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     

Synthesis of polyacrylonitrile via reverse atom transfer radical polymerization catalyzed by FeCl3/isophthalic acid

FeCl₃ coordinated by isophthalic acid was first used as a catalyst in the azobisisobutyronitrile‐initiated reverse atom transfer radical polymerization of acrylonitrile. N,N‐Dimethylformamide was used as a solvent to improve the solubility of the ligand. An FeCl₃‐to‐isophthalic acid ratio of 0.5 not only gave the best control of the molecular weight and its distribution but also provided rather a rapid reaction rate. The effects of different solvents on the polymerization of acrylonitrile were also investigated. The rate of the polymerization in N,N‐dimethylformamide was faster than that in propylene carbonate and toluene. The molecular weight of polyacrylonitrile agreed reasonably well with the theoretical molecular weight in N,N‐dimethylformamide. The rate of polymerization increased with increasing polymerization temperature, and the apparent activation energy was calculated to be 59.9 kJ mol^?1. Reverse atom transfer radical polymerization was first used to successfully synthesize acrylonitrile polymers with a molecular weight higher than 80,000 and a narrow polydispersity as low as 1.22. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 219–225, 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     

Electrical properties of polypyrrole/p‐InP structure

The polypyrrole/p‐InP structure has been fabricated by the electrochemical polymerization of the organic polypyrrole onto the p‐InP substrate. The current–voltage (I–V), capacitance–voltage (C–V), and capacitance–frequency (C–f) characteristics of the PPy/p‐InP structure have been determined at room temperature. The structure showed nonideal I–V behavior with the ideality factor and the barrier height 1.48 and 0.69 eV respectively. C–f measurements of the structure have been carried out using the Schottky capacitance spectroscopy technique and it has been seen that there is a good agreement between the experimental and theoretical values. Also, it has been seen that capacitance almost show a plateau up to a certain value of frequency, after which, the capacitance decreases. The higher values of capacitance at low frequencies were attributed to the excess capacitance resulting from the interface states in equilibrium with the p‐InP that can follow the a.c. signal. The interface state density N_ss and relaxation time τ of the structure were determined from C–f characteristics. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1572–1579, 2006     

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.     

Stability of copper(II) complexes with cellulose complexite in water-dioxane mixtures

The complexing properties of cellulose complexite with respect to copper(II) ions in water-1,4-dioxane (DO) mixtures are determined. The stoichiometry and stability constants of copper(II) complexes with the hydroxamic groups of the polymer are determined. The equilibrium speciation diagrams for the complexes at pH 2.0–6.0 are plotted; stereochemical configurations are suggested. The effect of the solvation parameters of the complexite on complex formation is analyzed.     

Numerical and experimental investigation of burner device for anode gas reburning

A complex numerical and experimental investigation of burner devices for a reburning of the anode gas of aluminum production was carried out. The chosen mathematical model of the processes of aerodynamics, heat exchange, and gas burning was identified and adapted on the basis of data of real-scale measurements. Basing on computational experiments the optimization of the design of elements of the system for anode gas detoxication and transport was carried out. A new system was proposed and tested for reburning the anode gases of electrolysis production, which consists of an improved burner device and a dust-sedimenting chamber with a possibility of regulating the amount of gas suction.     

Chaotic buffering and its mathematical models

We propose a general idea of obtaining different chains of coupled oscillators with chaotic buffering. As examples, we consider chains of diffusively coupled generalized cubic Schrödinger equations and nonlinear telegraph equations. We also give examples of systems that have an infinite-dimensional chaotic attractor.     

Depolymerization of chitin and chitosan in the course of base deacetylation

Depolymerization of chitin and chitosan in the course of deacetylation in an alkaline medium was studied, and the influence exerted on the process by the nature and concentration of the alkali (NaOH, KOH) and salts (NaCl, NaI, KI) was examined.