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The Influence of Salt Anions on Heavy Metal Ion Adsorption on the Example of Nickel

2018, Mende, Mandy, Schwarz, Dana, Steinbach, Christine, Boldt, Regine, Schwarz, Simona

The biodegradable polysaccharide chitosan possesses protonated and natural amino groups at medium pH values and has therefore been used as an adsorbing material for nickel salts in water treatment. Nickel is a problematic heavy metal ion which can cause various diseases and disorders in living organisms. Here, we show the influence of oxyanions (e.g., nitrate and sulfate) to the adsorption of nickel ions. Hence, simultaneously we are addressing the increasing global problem of nitrate and sulfate ion pollution in groundwater and surface water. A series of adsorption experiments was carried out in order to determine (i) the adsorption equilibrium, (ii) the adsorption capacity in dependence on the initial nickel ion concentration, and (iii) the influence of the anion presented in solution for the adsorption capacity. Surface morphology of chitosan flakes before and after the adsorption process has been studied with SEM-EDX analysis. The chitosan flakes exhibited promising adsorption capacities of 81.9 mg·g−1 and 21.2 mg·g−1 for nickel (sulfate) and nickel (nitrate), respectively. The calculated values of Gibbs free energy change ΔG0 confirm the higher adsorption of nickel ions in presence of sulfate ions. Hence, higher anion valence leads to a higher adsorption capacity.

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Further Enhancement of Mechanical Properties of Conducting Rubber Composites Based on Multiwalled Carbon Nanotubes and Nitrile Rubber by Solvent Treatment

2018, Keinänen, Pasi, Das, Amit, Vuorinen, Jyrki

Post-treatment removal of dispersion agents from carbon nanotube/rubber composites can greatly enhance the mechanical properties by increasing the filler–matrix interaction. In this study, multiwall carbon nanotubes (MWNT) were dispersed in water by sonication and nonionic surfactant, octyl-phenol-ethoxylate was used as a dispersion agent. The dispersed MWNTs were incorporated in thermo-reactive acrylonitrile butadiene rubber (NBR) latex and nanocomposite films were prepared by solution casting. As a post-treatment, the surfactant was removed with acetone and films were dried in air. Dispersion quality of the colloid before casting was determined, and mechanical, electrical and thermal properties of the composites before and after the acetone post-treatment were studied. It was found that removal of dispersion agent increased the storage modulus of films between 160–300% in all samples. Relative enhancement was greater in samples with better dispersion quality, whereas thermal conductivity changed more in samples with smaller dispersion quality values. Electrical properties were not notably affected.

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Preparation of Polymer Electrolyte Membranes via Radiation-Induced Graft Copolymerization on Poly(ethylene-alt-tetrafluoroethylene) (ETFE) Using the Crosslinker N,N′-Methylenebis(acrylamide)

2018, Ke, Xi, Drache, Marco, Gohs, Uwe, Kunz, Ulrich, Beuermann, Sabine

Polymer electrolyte membranes (PEM) prepared by radiation-induced graft copolymerization are investigated. For this purpose, commercial poly(ethylene-alt-tetrafluoroethylene) (ETFE) films were activated by electron beam treatment and subsequently grafted with the monomers glycidyl methacrylate (GMA), hydroxyethyl methacrylate (HEMA) and N,N′-methylenebis(acrylamide) (MBAA) as crosslinker. The target is to achieve a high degree of grafting (DG) and high proton conductivity. To evaluate the electrochemical performance, the PEMs were tested in a fuel cell and in a vanadium redox-flow battery (VRFB). High power densities of 134 mW∙cm−2 and 474 mW∙cm−2 were observed, respectively.

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First Report on Chitin in a Non-Verongiid Marine Demosponge: The Mycale euplectellioides Case

2018, Żółtowska-Aksamitowska, Sonia, Shaala, Lamiaa A., Youssef, Diaa T.A., Elhady, Sameh S., Tsurkan, Mikhail V., Petrenko, Iaroslav, Wysokowski, Marcin, Tabachnick, Konstantin, Meissner, Heike, Ivanenko, Viatcheslav N., Bechmann, Nicole, Joseph, Yvonne, Jesionowski, Teofil, Ehrlich, Hermann

Sponges (Porifera) are recognized as aquatic multicellular organisms which developed an effective biochemical pathway over millions of years of evolution to produce both biologically active secondary metabolites and biopolymer-based skeletal structures. Among marine demosponges, only representatives of the Verongiida order are known to synthetize biologically active substances as well as skeletons made of structural polysaccharide chitin. The unique three-dimensional (3D) architecture of such chitinous skeletons opens the widow for their recent applications as adsorbents, as well as scaffolds for tissue engineering and biomimetics. This study has the ambitious goal of monitoring other orders beyond Verongiida demosponges and finding alternative sources of naturally prestructured chitinous scaffolds; especially in those demosponge species which can be cultivated at large scales using marine farming conditions. Special attention has been paid to the demosponge Mycale euplectellioides (Heteroscleromorpha: Poecilosclerida: Mycalidae) collected in the Red Sea. For the first time, we present here a detailed study of the isolation of chitin from the skeleton of this sponge, as well as its identification using diverse bioanalytical tools. Calcofluor white staining, Fourier-transform Infrared Spcetcroscopy (FTIR), electrospray ionization mass spectrometry (ESI-MS), scanning electron microscopy (SEM), and fluorescence microscopy, as well as a chitinase digestion assay were applied in order to confirm with strong evidence the finding of a-chitin in the skeleton of M. euplectellioides. We suggest that the discovery of chitin within representatives of the Mycale genus is a promising step in their evaluation of these globally distributed sponges as new renewable sources for both biologically active metabolites and chitin, which are of prospective use for pharmacology and biomaterials oriented biomedicine, respectively.

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Enhanced Interfacial Shear Strength and Critical Energy Release Rate in Single Glass Fiber-Crosslinked Polypropylene Model Microcomposites

2018, Gohs, Uwe, Mueller, Michael Thomas, Zschech, Carsten, Zhandarov, Serge

Continuous glass fiber-reinforced polypropylene composites produced by using hybrid yarns show reduced fiber-to-matrix adhesion in comparison to their thermosetting counterparts. Their consolidation involves no curing, and the chemical reactions are limited to the glass fiber surface, the silane coupling agent, and the maleic anhydride-grafted polypropylene. This paper investigates the impact of electron beam crosslinkable toughened polypropylene, alkylene-functionalized single glass fibers, and electron-induced grafting and crosslinking on the local interfacial shear strength and critical energy release rate in single glass fiber polypropylene model microcomposites. A systematic comparison of non-, amino-, alkyl-, and alkylene-functionalized single fibers in virgin, crosslinkable toughened and electron beam crosslinked toughened polypropylene was done in order to study their influence on the local interfacial strength parameters. In comparison to amino-functionalized single glass fibers in polypropylene/maleic anhydride-grafted polypropylene, an enhanced local interfacial shear strength (+20%) and critical energy release rate (+80%) were observed for alkylene-functionalized single glass fibers in electron beam crosslinked toughened polypropylene.

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Complexing Methylene Blue with Phosphorus Dendrimers to Increase Photodynamic Activity

2017, Dabrzalska, Monika, Janaszewska, Anna, Zablocka, Maria, Mignani, Serge, Majoral, Jean Pierre, Klajnert-Maculewicz, Barbara

The efficiency of photodynamic therapy is limited mainly due to low selectivity, unfavorable biodistribution of photosensitizers, and long-lasting skin sensitivity to light. However, drug delivery systems based on nanoparticles may overcome the limitations mentioned above. Among others, dendrimers are particularly attractive as carriers, because of their globular architecture and high loading capacity. The goal of the study was to check whether an anionic phosphorus dendrimer is suitable as a carrier of a photosensitizer—methylene blue (MB). As a biological model, basal cell carcinoma cell lines were used. We checked the influence of the MB complexation on its singlet oxygen production ability using a commercial fluorescence probe. Next, cellular uptake, phototoxicity, reactive oxygen species (ROS) generation, and cell death were investigated. The MB-anionic dendrimer complex (MB-1an) was found to generate less singlet oxygen; however, the complex showed higher cellular uptake and phototoxicity against basal cell carcinoma cell lines, which was accompanied with enhanced ROS production. Owing to the obtained results, we conclude that the photodynamic activity of MB complexed with an anionic dendrimer is higher than free MB against basal cell carcinoma cell lines.

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Electrolytic Surface Treatment for Improved Adhesion between Carbon Fibre and Polycarbonate

2018, Kamps, Jan Henk, Henderson, Luke C., Scheffler, Christina, Van der Heijden, Ruud, Simon, Frank, Bonizzi, Teena, Verghese, Nikhil

To achieve good mechanical properties of carbon fibre-reinforced polycarbonate composites, the fibre-matrix adhesion must be dialled to an optimum level. The electrolytic surface treatment of carbon fibres during their production is one of the possible means of adapting the surface characteristics of the fibres. The production of a range of tailored fibres with varying surface treatments (adjusting the current, potential, and conductivity) was followed by contact angle, inverse gas chromatography and X-ray photoelectron spectroscopy measurements, which revealed a significant increase in polarity and hydroxyl, carboxyl, and nitrile groups on the fibre surface. Accordingly, an increase in the fibre-matrix interaction indicated by a higher interfacial shear strength was observed with the single fibre pull-out force-displacement curves. The statistical analysis identified the correlation between the process settings, fibre surface characteristics, and the performance of the fibres during single fibre pull-out testing.

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Unusual Enhancement of Doxorubicin Activity on Co-Delivery with Polyhedral Oligomeric Silsesquioxane (POSS)

2017, Sobierajska, Ewelina, Konopka, Malgorzata, Janaszewska, Anna, Piorecka, Kinga, Blauz, Andrzej, Klajnert-Maculewicz, Barbara, Stanczyk, Maciej, Stanczyk, Wlodzimierz A.

Polyhedral oligomeric silsesquioxane (POSS), bearing eight 3-chloroammoniumpropyl substituents, was studied as a potential nanocarrier in co-delivery systems with doxorubicin (DOX). The toxicity of doxorubicin and POSS:DOX complexes at four different molar ratios (1:1; 1:2, 1:4, 1:8) towards microvascular endothelial cells (HMEC-1), breast cancer cells (MCF-7), and human cervical cancer endothelial cells (HeLa) was determined. The rate of penetration of the components into the cells, their cellular localization and the hydrodynamic diameter of the complexes was also determined. A cytotoxicity profile of POSS:DOX complexes indicated that the POSS:DOX system at the molar ratio of 1:8 was more effective than free DOX. Confocal images showed that DOX co-delivery with POSS allowed for more effective penetration of doxorubicin through the cell membrane. Taking all the results into account, it can be claimed that the polyhedral oligomeric silsesquioxane (T8-POSS) is a promising, complex nanocarrier for doxorubicin delivery.

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Cononsolvency Transition of Polymer Brushes: A Combined Experimental and Theoretical Study

2018, Yong, Huaisong, Rauch, Sebastian, Eichhorn, Klaus-Jochen, Uhlmann, Petra, Fery, Andreas, Sommer, Jens-Uwe

In this study, the cononsolvency transition of poly(N-isopropylacrylamide) (PNiPAAm) brushes in aqueous ethanol mixtures was studied by using Vis-spectroscopic ellipsometry (SE) discussed in conjunction with the adsorption-attraction model. We proved that the cononsolvency transition of PNiPAAm brushes showed features of a volume phase transition, such as a sharp collapse, reaching a maximum decrease in thickness for a very narrow ethanol volume composition range of 15% to 17%. These observations are in agreement with the recently published preferential adsorption model of the cononsolvency effect.

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Why Should the “Alternative” Method of Estimating Local Interfacial Shear Strength in a Pull-Out Test Be Preferred to Other Methods?

2018, Zhandarov, Serge, Mäder, Edith, Gohs, Uwe

One of the most popular micromechanical techniques of determining the local interfacial shear strength (local IFSS, τd) between a fiber and a matrix is the single fiber pull-out test. The τd values are calculated from the characteristic forces determined from the experimental force–displacement curves using a model which relates their values to local interfacial strength parameters. Traditionally, the local IFSS is estimated from the debond force, Fd, which corresponds to the crack initiation and manifests itself by a “kink” in the force–displacement curve. However, for some specimens the kink point is hardly discernible, and the “alternative” method based on the post-debonding force, Fb, and the maximum force reached in the test, Fmax, has been proposed. Since the experimental force–displacement curve includes three characteristic points in which the relationship between the current values of the applied load and the crack length is reliably established, and, at the same time, it is fully determined by only two interfacial parameters, τd and the interfacial frictional stress, τf, several methods for the determination of τd and τf can be proposed. In this paper, we analyzed several theoretical and experimental force–displacement curves for different fiber-reinforced materials (thermoset, thermoplastic and concrete) and compared all seven possible methods of τd and τf calculation. It was shown that the “alternative” method was the most accurate and reliable one, while the traditional approach often yielded the worst results. Therefore, we proposed that the “alternative” method should be preferred for the experimental force–displacement curves analysis.