Photoinitiated atom transfer radical polymerization: Current status and future perspectives

In macromolecular and material science, atom transfer radical polymerization (ATRP) has intensely influenced the research strategies facilitating fabrication of a wide range of polymers with well‐defined structures and functions and their conjugation with biomolecules. Recently, the required copper (I) catalyst for ATRP process is generated by photoinduced redox reactions involving the in situ reduction of Cu(II) to Cu(I). Photochemically initiated reactions provide several distinct advantages, including temporal and spatial controls, rapid and energy efficient activation. The process is based on photoredox reactions of copper catalysts under various radiation sources with or without various photoinitiators. This Highlight focuses on the historical development, mechanistic aspects, limitations, and opportunities of photoinitiated ATRP along with selected examples. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2878–2888     

Synthesis and characterization of polymer/clay nanocomposites by intercalated chain transfer agent

In situ synthesis of poly(methyl methacrylate) (PMMA) and polystyrene (PS) nanocomposites by free radical polymerization using intercalated chain transfer agent (I-CTA) in the layers of montmorillonite (MMT) clay is reported. MMT clay was ion-exchanged with diethyl octyl ammonium ethylmercaptan bromide, which acts both as suitable intercalant and as chain transfer agent. These modified clays were then dispersed in methyl methacrylate (MMA) or styrene (St) monomers in different loading degrees to carry out the in situ free radical polymerization. The intercalation ability of the chain transfer agent and exfoliated nanocomposite structure were evidenced by both X-ray diffraction spectroscopy (XRD) and transmission electron microscopy (TEM). Thermal properties and morphologies of the resultant nanocomposites were also studied.     

Heavy metal removal from aqueous solution by Pseudevernia furfuracea (L.) Zopf

The present study was carried out in a batch system using a lichen (Pseudevernia furfuracea (L.) Zopf) for the sorption of nickel(II) and copper(II) ions from water. Particularly, the effect of pH, contact time and temperature were considered. Pseudevernia furfuracea exhibited nickel(II) and copper(II) uptake of 49.87 and 60.83 mg/g at an initial pH of 4 and 5-6 at 35 degrees C respectively. Both the Freundlich and Langmuir adsorption models were suitable for describing the biosorption of nickel(II) and copper(II) by the biosorbent. Biosorption showed pseudo first order rate kinetics for nickel and copper ions. Using the equilibrium constant values obtained at 25 and 35 degrees C, the thermodynamics properties of the biosorption (deltaG degrees, deltaH degrees and deltaS degrees) were determined. The biosorption of nickel(II) and copper(II) onto Pseudevernia furfuracea was found to be endothermic.     

Synthesis, photophysical and photochemical properties of poly(oxyethylene)-substituted zinc phthalocyanines

The synthesis, photophysical and photochemical properties of the tetra- and octa-poly(oxyethylene)substituted zinc (II) phthalocyanines are reported for the first time. The new compounds have been characterized by elemental analysis, IR, 1H and 13C NMR spectroscopy, electronic spectroscopy and mass spectra. General trends are described for photodegradation, singlet oxygen, triplet state and fluorescence quantum yields, and triplet and fluorescence lifetimes of these compounds in dimethylsulfoxide (DMSO). Photophysical and photochemical properties of phthalocyanine complexes are very useful for PDT applications. The effects of the substituents on the photophysical and photochemical parameters of the zinc(II) phthalocyanines (3a, 5a and 6a) are also reported. The singlet oxygen quantum yields (Phi(Delta)), which give an indication of the potential of the complexes as photosensitizers in applications where singlet oxygen is required (Type II mechanism) ranged from 0.60 to 0.72. Thus, these complexes show potential as Type II photosensitizers. The fluorescence of the complexes was quenched by benzoquinone (BQ).     

Investigation of structural,electronic and optical properties of pure and Ag‐doped TiO2 nanofibers fabricated by electrospinning

Pure and 1, 2, and 3 wt% Ag doped TiO₂ nanofibers were prepared by electrospinning method at different applied voltages and heights at a constant flow rate of 2 mL/h. Characterization of the prepared samples was performed by x‐ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microcopy (AFM),four point probe method (FPPM), the differential scanning calorimetry/the thermal gravimetric analysis (DSC/TGA), ultraviolet/visible spectrometry (UV/VIS), and energy dispersive X‐ray spectrometer (EDX). It was found that the thermally untreated pure TiO₂ nanofibers and thermally treated (at 500 °C) samples have the crystalline phase of anatase (A), and mixed anatase and rutile (A+R) phases, respectively. It was also observed that the content of the silver does not affect the crystal structure, but plays strengthening role in the rutile structure. SEM micrographs showed that all fabricated nanofiber samples have uniform morphologies, and AFM measurements indicated that the nanofibers were formed in three‐dimensional coils. The band gap values of the nanofiber samples obtained from UV/VIS measurements revealed that band gap values of the nanofiber samples decrease while the diameter of the nanofiber increases.     

Exploration of the superconducting properties of Y3Ba5Cu8O18 with and without Ca doping by magnetic measurements

The superconducting Y₃Ba₅Cu₈O₁₈ (Y-358) and Y₃Ba₅Ca₂Cu₈O₁₈ (YCa-358) compounds have been synthesized by using the sol–gel method. Hence, the influence of doping of Ca into the compound Y-358 has been studied by comparing the resistivities, DC magnetizations both M(H) and M(T),flux pinning properties, AC susceptibilities and critical current densities of the undoped and doped compounds, at low temperatures. The AC susceptibility and resistivity measurements showed that the superconducting transition temperature, T_c, is suppressed (about 6 K) with the addition of Ca into the main compound. The hysteresis loops of YCa-358 show peak like projecting parts at temperatures below 45 K and around zero applied field that may be due to the local modulation of the composition in YCa-358. Such a behavior has been observed for the first time. The critical current densities, J_c, determined from the hysteresis measurements decrease with the addition of Ca into Y-358. At 15 K, the maximum values of J_c, for the compounds Y-358 and YCa-358 are found to be 8 × 10⁴ A/cm² and 4.5 × 10⁴ A/cm², respectively. The flux pinning force, F_p, calculated from the field dependence of the J_c values shows that the irreversibility line shifts to lower magnetic fields with the doping of Ca into Y-358. Furthermore, the measurements of the inphase and out off components of the ACsusceptibilities clearly demonstrate that the superconducting volume fraction of Y-358 decreases with the addition of Ca.     

Quenched Free Energy and Large Deviations for Random Walks in Random Potentials

We study quenched distributions on random walks in a random potential on integer lattices of arbitrary dimension and with an arbitrary finite set of admissible steps. The potential can be unbounded and can depend on a few steps of the walk. Directed, undirected, and stretched polymers, as well as random walk in random environment, are covered. The restriction needed is on the moment of the potential, in relation to the degree of mixing of the ergodic environment. We derive two variational formulas for the limiting quenched free energy and prove a process‐level quenched large deviation principle (LDP) for the empirical measure. As a corollary we obtain LDPs for types of random walks in random environments not covered by earlier results. © 2012 Wiley Periodicals, Inc.     

Poly(propylene imine) dendrimers as hydrogen donor in Type II photoinitiated free radical polymerization

Three generations of poly(propylene imine) dendrimers, namely (PPI-16, PPI-32 and PPI-64; 16, 32 and 64 for generations 3, 4 and 5, respectively) were used as hydrogen donors in photoinitiated free radical polymerization of methyl methacrylate by using one of the following photosensitizers; benzophenone and thioxanthone. The effect of generation number of the dendrimer on photoinitiation efficiency and molecular weight of the resulting polymers was investigated. Glass transition temperatures and particle size measurements of the resulting polymers indicated the presence of nearly stretched polymer chains around the dendrimers. The location of hydrogen donating sites was evaluated by photolysis studies in the absence of monomer by using a stable radical namely, 2,2,6,6-tetramethylpiperidine-N-oxyl free radical (TEMPO) and showed that hydrogen abstraction occurs from the inner tertiary amino groups. The TEMPO attached dendrimers were further used in the nitroxide mediated radical polymerization (NMP) of styrene to yield star polymers.     

Polymer/clay nanocomposites through multiple hydrogen‐bonding interactions

An 2‐ureido‐4[1H]pyrimidinone (UPy) motif with self‐association capability (through quadruple hydrogen bonds) was successfully anchored onto montmorillonite clay layers. Polymer/clay nanocomposites were prepared by specific hydrogen bonding interactions between surface functionalized silica nanoclays and UPy‐bonded supramolecular poly(ethylene glycol) or poly(?‐caprolactone). The mixed morphologies including intercalated layers with a non‐uniform separation and exfoliated single layers isolated from any stack were determined by combined X‐ray diffraction and transmission electron microscopic measurements. Thermal analyses showed that all nanocomposites had higher decomposition temperatures and thermal stabilities compared with neat polymer. The differential scanning calorimetric data implied that the crystallinity of polymers did not show essential changes upon introduction of organomodified UPy clays. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 650–658     

In situ synthesis of A3‐type star polymer/clay nanocomposites by atom transfer radical polymerization

A series of A₃‐type star poly(methylmethacrylate)/clay nanocomposites is prepared by in situ atom transfer radical polymerization (ATRP) initiated from organomodified montmorillonite containing quaternary trifunctional ATRP initiator. The first order kinetic plot shows a linear behavior, indicating the controlled character of the polymerization. The resulting nanocomposites are characterized by spectroscopic (XRD), thermal (DSC and TGA), and microscopic (TEM) analyses. The exfoliated nanocomposite has been obtained when polymerization was conducted with 1% of organic clay loading. Thermal analyses show that all nanocomposites have higher glass transition values and thermal stabilities compared to neat polymer. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 5257–5262