Polymeric Nanocomposites—Polyhedral Oligomeric Silsesquioxanes (POSS) as Hybrid Nanofiller

Abstract

Polyhedral oligomeric silsesquioxane (POSS), a hybrid nanostructured macromer has been used in the last decade for preparation of polymeric nanocomposites. Its versatile chemistry, which lends it for almost infinite chemical modification, sets it apart from other nanostructured fillers like nanoclays, carbon nanotubes, and carbon nanofibers. Depending on its functionality, 3‐D network, bead or pendant type‐POSS based polymeric nanocomposites can be synthesized. These have the potential to be designed for products with specific nanostructures for specific end‐use applications. This article discusses the trends in current research involving use of POSS macromers for modification of mainly thermal and viscoelastic properties of various polymers.     

Graphene grafted silica‐coated Fe3O4 nanocomposite as absorbent for enrichment of carbamates from cucumbers and pears prior to HPLC

In this paper, a novel graphene (G) grafted silica‐coated Fe₃O₄ nanocomposite was fabricated by the chemical bonding of G onto the surface of silica‐coated Fe₃O₄ nanoparticles. Some carbamates (metolcarb, carbaryl, pirimicarb, and diethofencarb) in cucumber and pear samples were enriched by this nanocomposite prior to their determination by HPLC with UV detection. Experimental parameters that may affect the extraction efficiency were investigated. Under the optimum conditions, a linear response was achieved in the concentration range of 0.5–100.0 ng/g for metolcarb, carbaryl, and diethofencarb, and 1.0–100 ng/g for pirimicarb with the correlation coefficients (r) ranging from 0.9956 to 0.9984. The LOD (S/N = 3) of the method were found to be in the range from 0.08 to 0.2 ng/g. The RSDs were in the range from 2.4 to 5.8%. The results indicated that the G grafted silica‐coated Fe₃O₄ nanocomposite was stable and efficient for magnetic SPE and has a great application potential for the preconcentration of other organic pollutants from real samples.     

Recent developments in polymer–block–polypeptide and protein–polymer bioconjugate hybrid materials

In the last few years, polymer bioconjugates have been shown to be useful in many emerging areas of materials science. Consequently, the synthesis of polymer bioconjugates has suddenly become a central topic in polymer chemistry. The versatility and robust nature of modern synthetic methods such as controlled radical polymerisation (CLRP),¹ ring-opening polymerisation (ROP), and ‘click’ chemistry make them excellent tools for the preparation of tailor-made polymer bioconjugates. CLRP in combination with other techniques has been shown to be a mature technology for building tailor-made block copolymers and protein–polymer conjugates with a wide range of applications, especially in biomedical domains. This review describes the recent advances and progress in the rapidly expanding field of bioconjugation, outlining the work performed up to 2012.     

CuO‐CeO2 Nanocomposite: A Highly Efficient Recyclable Catalyst for the Green Synthesis of 1,8‐Dioxooctahydroxanthenes in Water

CuO‐CeO₂ nanocomposite is reported as a highly efficient and recyclable catalyst for the green synthesis of 1,8‐dioxooctahydroxanthenes in water. This catalyst can be recovered by simple filtration and recycled up to 8 consecutive runs without any losing of its efficiency.     

Preparation and Characterization of the Hybrids Containing Silica Nanoparticles by Sol-Gel Crosslinking Process

The organic/inorganic hybrid nanomaterials containing silica nanoparticles are synthesized by sol-gel crosslinking process. The tetraethoxysilane (TEOS) and γ-aminopropyltriethoxylsilane as coupling agents are used as a precursor. The 2,4,6-tri [(2-epihydrin-3-bimethyl-ammonium)propyl]-1,3,5-triazine chloride (Tri-EBAC) as crosslinking agent is used to form covalent bonds among the inorganic nanoparticles. The chemical and morphological structures of the organic/inorganic hybrid are characterized with FTIR spectra, ²⁹Si-NMR, x-ray diffraction (XRD), differential scanning calorimetry (DSC), scanning electron microscopy (SEM) and atomic force microscope (AFM). The results show that the organic/inorganic hybrid forms covalent bond between the inorganic nanoparticle and Tri-EBAC. The network organic/inorganic hybrid can form good film with even nanometer particles. The network organic/inorganic hybrids nanomaterial not only exhibits the thermal properties of inorganic compounds, but also exhibits the thermal properties of organic polymer.     

Hybrid phospholipid bilayer coatings for separations of cationic proteins in capillary zone electrophoresis

Protein separations in CZE suffer from nonspecific adsorption of analytes to the capillary surface. Semipermanent phospholipid bilayers have been used to minimize adsorption, but must be regenerated regularly to ensure reproducibility. We investigated the formation, characterization, and use of hybrid phospholipid bilayers (HPBs) as more stable biosurfactant capillary coatings for CZE protein separations. HPBs are formed by covalently modifying a support with a hydrophobic monolayer onto which a self‐assembled lipid monolayer is deposited. Monolayers prepared in capillaries using 3‐cyanopropyldimethylchlorosilane (CPDCS) or n‐octyldimethylchlorosilane (ODCS) yielded hydrophobic surfaces with lowered surface free energies of 6.0 ± 0.3 or 0.2 ± 0.1 mJ m^?2, respectively, compared to 17 ± 1 mJ m^?2 for bare silica capillaries. HPBs were formed by subsequently fusing vesicles comprised of 1,2‐dilauroyl‐sn‐glycero‐3‐phosphocholine or 1,2‐dioleoyl‐sn‐glycero‐3‐phosphocholine to CPDCS‐ or ODCS‐modified capillaries. The resultant HPB coatings shielded the capillary surface and yielded reduced electroosmotic mobility (1.3–1.9 × 10^?4 cm² V^?1s^?1) compared to CPDCS‐ and ODCS‐modified or bare capillaries (3.6 ± 0.2 × 10^?4 cm² V^?1s^?1, 4.8 ± 0.4 × 10^?4 cm² V^?1s^?1, and 6.0 ± 0.2 × 10^?4 cm² V^?1s^?1, respectively), with increased stability compared to phospholipid bilayer coatings. HPB‐coated capillaries yielded reproducible protein migration times (RSD ≤ 3.6%, n ≥ 6) with separation efficiencies as high as 200 000 plates/m.     

Effect of Process Variable on the Gelation Time of Sulfonated Polyacrylamide Nanocomposite Hydrogel

Among the methods available to reduce water production during oil recovery, injecting a gelling system composed of a polymer and a crosslinker has been widely used. In this study, a Plackett-Burman design was used for screening a large number of factors such as concentrations of polymer, crosslinker, pH, temperature, and presence or absence of NaCl, CaCl₂, MgCl₂, KCl, thiourea, sodium lactate, and nanoclay on the gelation time of sulfonated polyacrylamide nanocomposite hydrogels by rheological tests. Among these factors, temperature, pH, and CaCl₂ concentration were found to have the greatest effect on the gelation time. The effects of these three factors and their interactions on the gelation time were then determined by using central composite design of response surface method. As a result, the interactions of CaCl₂ concentration with temperature and pH were considerably more than the interactions of pH and temperature on the gelation time. At low pH (3 < pH < 7), the gelation time decreased by decrease of pH while at CaCl₂ concentration of 3750–11250 ppm and at 7 < pH < 11, the gelation time increased with the increase of pH. It was found that temperature was the most effective parameter to control the gelation time.     

线上线下混合式物理化学实验研究型教学改革

针对目前实验教学在创新型人才培养中存在的问题,介绍了北京航空航天大学化学学院物理化学实验教学的改革与实践情况。结合线上教学灵活、不受时空限制,以及线下教学培养学生动手操作能力和严谨求实的科学素养的特点,从递进式教学内容设计、个性化实验操作指导和训练、科研式论文报告总结、针对性展示和专题分析等方面进行了线上线下混合式研究型教学改革。将理论方法、虚拟操作、实际训练和总结提升等相结合,充分发挥教师指导和学生主体的优势,多维度培养和提升学生的科学素养、创新思维和综合创新能力,为提升实验教学质量和促进创新型人才培养提供了有益的借鉴。     

Poly(vinyl alcohol)/heteropolyacid nanocomposites as new materials for radiochromic dosimetry in radiation processing

Radiochromic films composed of polymer matrices and organic dyes are widely used for routine dosimetry purposes in operation of various radiation facilities—gamma and X-ray-irradiation, electron accelerators, and so on. However, the sensitivity of these films rapidly decreases at doses exceeding 30–50 kGy due to a saturation of their optical response, making them unsuitable for accurate dosimetry in radiation processing of polymers and composites where doses up to 200 kGy are typically employed. To overcome this limitation, the use of inorganic substances as the coloring agents of polymer-based radiochromic films was proposed in this paper, specifically, heteropolyacidacid H₃PW₁₂O₄₀ (tungstophosphoric acid) in the matrix of poly(vinyl alcohol) (PVA). Nanocomposite PVA/H₃PW₁₂O₄₀ films were prepared by solution casting and their optical responses toward ⁶⁰Co gamma radiation and beams of 6 MeV electrons for a dose range of 10–200 kGy were investigated. It was established that upon exposure to gamma rays and electron beams, the films turn blue and a broad absorption band at 750 nm appears in their spectra. Importantly, the radiation-induced optical absorption increases in a linear fashion up to the dose of 150 kGy and only slightly deviates from linearity at 200 kGy. Moreover, it was found that the PVA/H₃PW₁₂O₄₀ films have a long shelf life, are dose-rate independent within a wide range, and color-stable after irradiation. All these features make the nanocomposite PVA/H₃PW₁₂O₄₀ films promising for use as routine dosimeters and dose labels in a much wider range of high doses as compared to radiochromic films based on organic dyes.