Graft polymerization of vinyl monomers inside macroporous polyacrylamide gel,cryogel, in aqueous and aqueous‐organic media initiated by diperiodatocuprate(III) complexes

Graft polymerization initiated by diperiodatocuprate(III) complex (Cu(III)) initiator was found to be an effective and convenient method for graft polymerization of vinyl monomers onto macroporous polyacrylamide gels, the so‐called cryogels (pAAm‐cryogels). The effect of time, temperature, monomer and initiator concentration during the graft polymerization in aqueous and aqueous‐organic media was studied. The graft polymerization of water‐soluble monomers as [2‐(methacryloyloxy)ethyl]‐trimethylammonium chloride, 2‐hydroxyethyl methacrylate, N‐isopropylacrylamide, and N,N‐dimethylacrylamide proceeds with higher grafting yield in aqueous medium, as compared with that in aqueous‐organic media. Graft polymerization in aqueous‐organic media such as water–DMSO solutions allows grafting of water‐insoluble monomers such as glycidyl methacrylate and N‐tert‐butylacrylamide with high grafting degrees of 100 and 410%, respectively. It was found that the deposition of initiator on the pore surface of cryogels promoted graft polymerization by facilitating the formation of the redox couple Cu(III)‐acrylamide group. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1952–1963, 2006     

Highly soluble and optically transparent poly (ether imide)s based on 2,6‐ or 2,7‐bis(3,4‐dicarboxyphenoxy)naphthalene dianhydride and aromatic bis(ether amine)s bearing trifluoromethyl groups

Two series of novel fluorinated poly(ether imide)s (coded IIIA and IIIB ) were prepared from 2,6‐bis(3,4‐dicarboxyphenoxy)naphthalene dianhydride and 2,7‐bis(3,4‐dicarboxyphenoxy)naphthalene dianhydride, respectively, with various trifluoromethyl‐substituted aromatic bis(ether amine)s by a standard two‐step process with thermal or chemical imidization of the poly(amic acid) precursors. These fluorinated poly(ether imide)s showed good solubility in many organic solvents and could be solution‐cast into transparent, flexible, and tough films. These films were nearly colorless, with an ultraviolet–visible absorption edge of 364–386 nm. They also showed good thermal stability with glass‐transition temperatures of 221–298 °C, 10% weight loss temperatures in excess of 489 °C, and char yields at 800 °C in nitrogen greater than 50%. The 2,7‐substituted IIIB series also showed better solubility and higher transparency than the isomeric 2,6‐substituted IIIA series. In comparison with nonfluorinated poly (ether imide)s, the fluorinated IIIA and IIIB series showed better solubility, higher transparency, and lower dielectric constants and water absorption. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5909–5922, 2006     

Synthesis and properties of poly(phenylacetylenes) having two polar groups or one cyclic polar group on the phenyl ring

Phenylacetylene (PA) derivatives having two polar groups (ester, 2a – d ; amide, 4) or one cyclic polar group (imide, 5a – c ) were polymerized using (nbd)Rh⁺[(η⁶‐C₆H₅)B^?(C₆H₅)₃] catalyst to afford high molecular weight polymers (～1 × 10⁶ – 4 × 10⁶). The hydrolysis of ester‐containing poly(PA), poly( 2a) , provided poly(3,4‐dicarboxyPA) [poly ( 3 )], which could not be obtained directly by the polymerization of the corresponding monomer. The solubility properties of the present polymers were different from those of poly(PA) having no polar group; that is, poly( 2a )–poly( 2d ) dissolved in ethyl acetate and poly( 4 ) dissolved in N,N‐dimethylformamide, while poly(PA) was insoluble in such solvents. Ester‐group‐containing polymers [poly( 2a )–poly( 2d )] afforded free‐standing membranes by casting from THF solutions. The membrane of poly( 2a ) showed high carbon dioxide permselectivity against nitrogen (PCO₂/PN₂ = 62). © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5943–5953, 2006     

Synthesis and luminescence characteristics of conjugated dendrimers with 2,4,6‐triaryl‐1,3,5‐triazine periphery

We have synthesized conjugated dendrimer with triazine peripheries, and their luminescence properties were investigated. The dendrimers consist of dendritic triazine wedges for electron transport, distyrylbenzene core as an emitting moiety, and t‐butyl peripheral groups for good processing properties. The dendrimers have LUMO values of about ?2.7 eV possibly because of the triazine moiety with high electron affinity. Photoluminescence study indicates that energy transfer occurs from the triazine wedges to the stilbene bridge, and finally to the core chromophore units due to a cascade decrease of bandgap from the peripheral wedge to core moiety. Therefore, the emission wavelength was determined by the structure of the core unit. The energy transfer efficiency of distyrylbenzene‐cored dendrimers was about 75 and 55% for Trz‐1GD‐DSB and Trz‐2GD‐DSB, respectively. A preliminary electroluminescence property also was investigated. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 254–263, 2006     

Synthesis and application as polymer electrolyte of hyperbranched polyether made by cationic ring‐opening polymerization of 3‐{2‐[2‐(2‐hydroxyethoxy)ethoxy]ethoxymethyl}‐3′‐methyl‐oxetane

A novel cyclic ether monomer 3‐{2‐[2‐(2‐hydroxyethoxy)ethoxy]ethoxy‐methyl}‐3′‐methyloxetane (HEMO) was prepared from the reaction of 3‐hydroxymethyl‐3′‐methyloxetane tosylate with triethylene glycol. The corresponding hyperbranched polyether (PHEMO) was synthesized using BF₃·Et₂O as initiator through cationic ring‐opening polymerization. The evidence from ¹H and ¹³C NMR analyses revealed that the hyperbranched structure is constructed by the competition between two chain propagation mechanisms, i.e. active chain end and activated monomer mechanism. The terminal structure of PHEMO with a cyclic fragment was definitely detected by MALDI‐TOF measurement. A DSC test implied that the resulting polyether has excellent segment motion performance potentially beneficial for the ion transport of polymer electrolytes. Moreover, a TGA assay showed that this hyperbranched polymer possesses high thermostability as compared to its liquid counterpart. The ion conductivity was measured to reach 5.6 × 10^?5 S/cm at room temperature and 6.3 × 10^?4 S/cm at 80 °C after doped with LiTFSI at a ratio of Li:O = 0.05, presenting the promise to meet the practical requirement of lithium ion batteries for polymer electrolytes. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3650–3665, 2006     

Preparation and characterization of optically active polystyrene via a chiral nitroxide‐mediated polymerization

2,2,6,6‐Tetramethyl‐4‐[d‐(+)‐10‐camphorsulfonyl]‐1‐piperidinyloxy was synthesized and used as a chiral nitroxide for the bulk polymerizations of styrene initiated with benzoyl peroxide (BPO), tetraethylthiuram disulfide (TETD), and thermal initiation. The results showed that the polymerizations proceeded in a controlled/living way; that is, the kinetics presented approximately first‐order plots, and the number‐average molecular weights of the polymers with narrow molecular weight distributions (weight‐average molecular weight/number‐average molecular weight) increased with the monomer conversion linearly. The molecular weight distributions in the case of thermal initiation were narrower than those in the case of BPO and TETD, whereas the polymerization rate with BPO or TETD as an initiator was obviously faster than that with thermal initiation. In addition, successful chain‐extension reactions were carried out, and the structures of the obtained polymers were characterized by gel permeation chromatography and ¹H NMR. The specific rotations of the polymers were also measured by polarimetric analysis. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1522–1528, 2006     

Selective and simultaneous determination of phosphate and silicate ions in leaching process waters for ceramics glaze raw materials of narutal origin by ion-exclusion chromatography coupled with UV-detection after postcolumn derivatization.

The selective and simultaneous ion-exclusion chromatography (IEC) with UV-detection on a weakly acidic cation-exchange resin column in the H+ -form (TSKgel Super IC-A/C) was developed and applied for the simultaneous determination of phosphate and silicate ions as the water quality parameters required for optimizing the water-leaching process for ceramics glaze raw materials of natural origin including feldspar, woods-ash, and straw-ash. Phosphate and silicate ions in these water-leaching process water samples were separated selectively from the coexisting anions such as sulfate, chloride, nitrate and carbonate ions, based on the ion-exclusion separation mechanism. They were detected selectively and simultaneously by a postcolumn derivatization with molybdenum-yellow using the UV-detector. Under the optimized separation and detection conditions (eluent, 0-1 mM sulfuric acid; reactant, 10 mM sodium molybdate-25 mM sulfuric acid; detector, UV at 370 nm; temperature, 45 degrees C), the linearity of calibration was in the range 0.1 - 10 ppm for both phosphate and silicate ions, and the detection limits at S/N = 3 were 2.58 ppb for silicate ions and 4.75 ppb for phosphate ions. The effectiveness of this method was demonstrated in practical applications to the water-leaching process for some ceramics glaze raw materials.     

Electrochemical characteristics of gatifloxacin and its interaction with DNA.

The electrochemical behavior of gatifloxacin (GTFX) and its interaction with natural calf thymus DNA (ctDNA) is investigated by differential pulse voltammetry (DPV) on a carbon paraffined electrode. According to the suggested electrochemical equation, a binding constant of 1.7058 x 10(5) (mol L(-1))(-1) and binding sizes s = 3.09 (base pairs) of GTFX with ctDNA are obtained by nonlinear fit analysis of electrochemical data. The results demonstrate that GTFX has the properties of an intercalative binder.     

Pyraflufen-ethyl residues in soil by solid phase extraction and high-performance liquid chromatography with UV detection.

Solid-phase extraction (SPE) procedure for cleanup followed by HPLC-UV method has been investigated for the determination of pyraflufen-ethyl residues in soil. The pesticide is extracted from the sample with acetone-water (80:20, v/v) and the extract is loaded onto an octadecyl (C(18)) column. The pesticide is eluted with acetonitrile and determined by HPLC with a UV detector. Using an acetone-water extraction followed by a C(18) cleanup, this method is characterized by recovery >90.1%, precision <5.8% RSD and sensitivity of 0.01 mg/kg. The proposed method has been successfully employed for the determination of the degradation dynamics of pyraflufen-ethyl in four agricultural soil samples under laboratory conditions.