Zeolite Synthesis in the Presence of Metallosiloxanes for the Quantitative Encapsulation of Metal Species for the Selective Catalytic Reduction (SCR) of NOx.

Metal encapsulation in zeolitic materials through one-pot hydrothermal synthesis (HTS) is an attractive technique to prepare zeolites with a high metal dispersion. Due to its simplicity and the excellent catalytic performance observed for several catalytic systems, this method has gained a great deal of attention over the last few years. While most studies apply synthetic methods involving different organic ligands to stabilize the metal under synthesis conditions, here we report the use of metallosiloxanes as an alternative metal precursor. Metallosiloxanes can be synthesized from simple and cost-affordable chemicals and, when used in combination with zeolite building blocks under standard synthesis conditions, lead to quantitative metal loading and high dispersion. Thanks to the structural analogy of siloxane with TEOS, the synthesis gel stabilizes by forming siloxane bridges that prevent metal precipitation and clustering. When focusing on Fe-encapsulation, we demonstrate that Fe-MFI zeolites obtained by this method exhibit high catalytic activity in the NH3 -mediated selective catalytic reduction (SCR) of NOx along with a good H2 O/SO2 tolerance. This synthetic approach opens a new synthetic route for the encapsulation of transition metals within zeolite structures.

Internalization study of nanosized zeolite crystals in human glioblastoma cells.

While the use of nanozeolites for cancer treatment holds a great promise, it also requires a better understanding of the interaction between the zeolite nanoparticles and cancer cells and notably their internalization and biodistribution. It is particularly important in situation of hypoxia, a very common situations in aggressive cancers, which may change the energetic processes required for cellular uptake. Herein, we studied, in vitro, the kinetics of the internalization process and the intracellular localization of nanosized zeolite X (FAU-X) into glioblastoma cells. In normoxic conditions, scanning electron microscopy (SEM) showed a rapid cell membrane adhesion of zeolite nanoparticles (< 5 min following application in the cell medium), occurring before an energy-dependent uptake which appeared between 1 h and 4 h. Additionally, transmission electron microscopy (TEM) and flow cytometry analyzes, confirmed that the zeolite nanoparticles accumulate over time into the cytoplasm and were mostly located into vesicles visible at least up to 6 days. Interestingly, the uptake of zeolite nanoparticles was found to be dependent on oxygen concentration, i.e. an increase in internalization in severe hypoxia (0.2 % of O2) was observed. No toxicity of zeolite FAU-X nanoparticles was detected after 24 h and 72 h. The results clearly showed that the nanosized zeolites crystals were rapidly internalized via energy-requiring mechanism by cancer cells and even more in the hypoxic conditions. Once the zeolite nanoparticles were internalized into cells, they appeared to be safe and stable and therefore, they are envisioned to be used as carrier of various compounds to target cancer cells.

Ruthenium tris(2,2'-bipyridyl) complex encapsulated in nanosized faujasite zeolite as intracellular localization tracer.

Designing zeolites for medical applications is a challenging task that requires introducing new functionalities without altering the intrinsic properties such as morphology, crystallinity, colloidal stability, surface charge, and porosity. Herein, we present the encapsulation of luminescent ruthenium-tris(2,2'-bipyridyl) complex in faujasite (FAU) zeolite nanocrystals (Ru(bpy)3-FAU) and their use as an intracellular localization tracer. Upon exciting the Ru(bpy)3-FAU zeolite at 450 nm, the sample gives rise to an orange-red emission at 628 nm, thus permitting its use for cellular imaging and localization of the zeolite nanoparticles. The nanosized Ru(bpy)3-FAU zeolite is characterized in terms of size, charge, crystallinity, morphology, porosity, thermal stability, and sorption capacity. The potential toxicity of Ru(bpy)3-FAU on U251-MG glioblastoma cells was evaluated. A safe concentration (50-100 µg/ml) for the Ru(bpy)3-FAU zeolite is identified. The luminescent properties of the ruthenium complex confined in the zeolite nanocrystals allow their localization in the U251-MG cells with a main accumulation in the cytoplasm. The Ru(bpy)3-FAU nanosized zeolite is a potential candidate for biological applications for being stable, safe, capable of loading respiratory gases, and easily probed in the cells owing to its luminescent properties.

Efficiency and selectivity of ionic liquids in microwave-assisted extraction of major lichen phenolic compounds: a scalable process with recycling of ionic liquids.

INTRODUCTION: Pseudevernia furfuracea, a lichen used classically for cosmetic applications, contains interesting metabolites possessing antimicrobial and anti-inflammatory or antioxidant properties. OBJECTIVES: Ionic liquid combined to microwave-assisted extraction (IL-MAE) was successfully applied for metabolites extraction from Pseudevernia furfuracea. MATERIALS AND METHODS: Three imidazolium and pyridinium-based ionic liquids (ILs): 1,3-dimethylimidazolium methylsulphate [C1 C1 Im][MeSO4 ], 1-ethyl-3-methylimidazolium ethylsulphate [C2 C1 Im][EtSO4 ], and N-ethylpyridinium ethylsulphate [C2 Py][EtSO4 ] were assessed for this process. The efficiency of the extraction method was evaluated using thin-layer chromatography (TLC) coupled to a Camag® spectrophotodensitometer and using high-performance liquid chromatography (HPLC) analysis. RESULTS: ILs under MAE showed extraction time efficiency (15 min vs. 24 h for conventional heating) and high selectivity in extracting the targeted metabolites: atranorin (AT), methyl-ß-orcinol carboxylate (MOC), fumarprotocetraric acid (Fum. Ac.), and physodic acid (Phys. Ac.) despite the increased degradation of AT under MAE. We showed a tunable selectivity of ILs towards extracting metabolites by changing anion or cation due to the modification of the interaction between the IL and the metabolites. While [C2 Py][EtSO4 ] was the most efficient IL and could extract all the targeted metabolites, [C2 C1 Im][EtSO4 ] was the most selective. It fully extracted AT and partially Fum. Ac. Moreover, the lichen prepared by mixing procedure provided AT and Fum. Ac. more than the milled one. A 100 times scale-up extraction was successfully performed on mixed samples with full IL recycling after back extraction. CONCLUSION: IL-MAE is reliable for lichen metabolites extraction. The method is reproducible, scalable, with possible IL recycling, opening the door for potential industrial applications.

Nanosized zeolites as a gas delivery platform in a glioblastoma model.

Approaches able to counteract, at least temporarily, hypoxia, a well-known factor of resistance to treatment in solid tumors are highly desirable. Herein, we report the use of nanosized zeolite crystals as hyperoxic/hypercapnic gas carriers for glioblastoma. First, the non-toxic profile of nanosized zeolite crystals in living animals (mice, rats and non-human primates) and in various cell types is presented. Second, the ability of the nanosized zeolites to act as a vasoactive agent for a targeted re-oxygenation of the tumor after intravenous injection is shown. As attested by an MRI protocol, the zeolites were able to increase oxygenation and blood volume specifically within the brain tumor whilst no changes in the healthy-non tumoral brain-were observed. The first proof of concept for the use of metal-containing nanosized zeolites as a tool for vectorization of hyperoxic/hypercapnic gases in glioblastoma is revealed.

Incorporation of trivalent cations in NaX zeolite nanocrystals for the adsorption of O2 in the presence of CO2.

The O2 and CO2 sorption properties of nanosized zeolite X with faujasite type structure through a partial ionic exchange of sodium (Na+) by trivalent cations (Gd3+ and Ce3+) were evaluated. Three faujasite samples were studied, the as-synthesized Na-X possessing Na+ solely, and the modified samples Na-Gd-X and Na-Ce-X containing Gd3+ (1.8 wt%) and Ce3+ (0.82 wt%), respectively. Incorporating scarce amounts of trivalent cations modified the adsorption affinity of zeolites towards O2 and CO2 as demonstrated by in situ Fourier-transform infrared spectroscopy (FTIR). While Na-Ce-X encounters the highest O2 physisorption capacity, the Na-Gd-X is adsorbing the highest quantities of molecular CO2. All three samples exhibit the chemisorbed CO2 in the form of carbonates, while the Na-X stores carbonates in monodentate and polydentate forms, the Na-Gd-X and Na-Ce-X allow the formation of polydentate carbonates only. Density functional theory (DFT) calculations revealed that trivalent cations tend to adsorb gases through two cations simultaneously which explains the presence of polydentate carbonates exclusively in the corresponding modified zeolites. The DFT results confirmed the higher affinity of Na-Gd-X and Na-Ce-X nanocrystals towards O2 in the presence of CO2. The affinity of Na-Gd-X and Na-Ce-X nanocrystals towards O2 opens the door of their use as oxygen transporters for medical applications where CO2 is constantly present. The toxicity of the nanosized zeolites and their performance in O2 release are reported too.

A Facile Route toward the Increase of Oxygen Content in Nanosized Zeolite by Insertion of Cerium and Fluorinated Compounds.

Enriching oxygen content within nanosized zeolite X (as synthesized Na-X) by insertion of cerium (ion exchanged Ce-X) and functionalization with bromoperfluoro-n-octane (fluorinated F-X) is reported. The materials were fully characterized by powder X-ray diffraction (XRD), dynamic light scattering (DLS), zeta potential, thermogravimetric analysis (TGA), nitrogen adsorption, and nuclear magnetic resonance (19F NMR). The O2 adsorption in the zeolite samples at various concentrations (0 to 165 Torr) at -196 °C was studied by in situ FTIR. The modification of nanosized zeolites did not alter their colloidal stability, crystallinity, porosity, and particle size distribution. The inclusion of cerium and bromoperfluoro-n-octane considerably increase the oxygen capacity by 33% for samples Ce-X and F-X in comparison to the as-synthesized Na-X zeolite. Further, toxicity tests revealed that these materials are safe, which opens the door for their implementation in medical applications, where controlled delivery of oxygen is highly desirable.

Acute Toxicity of Silver Free and Encapsulated in Nanosized Zeolite for Eukaryotic Cells.

The potential toxicity of encapsulated silver in EMT-type nanosized zeolites on prokaryotic cells, human tumor cell lines from various origins, and primary cultures of neurons and astrocytes was investigated. Silver in cationic form (Ag+) was encapsulated in EMT-type nanosized zeolites via an ion exchange process (Ag+-EMT) and compared with the reduced silver (Ag0) in the zeolite (Ag0-EMT). As reference samples for the toxicity measurements, pure EMT-type zeolite and silver perchlorate were used. Cells were exposed to silver-containing zeolites (50, 100, and 400 µg/mL) for 24 and 48 h. After exposure to Ag+-EMT (50 µg/mL) for 24 h, a loss in cell viability independent of the cell type was observed, ranging from -34.37 ± 23.90% for astrocytes to -99.5 ± 0.24% for U87-MG cells. These results were comparable with the toxicity for silver perchlorate. The Ag0-EMT sample showed lower toxicity on human cell lines in comparison to that of Ag+-EMT. A decrease in cell viability, i.e., -73.46 ± 20.78% and -62.3 ± 17.96% for U87-MG and HEK 293 cells, respectively, under exposure only to high concentration of Ag0-EMT (400 µg/mL) for 24 h was measured. However, the Ag0-EMT was as toxic as the Ag+-EMT for astrocytes and neurons (-97.95 ± 3.31% and -100 ± 1.11%, respectively, after exposure to 50 µg/mL for 24 h). No decrease in cell viability exposed to pure EMT zeolite was found. The results demonstrate the severe toxicity of silver cations, either free or encapsulated, in comparison to reduced silver encapsulated in zeolite nanocrystals. Therefore, silver cations, either free or encapsulated, must be used with great caution regarding their toxicity on eukaryotic cells.

Sample preparation for an optimized extraction of localized metabolites in lichens: Application to Pseudevernia furfuracea.

Lichens are symbiotic organisms known for producing unique secondary metabolites with attractive cosmetic and pharmacological properties. In this paper, we investigated three standard methods of preparation of Pseudevernia furfuracea (blender grinding, ball milling, pestle and mortar). The materials obtained were characterized by electronic microscopy, nitrogen adsorption and compared from the point of view of extraction. Their microscopic structure is related to extraction efficiency. In addition, it is shown using thalline reactions and mass spectrometry mapping (TOF-SIMS) that these metabolites are not evenly distributed throughout the organism. Particularly, atranorin (a secondary metabolite of interest) is mainly present in the cortex of P. furfuracea. Finally, using microwave assisted extraction (MAE) we obtained evidence that an appropriate preparation can increase the extraction efficiency of atranorin by a factor of five.