New Phenomena in Organometallic‐Mediated Radical Polymerization (OMRP) and Perspectives for Control of Less Active Monomers

The impact of reversible bond formation between a growing radical chain and a metal complex (organometallic‐mediated radical polymerization (OMRP) equilibrium) to generate an organometallic intermediate/dormant species is analyzed with emphasis on the interplay between this and other one‐electron processes involving the metal complex, which include halogen transfer in atom transfer radical polymerization (ATRP), hydrogen‐atom transfer in catalytic chain transfer (CCT), and catalytic radical termination (CRT). The challenges facing the controlled polymerization of “less active monomers” (LAMs) are outlined and, after reviewing the recent achievements of OMRP in this area, the perspectives of this technique are analyzed.     

Fluoroalkyl Radical Generation by Homolytic Bond Dissociation in Pentacarbonylmanganese Derivatives

Thermal decarbonylation of the acyl compounds [Mn(CO)₅(COR_F)] (R_F=CF₃, CHF₂, CH₂CF₃, CF₂CH₃) yielded the corresponding alkyl derivatives [Mn(CO)₅(R_F)], some of which have not been previously reported. The compounds were fully characterized by analytical and spectroscopic methods and by several single-crystal X-ray diffraction studies. The solution-phase IR characterization in the CO stretching region, with the assistance of DFT calculations, has allowed the assignment of several weak bands to vibrations of the [Mn(¹²CO)₄(eq-¹³CO)(R_F)] and [Mn(¹²CO)₄(ax-¹³CO)(R_F)] isotopomers and a ranking of the R_F donor power in the order CF₃<CHF₂<CH₂CF₃≈CF₂CH₃. The homolytic Mn−R_F bond cleavage in [Mn(CO)₅(R_F)] at various temperatures under saturation conditions with trapping of the generated R_F radicals by excess tris(trimethylsilyl)silane yielded activation parameters ΔH^≠ and ΔS^≠ that are believed to represent close estimates of the homolytic bond dissociation thermodynamic parameters. These values are in close agreement with those calculated in a recent DFT study (J. Organomet. Chem. 2018 , 864, 12–18). The ability of these complexes to undergo homolytic Mn−R_F bond cleavage was further demonstrated by the observation that [Mn(CO)₅(CF₃)] (the compound with the strongest Mn−R_F bond) initiated the radical polymerization of vinylidene fluoride (CH₂=CF₂) to produce poly(vinylidene fluoride) in good yields by either thermal (100 °C) or photochemical (UV or visible light) activation.     

Isolation of Bisphenol A-Tolerating/degrading Shewanella haliotis Strain MH137742 from an Estuarine Environment

Applied Biochemistry and Biotechnology - The human exposure to bisphenol A (BPA) occurs frequently. Once, this compound was one of the highest volume chemicals produced worldwide and used as a...     

Elektrolytische Bestimmungen und Trennungen

Ohne Zusammenfassung     

Spectrofluorimetric Method for the Determination of Aluminum with Alizarin Red PS

 A simple and direct spectrofluorimetric method has been developed for the determination of aluminum using alizarin red PS (1,2,4-trihydroxy 9,10-anthraquinone-3-sulfonic acid). The method is based on the strong fluorescence (480/564 nm) of Al³⁺ and alizarin red. Experimental parameters such as pH, concentration of the ligand, ionic strength of the solution, reaction time and temperature were optimized in order to maximize the analytical signal. Interferences of several ions (anions and cations) were studied and evaluated. The linear range of the method extends from 3 to 100 μg L⁻¹. Limit of detection (3s_b) was 0.9 μg L⁻¹. The method was tested with a silicate certified reference material. Interferences were eliminated by a liquid extraction with cupferron. Author for correspondence. E-mail: aucelior@rdc.puc-rio.br Received September 10, 2002; accepted January 15, 2003 Published online May 5, 2003     

Impact of photodepletion to amplified spontaneous emission of proton-transfer dyes in polymeric matrices

A six level rate equation system was used to investigate the impact of photodepletion to amplified spontaneous emission (ASE) of intramolecular proton-transfer (IPT) dyes incorporated into polymeric hosts. The model includes the most important transitions for the normal and tautomer form of the molecule as well as intersystem crossing and triplet–triplet transitions. The experimentally observed pulse shape as well as photodepletion phenomena, i.e. a first order exponential decay of the ASE intensity and a shortening in ASE pulse width, have been simulated successfully. Additionally, the model was used to propose an explanation of the unexpected high photodepletion of proton-transfer dyes in solids. The results show that the emission cross section and reabsorption cross section of the tautomer form of the molecule are the most important parameter not only for efficiency but also for photodepletion. The model was tested by comparison with experimental results of 2-(2’-hydroxyphenyl)benzimidazole in polymethylmethacrylate (PMMA), polystyrene (PS) and a 1:1 alternating copolymer matrix PS-co-PMMA. PACS 78.45.th; 42.55.Mv; 42.70.Jk     

Electrochemical impedance spectroscopy and linear polarization applied to evaluation of porosity of phosphate conversion coatings on electrogalvanized steels

In this work, electrochemical impedance spectroscopy and linear polarization are used in determining porosity of zinc phosphates, and of nickel and manganese modified zinc phosphates on electrogalvanized steel. The porosity of the phosphate layers ranges from 0.1% for the manganese-modified hopeite to 8% for hopeite, using the linear polarization and the electrochemical impedance spectroscopy techniques. The porosity values measured using the two techniques were in agreement. All impedance spectra of coated samples showed two steps, with two capacitive arcs and an inductive looping.     

Estimates for the Poisson kernel and Hardy spaces on compact manifolds

We study Hardy spaces on the boundary of a smooth open subset or Rn and prove that they can be defined either through the intrinsic maximal function or through Poisson integrals, yielding identical spaces. This extends to any smooth open subset of Rn results already known for the unit ball. As an application, a characterization of the weak boundary values of functions that belong to holomorphic Hardy spaces is given, which implies an F. and M. Riesz type theorem.     

On the optimization of the initial boundary value problem for a conservation law

In the present note, the theory of shift differentiability for the Cauchy problem is extended to the case of an initial boundary value problem for a conservation law. This result allows to exhibit an Euler-Lagrange equation to be satisfied by the extrema of integral functionals defined on the solutions of initial boundary value problems of this kind.