Visible light-induced synthesis of polysulfone-based graft copolymers by a grafting from approach

The synthesis of polysulfone (PSU) graft copolymers by a two-step “grafting from” approach is described. First, a chlorofunctional PSU (PSU-Cl) is formed via chloromethylation of a commercial PSU. The formed polymers are used macroinitiator for the dimanganese decacarbonyl assisted free-radical polymerization of tert-butyl acrylate, methyl methacrylate, and styrene to give the desired graft copolymers. Moreover, amphiphilic graft copolymers are also formed via posthydrolyzation of poly(tert-butyl acrylate) containing graft copolymers. The intermediates at various stages and the ultimate graft copolymers are characterized by various analysis techniques. © 2020 Wiley Periodicals, Inc. J. Polym. Sci. 2020 , 58, 412–416     

Kinetic modeling of Fischer–Tropsch-to-olefins process via advanced optimization

The reaction kinetics of a Fischer–Tropsch (FT) process to produce lower olefins was modeled utilizing the experimental data produced using an in-house synthesized iron-based catalyst. Along with FT chain growth reaction that is assumed to follow alkyl mechanism, water–gas shift reaction was also taken into consideration due to its significance. Not only the rate constants but also apparent activation energies were obtained via an integrated approach utilizing multiobjective and constrained nonlinear minimization methods in order to define a model valid at a temperature range instead of a single point. The adaption of a hybrid optimization method utilizing both population- and individual-based techniques enhanced prediction accuracy compared with the case where only multiobjective genetic algorithm is used. Thanks to the developed model, the effect of process parameters on product distribution was investigated. Finally, the kinetic model was compared with Anderson–Schulz–Flory model and the deviations observed were discussed.     

Synthesis and characterization of liquid crystalline unsymmetrically substituted phthalocyanines

The synthesis of unsymmetrically substituted phthalocyanines bearing two p-tolyl-sulfonyl (tosyl)amido and six alkylthio moieties was achieved by cyclotetramerisation of two different phthalonitrile derivatives, namely 1,2-di(alkylthio)-4,5-dicyanobenzene and 4,5-dicyano-N,N′-ditosyl-o-phenylenediamine in the presence of an anhydrous metal salt and strong base. The new compounds were characterized by elemental analyses, UV/Vis, IR, NMR and mass spectra. The mesogenic properties of these new materials were studied by differential scanning calorimetry (DSC) and polarizing optical microscopy. The mesogenic properties of these compounds were compared to that of their symmetric analogous, octaalkythia substituted phthalocyanine derivatives.     

Synthesis and characterization of new mesomorphic octakis(alkylthio)-substituted lead phthalocyanines and their films

The syntheses of new octakis (alkylthio)-substituted phthalocyanines of Pb(II) (1a and 2a) are described. These compounds are very soluble in most common organic solvents. They have been fully characterized using elemental analysis, NMR, infrared and UV–Vis spectroscopy. The mesogenic properties of these new materials were studied by differential scanning calorimetry and optical microscopy. These phthalocyanine derivatives are liquid at room temperature and form columnar-hexagonal (Col_h) mesophases below −10 °C. It has been indicated that the addition of methylene bridges to the phthalocyanine (Pc) core increases the clearing point temperatures. Also, the coordination of Pb²⁺ with the phthalocyanine core decreases the clearing point temperatures and the liquid crystal phase transition temperatures. Thin films of octakis(alkylthio)-substituted Pb(II) phthalocyanines 1a and 2a were prepared by the method of spin-coating. To obtain films with an ordered structure the film of 1a was slowly cooled from room temperature down to −10 °C. Sandwich structures of the form Au/PbPc(1a)/Au were prepared for the investigation of their electrical properties. It was shown that a slowly cooled Au/PbPc(1a)/Au structure demonstrates repeatable and stable electrical switching behaviour for applied bias voltages between −1 V and +1 V.     

A set of highly water-soluble tetraethyleneglycol-substituted Zn(II) phthalocyanines: synthesis, photochemical and photophysical properties, interaction with plasma proteins and in vitro phototoxicity

Three Zn(II) phthalocyanines substituted by hydroxyl-terminated tetraethylene glycol chains have been synthesized. In order to evaluate the potential of these highly water-soluble phthalocyanines as type II-photosensitisers for photodynamic therapy, their structure-activity relationship was assessed by determining relevant photophysical and photochemical properties, such as their aggregation behaviour in aqueous buffers, their fluorescence properties and their efficiency with regard to the generation of singlet oxygen. In addition, evidence for a negligible interaction with plasma proteins in undiluted human plasma was obtained using a recently developed bioanalytical method and compared with the fluorescence quenching approach. These results combined with in vitro data regarding the phototoxicity of these phthalocyanines against HT-29 cancer cells provide evidence for the relevance of the non-peripherally substituted derivative for further in vivo investigations.     

Pre-concentration and determination of 90Sr in radioactive wastes using solid phase extraction techniques

This paper describes the use of IBC??s AnaLig^®Sr-01 molecular recognition technology product to effectively and selectively pre-concentrate, separate and recover strontium from radioactive waste samples. The use and effectiveness of AnaLig^®Sr-01 gel was successfully validated by analysis of International Atomic Energy Agency (IAEA 375) reference soil and National Physical Laboratory (NPL)?CHigh Alpha?CBeta (2003) liquid sample. The second part of this paper focuses on analysis of radioactive waste samples from nuclear power plant A1 Jaslovske Bohunice in Slovak Republic (NPP A1).     

Value-at-risk estimation with wavelet-based extreme value theory: Evidence from emerging markets

This paper introduces wavelet-based extreme value theory (EVT) for univariate value-at-risk estimation. Wavelets and EVT are combined for volatility forecasting to estimate a hybrid model. In the first stage, wavelets are used as a threshold in generalized Pareto distribution, and in the second stage, EVT is applied with a wavelet-based threshold. This new model is applied to two major emerging stock markets: the Istanbul Stock Exchange (ISE) and the Budapest Stock Exchange (BUX). The relative performance of wavelet-based EVT is benchmarked against the Riskmetrics-EWMA, ARMA-GARCH, generalized Pareto distribution, and conditional generalized Pareto distribution models. The empirical results show that the wavelet-based extreme value theory increases predictive performance of financial forecasting according to number of violations and tail-loss tests. The superior forecasting performance of the wavelet-based EVT model is also consistent with Basel II requirements, and this new model can be used by financial institutions as well.     

Direct imaging of localized surface plasmon polaritons

In this Letter, we report on dark field imaging of localized surface plasmon polaritons (SPPs) in plasmonic waveguiding bands formed by plasmonic coupled cavities. We image the light scattered from SPPs in the plasmonic cavities excited by a tunable light source. Tuning the excitation wavelength, we measure the localization and dispersion of the plasmonic cavity mode. Dark field imaging has been achieved in the Kretschmann configuration using a supercontinuum white-light laser equipped with an acoustooptic tunable filter. Polarization dependent spectroscopic reflection and dark field imaging measurements are correlated and found to be in agreement with finite-difference time-domain calculations.     

Anticarcinogenic and antimitotic effects of Turkish propolis and mitomycin-C on tissue cultures of bladder cancer

The in vitro anticarcinogenic and antimitotic effects of propolis and mitomycin-C (MMC) on transitional carcinoma cell cultures were investigated. Tissue samples were obtained from 22 patients with bladder carcinomas, which were exposed to propolis (0.1 mL) and MMC (1.6 microL). The mean MI rates for control, propolis and MMC were 8.327 +/- 0.624, 6.990 +/- 0.519 and 5.423 +/- 0.479, respectively. The differences between the control and exposed cells were significant (p < 0.05). We conclude that exposure to propolis can decrease cell division and it may be used as an antimitotic and anticarcinogenic agent.