The influence of magnetic particle incorporation on bisphenol A removal by ß-cyclodextrin-derived sorbent.

A novel, biomass-derived hybrid sorbent Ban-CD-EPI-Fe was successfully synthesized in a coprecipitation method, in which ß-cyclodextrin copolymerized with banana peel extract and epichlorohydrin was grafted onto an iron oxide surface. The composition, presence of functional groups, morphology, thermal stability, and magnetic properties of the obtained material were characterized by Powder X-Ray Diffraction (XRD), X-Ray Photoelectron Spectroscopy (XPS), Fourier Transform Infrared Spectroscopy (FTIR), Scanning Electron Microscopy and Energy Dispersive X-Ray Spectroscopy (SEM-EDS), Thermogravimetric Analysis (TGA), and Physical Properties Measurement System (PPMS). The material bearing around 28% of ß-cyclodextrin units has mesoporous structure with plate-like morphology and active surface area determined by BET and Langmuir models equal to 38.35 and 53.59 m2 g-1, respectively. The sorption studies aimed to remove an endocrine disruptor - bisphenol A (BPA), from water. The results showed that the time evolution could be fitted with pseudo-second kinetic order with a rate constant k equal to 0.05 g mg-1 min-1. According to the Langmuir isotherm, a monolayer is created during BPA sorption, and the maximum sorption capacity was estimated as 93.5 mg g-1. After BPA sorption, the hybrid material could be easily separated by an external magnet and regenerated under mild conditions keeping its recyclability in at least eight cycles.

Photoresponsive Amide-Based Derivatives of Azobenzene-4,4'-Dicarboxylic Acid-Experimental and Theoretical Studies.

Azobenzene derivatives are one of the most important molecular switches for biological and material science applications. Although these systems represent a well-known group of compounds, there remains a need to identify the factors influencing their photochemical properties in order to design azobenzene-based technologies in a rational way. In this contribution, we describe the synthesis and characterization of two novel amides (L1 and L2) containing photoresponsive azobenzene units. The photochemical properties of the obtained compounds were investigated in DMSO by UV-Vis spectrophotometry, as well as 1H NMR spectroscopy, and the obtained results were rationalized via Density Functional Theory (DFT) methods. After irradiation with UV light, both amides underwent trans to cis isomerization, yielding 40% and 22% of the cis isomer of L1 and L2 amides, respectively. Quantum yields of this process were determined as 6.19% and 2.79% for L1 and L2, respectively. The reverse reaction (i.e., cis to trans isomerization) could be achieved after thermal or visible light activation. The analysis of the theoretically determined equilibrium structure of the transition-state connecting cis and trans isomers on the reaction path indicated that the trans-cis interconversion is pursued via the flipping of the substituent, rather than its rotation around the N=N bond. The kinetics of thermal back-reaction and the effect of the presence of the selected ions on the half-life of the cis form were also investigated and discussed. In the case of L1, the presence of fluoride ions sped the thermal relaxation up, whereas the half-life time of cis-L2 was extended in the presence of tested ions.

ß-cyclodextrin-containing polymer based on renewable cellulose resources for effective removal of ionic and non-ionic toxic organic pollutants from water.

A novel, bio-derived cyclodextrin-based trifunctional adsorbent has been successfully synthesized for efficient, rapid and simultaneous removal of a broad-spectrum of toxic ionic (anionic and cationic dyes) and non-ionic organic pollutants from water. The composition, morphology and the presence of functional groups in the obtained sorption material were characterized by elemental analysis, XRD, SEM, and FTIR spectroscopy. The adsorption results were represented by cationic dye (crystal violet, CV) and endocrine disrupting compound (bisphenol A, BPA) as an adsorbate. The sorption processes of the model pollutants were studied with both kinetic and equilibrium models. The results showed that the sorption was rapid (less than 1 min) and the time evolution could be fitted using a pseudo-second order model. According to Langmuir isotherm model, the maximum adsorption capacities were found at 113.64 and 43.10 mg g-1 for BPA and CV, respectively. The adsorption ability of ß-CDPs was kept nearly on the same level after five regeneration cycles. Furthermore, almost complete removal of the pollutants was observed during the treatment of real effluents samples thus the bio-derived, cheap and reusable BAN-EPI-CDP has a promising potential for practical applications.

Effect of chemical structure on complexation efficiency of aromatic drugs with cyclodextrins: The example of dibenzazepine derivatives.

It is widely believed that the hydrophobic effect governs the binding of guest molecules to cyclodextrins (CDs). However, it is also known that high hydrophobicity of guest molecules does not always translate to the formation of stable inclusion complexes with CDs. Indeed, a plethora of other factors can play a role in the efficiency of guest-CD interactions, rendering structure-based prediction of the complexation efficiency with CDs a non trivial task. In this combined experimental and computational study, we examine the major structural factors governing complexation efficiency of polycyclic aromatic drug-like compounds with natural CDs, using as an example iminostilbene and its N-substituted derivatives. We find that purely hydrophobic IS derivatives show negligible complexation efficiency with CDs and only IS with hydrophilic substituents form stable inclusion complexes in water. We show that the balance between the guest solubility and its affinity to CDs is critical for the effective formation of inclusion complexes. Finally, our results demonstrate that guest-host hydrogen bonds facilitate the formation of crystalline inclusion complexes with CDs.