Binding of Ionic Pyrene Derivatives to Polyelectrolytes. A Uv Absorption and Fluorescence Study

Abstract

The binding of pyrenesulfonic acid and pyrenebutyric acid to poly(vinyl benzyl trimethylammonium) chloride was investigated by UV and fluorescence spectroscopy. It was found that the binding constant was 7.5 × 10⁴ and 3.5 × 10⁴M^?1, respectively. The addition of the polyelectrolyte quenches the fluorescence of the pyrene group, and at the same time the typical excimer emission appears. This emission originates in pre-formed ground state aggregates of the pyrene derivatives incorporated into the polyion domain. Similar effects were observed when anionic polyelectrolytes, poly(styrene sulfonic), and poly(vinyl sulfonic) acids were added to cationic pyrene derivatives. The binding constants depend on the length of the aliphatic sidechain of the derivatives.     

RADICAL POLYMERIZATION OF METHYL METHACRYLATE WITH DIPHENYL DISELENIDE UNDER THERMAL OR PHOTOIRRADIATIONAL CONDITIONS

Polymerization of methyl methacrylate (MMA) with diphenyl diselenide (DPDSE) in the presence of AIBN at 60°C was investigated. DPDSE was worked as a chain transfer agent (CTA). The chain transfer constant (C_tr) of DPDSE for MMA was estimated to be 1.43. On the other hand, DPDSE was functioned as a photoiniferter for the photopolymerization of MMA. In a limited range of conversion, both the polymer yield and number average of molecular weight ([Mbar]_n) increased with the reaction time, and the [Mbar]_n linearly increased with the yield. The terminal structure of poly(MMA) was investigated by the ⁷⁷Se NMR spectrum based on Methyl α-phenylseleno isobutylate (MSEPI) as model compound of the ω-chain end of poly(MMA). Further, photopolymerization of poly (MMA) containing phenylseleno group at ω-chain end as a polymeric photoiniferter with MMA effectively afforded a poly (MMA) having higher molecular weight.     

Synthesis and Characterization of New Alumina and Titania-Containing Hybrid Network Ceramer Materials from Sol-Gel Processing

Transparent hybrid materials have been prepared by incorporating either an alumina or titania alkoxide sol with triethoxysilane end-capped polytetramethylene oxide (PTMO) oligomer. In order to avoid undesirable precipitation after the addition of water, a β-dicarbonyl ligand, ethyl acetoacetate, was used. Triethoxysilane endcapped polytetramethylene oxide with a molecular weight of 2000 (g/mol) was chosen to react with either the alumina or titania sol to demonstrate the features of the reaction scheme. The extent of reaction leading to network formation has been qualitatively followed by infrared spectroscopy. A series of solid films were prepared by varying the molar ratio of either aluminum tri(sec-butoxide) or titanium tetraisopropoxide to ethyl acetoacetate, and the weight fraction of alumina or titania to that of PTMO. The refractive index as well as the general structure-property behavior of these hybrid materials were studied.     

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.     

Analysis of Nonionic Surfactants by High Performance Liquid Chromatography

Abstract

This review discusses the principles of immobilized metal ion affinity chromatography (IMAC) and its applications to protein separations. IMAC functions by binding the accessible electron-donating pendant groups of a protein - such as histidine, cysteine, and tryptophan - to a metal ion which is held by a chelating group covalently attached on a stationary support. A common chelating group is iminodiacetate. The ions commonly used are of borderline or soft metals, such as Cu²⁺, Ni²⁺, Co²⁺, and Zn²⁺. Protein retention in IMAC depends on the number and type of pendant groups which can interact with the metal. The interaction is affected by a variety of independent variables such as pH, temperature, solvent type, salt type, salt concentration, nature of immobilized metal and chelate, ligand density, and protein size. Proteins are usually eluted by a decreasing pH gradient or by an increasing gradient of a competitive agent, such as imidazole, in a buffer. There are still several unresolved issues in IMAC. The exact structures of protein-immobilized metal complexes need to be known so that retention behavior of proteins can be fully understood and sorbent structures can be optimized. Engineering parameters, such as adsorption/desorption rate constants, sorbent capacities, and intraparticle diffusivities, need to be developed for most protein systems. Engineering analysis and quantitative understanding are also needed so that IMAC can be used efficiently for large scale protein separations.     

Discrimination and simultaneous determination of hydroquinone and catechol by tunable polymerization of imidazolium-based ionic liquid on multi-walled carbon nanotube surfaces

Tunable polymerization of ionic liquid on the surfaces of multi-walled carbon nanotubes (MWCNTs) was achieved by a mild thermal-initiation-free radical reaction of 3-ethy-1-vinylimidazolium tetrafluoroborate in the presence of MWCNTs. Successful modification of polymeric ionic liquid (PIL) on MWCNTs surfaces (PIL-MWCNTs) was demonstrated by scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis and X-ray photoelectron spectroscopy. The resulting PIL-MWCNTs possessed unique features of high dispersity in aqueous solution and tunable thickness of PIL layer, due to positive imidazole groups along PIL chains and controllable ionic liquid polymerization by tuning the ratio of precursor. Based on cation-π interaction between the positive imidazole groups on PIL-MWCNTs surface and hydroquinone (HQ) or catechol (CC), excellent discrimination ability toward HQ and CC and improved simultaneous detection performance were achieved. The linear range for HQ and CC were 1.0 × 10⁻⁶ to 5.0 × 10⁻⁴ M and 1.0 × 10⁻⁶ to 4.0 × 10⁻⁴ M, respectively. The detection limit for HQ was 4.0 × 10⁻⁷ M and for CC 1.7 × 10⁻⁷ M (S/N = 3), correspondingly.     

Synthesis, characterization and ion transport properties of hot-pressed solid polymer electrolytes (1−x) PEO:x KI

Synthesis and ion transport properties of hot-pressed solid polymer electrolytes (SPEs), (1-x) PEO: x KI, where x is the content of KI in wt%, are reported. A hot-press technique has been used for the formation of the polymeric membranes in place of the usual solution cast method. The composition (80PEO:20KI) was identified as the highest conducting polymer electrolyte on the basis of compositional dependent conductivity studies of PEO:KI films. A conductivity enhancement of more than two orders of magnitude from that of the pure PEO was achieved. Materials characterization and ion transport mechanism were explained by using various experimental techniques.     

悬浮聚合制备大尺寸梭形聚苯乙烯粒子新方法及机理研究

利用氢氧化钾对苯乙烯-马来酸酐交替共聚物(SMA)进行水解,所得中等皂化程度的SMA水解产物(SMAA)在水溶液中具有刚性棒状直链构型;将此特殊结构的大分子作为分散剂用于苯乙烯悬浮聚合,通过控制搅拌速度和油水比,可得到梭形聚苯乙烯粒子;在优化条件下,粒子平均长度6.8 mm,宽度1.4 mm,厚度0.5 mm,长径比约5.0.其可能的机理为,中等皂化程度的刚棒直链型SMAA在聚合物"软粒子"表面能形成难以"回复"的有效保护层,使由剪切形成的变形聚合物"软粒子"在聚合过程中能保持形状和尺寸的稳定,从而得到梭形聚合物粒子.     

Crystal growth,spectral characterization and structural studies of a luminescent coordination polymer of calcium(II) complex of benzilic acid

Single crystals of a new calcium(II) complex of benzilic acid, [Ca(C₁₄H₁₁O₃)₂(C₁₄H₁₂O₃)₂] have been successfully grown by gel diffusion technique at room temperature. Single crystal X-ray diffraction study reveals that the compound belongs to orthorhombic system with space group Fddd. The adjacent CaO₈ units are linked via O–H–O interaction to form one dimensional polymeric chains. The extensive hydrogen bonding interactions lead to a supramolecular structure. The grown crystals were further characterized by elemental analysis, FT-IR, UV–Visible, thermogravimetric, powder X-ray diffraction and solid state photoluminescence studies.