Search Results (24)

Mining activities have a significant impact on the quality of river water in the Roșia Montană area. This region, known for its gold and other precious metal mining, serves as an example of the interaction between anthropogenic activities and the natural environment. Water from mine drainage is metal-rich and contaminates the environment, inhibiting the growth and reproduction of aquatic plants and animals, while also having corrosive effects on infrastructure. As part of the study, parameters such as pH, dissolved oxygen, biochemical oxygen demand, chemical oxygen demand, sulfates, and heavy metals were monitored for the rivers in the area (Roșia Montană, Săliște, Corna, Abrud, and Arieș). Roșia Montană river shows a decrease in pH to highly acidic values (2.69–3.95), especially in the downstream sections. Sulfate concentrations exceed 3600 mg/L, and heavy metal concentrations (Fe, Zn, As, Mn) increase significantly, indicating severe pollution, primarily originating from the Gura Mine gallery. These frequently exceed the thresholds corresponding to water quality classes I and II, and in some cases even surpass the limits of class V (the most polluted). The presence of As (27.60 µg/L) in Roșia Montană River indicates a significant ecotoxicological risk. In an attempt to treat the acid mine drainage from Roșia Montană, a natural zeolite was used at different doses. The results obtained show good efficiency of zeolite in removing the metal ions (Fe, Zn, and Mn). The results provide valuable information on the quality of river waters in the mining area of Roșia Montană and suggest that zeolite can be used effectively to decontaminate mine waters. Full article

The advancement of both porous materials and nanomaterials has brought about porous nanomaterials. These new materials present advantages both due to their porosity and nano-size: small size apt for micro/nano device integration or in vivo transport, large surface area for guest/target molecule adsorption and interaction, porous channels providing accessibility to active/surface sites, and exposed reactive surface/active sites induced by uncoordinated bonds. These properties prove useful for the development of different porous composition types (metal oxides, silica, zeolites, amorphous oxides, nanoarrays, precious metals, non-precious metals, MOFs, carbon nanostructures, MXenes, and others) through different synthetic procedures—templating, colloidal synthesis, hydrothermal approach, sol-gel route, self-assembly, dealloying, galvanostatic replacement, and so—for different applications, such as catalysis (water-splitting, etc.), biosensing, energy storage (batteries, supercapacitors), actuators, SERS, and bio applications. Here, these are presented according to different material types showing the evolution of the structure design and development towards the formation of hierarchical porous structures, emphasizing that the formation of porous nanostructures came about out of the desire and need to form hierarchical porous nanostructures. Common trends observed across these different composition types include similar (aforementioned) applications and the use of porous nanomaterials as templates/precursors to create novel ones. Towards the end, a discussion on the link between technological advancements and the development of porous nanomaterials paves the way to present future perspectives on these nanomaterials and their hierarchical porous architectures. Together with a summary, these are given in the conclusion. Full article

Resveratrol is a polyphenolic compound that has gained considerable attention in the past decade due to its multifaceted therapeutic potential, including anti-inflammatory and anticancer properties. However, its anticancer efficacy is impeded by low water solubility, dose-limiting toxicity, low bioavailability, and rapid hepatic metabolism. To overcome these hurdles, various nanoparticles such as organic and inorganic nanoparticles, liposomes, polymeric nanoparticles, dendrimers, solid lipid nanoparticles, gold nanoparticles, zinc oxide nanoparticles, zeolitic imidazolate frameworks, carbon nanotubes, bioactive glass nanoparticles, and mesoporous nanoparticles were employed to deliver resveratrol, enhancing its water solubility, bioavailability, and efficacy against various types of cancer. Resveratrol-loaded nanoparticle or resveratrol-conjugated nanoparticle administration exhibits excellent anticancer potency compared to free resveratrol. This review highlights the latest developments in nanoparticle-based delivery systems for resveratrol, focusing on the potential to overcome limitations associated with the compound’s bioavailability and therapeutic effectiveness. Full article

Preserving ultrasmall sizes of metal particles is a key challenge in the study of heterogeneous metal-based catalysis. Confining the ultrasmall metal clusters in a well-defined crystalline porous zeolite has emerged as a promising approach to stabilize these metal species. Successful encapsulation can be achieved by the addition of ligated metal complexes to zeolite synthesis gel before hydrothermal synthesis. However, controlling the metal particle size during post-reduction treatment remains a major challenge in this approach. Herein, an in situ incorporation strategy of pre-made atomically precise gold clusters within Na-LTA zeolite was established for the first time. With the assistance of mercaptosilane ligands, the gold clusters were successfully incorporated within the Na-LTA without premature precipitation and metal aggregation during the synthesis. We have demonstrated that the confinement of gold clusters within the zeolite framework offers high stability against sintering, leading to superior CO oxidation catalytic performance (up to 12 h at 30 °C, with a space velocity of 3000 mL g⁻¹ h⁻¹). Full article

Two multifunctional catalytic systems comprising Sn-based/doped crystalline zeolite Beta were synthesized, and they were employed as heterogeneous catalysts in the selective conversion of glycerol to methyl lactate. The first catalytic system, named Au-Pd-Sn-deAl-7.2-Beta-DP, was created through the post-synthesis dealumination of the parent zeolite Beta (Si/Al = 10) using 7.2 M HNO₃. Subsequently, it was grafted with 27 mmol of SnCl₄, resulting in Sn-deAl-7.2-Beta. Following this, Au and Pd nanoparticles were supported on this catalyst using the deposition–precipitation (DP) method. The second catalytic system was a physical mixture of Au and Pd nanoparticles supported on functionalized carbon nanotubes (Au-Pd-F-CNTs) and Sn-containing zeolite Beta (Sn-deAl-7.2-Beta). Both catalytic systems were employed in glycerol partial oxidation to methyl lactate under the following conditions: 140 °C for 4.5 h under an air pressure of 30 bar. The Au-Pd-Sn-deAl-7.2-Beta-DP catalytic system demonstrated 34% conversion of glycerol with a 76% selectivity for methyl lactate. In contrast, the physical mixture of Au-Pd-F-CNTs and Sn-deAl-7.2-Beta exhibited higher activity, achieving 58% glycerol conversion and a nearly identical selectivity for methyl lactate (77%). The catalytic results and catalyst structure were further analyzed using various characterization techniques, such as X-ray diffraction (XRD), N₂ physisorption, scanning electron microscopy (SEM), X-ray fluorescence (XRF), transmission electron microscopy (TEM), UV-vis spectroscopy, and pyridine Fourier transform infrared (FTIR). These analyses emphasized the significance of adjusting the quantity of active sites, particle size, and active sites proximity under the chosen reaction conditions. Full article

The mycotoxin deoxynivalenol (DON) is a prevalent contaminant in cereals that threatens the health of both humans and animals and causes economic losses due to crop contamination. The rapid and sensitive detection of DON is essential for food safety. Herein, a colorimetric biosensor based on horseradish peroxidase- and gold nanoparticle-encapsulated zeolitic imidazolate framework-8 (HRP&Au@ZIF-8) was developed for the sensitive screening of DON. The synthesized HRP&Au@ZIF-8 probes not only held great potential for signal amplification but also exhibited stable catalytic activity even under extreme conditions, which endowed the biosensor with both good sensitivity and stability. Under the optimized conditions, qualitative measurement of DON can be achieved through visual inspection, and quantitative evaluation can be performed via absorbance measurements at a characteristic wavelength of 450 nm. The proposed method has demonstrated high sensitivity with a linear detection range of 1–200 ng/mL and a detection limit of 0.5068 ng/mL. It also presented good selectivity and reliability. Furthermore, DON in spiked cereal samples has been quantified successfully using this method. This novel approach demonstrates significant potential for the facile and expeditious detection of DON in cereal products and brings us one step closer to enhancing food safety. Full article

The present work reports the synthesis of efficient Ti–Au/zeolite Y photocatalysts by different processing of aluminosilicate gel and studies the effect of titania content on the structural, morphological, textural, and optical properties of the materials. The best characteristics of zeolite Y were obtained by aging the synthesis gel in static conditions and mixing the precursors under magnetic stirring. Titania (5, 10, 20%) and gold (1%) species were incorporated in zeolite Y support by the post-synthesis method. The samples were characterized by X-ray diffraction, N₂-physisorption, SEM, Raman, UV–Vis and photoluminescence spectroscopy, XPS, H₂-TPR, and CO₂-TPD. The photocatalyst with the lowest TiO₂ loading shows only metallic Au on the outermost surface layer, while a higher content favors the formation of additional species such as: cluster type Au, Au¹⁺, and Au³⁺. A high TiO₂ content contributes to increasing the lifetime of photogenerated charge careers, and the adsorption capacity of the pollutant. Therefore, an increase in the photocatalytic performances (evaluated in degradation of amoxicillin in water under UV and visible light) was evidenced with the titania content. The effect is more significant in visible light due to the surface plasmon resonance (SPR) effect of gold interacting with the supported titania. Full article

In this study, a novel “on-off-enhanced on” approach to highly sensitive rapid sensing of biothiols was developed, based on competitive modulation of gold nanoclusters (AuNCs) and Hg²⁺ ions. In our approach, the AuNCs were encapsulated into a zeolite imidazole framework (ZIF) for predesigned competitive aggregation-induced luminescence (AIE) emission. To readily operate this approach, the Hg²⁺ ions were selected as mediators to quench the fluorescence of AuNCs. Then, due to the stronger affinities between the interactions of Hg²⁺ ions with -SH groups in comparison to the AuNCs with -SH groups, the quenched probe of AuNCs@ZIF-8/Hg²⁺ displayed enhanced fluorescence after the Hg²⁺ ions were competitively interacted with -SH groups. Based on enhanced fluorescence, the probe for AuNCs@ZIF-8/Hg²⁺ had a sensitive and specific response to trace amounts of biothiols. The developed fluorescence strategy had limit of quantification (LOQ) values of 1.0 μM and 1.5 μM for Cys and GSH molecules in serum, respectively. This competitive AIE strategy provided a new direction for developing biological probes and a promising method for quantifying trace amounts of biothiols in serum. It could promote progress in disease diagnosis. Full article

Gold (Au) and palladium (Pd) are platinum group metals (PGMs) that are considered critical in society because they are required in several industrial applications. Their shortage has caused the urgent need for their recovery from secondary resources. Therefore, there is a need to develop functional materials with high adsorption capacity and selectivity for recovery of PGMs from various secondary sources. In this study, a Zn-Al-layered double hydroxide@zeolitic imidazolate framework-8 (Zn–Al–LDH@ZIF–8) nanocomposite was used as an adsorbent for the recovery of Au and Pd from ore concentrates. The Zn–Al–LDH@ZIF–8 nanocomposite was characterised using scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), transmission electron spectroscopy, Fourier-transform infrared (FTIR) spectroscopy, zeta potential, and X-ray diffraction (XRD) spectroscopy. The recovery of Au(III) and Pd(II) was achieved using ultrasound-assisted dispersive µ-solid-phase extraction (UA-D-µ-SPE) and their quantification was attained using an inductively coupled plasma mass spectrometer (ICP-MS). The results showed that the surface of the adsorbent remained positively charged in a wide pH range, which endowed the nanocomposite with high adsorption affinity towards Au(III) and Pd(II). Under optimised conditions, the equilibrium studies revealed that the adsorption of Au(III) and Pd(II) ions followed the Langmuir isotherm model with maximum sorption capacities of 163 mg g⁻¹ and 177 mg g⁻¹ for Au(III) and Pd(II), respectively. The nanocomposite possessed relatively good regeneration, reusability, and stability characteristics, with its performance decreasing by only 10% after five adsorption–desorption cycles. Full article

New photocatalysts were obtained by immobilization of titanium and gold species on zeolite Y, hierarchical zeolite Y, MCM-48 and KIT-6 supports with microporous, hierarchical and mesoporous cubic structure. The obtained samples were characterized by X-ray diffraction (XRD), N₂-physisorption, scanning and transmission electron microscopy (SEM/TEM), diffuse reflectance UV–Vis spectroscopy (DRUV-Vis), X-ray photoelectron spectroscopy (XPS), Raman and photoluminescence spectroscopy. The photocatalytic properties were evaluated in degradation of amoxicillin (AMX) from water, under UV (254 nm) and visible light (532 nm) irradiation. The higher degradation efficiency and best apparent rate constant were obtained under UV irradiation for Au-TiO₂-KIT-6, while in the visible condition for the Au-TiO₂-MCM-48 sample containing anatase, rutile and the greatest percent of Au metallic clusters were found (evidenced by XPS). Although significant values of amoxicillin degradation were obtained, total mineralization was not achieved. These results were explained by different reaction mechanisms, in which Au species act as e⁻ trap in UV and e⁻ generator in visible light. Full article

Activity of gold supported catalysts strongly depends on the type and composition of support, which determine the size of Au nanoparticles (Au NPs), gold-support interaction influencing gold properties, interaction with the reactants and, in this way, the reaction pathway. The aim of this study was to use two types of zeolites: the three dimensional HBeta and the layered two-dimensional MCM-36 as supports for gold, and modification of their properties towards the achievement of different properties in oxidation of glucose to gluconic acid with molecular oxygen and hydrogen peroxide. Such an approach allowed establishment of relationships between the activity of gold catalysts and different parameters such as Au NPs size, electronic properties of gold, structure and acidity of the supports. The zeolites were modified with (3-aminopropyl)-trimethoxysilane (APMS), which affected the support features and Au NPs properties. Moreover, the modification of the zeolite lattice with boron was applied to change the strength of the zeolite acidity. All modifications resulted in changes in glucose conversion, while maintaining high selectivity to gluconic acid. The most important findings include the differences in the reaction steps limiting the reaction rate depending on the nature of the oxidant applied (oxygen vs. H₂O₂), the important role of porosity of the zeolite supports, and accumulation of negative charge on Au NPs in catalytic oxidation of glucose. Full article

Four different methods for gold deposition on Beta zeolite, namely impregnation, ion-exchange, deposition-reduction, and grafting on (3-aminopropyl)trimethoxysilane functionalized support, were applied to investigate their influence on textural/structural changes in the zeolite support and its surface acidity. The as-prepared materials were fully characterized by XRD, N₂ physisorption, ICP-OES, XPS, TEM, and pyridine adsorption. The obtained results indicated that bifunctional redox–acidic materials prepared within this work were characterized not only by different gold loading and gold particle size, but also different textural parameters and acidity. All these features were strongly affected by the procedure applied for gold deposition. The introduction of Au into Beta zeolite by ion exchange caused a significant decrease in the Si/Al ratio in the zeolite framework. The size of Au particles determined the textural parameters of the zeolite and the number of Lewis acid sites (LAS). The Brønsted acid sites (BAS) number was decreased if (3-aminopropyl)trimethoxysilane or NaBH₄ were used in the procedure of gold deposition. The highest BAS/LAS ratio was achieved for the sample prepared by ion exchange in the ammonium form of Beta zeolite. The presented results permit making a proper choice of the gold modification procedure for the preparation of bifunctional (redox–acidic) materials, addressed to a desired application. Full article

A sensitive fluorescence resonance energy transfer (FRET) biosensor is proposed to detect 8-hydroxy-2′-deoxyguanosine (8-OHdG), which is a typical DNA oxidation damage product excreted in human urine. The FRET biosensor was based on carbon dots (CDs)-modified nanoporous alumina membrane with CDs as fluorescence donors. Gold nanoparticles were encapsulated in zeolitic imidazolate framework-8 to form Au@ZIF-8 nanoparticles as signal quenchers. CDs and Au@ZIF-8 nanoparticles were biofunctionalized by 8-OHdG antibody. The capture of 8-OHdG on the membrane substrates can bring Au@ZIF-8 nanoparticles closely to CDs. With 350 nm excitation, the fluorescence of CDs was quenched by Au@ZIF-8 nanoparticles and FRET effect occurred. The quenching efficiency was analyzed. The limit of detection (LOD) was 0.31 nM. Interference experiments of the FRET biosensor showed good specificity for 8-OHdG detection. The biosensor could detect urinary 8-OHdG sensitively and selectively with simple sample pretreatment processes. It shows applicability for detecting biomarkers of DNA damage in urine or other biological fluids. Full article

We introduce fluoride-selective anion exchange resin sorbents as sensitisers into membranes for water-gated field effect transistors (WGTFTs). Sorbents were prepared via metal (La or Al)-loading of a commercial macroporous aminophosphonic acid resin, Puromet^TM MTS9501, and were filled into a plasticised poly(vinyl chloride) (PVC) phase transfer membrane. We found a potentiometric response (membrane potential leading to WGTFT threshold shift) to fluoride following a Langmuir–Freundlich (LF) adsorption isotherm with saturated membrane potential up to ~480 mV, extremely low characteristic concentration c_1/2 = 1/K, and picomolar limit of detection (LoD), even though ion exchange did not build up charge on the resin. La-loading gave a superior response compared to Al-loading. Membrane potential characteristics were distinctly different from charge accumulating sensitisers (e.g., organic macrocycles) but similar to the Cs⁺ (cation) selective ion-exchanging zeolite mineral ‘mordenite’. We propose a mechanism for the observed threshold shift and investigate interference from co-solutes. Strong interference from carbonate was brought under control by ‘diluting’ metal loading in the resin. This work sets a template for future studies using an entirely new ‘family’ of sensitisers in applications where very low limit of detection is essential such as for ions of arsenic, mercury, copper, palladium, and gold. Full article

Immobilization of gold nanoparticles (AuNPs) on the surface of zeolite has received a great interest due to Au@zeolite’s unique characteristics and high performance for catalysis. In this work we studied the grafting of two different functional molecules; one having an amine group (3-aminopropyl)triethoxysilane (APTES) and the second having a thiol group (3-mercaptopropyl)trimethoxysilane (MPTES) on the surface of zeolite using the same wet chemistry method. The modified zeolite surfaces were characterized using zeta potential measurements; diffuse reflectance infrared fourier transform (DRIFT) and X-ray photoelectron spectroscopy (XPS). The results confirmed a successful deposition of both functional groups at the topmost surface of the zeolite. Furthermore; transmission electron microscopy (TEM), ultraviolet-visible (UV-Vis) spectroscopy and XPS results clearly evidenced that APTES provided a better AuNPs immobilization than MPTES as a result of; (1) less active functions obtained after MPTES deposition, and (2) the better attaching ability of thiol to the gold surface. Full article