethanesulphonyl)imide ([A(Benzo15C5)HIM][N(SO₂CF₃)₂]) as selective stationary phases. Owing to the introduction of trimethoxysilypropyl to the imidazole cation, the [TMSP(Benzo15C5)HIM][N(SO₂CF₃)₂] could be chemically bonded to the formed sol–gel silica substrate through the hydrolysis and polycondensation reaction. Similarly, the [A(Benzo15C5)HIM][N(SO₂CF₃)₂] was able to participate in the formation of the organic–inorganic copolymer coatings through the free radical crosslinking reaction. These two fibers were determined to have “bubble-like” surface characteristics analogous to a previously prepared [A(Benzo15C5)HIM][PF₆]-based fiber. Their thermal stabilities were much higher than that of the [A(Benzo15C5)HIM][PF₆]-based coating. They were capable of withstanding temperatures as high as 400 °C without evident loss of the crown ether FILs. They also had strong solvent, acid and alkali resistance, good coating preparation reproducibility and high selectivity for medium polar to polar compounds. The high selectivity of these two fibers could be attributed to the strong ion-dipole, hydrogen bonding and π–π interactions provided by the synergetic effect of ILs and benzo-15-crown-5 functionalities. Moreover, the selectivity of these two fibers was rather different although the structures of these two crown ether FILs were very similar. This is maybe because the relative contents of the crown ether FILs chemically bonded to the organic–inorganic copolymer coatings were quite different when prepared by different sol–gel reaction approaches.     

A competitive immunoassay for sensitive detection of small molecules chloramphenicol based on luminol functionalized silver nanoprobe

Chloramphenicol (CHL) as a broad-spectrum antibiotic has a broad action spectrum against Gram-positive and Gram-negative bacteria, as well as anaerobes. The use of CHL is strictly restricted in poultry because of its toxic effect. However, CHL is still illegally used in animal farming because of its accessibility and low cost. Therefore, sensitive methods are highly desired for the determination of CHL in foodstuffs. The immunoassays based on labeling as an important tool have been reported for the detection of CHL residues in food-producing animals. However, most of the labeling procedures require multi-step reactions and purifications and thus they are complicated and time-consuming. Recently, in our previous work, luminol functionalized silver nanoparticles have been successfully synthesized, which exhibits higher CL efficiency than luminol functionalized gold nanoparticles. In this work, the new luminol functionalized silver nanoparticles have been used for the labeling of small molecules CHL for the first time and a competitive chemiluminescent immunoassay has been developed for the detection of CHL. Owing to the amplification of silver nanoparticles, high sensitivity for CHL could be achieved with a low detection limit of 7.6 × 10⁻⁹ g mL⁻¹ and a wide linear dynamic range of 1.0 × 10⁻⁸–1.0 × 10⁻⁶ g mL⁻¹. This method has also been successfully applied to determine CHL in milk and honey samples with a good recoveries (92% and 102%, 99% and 107% respectively), indicating that the method is feasible for the determination of CHL in real milk and honey samples. The labeling procedure is simple, convenient and fast, superior to previously reported labeling procedures. The immunoassay is also simple, fast, sensitive and selective. It is of application potential for the determination of CHL in foodstuffs.     

Fabrication of durable superhydrophobic nanofibrous filters for oil‐water separation using three novel modified nanoparticles (ZnO‐NSPO,AlOO‐NSPO,and TiO2‐NSPO)

Three reusable and durable superhydrophobic nanofibrous filters were prepared by dip coating the nanofibrous fabric in the three different dispersed solutions of the newly modified nanoparticles (ZnO‐NSPO, AlOO‐NSPO, and titanium dioxide [TiO₂]‐NSPO). The contact angle results proved that the TiO₂‐NSPO coated nanofibrous polyacrylonitrile (PAN) filter was hydrophobic with the water contact angle (WCA) of 141° while the ZnO‐NSPO and AlOO‐NSPO coated nanofibrous PAN filters were superhydrophobic with the WCA of 168° and 152°, respectively. The as‐prepared filters can be utilized as an effective martial for oil‐water separation with separation efficiency of over 98%.     

Functionalized graphene/thermoplastic polyester elastomer nanocomposites by reactive extrusion‐based masterbatch: preparation and properties reinforcement

A reactive extrusion process was developed to fabricate polymer/graphene nanocomposites with good dispersion of graphene sheets in the polymer matrix. The functionalized graphene nanosheet (f‐GNS) activated by diphenylmethane diisocyanate was incorporated in thermoplastic polyester elastomer (TPEE) by reactive extrusion process to produce the TPEE/f‐GNS masterbatch. And then, the TPEE/f‐GNS nanocomposites in different ratios were prepared by masterbatch‐based melt blending. The structure and morphology of functionalized graphene were characterized by Fourier transform infrared, X‐ray photoelectron spectroscopy, X‐ray diffraction and transmission electron microscopy (TEM). The incorporation of f‐GNS significantly improved the mechanical, thermal and crystallization properties of TPEE. With the incorporation of only 0.1 wt% f‐GNS, the tensile strength and elongation at break of nanocomposites were increased by 47.6% and 30.8%, respectively, compared with those of pristine TPEE. Moreover, the degradation temperature for 10 wt% mass loss, storage modulus at ?70°C and crystallization peak temperature (T_cp) of TPEE nanocomposites were consistently improved by 17°C, 7.5% and 36°C. The remarkable reinforcements in mechanical and thermal properties were attributed to the homogeneous dispersion and strong interfacial adhesion of f‐GNS in the TPEE matrix. The functionalization of graphene was beneficial to the improvement of mechanical properties because of the relatively well dispersion of graphene sheets in TPEE matrix, as suggested in the TEM images. This simple and effective approach consisting of chemical functionalization of graphene, reactive extrusion and masterbatch‐based melt blending process is believed to offer possibilities for broadening the graphene applications in the field of polymer processing. Copyright © 2014 John Wiley & Sons, Ltd.     

3D Microporous Base‐Functionalized Covalent Organic Frameworks for Size‐Selective Catalysis

The design and synthesis of 3D covalent organic frameworks (COFs) have been considered a challenge, and the demonstrated applications of 3D COFs have so far been limited to gas adsorption. Herein we describe the design and synthesis of two new 3D microporous base‐functionalized COFs, termed BF‐COF‐1 and BF‐COF‐2, by the use of a tetrahedral alkyl amine, 1,3,5,7‐tetraaminoadamantane (TAA), combined with 1,3,5‐triformylbenzene (TFB) or triformylphloroglucinol (TFP). As catalysts, both BF‐COFs showed remarkable conversion (96 % for BF‐COF‐1 and 98 % for BF‐COF‐2), high size selectivity, and good recyclability in base‐catalyzed Knoevenagel condensation reactions. This study suggests that porous functionalized 3D COFs could be a promising new class of shape‐selective catalysts.     

Selective Solid‐phase Extraction of Cu2+ by a Novel Cu(II)‐imprinted Silica Gel

A new Cu(II)‐imprinted salen functionalized silica gel adsorbent was synthesized by surface imprinting technique and was employed as a selective solid phase extraction material for Cu²⁺ removal from aqueous solutions. The samples were characterized by FT‐IR, ¹HNMR, ¹³CNMR, CHNS and DTG techniques. The BET surface area of the silica gel was also determined. The adsorbent was then used for removal of Cu²⁺ from aqueous solutions under different experimental conditions. It was concluded that the synthesized imprinted silica gel had higher selectivity and capacity compared to the non‐imprinted silica gel and the maximal adsorption capacity of 67.3 and 56.5 mg.g^?1 was obtained respectively for ion‐imprinted and non‐imprinted adsorbents. The relative selectivity factor (β) of 50.32 and 31.94 was obtained respectively for Cu²⁺/Ni²⁺ and Cu²⁺/Zn²⁺ pairs. The dynamic adsorption capacity of the imprinted adsorbent was close to the static adsorption capacity due to the fast kinetic of adsorption. Furthermore, the ion‐imprinted adsorbent was recovered and repeatedly used and satisfactory adsorption capacity with acceptable precision was obtained. Each experiment was repeated at least for three times and the mean and the standard deviation for each measurement were calculated. The applicability of the method was examined for Zayandehrood water as real sample. Acceptabe standard deviation was obtained.