Low-cost zeolitic carriers for delivery of hydroxychloroquine immunomodulatory agent with antiviral activity.

The coronavirus pandemic prompted scientists to look for active pharmaceutical ingredients that could be effective in treating COVID-19. One of them was hydroxychloroquine, an antimalarial and immunomodulatory agent exhibiting antiviral activity. The anchoring of this drug on porous carriers enables control of its delivery to a specific place in the body, and thus increases bioavailability. In this work, we developed low-cost zeolitic platforms for hydroxychloroquine. The waste solution generated during zeolite production from fly ashes was used in the synthesis of Na-A and Na-X carriers at laboratory and technical scale. The materials were characterized by high purity and single mineral phase composition. The surface charge of zeolites varied from negative at pH 5.8, and 7.2, to positive at pH 1.2. All samples indicated good sorption ability towards hydroxychloroquine. The mechanism of drug adsorption was based on electrostatic interactions and followed the Freundlich model. Zeolitic carriers modified the hydroxychloroquine release profiles at conditions mimicking the pH of body fluids. The mode of drug liberation was affected by particle size distributions, morphological forms, and chemical compositions of zeolites. The most hydroxychloroquine controlled release at pH 5.8 for the Na-X material was noted, which indicates that it can enhance the drug therapeutic efficacy.

Recycling of Waste Solution after Hydrothermal Conversion of Fly Ash on a Semi-Technical Scale for Zeolite Synthesis.

Nowadays, using fly ash for zeolites production has become a well-known strategy aimed on sustainable development. During zeolite synthesis in a hydrothermal conversion large amount of post-reaction solution is generated. In this work, the solution was used as a substrate for Na-A and Na-X zeolites synthesis at laboratory and technical scale. Obtained materials were characterized using particle size analysis, X-ray diffraction (XRD), X-ray fluorescence spectroscopy (XRF), transmission electron microscopy (TEM), Fourier transformed infrared spectroscopy (FTIR), and nitrogen adsorption/desorption isotherm. Produced zeolites revealed high purity (>98%) and monomineral zeolitic phase composition. The SiO2 content was in the range 39-42% and 40-38%, whereas Al2O3 content was 23-22% and 25-26% for Na-X and Na-A, respectively. TEM and BET analyses revealed Na-X zeolite pores were almost identical to commercial 13X with SBET in the range 671-734 m2/g. FTIR indicated slight differences between materials obtained at laboratory and technical scale in Si-O-(Si/Al) bridges of the zeolitic skeleton. The results showed good replicability of the laboratory process in the larger scale. The proposed method allows for waste solution reusability with a view to highly pure zeolites production in line with circular economy assumptions.

Sorption of Heavy Metal Ions of Chromium, Manganese, Selenium, Nickel, Cobalt, Iron from Aqueous Acidic Solutions in Batch and Dynamic Conditions on Natural and Synthetic Aluminosilicate Sorbents.

Zeolites are materials with known sorption properties. The sorption is thought to progress mainly by ion exchange with Na+, K+, Mg2+, Ca2+ or H+ from the zeolite exchange sites. The aim of the study was to compare the sorption properties of natural and synthetic zeolites on the example of the removal of selected metals from aqueous acidic solutions. Uptake experiments for selected ions of chromium, manganese, selenium, nickel, cobalt, and iron were performed using the batch and kinetic column methods. The sorption of the individual metal ions in mg per 1g of sorbent was determined for each sorbent. The relative affinity sequence of the examined cations toward the various sorbent was presented. The Langmuir model was used to model the adsorption equilibrium. Vermiculite under 1 mm of diameter (SF), Na-X, and Na-A were proved to be the most suitable for the individual uptake of studied metal ions. It was observed that the behavior of selenium ions differed from the remaining ones which was interpreted that selenium undergoes adsorption in the anionic form. The fixed-bed column studies were performed using Na-A, ensuring the sorption of selenium in the presence of iron(III) ions. The experiments were conducted using Na-X zeolite pre-loaded by Fe(III) as well as unmodified sorbent eluted by an equimolar mixture containing 100 ppm of Fe and Se. Obtained results prove that selenium sorption improves if other metal ions such as iron appear in the acidic solution. That efficient selenium sorption conditions can be applied to remove selenium which was recognized as toxic at higher levels.

Impact of fly ash fractionation on the zeolitization process.

Coal combustion product in the form of fly ash has been sieved and successfully utilised as a main substrate and a carrier of silicon and aluminium in a set of hydrothermal syntheses of zeolites. The final product was abundant in zeolite X phase (Faujasite framework). Raw fly ash as well as its derivatives, after being sieved (fractions: ≤ 63, 63-125, 125-180 and ≥ 180 µm), and the obtained zeolite materials were subjected to mineralogical characterisation using powder X-ray diffraction, energy-dispersive X-ray fluorescence, laser diffraction-based particle size analysis and scanning electron microscopy. The influence of fraction separation on the zeolitization process under hydrothermal synthesis was investigated. Analyses performed on the derived zeolite X samples revealed a meaningful impact of the given fly ash fraction on synthesis efficiency, chemistry, quality as well as physicochemical properties, while favouring a given morphological form of zeolite crystals. The obtained zeolites possess great potential for use in many areas of industry and environmental protection or engineering.

Zeolites in Phenol Removal in the Presence of Cu(II) Ions-Comparison of Sorption Properties after Chitosan Modification.

Nowadays, the contamination of water with phenol is a serious environmental problem. This compound occurs very often with heavy metal ions which makes purification of water even more difficult. This article presents the problem of the removal of phenol from aqueous solutions in the presence of Cu(II) ions on synthetic zeolite NaP1 and zeolite NaP1 modified with chitosan. The adsorbents were determined with the use of Fourier transform infrared spectroscopy (FT-IR), nitrogen adsorption/desorption isotherm, and scanning electron microscopy (SEM). The studies on isotherms and batch kinetics under diversified experimental conditions with respect to initial concentration, contact time, and pH were discussed. Both Cu(II) and phenol adsorption increases with the initial concentration. Different isotherm models correspond well with the data acquired through experiments. The kinetics of adsorption follows the pseudo-second order rate equation. The studies indicate that the obtained sorbents can be employed for efficient removal of phenol from wastewater in the presence of Cu(II) ions.