Specifically designed nanofibers enriched with chemically active nanoparticles, capable of destruction of chemical warfare agents (CWA's) and other toxic chemicals are highly desirable for the incorporation in personal protective equipment and decontamination items. In this work, we prepared six types of nanofibrous materials, based on the two types of polymers, polyvinylchloride (PVC) and polyvinylbutyral (PVB). As carriers of active chemistry, nanoparticles of cerium-dioxide (CeO2) and zirconium(IV)hydroxide (Zr(OH)4) were used. The morphology of the samples obtained and their qualitative chemical composition was investigated by scanning electron microscopy (SEM). The degradation ability of the nanofibrous mats was firstly investigated in an aqueous environment, over wide range of buffered pH conditions, using spectrophotometric method and paraoxon-ethyl as a model compound. A rather slow, but significant degradation of paraoxon-ethyl was observed on nanofibers which contained CeO2 nanoparticles in neutral conditions. The sulphur mustard (HD) adsorption was investigated in non-aqueous environment using GC-MS method. The samples made of PVC exerted strong adsorption of HD with almost six fold reduction in HD concentration but without any degradation of the test compound. In conclusion, nanofibers obtained showed strong adsorption ability in non-polar solvents, but further modification of CeO2 and Zr(OH)4 nanoparticles are necessary to enhance their CWA degradation ability.
Organophosphorous chemical warfare agents (i.e., nerve agents) exhibit toxic effects mainly through covalent, irreversible inhibition of acetylcholinesterase (EC 3.1.1.7), an enzyme that terminates cholinergic neurotransmission, by hydrolyzing acetylcholine at nerve and nerve-muscle junctions. Use of nerve agents is strictly limited to research purposes only and it is under control of Organisation for the Prohibition of Chemical Weapons, OPCW. Despite all efforts to limit the use of nerve agents, unfortunately the danger of nerve agents being used in war aggression and terrorist attacks is still present. The reversible inhibition of AChE was suggested as the pre-treatment option against nerve agents' intoxications. Aiming to investigate novel pre-treatment options, we designed and synthesized the four novel compounds of tacrine and aroylacrylic acid phenylamide moieties, connected via a long methylene chain to target two distinct topologically separated anionic areas on the AChE. The inhibitory activity of the compounds toward the Electric eel AChE's as well as the horse serum BChE was determined by Ellman assay. The designed compounds may represent a new class of promising leads for developing more effective pre-treatment options.
Biochar has emerged as a highly attractive, sustainable support for enzyme immobilization, with dual benefits: valorization of available lignocellulosic waste and use as a stable, porous matrix for enzyme binding. This study investigated acid-modified sour cherry stone biochar (SCBM) as support for two laccases of different origins: crude laccase (Bjerkandera adusta TMF1 (CL)) and purified commercial laccase (Trametes versicolor (TvL)). The aim was to compare immobilization efficiency, activity retention and Brilliant Green (BG) decolorization in batch and air-lift reactors (ALRs). Immobilization of crude (SCBM-CL) and commercial (SCBM-TvL) laccase was successfully achieved and confirmed by SEM-EDX and FTIR-ATR analyses. Under optimized batch conditions, SCBM-TvL achieved approximately 92% of BG removal within 4 h and maintained high catalytic activity over nine consecutive cycles, whereas SCBM-CL reached almost 66% removal, with a progressive loss of activity upon reuse. In the ALR, using a 25-fold lower biochar-to-solution ratio, SCBM-TvL achieved almost complete BG decolorization within 4 h, while SCBM-CL achieved 57% within the same time. After treatment, BG solution exhibited a phytostimulatory effect, no antimicrobial activity, and 87% COD reduction, indicating reduced toxicity and organic load after enzyme treatment. Furthermore, the BG decolorization achieved by SCBM-TvL in ALRs highlights the economic advantage of this system and supports its potential for further scale-up.