The main goal of this experimental work is screening of different natural and synthetic nanomaterials and biopolymers that may improve elimination of stable micropollutants from water phase. In this work, as a target chemical acting as the micropollutant molecule, the Brilliant Blue (BB) dye was selected. We tested different active matrices dispersed in water phase including activated carbon (AC), lyophilized graphene oxide (GO), β-cyclodextrin (CD), raw dandelion pappus (DP), microcrystalline cellulose(MC), and raw pine pollen (PP), as well as two types of Egyptian Blue mineral pigments (EB1 and EB2). Graphene oxide and Egyptian Blue nanomaterials were synthesized in our laboratory. We investigated potential application of such nanoparticles and biopolymer conglomerates as additives that may tune the activated sludge (AS) microorganisms or duckweed water plant (DW) and increase efficiency of micropollutants removal from wastewater. Studied nanomaterials/biopolymers were used in two different experimental modes involving real activated sludge microorganisms (24 h experiment) as well as duckweed plant (16 day experiment). Quantitative data of BB were obtained using microfluidic type device based on micro-TLC plate. This approach enabled direct determination of target component without sample pre-treatment like pre-concentration or pre-purification. Within single analytical run calibration line, retention standard spots (methyl red) and multiple samples were analyzed simultaneously. Due to the multivariate nature of these experiments, quantitative data were explored with chemometric tools including AHC (agglomerative hierarchical clustering), PCA (principal component analysis), and FA (factor analysis). Experimental data and multivariate calculations revealed that BB is strongly resistant on biodegradation, however, inclusion complexes formation with β-cyclodextrinmay induce degradation of this dye in the presence of duckweed. It is hoped that results of our experimental work can be used for designing of future experiments for fast screening of different additives and improvement of technological processes, focusing on purification of sewage and water from micropollutants.

This research communication significantly extends our previous studies focusing on the temperature effects related to the unexpected chromatographic behavior of 1-acenaphthenol in the presence of native β-cyclodextrin (β-CD) additive, working under thin-layer chromatographic (TLC) conditions. We have applied complementary and orthogonal techniques including (i) temperature-controlled ultraviolet-visible (UV-VIS) spectroscopy, (ii) thermostated microplanar high-performance chromatography (micro-HPTLC) and (iii) temperature-dependent inclusion chromatography based on high-performance liquid chromatography (HPLC) to investigate the retention behavior of related host molecules. Particularly, various symmetric and asymmetric molecules were tested, such as: naphthalene and its derivatives including acenaphthylene, acenaphthene and selected dimethynaphthalenes: 1,8-DMN, 1,5-DMN, 2,3-DMN and 2,6-DMN. Reported raw experimental data, particularly performed in liquid phase and detected by UV-Vis spectrophotometry, may suggest that solubility changes of the supramolecular complexes studied and differences in total analysis time between TLC and HPLC separation can trigger strong retention of target components in planar chromatographic systems. This was also supported by principal component analysis (PCA) of the multi-source data obtained. It is hoped that the reported analyses enable the adjustment of phenomenological models describing liquid chromatography retention and the solubility behavior of low-molecular mass guest molecules, controlled by supramolecular interactions with selected macrocycles. It should be noted that the reported phenomenon, specifically supramolecular complexes precipitation, may have a number of practical applications. This can be used to improve the efficiency and selectivity of planar and/or microfluidic systems. On the other hand, precipitation via host-guest interactions may be applied for highly selective water purification technological processes that will be designed for the removal of given organic micropollutants.