Crystal Clear: Metal-Organic Frameworks Pioneering the Path to Future Drug Detox.

The growing number of acute drug abuse overdoses demands the development of innovative detoxification strategies for emergency purposes. In this study, an innovative approach for the application of porous Zr-based metal-organic frameworks for the treatment of acute overdoses of popular drugs of abuse including amphetamine, methamphetamine, cocaine, and MDMA is presented. A comprehensive approach determining the efficacy and the kinetics of drug removal, considering dosage, adsorption time, and adsorption mechanisms, was tested and corroborated with density functional theory (DFT) modeling. The experimental results showed high removal efficiency reaching up to 90% in the case of the application of the NU-1000 metal-organic framework. The difference Raman spectroscopy method presented in this study corroborated with DFT-based vibrational analysis allows the detection of drug adsorbed in the MOF framework even with as low a concentration as 5 mg/g. Additionally, the drug adsorption mechanisms were modeled with DFT, showing the π-π stacking in a vast majority of considered cases. The performance and influence on the living organisms were evaluated throughout the in vitro and in vivo experiments, indicating that Zr-based MOFs could serve as efficient, organic, safe drug adsorbents.

A new synthetic ultrasound-assisted method for dibenzoepines.

In this study, we have developed a new ultrasonic synthesis method of dibenzoepines using olanzapine and quetiapine, which are well-known drugs for the treatment of schizophrenia and bipolar disorder. The method is based on the N-alkylation reaction of the piperazine fragment in tricyclic compounds with methyl iodide or 2-(2-chloroethoxy)ethanol as the alkylating agent, respectively. The synthesis reactions were carried out in an ultrasonic bath with solvents such as acetonitrile or dimethylformamide in the presence of potassium or sodium carbonate or sodium hydroxide and metal-free, ecological phase transfer catalyst at a temperature of 40-50 °C. This allowed us to obtain olanzapine in 1 h (Y = 67%), and quetiapine in 3 h (Y = 72%). An ultrasonic reactor (Qsonica Q700) was used in the synthesis of olanzapine and made it possible to shorten the reaction time to 10 min and obtain 90% yield with very high purity. The developed method allows obtaining compounds in mild conditions and in a short time, thanks to which the process is more ecological than others described in the literature.

From crystal phase mixture to pure metal-organic frameworks - Tuning pore and structure properties.

In this study, a sonochemical route for the preparation of a new Hf-MIL-140A metal-organic framework from a mixture of UiO-66/MIL-140A is presented. The sonochemical synthesis route not only allows the phase-pure MIL-140A structure to be obtained but also induces structural defects in the MIL-140A structure. The synergic effect between the sonochemical irradiation and the presence of a highly acidic environment results in the generation of slit-like defects in the crystal structure, which increases specific surface area and pore volume. The BET-specific surface area in the case of sonochemically derived Zr-MIL-140A reaches 653.3 m2/g, which is 1.5 times higher than that obtained during conventional synthesis. The developed Hf-MIL-140A structure is isostructural to Zr-MIL-140A, which was confirmed by synchrotron X-ray powder diffraction (SR-XRD) and by continuous rotation electron diffraction (cRED) analysis. The obtained MOF materials have high thermal and chemical stability, which makes them promising candidates for applications such as gas adsorption, radioactive waste removal, catalysis, and drug delivery.

Iron inactivation by Sporobolomyces ruberrimus and its potential role in plant metal stress protection. An in vitro study.

The endophytic Basidiomycete Sporobolomyces ruberrimus protects its host Arabidopsis arenosa against metal toxicity. Plants inoculated with the fungus yielded more biomass and exhibited significantly fewer stress symptoms in medium mimicking mine dump conditions (medium supplemented with excess of Fe, Zn and Cd). Aside from fine-tuning plant metal homeostasis, the fungus was capable of precipitating Fe in the medium, most likely limiting host exposure to metal toxicity. The precipitated residue was identified by Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), X-Ray Diffraction (XRD) and electron microscopy (SEM/TEM) with energy dispersive X-Ray analysis (EDX/SAED) techniques. The performed analyses revealed that the fungus transforms iron into amorphous (oxy)hydroxides and phosphates and immobilizes them in the form of a precipitate changing Fe behaviour in the MSR medium. Moreover, the complexation of free Fe ions by fungi could be obtained by biomolecules such as lipids, proteins, or biosynthesized redox-active molecules.

Zirconium-Based Metal-Organic Frameworks as Acriflavine Cargos in the Battle against Coronaviruses─A Theoretical and Experimental Approach.

In this study, we present a complementary approach for obtaining an effective drug, based on acriflavine (ACF) and zirconium-based metal-organic frameworks (MOFs), against SARS-CoV-2. The experimental results showed that acriflavine inhibits the interaction between viral receptor-binding domain (RBD) of spike protein and angiotensin converting enzyme-2 (ACE2) host receptor driving viral cell entry. The prepared ACF@MOF composites exhibited low (MOF-808 and UiO-66) and high (UiO-67 and NU-1000) ACF loadings. The drug release profiles from prepared composites showed different release kinetics depending on the local pore environment. The long-term ACF release with the effective antiviral ACF concentration was observed for all studied ACF@MOF composites. The density functional theory (DFT) calculations allowed us to determine that π-π stacking together with electrostatic interaction plays an important role in acriflavine adsorption and release from ACF@MOF composites. The molecular docking results have shown that acriflavine interacts with several possible binding sites within the RBD and binding site at the RBD/ACE2 interface. The cytotoxicity and ecotoxicity results have confirmed that the prepared ACF@MOF composites may be considered potentially safe for living organisms. The complementary experimental and theoretical results presented in this study have confirmed that the ACF@MOF composites may be considered a potential candidate for the COVID-19 treatment, which makes them good candidates for clinical trials.

In Search of Effective UiO-66 Metal-Organic Frameworks for Artificial Kidney Application.

The removal of uremic toxins from patients with acute kidney injury is a key issue in improving the quality of life for people requiring peritoneal dialysis. The currently utilized method for the removal of uremic toxins from the human organism is hemodialysis, performed on semipermeable membranes where the uremic toxins, along with small molecules, are separated from proteins and blood cells. In this study, we describe a mixed-linker modulated synthesis of zirconium-based metal-organic frameworks for efficient removal of uremic toxins. We determined that the efficient adsorption of uremic toxins is achieved by optimizing the ratio between -amino functionalization of the UiO-66 structure with 75% of -NH2 groups within organic linker structure. The maximum adsorption of hippuric acid and 3-indoloacetic acid was achieved by UiO-66-NH2 (75%) and by UiO-66-NH2 (75%) 12.5% HCl prepared by modulated synthesis. Furthermore, UiO-66-NH2 (75%) almost completely adsorbs 3-indoloacetic acid bound to bovine serum albumin, which was used as a model protein to which uremic toxins bind in the human body. The high adsorption capacity was confirmed in recyclability test, which showed almost 80% removal of 3-indoloacetic acid after the third adsorption cycle. Furthermore, in vitro cytotoxicity tests as well as hemolytic activity assay have proven that the UiO-66-based materials can be considered as potentially safe for hemodialytic purposes in living organisms.

A high performance barium-promoted cobalt catalyst supported on magnesium-lanthanum mixed oxide for ammonia synthesis.

Ammonia synthesis was performed over a barium-promoted cobalt catalyst supported on magnesium-lanthanum mixed oxide. The rate of NH3 formation over this catalyst was about 3.5 times higher than that over the unpromoted catalyst at 9 MPa and 400 °C. Furthermore, no sign of thermal deactivation was observed during long-term overheating at 600 °C for 360 h. The results of physicochemical studies, including XRPD, DRIFTS, H2-TPD, CO2-TPD, Nads + H2 TPSR and kinetic analysis, revealed that the addition of Ba promoter increased the surface basicity of the catalyst and modified the adsorption properties of the Co surface towards H2 and NH3. The decreased adsorption strength of the corresponding sites towards hydrogen and ammonia resulted in greater availability of active sites in the Ba-promoted cobalt catalyst. These characteristics are considered to have a profound effect on the performance of this catalyst in NH3 synthesis.

Cracking the Chloroquine Conundrum: The Application of Defective UiO-66 Metal-Organic Framework Materials to Prevent the Onset of Heart Defects-In Vivo and In Vitro.

In this study, we present a modulated synthesis nanocrystalline defective UiO-66 metal-organic framework as a potential chloroquine diphosphate (CQ) delivery system. Increasing the concentration of hydrochloric acid during the modulated synthesis resulted in a considerable increase of pore volume, which enhanced the CQ loading in CQ@UiO-66 composites. Drug release tests for CQ@UiO-66 composites have confirmed prolonged CQ release in comparison with pure CQ. In vivo tests on a Danio reiro model organism have revealed that CQ released from CQ@UiO-66 25% showed lower toxicity and fewer cardiotoxic effects manifested by cardiac malformations and arrhythmia in comparison to analogous doses of CQ. Cytotoxicity tests proved that the CQ loaded on the defective UiO-66 cargo resulted in increased viability of cardiac cells (H9C2) as compared to incubation with pure CQ. The experimental results presented here may be a step forward in the context of reducing the cardiotoxicity CQ.

Analysis of Entropy Production in Structured Chemical Reactors: Optimization for Catalytic Combustion of Air Pollutants.

Optimization of structured reactors is not without some difficulties due to highly random economic issues. In this study, an entropic approach to optimization is proposed. The model of entropy production in a structured catalytic reactor is introduced and discussed. Entropy production due to flow friction, heat and mass transfer and chemical reaction is derived and referred to the process yield. The entropic optimization criterion is applied for the case of catalytic combustion of methane. Several variants of catalytic supports are considered including wire gauzes, classic (long-channel) and short-channel monoliths, packed bed and solid foam. The proposed entropic criterion may indicate technically rational solutions of a reactor process that is as close as possible to the equilibrium, taking into account all the process phenomena such as heat and mass transfer, flow friction and chemical reaction.

DeNOx Abatement over Sonically Prepared Iron-Substituted Y, USY and MFI Zeolite Catalysts in Lean Exhaust Gas Conditions.

Iron-substituted MFI, Y and USY zeolites prepared by two preparation routes-classical ion exchange and the ultrasound modified ion-exchange method-were characterised by micro-Raman spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), and ultraviolet (UV)/visible diffuse reflectance spectroscopy (UV/Vis DRS). Ultrasound irradiation, a new technique for the preparation of the metal salt suspension before incorporation to the zeolite structure, was employed. An experimental study of selective catalytic reduction (SCR) of NO with NH3 on both iron-substituted reference zeolite catalysts and those prepared through the application of ultrasound conducted during an ion-exchange process is presented. The prepared zeolite catalysts show high activity and selectivity in SCR deNOx abatement. The MFI-based iron catalysts, especially those prepared via the sonochemical method, revealed superior activity in the deNOx process, with almost 100% selectivity towards N2. The hydrothermal stability test confirmed high stability and activity of MFI-based catalysts in water-rich conditions during the deNOx reaction at 450 °C.

Generalised two-dimensional correlation analysis of the Co, Ce, and Pd mixed oxide catalytic systems for methane combustion using in situ infrared spectroscopy.

The process of methane combustion over the surface of a catalyst is still not fully understood. The identification of the reaction path and the intermediates created during catalysis is crucial for understanding the transformation of methane molecules. Two-dimensional (2D) correlation spectroscopy was engaged as a tool for the quantitative analysis of a series of temperature-dependent infrared spectra registered in situ during methane combustion. The prepared samples of catalysts were based on a Co, Pd and Ce mixed oxide adsorbed on an aluminium oxide layer deposited on kanthal steel. The registered spectra were transformed into 2D synchronous and asynchronous contour maps. The sequential order of spectral intensity changes was determined, and the resolution enhancement of overlapping IR bands by 2D correlation was demonstrated. The changes in the bands' intensity and information about band position can be correlated with a specific bond, and thus, the possible process intermediates can be identified. The 2DCoS analysis proved to be a powerful tool for band enhancement and revealed the changes occurring within the analysed catalyst systems as responses to increased temperature.

Antimicrobial Properties of Silver Cations Substituted to Faujasite Mineral.

A goal of our study was to find an alternative to nano-silver-based antimicrobial materials which would contain active silver immobilized in a solid matrix that prevents its migration into the surrounding environment. In this study, we investigated whether silver cations dispersed in an atomic form and trapped in an ion-exchanged zeolite show comparable antimicrobial activity to silver nanoparticles (NPs). The biocidal active material was prepared from the sodium form of faujasite type zeolite in two steps: (1) exchange with silver cations, (2) removal of the external silver oxide NPs by elution with Na2EDTA solution. The modified biocidal zeolite was then added to paper pulp to obtain sheets. The zeolite paper samples and reference samples containing silver NPs were tested in terms of biocidal activity against an array of fungi and bacteria strains, including Escherichia coli, Serratia marcescens, Bacillus subtilis, Bacillus megaterium, Trichoderma viride, Chaetomium globosum, Aspergillus niger, Cladosporium cladosporioides, and Mortierella alpina. The paper with the modified faujasite additive showed higher or similar antibacterial and antifungal activities towards the majority of tested microbes in comparison with the silver NP-filled paper. A reverse effect was observed for the Mortierella alpina strain.

Non-Noble Metal Oxide Catalysts for Methane Catalytic Combustion: Sonochemical Synthesis and Characterisation.

The aim of this study was to obtain nanocrystalline mixed metal-oxide-ZrO2 catalysts via a sonochemically-induced preparation method. The effect of a stabiliser's addition on the catalyst parameters was investigated by several characterisation methods including X-ray Diffraction (XRD), nitrogen adsorption, X-ray fluorescence (XRF), scanning electron microscopy (SEM) equipped with energy dispersive X-ray spectrometer (EDS), transmission electron microscopy (TEM) and µRaman. The sonochemical preparation method allowed us to manufacture the catalysts with uniformly dispersed metal-oxide nanoparticles at the support surface. The catalytic activity was tested in a methane combustion reaction. The activity of the catalysts prepared by the sonochemical method was higher than that of the reference catalysts prepared by the incipient wetness method without ultrasonic irradiation. The cobalt and chromium mixed zirconia catalysts revealed their high activities, which are comparable with those presented in the literature.

2D-COS of in situ µ-Raman and in situ IR spectra for structure evolution characterisation of NEP-deposited cobalt oxide catalyst during n-nonane combustion.

New catalytic systems are still in development to meet the challenge of regulations concerning the emission of volatile organic compounds (VOCs). This is because such compounds have a significant impact on air quality and some of them are toxic to the environment and human beings. The catalytic combustion process of VOCs over non-noble metal catalysts is of great interest to researchers. The high conversion parameters and cost effective preparation makes them a valuable alternative to monoliths and noble metal catalysts. In this study, the cobalt catalyst was prepared by non-equilibrium plasma deposition of organic precursor on calcined kanthal steel. Thus prepared, cobalt oxide based microstructural short-channel reactors were tested for n-nonane combustion and the catalyst surfaces were examined by in situ µ-Raman spectroscopy and in situ infrared spectroscopy. The spectra collected at various temperatures were used in generalised two-dimensional correlation analysis to establish the sequential order of spectral intensity changes and correlate the simultaneous changes in bands selectively coupled by different interaction mechanisms. The 2D synchronous and asynchronous contour maps were proved to be a valuable extension to the standard analysis of the temperature dependent 1D spectra.