Search Results (106)

Mesoporous silicas of MCM-41 and MCM-48 types were synthesized and modified with copper using the ammonia-driven deposition precipitation (ADP) method, resulting in highly dispersed copper species. Samples with varying copper loadings were thoroughly characterized in terms of their porous structure, metal content, copper species’ aggregation, and the stability of deposited forms under reaction conditions. Copper-modified mesoporous silicas exhibited excellent catalytic performance in the low-temperature NH₃-SCR process. Their activity in NO to NO₂ oxidation suggests that the fast-SCR pathway plays a significant role in NO_x conversion at low temperatures. However, direct ammonia oxidation limited SCR efficiency at higher temperatures. These findings demonstrate the potential of ADP-modified copper–silica catalysts for effective and selective NO_x removal under low-temperature conditions. Full article

This work shows a sustainable methodology for the synthesis of biogenic materials designed for the removal and photodegradation of rhodamine B (RhB), a highly dangerous environmental pollutant that induces reproductive toxicity. The classical synthesis of MCM-41-ordered mesoporous materials was modified using biocompatible rice husk as the silica template. Iron was incorporated and the so-prepared biogenic photocatalysts were characterized by X-ray diffraction, N₂ adsorption–desorption isotherms, transmission electron microscopy, diffuse reflectance UV-Vis, surface pH, cyclic voltammetry, and Fourier transform infrared spectral analysis of pyridine adsorption. The photocatalytic performance of the materials was evaluated following the removal by adsorption and the photon-driven degradation of RhB. The adsorption capacity and photocatalytic activity of the biogenic materials were correlated with their properties, including iron content, texture, surface content, and electrochemical properties. The best biogenic material boosted the degradation rates of RhB under UV irradiation up to 4.7 and 2.2 times greater than the direct photolysis and the benchmark semiconductor TiO₂-P25. It can be concluded that the use of rice husks for the synthesis of biogenic Fe-modified mesoporous materials is a promising strategy for wastewater treatment applications, particularly in the removal of highly toxic organic dyes. Full article

In the presented work, titanosilicate with the MWW structure (Ti-MWW) was hydrothermally synthesized using boron and titanium precursors, with piperidine as a structure-directing agent. The resulting layered zeolite precursor, with a Si/Ti molar ratio of 50, was treated in an HNO₃ solution to remove extraframework Ti and B species. The acid-modified zeolite was functionalized with transition metal cations (Cu²⁺, Fe²⁺, Mn²⁺) and trinuclear oligocations (Fe(3) and Mn(3)). The application of this catalytic system is supported by the presence of titanium in the catalytic support structure—similar to a commercial system, V₂O₅–TiO₂. The obtained samples were characterized with respect to their structure (P-XRD, DRIFT), textural parameters (low-temperature N₂ sorption), surface acidity (NH₃-TPD), transition metal content (ICP-OES) and form (UV–vis DRS) as well as catalyst’s reducibility (H₂-TPR). Ti-MWW zeolite samples modified with transition metals were evaluated as catalysts for the selective catalytic reduction of NO with ammonia (NH₃-SCR). The effective temperature range for the NO conversion varied depending on the type of active phase used to functionalize the porous support. The catalytic performance was influenced by transition metal content, its form, and accessibility for reactants as well as interactions between the active phase and titanium-containing support. Among the catalysts tested, the copper-modified Ti-MWW zeolite showed the most promising results, maintaining 90% NO conversion rates across a relatively broad temperature range from 200 to 325 °C. This catalyst meets the requirements of modern NH₃-SCR installations, which aim to operate in the low-temperature region, below 250 °C. Full article

Background: This study explored the potential of MCM-48 mesoporous silica matrices as a drug delivery system for metformin hydrochloride, aimed at improving the therapeutic management of type 2 diabetes mellitus. The objectives included the synthesis and characterization of MCM-48, assessment of its drug loading capacity, analysis of drug release profiles under simulated physiological conditions, and the development of a multifractal dynamics-based theoretical framework to model and interpret the release kinetics. Methods: MCM-48 was synthesized using a sol–gel method and characterized by SEM-EDX, TEM, and nitrogen adsorption techniques. Drug loading was performed via adsorption at pH 12 using metformin hydrochloride solutions of 1 mg/mL (P-1) and 3 mg/mL (P-2). In vitro dissolution studies were conducted to evaluate the release profiles in simulated gastric and intestinal fluids. A multifractal dynamics model was developed to interpret the release kinetics. Results: SEM-EDX confirmed the uniform distribution of silicon and oxygen, while TEM images revealed a highly ordered cubic mesoporous structure. Nitrogen adsorption analyses showed a high specific surface area of 1325.96 m²/g for unloaded MCM-48, which decreased with drug loading, confirming efficient incorporation of metformin hydrochloride. The loading capacities were 59.788 mg/g (P-1) and 160.978 mg/g (P-2), with efficiencies of 99.65% and 89.43%, respectively. In vitro dissolution studies showed a biphasic release profile: an initial rapid release in gastric conditions followed by sustained release in intestinal fluids, achieving cumulative releases of 92.63% (P-1) and 82.64% (P-2) after 14 hours. The multifractal dynamics-based theoretical release curves closely matched the experimental data. Conclusions: MCM-48 mesoporous silica effectively enhanced metformin delivery, offering a controlled release profile well-suited for type 2 diabetes management. The multifractal theoretical framework provided valuable insights into drug release dynamics, contributing to the advancement of innovative drug delivery systems. Full article

We have previously shown that 2-thiouridine (S2U), either as a single nucleoside or as an element of RNA chain, is effectively desulfurized under applied in vitro oxidative conditions. The chemically induced desulfuration of S2U resulted in two products: 4-pyrimidinone nucleoside (H2U) and uridine (U). Recently, we investigated whether the desulfuration of S2U is a natural process that also occurs in the cells exposed to oxidative stress or whether it only occurs in the test tube during chemical reactions with oxidants at high concentrations. Using different types of eukaryotic cells, such as baker’s yeast, human cancer cells, or modified HEK293 cells with an impaired antioxidant system, we confirmed that 5-substituted 2-thiouridines are oxidatively desulfurized in the wobble position of the anticodon of some tRNAs. The quantitative LC-MS/MS-MRMhr analysis of the nucleoside mixtures obtained from the hydrolyzed tRNA revealed the presence of the desulfuration products of mcm5S2U: mcm5H2U and mcm5U modifications. We also observed some amounts of immature cm5S2U, cm5H2U and cm5U products, which may have indicated a disruption of the enzymatic modification pathway at the C5 position of 2-thiouridine. The observed process, which was triggered by oxidative stress in the living cells, could impair the function of 2-thiouridine-containing tRNAs and alter the translation of genetic information. Full article

Application of the FOLFOX scheme to colorectal cancer (CRC) patients often results in the development of chemo-resistance, leading to therapy failure. This study aimed to develop a functional and easy-to-use algorithm to predict patients’ response to FOLFOX treatment. Transcriptomic data of CRC patient’s samples treated with FOLFOX were downloaded from the Gene Expression Omnibus database (GSE83129, GSE28702, GSE69657, GSE19860 and GSE41568). Comparing the expression of top up- and downregulated genes in FOLFOX responder and non-responder patients’ groups, we selected 30 potential markers that were used to create a step-by-step eliminative procedure based on modified radial data visualization, which depicts the interplay between the expression level of chosen attributes (genes) to locate data points in low-dimensional space. Our analysis proved that FOLFOX-resistant CRC samples are predominantly characterized by upregulated expression levels of TMEM182 and MCM9 and downregulated LRRFIP1. Additionally, the procedure developed based on expression levels of TMEM182, MCM9, LRRFIP1, LAMP1, FAM161A, KLHL36, ETV5, RNF168, SRSF11, NCKAP5, CRTAP, VAMP2, ZBTB49 and RIMBP2 proved to be capable in predicting FOLFOX therapy response. In conclusion, our approach can give a unique insight into clinical decision-making regarding therapy scheme administration, potentially increasing patients’ survival and, consequently, medical futility due to incorrect therapy application. Full article

The High-Temperature Gas-Cooled Pebble Bed Reactor (HTG-PBR) is notable in the advanced reactor realm for its online refueling capabilities and inherent safety features. However, the multiphysics coupling nature of HTG-PBR, involving neutronic analysis, pebble flow movement, and thermo-fluid dynamics, creates significant challenges for its development, optimization, and safety analysis. This study focuses on the high-fidelity neutronic modelling and analysis of HTG-PBR with an emphasis on achieving an equilibrium state of the reactor for long-term operations. Computational approaches are developed to perform high-fidelity neutronics analysis by coupling the superior modelling capacities of the Monte Carlo Method (MCM) and Discrete Element Method (DEM). The MCM-based code OpenMC and the DEM-based code LIGGGHTS are employed to simulate the neutron transport and pebble movement phenomena in the reactor, respectively. To improve the computational efficiency to expedite the equilibrium core search process, the reactor core is discretized by grouping pebbles in axial and radial directions with the incorporation of the pebble position information from DEM simulations. The OpenMC model is modified to integrate fuel circulation and fresh fuel loading. All of these measures ultimately contribute to a successful generation of an equilibrium core for HTG-PBR. For demonstration, X-energy’s Xe-100 reactor—a 165 MW thermal power HTG-PBR—is used as the model reactor in this study. Starting with a reactor core loaded with all fresh pebbles, the equilibrium core search process indicates the continuous loading of fresh fuel is required to sustain the reactor operation after 1000 days of fuel depletion with depleted fuel circulation. Additionally, the model predicts 213 fresh pebbles are needed to add to the top layer of the reactor to ensure the k_eff does not reduce below the assumed reactivity limit of 1.01. Full article

Plastic pollution is a critical environmental issue due to the widespread use of plastic materials and their long degradation time. Hydrocracking (HDC) offers a promising solution to manage plastic waste by converting it into valuable products, namely chemicals or fuels. This work aims to investigates the effect of catalyst accessibility and acidity on the HDC reaction of high density polyethylene (HDPE). Therefore, a variety of materials with significant differences in both textural and acidic properties were tested as catalysts. These include H-USY and H-ZSM.5 zeolites with various Si/Al molar ratios (H-USY: Si/Al = 2.9, 15, 30 and 40; H-ZSM-5: Si/Al = 11.5, 40, 500) and mesostructured MCM-41 materials modified with Ga and Al, also with different Si/metal ratios (Si/Al = 16 and 30; Si/Ga = 63 and 82). Thermogravimetric analysis under hydrogen atmosphere was used as a preliminary screening tool to evaluate the potential of the various catalysts for this application in terms of energy requirements. In addition, batch autoclave reactor experiments (T = 300 °C, PH₂ = 20 bar, t = 60 min) were conducted to obtain further information on conversion, product yields and product distribution for the most promising systems. The results show that the catalytic performance in HDPE hydrocracking is determined by a balance between the acidity of the catalyst and its structural accessibility. Accordingly, for catalyst series where the structural and textural properties do not vary with the Si/Al ratio, there is a clear correlation of the HDPE degradation temperature and of the HDPE conversion with the Si/metal ratio (which relates to the acidic properties). In contrast, for catalyst series where the structural and textural properties vary with the Si/Al ratio, no consistent trend is observed and the catalytic performance is determined by a balance between the acidic and textural properties. The product distribution was also found to be influenced by the physical and chemical properties of the catalyst. Catalysts with strong acidity and smaller pores were observed to favor the formation of lighter hydrocarbons. In addition to the textural and acidic properties of the catalyst, the role of coke formation should not be neglected to ensure a comprehensive analysis of the catalytic performance. Full article

A siliceous material in which a framework order was established with a surfactant with sixteen carbon atoms in alkyl chains, MCM-41-C16, was synthesised, surface-modified, and tested regarding the selected physical properties. The pristine material was extracted in an acidic aqueous alcohol and then lined with different surface groups. The properties of four adsorbents were investigated using XRD, X-ray photoelectron spectroscopy, and N2 physisorption techniques. The unit–cell constant was determined from X-ray diffractograms, being in fixed relation to the edge length of the hexagonal frame. The specific surface areas of mesopores and whole crystallites were determined from low-temperature N2-physisorption isotherms. The novelty of this work is a mathematical model of a crystalline microstructure explaining the sizes and shapes of crystalline grains in relation to adsorption features, proposed and successfully tested with the aforementioned experimental data. The roughness of the surface is different from one that is necessary to explain the experimental characteristics quantitatively. Full article

Organic amine-modified mesoporous carriers are considered potential CO₂ sorbents, in which the CO₂ adsorption performance was limited by the agglomeration and volatility of liquid amines. In this study, four additives of ether compounds were separately coimpregnated with polyethylene polyamine (PEPA) into MCM-41 to prepare the composite chemisorbents for CO₂ adsorption. The textural pore properties, surface functional groups and elemental contents of N for MCM-41 before and after functionalization were characterized; the effects of the type and amount of additives, adsorption temperature and influent velocity on CO₂ adsorption were investigated; the amine efficiency was calculated; and the adsorption kinetics and regeneration for the optimized sorbent were studied. For 40 wt.% PEPA-loaded MCM-41, the CO₂ adsorption capacity and amine efficiency at 60 °C were 1.34 mmol/g and 0.18 mol CO₂/mol N, when the influent velocity of the simulated flue gas was 30 mL/min, which reached 1.81 mmol/g and 0.23 mol CO₂/mol N after coimpregnating 10 wt.% of 2-propoxyethanol (1E). The maximum adsorption capacity of 2.16 mmol/g appeared when the influent velocity of the simulated flue gas was 20 mL/min. In addition, the additive of 1E improved the regeneration and kinetics of PEPA-loaded MCM-41, and the CO₂ adsorption process showed multiple adsorption routes. Full article

Polyphenolic extracts from wild bilberries (Vaccinium myrtillus L.) have shown antioxidant and anti-inflammatory effects, but they are prone to degradation when exposed to environmental factors, limiting their use in biomedical applications. To overcome this issue, this study proposed the embedding of wild bilberry fruit ethanolic extracts in pristine mesoporous silica functionalized with organic groups (mercaptopropyl and propionic acid), as well as coated with fucoidan, a biopolymer. Herein, we report a stability study of free and incorporated extracts in mesoporous silica-type supports in high-humidity atmospheres at 40 °C up to 28 days, using HPLC analysis, thermal analysis, and radical scavenging activity determination. Better chemical and thermal stability over time was observed when the extracts were incorporated in mesoporous silica-type supports. After 12 months of storage, higher values of antioxidant activity were determined for the extract embedded in the supports, silica modified with mercaptopropyl groups (MCM-SH), and fucoidan-coated silica (MCM-SH-Fuc) than that of the free extract due to a synergistic activity between the support and extract. All encapsulated extracts demonstrated remarkable effects in reducing NO production in LPS-stimulated RAW 264.7 cells. The treatment with extract embedded in MCM-SH-Fuc in a dose of 10 μg/mL surpassed the effect of free extract in the same concentration. For the extract encapsulated in an MCM-SH support, a lower IC₅₀ value (0.69 μg/mL) towards COX-2 was obtained, comparable with that of Indomethacin (0.6 μg/mL). Also, this sample showed a higher selectivity index (2.71) for COX-2 than the reference anti-inflammatory drug (0.98). The developed formulations with antioxidant and anti-inflammatory properties could be further used in nutraceuticals. Full article

Curcumin is a polyphenol of the Curcuma longa plant, which can be used for various medicinal purposes, such as inflammation and cancer treatment. In this context, two symmetric curcumin derivatives (D1—(1E,6E)-1,7-bis(4-acetamidophenyl)hepta-1,6-diene-3,5-dione and D2—p,p-dihydroxy di-cinnamoyl methane) were obtained by the microwave-based method and evaluated for their antitumoral effect on human cervix cancer in comparison with toxicity on non-tumoral cells, taking into account that they were predicted to act as apoptosis agonists or anti-inflammatory agents. The HeLa cell line was incubated for 24 and 72 h with a concentration of 50 μg/mL of derivatives that killed almost half of the cells compared to the control. In contrast, these compounds did not alter the viability of MRC-5 non-tumoral lung fibroblasts until 72 h of incubation. The nitric oxide level released by HeLa cells was higher compared to MRC-5 fibroblasts after the incubation with 100 μg/mL. Both derivatives induced the decrease of catalase activity and glutathione levels in cancer cells without targeting the same effect in non-tumoral cells. Furthermore, the Western blot showed an increased protein expression of HSP70 and a decreased expression of HSP60 and MCM2 in cells incubated with D2 compared to control cells. We noticed differences regarding the intensity of cell death between the tested derivatives, suggesting that the modified structure after synthesis can modulate their function, the most prominent effect being observed for sample D2. In conclusion, the outcomes of our in vitro study revealed that these microwave-engineered curcumin derivatives targeted tumor cells, much more specifically, inducing their death. Full article

Peanut shells, a major economic and oil crop in China, boast an abundant availability and remarkably high lignin content compared to other agricultural residues. Previous work indicated that the modified hierarchical zeolite (Zn-ZSM-5/MCM41) was effective in promoting the conversion of intermediate macromolecules during the lignin pyrolysis reaction and enhancing the yield and selectivity of liquid products. Thereby, this study aims to improve the quality of liquid products in the ex situ catalytic microwave co-pyrolysis of peanut shells and LDPE by utilizing Zn-ZSM-5/MCM41. Employing a compound center experimental design, we optimized reaction conditions through response surface analysis. The impact of microwave pyrolysis temperature and the catalyst-to-feedstock ratio on yield distribution and liquid product selectivity was explored. Results indicated a marginal increase in liquid product yield with rising pyrolysis temperatures. Moreover, an initial increase followed by a subsequent decrease in liquid product yield was observed with an increase in the catalyst-to-feedstock ratio. Optimal conditions of 450 °C and a catalyst-to-peanut hull ratio of 2.34% yielded the highest bio-oil yield at 34.25%. GC/MS analysis of the bio-oil revealed a peak in hydrocarbon content at 68.36% under conditions of 450 °C and a catalyst-to-feedstock ratio of 13.66%. Additionally, the quadratic model effectively predicted bio-oil yield and the selectivity for major chemical components. This study underscores the potential of Zn-ZSM-5/MCM41 in optimizing liquid product quality during catalytic co-pyrolysis, offering insights into bio-oil production and its chemical composition. Full article

The deficient management of plastic waste has caused a serious worldwide environmental problem. Thus, one of the main challenges for the industry in the plastics sector in contributing to sustainability and a circular economy consists of providing a subsequent service life to this waste. For that purpose, the appropriate incorporation of antioxidants will play a key role in preventing or postponing the degradation of plastic waste, where the formation of radicals is initiated during its previous lifetime by the action of degrading agents. Functionalized particles, based on mesoporous MCM-41 silica with Irganox 1076, were prepared with two different protocols and were further incorporated into a material containing virgin PP and 30 wt.% of recycled PP, with the purpose of guaranteeing thermal stability during its next service life. A very significant increase in the thermal stability of the resulting composites was found, attributable to the synergistic action between the Irganox 1076 antioxidant and the MCM-41 particles. In addition, the presence of hybrid particles leads to an important nucleating effect for the crystallization of PP. Moreover, a reinforcing role was also played by these modified mesoporous silicas in the resultant systems. The presented methodology constitutes, therefore, a promising strategy for contributing to the circular economy—since the synergy between the Irganox 1076 antioxidant and MCM-41 particles was found to play an important role in the ultimate performance of recycled polyolefins. Full article

We explore the use of industrial sources of silicon and surfactant for obtaining low-cost MCM-41 materials and evaluate their performances as CO₂ adsorbents. All of them presented a high specific surface area with different structural characteristics and textural properties. Interestingly, the MCM-41 manufactured with the most economical reagents presented a S_BET of 1602 m²·g⁻¹. The template was removed by using thermal treatments in an air atmosphere or a washing process. Preservation of silanol groups proved to be more effective under washing or mild thermal treatment conditions with the advantage of their lower cost and environmental benefit. Surface reactivity against CO₂ was enhanced by anchoring APTS to silanol groups through wet grafting. All amino-functionalized materials showed a performance as CO₂ adsorbents comparable to those reported in the literature, reaching values close to 30 cm³·g⁻¹ at 25 °C and 760 mmHg. Samples with a higher concentration of silanol groups showed better performance. Our studies indicate that adsorbed CO₂ is retained at least up to 50 °C, and the CO₂ is chemisorbed on the silica modified with amine groups. The chemisorbed gas at very low pressures points to the potential use of these materials for CO₂ storage. Full article