Search Results (19)

A helium ion microscope (HIM) with a focused He⁺-ion beam of variable flux and energy can be used as a tool for local nanoscale surface modification. In this work, we demonstrate a simple but versatile use of the HIM focused He ion beam to fabricate conducting metallic nano- and microstructures on arbitrary substrates of varied types and shapes by directly patterning pre-deposited initially discontinuous and highly insulating (>10 TΩ/sq.) ultrathin metal films. Gold or silver films, measuring 3 nm in thickness, thermally evaporated on solid substrates have a discontinuous nanocluster morphology. Such highly resistive films can be made locally conductive using moderate doses (2 × 10¹⁶–10¹⁷ cm⁻²) of low-energy (30 KeV) ion bombardment. We show that an HIM can be used to directly “draw” Au and Ag conductive lines and other patterns with a variable sheet resistance as low as 10 kΩ/sq. without the use of additional precursors. This relatively straightforward, high-definition technique of direct writing with an ion beam, free from complex in vacuo catalytic or precursor chemistries, opens up new opportunities for directly fabricating elements of conformal metallic nanocircuits (interconnects, resistors, and contacts) on arbitrary organic or inorganic substrates, including those with highly curved surfaces. Full article

The proposed paper describes a simple and environmentally friendly method for the synthesis of three-component polymer–inorganic composites, which includes the modification of zinc oxide or montmorillonite (MMT) with chitosan (CS), followed by the immobilization of palladium on the resulting two-component composites. The structures and properties of the obtained composites were characterized by physicochemical methods (IRS, TEM, XPS, SEM, EDX, XRD, BET). Pd–CS species covered the surface of inorganic materials through two different mechanisms. The interaction of chitosan polyelectrolyte with zinc oxide led to the deprotonation of its amino groups and deposition on the surface of ZnO. The immobilization of Pd on CS/ZnO occurred by the hydrolysis of [PdCl₄]²⁻, followed by forming PdO particles by interacting with amino groups of chitosan. In the case of CS/MMT, protonated amino groups of CS interacted with negative sites of MMT, forming a positively charged CS/MMT composite. Furthermore, [PdCl₄]²⁻ interacted with the –NH³⁺ sites of CS/MMT through electrostatic force. According to TEM studies of 1%Pd–CS/ZnO, the presence of Pd nanoclusters composed of smaller Pd nanoparticles of 3–4 nm in size were observed on different sites of CS/ZnO. For 1%Pd–CS/MMT, Pd nanoparticles with sizes of 2 nm were evenly distributed on the support surface. The prepared three-component CS–inorganic composites were tested through the hydrogenation of 2-propen-1-ol and acetylene compounds (phenylacetylene, 2-hexyn-1-ol) under mild conditions (T—40 °C, P_H2—1 atm). It was shown that the efficiency of 1%Pd–CS/MMT is higher than that of 1%Pd–CS/ZnO, which can be explained by the formation of smaller Pd particles that are evenly distributed on the support surface. The mechanism of 2-hexyn-1-ol hydrogenation over an optimal 1%Pd–CS/MMT catalyst was proposed. Full article

Gold nanoclusters are peculiar objects promising in view of qualitative and quantitative determination of various species, including heavy metal ions and biological molecules. We have recently discovered that introducing sodium azide in the reaction mixture during gold nanocluster synthesis in the presence of citrate and adenosine monophosphate can tune the product emission from blue to yellow. Taking advantage of the factorial design of the experiment, we have optimized the synthesis conditions to obtain pure blue and yellow emitters and investigate their sensitivity to a series of inorganic salts. The experiments have revealed selective quenching of the nanocluster’s fluorescence in the presence of mercury(II) ions. Full article

Herein, we synthesized two isostructural supertetrahedral T3 cluster-based chalcogenide compounds by an ionic liquid-assisted precursor technique, namely [Bmmim]₆In₁₀Q₁₆Cl₄∙(MIm)₄ (Q = S (In-S), Q = Se (In-Se), Bmmim = 1-butyl-2,3-dimethylimidazolium, MIm = 1- methylimidazole). The two compounds consist of a pure inorganic discrete supertetrahedral [In₁₀Q₁₆Cl₄]^6- T3 cluster and six charge-balancing [Bmmim]⁺ anions. The T3 clusters could be highly dispersed in dimethyl sulfoxide (DMSO), exposing more photocatalytic active sites, which makes the highly-dispersed In-Se cluster exhibit ~5 times higher photocatalytic H₂ evolution activity than that of the solid-state under visible light irradiation. Comparatively, the photocatalytic performance of the highly-dispersed In-S cluster is only slightly higher than that of the solid state, as its inferior visible-light absorption capability limits the effective utilization of photons. More importantly, through tracking the photogenerated carriers dynamics of highly-dispersed T3 clusters by ultrafast transient absorption (TA) spectroscopy, we found that the photogenerated electrons in the In-S cluster would suffer a rapid internal deactivation process under illumination, whereas the photoexcited electrons in the In-Se cluster can be captured by its surface active centers that would effectively reduce its photogenerated carrier recombination, contributing to the significantly enhanced photocatalytic activity. This work enriches the species of highly-dispersed metal-chalcogenide nanoclusters and firstly investigates the relationship between the structures and photocatalytic performances of nanoclusters by ultrafast excited-state dynamics, which is expected to promote the development of atomically precise nano-chemistry. Full article

Effective removal of toxic inorganic and organic pollutants is one of the current leading challenges of wastewater treatment. In this study, the decomposition of methylene blue (MB) under UV light irradiation was investigated in the presence of copper nanoclusters (NCs)-deposited polyethylene terephthalate (PET) track-etched hybrid membranes. PET track-etched membranes (TeMs) with an average pore size of ~400 nm were grafted by functional acrylic acid (AA) monomer under electron beam irradiation after oxidation with H₂O₂/UV system. The radiation dose varied between 46 and 200 kGy. For the deposition of copper NCs, poly(acrylic acid) (PAA)-grafted membranes saturated with Cu(II) ions were irradiated either by electron beam or γ-rays to obtain copper-based NCs for the catalytic degradation of MB. Irradiation to 100 kGy with accelerated electrons resulted in the formation of small and uniform copper hydroxide (Cu(OH)₂) nanoparticles homogeneously distributed over the entire volume of the template. On the other hand, irradiation under γ-rays yielded composites with copper NCs with a high degree of crystallinity. However, the size of the deposited NCs obtained by γ-irradiation was not uniform. Nanoparticles with the highest uniformity were obtained at 150 kGy dose. Detailed analysis by X-ray diffraction (XRD) and scanning electron microscopy (SEM) confirmed the loading of copper nanoparticles with an average size of 100 nm on the inner walls of nanochannels and on the surface of PET TeMs. Under UV light irradiation, composite membranes loaded with NCs exhibited high photocatalytic activity. It was determined that the highest catalytic activity was observed in the presence of Cu(OH)₂@PET-g-PAA membrane obtained at 250 kGy. More than 91.9% of the initial dye was degraded when this hybrid membrane was employed for 180 min, while only 83.9% of MB was degraded under UV light using Cu@PET-g-PAA membrane. Cu(OH)₂@PET-g-PAA membranes obtained under electron beam irradiation demonstrated a higher photocatalytic activity compared to Cu@PET-g-PAA membranes attained by γ-rays. Full article

Silver nanoclusters (Ag NCs) are nanoscale aggregates that possess molecular-like discrete energy levels, resulting in electronic configuration-dependent tunable luminescence spanning the entire visible range. Benefiting from the efficient ion exchange capacity, nanometer dimensional cages, and high thermal and chemical stabilities, zeolites have been employed as desirable inorganic matrices to disperse and stabilize Ag NCs. This paper reviewed the recent research progresses on the luminescence properties, spectral manipulation, as well as the theoretical modelling of electronic structure and optical transition of Ag NCs confined inside various zeolites with different topology structures. Furthermore, potential applications of the zeolite-encaged luminescent Ag NCs in lighting, gas monitoring and sensing were presented. This review concludes with a brief comment on the possible future directions in the study of zeolite-encaged luminescent Ag NCs. Full article

Atomically precise metal nanoclusters are a new kind of nanomaterials that appeared in recent years; a pair of isomer nanoclusters have the same metal types, numbers of metal atoms, and surface-protected organic ligands but different metal atom arrangements. This article summarizes the structure features of isomer nanoclusters and concentrates on synthesis methods that could lead to isomer structure. The pairs of isomer inorganic nanoclusters’ conversion to each other and their applications in catalyst and photoluminescence are also discussed. We found that the structure conversions are relevant to their stability. However, with the same molecule formulas, different atom arrangements significantly influence their performance in applications. Finally, the existing challenges and some personal perspectives for this novel field in the nano-science investigation are proposed. We hope this minireview can offer a reference for researchers interested in inorganic isomer nanoclusters. Full article

Over the last decades, the global life expectancy of the population has increased, and so, consequently, has the risk of cancer development. Despite the improvement in cancer therapies (e.g., drug delivery systems (DDS) and theranostics), in many cases recurrence continues to be a challenging issue. In this matter, the development of nanotechnology has led to an array of possibilities for cancer treatment. One of the most promising therapies focuses on the assembly of hierarchical structures in the form of nanoclusters, as this approach involves preparing individual building blocks while avoiding handling toxic chemicals in the presence of biomolecules. This review aims at presenting an overview of the major advances made in developing nanoclusters based on polymeric nanoparticles (PNPs) and/or inorganic NPs. The preparation methods and the features of the NPs used in the construction of the nanoclusters were described. Afterwards, the design, fabrication and properties of the two main classes of nanoclusters, namely noble-metal nanoclusters and hybrid (i.e., hetero) nanoclusters and their mode of action in cancer therapy, were summarized. Full article

Lab-on-paper technologies, also known as paper-based analytical devices (PADs), have received increasing attention in the last years, and nowadays, their use has spread to virtually every application area, i.e., medical diagnostic, food safety, environmental monitoring, etc. Advantages inherent to on-field detection, which include avoiding sampling, sample preparation and conventional instrumentation in central labs, are undoubtedly driving many developments in this area. Heavy metals represent an important group of environmental pollutants that require strict controls due to the threat they pose to ecosystems and human health. In this overview, the development of PADs for Hg monitoring, which is considered the most toxic metal in the environment, is addressed. The main emphasis is placed on recognition elements (i.e., organic chromophores/fluorophores, plasmonic nanoparticles, inorganic quantum dots, carbon quantum dots, metal nanoclusters, etc.) employed to provide suitable selectivity and sensitivity. The performance of both microfluidic paper-based analytical devices and paper-based sensors using signal readout by colorimetry and luminescence will be discussed. Full article

For sensitive and fast detection of Escherichia coli O157:H7, organic and inorganic hybrid Au/Fe³⁺ nanoclusters (NCs) were synthesized for the first time using gold nanoparticles (GNPs), bovine serum albumin, ferric chloride, phosphate-buffered saline, and antibodies. The Au/Fe³⁺ porous spongy NCs with large surface area showed excellent bio-specific capability for E. coli O157:H7. GNPs in Au/Fe³⁺ NCs functioned as signal enhancers, significantly increasing the Raman signal via the metathesis reaction product of Prussian blue and obviously improving the detection sensitivity. We combined the novel Au/Fe³⁺ NCs with antibody-modified magnetic nanoparticles to create a biosensor capable of sensitive detection of E. coli O157:H7, which showed a good linear response (10¹ to 10⁶ cfu/mL), high detection sensitivity (2 cfu/mL), and good recovery rate (93.60–97.50%) in spiked food samples. These results make the biosensor well-suited for food safety monitoring. This strategy achieves the goal of sensitive and quantitative detection of E. coli O157:H7. Full article

Emerging contaminants (ECs) represent a wide range of compounds, whose complete elimination from wastewaters by conventional methods is not always guaranteed, posing human and environmental risks. Advanced oxidation processes (AOPs), based on the generation of highly oxidizing species, lead to the degradation of these ECs. In this context, TiO₂ and ZnO are the most widely used inorganic photocatalysts, mainly due to their low cost and wide availability. The addition of small amounts of nanoclusters may imply enhanced light absorption and an attenuation effect on the recombination rate of electron/hole pairs, resulting in improved photocatalytic activity. In this work, we propose the use of silver nanoclusters deposited on ZnO nanoparticles (ZnO–Ag), with a view to evaluating their catalytic activity under both ultraviolet A (UVA) and visible light, in order to reduce energetic requirements in prospective applications on a larger scale. The catalysts were produced and then characterized by scanning electron microscopy (SEM), X-ray diffractometry (XRD) and inductively coupled plasma-optical emission spectrometry (ICP-OES). As proof of concept of the capacity of photocatalysts doped with nanoclusters, experiments were carried out to remove the azo dye Orange II (OII). The results demonstrated the high photocatalytic efficiency achieved thanks to the incorporation of nanoclusters, especially evident in the experiments performed under white light. Full article

We report the results of a computational study of TiO₂ nanoclusters of various sizes as well as of complex systems with various molecules adsorbed onto the clusters to set the ground for the modeling of charge transfer processes in hybrid organic–inorganic photovoltaics or photocatalytic degradation of pollutants. Despite the large number of existing computational studies of TiO₂ clusters and in spite of the higher computing power of the typical available hardware, allowing for calculations of larger systems, there are still studies that use cluster sizes that are too small and not appropriate to address particular problems or certain complex systems relevant in photovoltaic or photocatalytic applications. By means of density functional theory (DFT) calculations, we attempt to find acceptable minimal sizes of the Ti_nO_2n+2H₄ (n = 14, 24, 34, 44, 54) nanoclusters in correlation with the size of the adsorbed molecule and the rigidity of the backbone of the molecule to model systems and interface processes that occur in hybrid photovoltaics and photocatalysis. We illustrate various adsorption cases with a small rigid molecule based on coumarin, a larger rigid oligomethine cyanine dye with indol groups, and the penicillin V antibiotic having a flexible backbone. We find that the use of the n = 14 cluster to describe adsorption leads to significant distortions of both the cluster and the molecule and to unusual tridentate binding configurations not seen for larger clusters. Moreover, the significantly weaker bonding as well as the differences in the density of states and in the optical spectra suggest that the n = 14 cluster is a poor choice for simulating the materials used in the practical applications envisaged here. As the n = 24 cluster has provided mixed results, we argue that cluster sizes larger than or equal to n = 34 are necessary to provide the reliability required by photovoltaic and photocatalytic applications. Furthermore, the tendency to saturate the key quantities of interest when moving from n = 44 to n = 54 suggests that the largest cluster may bring little improvement at a significantly higher computational cost. Full article

Advances in surfactant-assisted chemical approaches have led the way for the exploitation of nanoscale inorganic particles in medical diagnosis and treatment. In this field, magnetically-driven multimodal nanotools that perform both detection and therapy, well-designed in size, shape and composition, are highly advantageous. Such a theranostic material—which entails the controlled assembly of smaller (maghemite) nanocrystals in a secondary motif that is highly dispersible in aqueous media—is discussed here. These surface functionalized, pomegranate-like ferrimagnetic nanoclusters (40–85 nm) are made of nanocrystal subunits that show a remarkable magnetic resonance imaging contrast efficiency, which is better than that of the superparamagnetic contrast agent Endorem^©. Going beyond this attribute and with their demonstrated low cytotoxicity in hand, we examine the critical interaction of such nanoprobes with cells at different physiological environments. The time-dependent in vivo scintigraphic imaging of mice experimental models, combined with a biodistribution study, revealed the accumulation of nanoclusters in the spleen and liver. Moreover, the in vitro proliferation of spleen cells and cytokine production witnessed a size-selective regulation of immune system cells, inferring that smaller clusters induce mainly inflammatory activities, while larger ones induce anti-inflammatory actions. The preliminary findings corroborate that the modular chemistry of magnetic iron oxide nanoclusters stimulates unexplored pathways that could be driven to alter their function in favor of healthcare. Full article

Herein we describe the preparation of hybrid polymer–inorganic interfaces by the immobilization of polyoxometalate nanoclusters on functionalized polymer surfaces. The polymeric surfaces were made of polystyrene-b-poly(acrylic acid)/polystyrene (PS-b-PAA/PS) blends by spin coating on a silicon wafer. The functionalization of the polymer film was obtained by interfacial migration of the amphiphilic block copolymer toward the interface upon water vapor annealing. The carboxylic acid functional groups contained in the PAA block were then employed to anchor the [Ln^III(α-SiW₁₁O₃₉)]⁵⁻ polyoxometalates (Ln: Ce, Er). This purpose was achieved by immersing the films in aqueous solutions of the in situ-formed inorganic nanoclusters. X-ray photoelectron and confocal Raman spectroscopies, together with atomic force microscopy, confirmed the immobilization of the inorganic species at the interface. Full article

Knowing the possible structures of individual clusters in nanostructured materials is an important first step in their design. With previous structure prediction data for BaO nanoclusters as a basis, data mining techniques were used to investigate candidate structures for magnesium oxide, calcium oxide and strontium oxide clusters. The lowest-energy structures and analysis of some of their structural properties are presented here. Clusters that are predicted to be ideal targets for synthesis, based on being both the only thermally accessible minimum for their size, and a size that is thermally accessible with respect to neighbouring sizes, include global minima for: sizes $n=9,15,16,18$ and 24 for (MgO) ${}_n$ ; sizes $n=8,9,12,16,18$ and 24 for (CaO) ${}_n$ ; the greatest number of sizes of (SrO) ${}_n$ clusters ( $n=8,9,10,12,13,15,16,18$ and 24); and for (BaO) ${}_n$ sizes of $n=8,10$ and 16. Full article