A. Karantonis

Study of corrosion of copper in industrial cooling systems

Purpose – The purpose of this paper is to perform the evaluation of copper susceptibility to corrosion in industrial cooling systems. Microstructure and defects of copper are observed, while divergences from optimum structure are discussed. Design/methodology/approach – Various types of corrosion are examined. Electrochemical techniques such as electrochemical impedance spectroscopy and potentiodynamic polarisation are applied in these materials, using corrosion inhibitors. Microscopic observations and electrochemical measurements are interpreted according to possible mechanistic scenarios. Findings – It is evident that, under specific conditions (e.g. high pH), water cooling ingredients can enhance corrosion, leading to significant copper mass loss from the inner surface of the pipe and thus leading to failure. Originality/value – Evaluation of copper corrosion in cooling industrial systems was done, as well as studies of copper corrosion in sodium chloride.

Direct electron transfer of lytic polysaccharide monooxygenases (LPMOs) and determination of their formal potentials by large amplitude Fourier transform alternating current cyclic voltammetry

MtLPMO9 and FoLPMO9 are two lytic polysaccharide monooxygenases (LPMOs), from the filamentous fungi Thermothelomyces thermophila and Fusarium oxysporum, respectively. In the present study an attempt has been made to achieve direct electron transfer between these enzymes and a glassy carbon electrode by immobilization in Nafion polyelectrolyte. The method used to ascertain the feasibility of direct electron transfer was large amplitude Fourier transform alternating current voltammetry (FTacV) and the formal potentials of these enzymes were determined at different temperatures. The findings of this paper indicate that LPMOs can be studied by direct electron transfer, which could be exploited in the near future for their biochemical characterization.

Kinetic and amperometric study of the MtPerII peroxidase isolated from the ascomycete fungus Myceliophthora thermophila

The enzyme MtPerII is a new peroxidase which has been isolated only recently from fungus Myceliophthora thermophila and has significant thermostability and stability at high H2O2 concentrations. In the present work, an electrochemical kinetic study, based on cyclic voltammetry, is performed for the first time for the catalytic decomposition of H2O2 by MtPerII, at 18°C. Leuco methylene blue (LMB) is used as a mediator and the catalytic and Michaelis constants are determined, assuming a Michaelis-Menten mechanism. Experimental evidence suggest the absence of inhibition by H2O2, for concentrations up to 16mM, and increasing catalytic activity for temperatures up to 50°C. Moreover, a modified electrode is constructed, by attempting the entrapment of MtPerII on a dodecanothiol self-assembled monolayer on gold. The modified electrode is studied chronoamperometrically in solutions containing methylene blue mediator and different concentrations of H2O2. It is shown that adsorbed MtPerII retains its activity and the modified electrode exhibits a considerably high linear region for the detection of H2O2. The experimental findings indicate that MtPerII is a new candidate for analytical and industrial applications.

Effect of lignin fractions isolated from different biomass sources on cellulose oxidation by fungal lytic polysaccharide monooxygenases

BackgroundLytic polysaccharide monooxygenases (LPMOs) are copper-dependent enzymes that oxidatively cleave recalcitrant lignocellulose in the presence of oxygen or hydrogen peroxide as co-substrate and a reducing agent as electron donor. One of the possible systems that provide electrons to the LPMOs active site and promote the polysaccharide degradation involves the mediation of phenolic agents, such as lignin, low-molecular-weight lignin-derived compounds and other plant phenols. In the present work, the interaction of the bulk insoluble lignin fraction extracted from pretreated biomass with LPMOs and the ability to provide electrons to the active site of the enzymes is studied.ResultsThe catalytic efficiency of three LPMOs, namely MtLPMO9 with C1/C4 regioselectivity, PcLPMO9D which is a C1 active LPMO and NcLPMO9C which is a C4 LPMO, was evaluated in the presence of different lignins. It was correlated with the physicochemical and structural properties of lignins, such as the molecular weight and the composition of aromatic and aliphatic hydroxyl groups. Moreover, the redox potential of lignins was determined with the use of large amplitude Fourier Transform alternating current cyclic voltammetry method and compared to the formal potential of the Cu (II) center in the active site of the LPMOs, providing more information about the lignin-LPMO interaction. The results demonstrated the existence of low-molecular weight lignin-derived compounds that are diffused in the reaction medium, which are able to reduce the enzyme active site and subsequently utilize additional electrons from the insoluble lignin fraction to promote the LPMO oxidative activity. Regarding the bulk lignin fractions, those isolated from the organosolv pretreated materials served as the best candidates in supplying electrons to the soluble compounds and, finally, to the enzymes. This difference, based on biomass pretreatment, was also demonstrated by the activity of LPMOs on natural substrates in the presence and absence of ascorbic acid as additional reducing agent.ConclusionsLignins can support the action of LPMOs and serve indirectly as electron donors through low-molecular-weight soluble compounds. This ability depends on their physicochemical and structural properties and is related to the biomass source and pretreatment method.

Encapsulation of Antifouling Organic Biocides in Poly(lactic acid) Nanoparticles

The scope of the current research was to assess the feasibility of encapsulating three commercial antifouling compounds, Irgarol 1051, Econea and Zinc pyrithione, in biodegradable poly(lactic acid) (PLA) nanoparticles. The emulsification–solvent evaporation technique was herein utilized to manufacture nanoparticles with a biocide:polymer ratio of 40%. The loaded nanoparticles were analyzed for their size and size distribution, zeta potential, encapsulation efficiency and thermal properties, while the relevant physicochemical characteristics were correlated to biocide–polymer system. In addition, the encapsulation process was scaled up and the prepared nanoparticles were dispersed in a water-based antifouling paint in order to examine the viability of incorporating nanoparticles in such coatings. Metallic specimens were coated with the nanoparticles-containing paint and examined regarding surface morphology.

Electrochemical resonance under harmonic current perturbations and chaotic potential perturbations

The resonating properties of the electrochemical interface are studied under harmonic perturbations in galvanostatic control and under chaotic perturbations in potentiostatic control. The resonance conditions in galvanostatic control are derived analytically and explored numerically. The theoretical findings are confirmed experimentally for the Ni | 1 M H2SO4 system. The implementation of a Rössler and a Chua chaotic perturbation to an electrochemical resonator is explored numerically. It is shown that the electrochemical resonator acts effectively as a band pass filter thus enhancing the periodicity of the chaotic input.