Search Results (46)

This work investigates photoactive inorganic powders (SiO₂, IrSiO₂, and IrO₂/IrSiO₂) and their derivatives modified with metallated porphyrin, focusing on their ability to generate reactive oxygen species (ROS) under visible light exposure. The core material, SiO₂, exhibits a tubular morphology and a high density of optically active defects. Modifiers such as metallic and iridium oxide nanoparticles, along with porphyrin, are employed to enhance light absorption and the generation of singlet oxygen (¹O₂) for potential biomedical applications. The time-dependent photogeneration of singlet oxygen is monitored using a Singlet Oxygen Green Sensor (SOSG), and its reactivity is evaluated in relation to DL α-Tocopherol through a spectrofluorimetric analysis. The photoactive materials, both before and after porphyrin modification, are characterized using Scanning Electron Microscopy (SEM), Atomic Force Microscopy (AFM), X-ray Diffraction (XRD), X-ray Fluorescence (XRF), UV–Vis Spectroscopy, X-ray Photoelectron Spectroscopy (XPS), N₂ adsorption–desorption measurements, and zeta potential measurements. Full article

The aim of this work is to incorporate lanthanide-cored upconversion nanoparticles (UCNP) into the surface of microengineered biomedical implants to create a spatially controlled and optically releasable model drug delivery device in an integrated fashion. Our approach enables silicone-based microelectrocorticography (ECoG) implants holding platinum/iridium recording sites to serve as a stable host of UCNPs. Nanoparticles excitable in the near-infrared (lower energy) regime and emitting visible (higher energy) light are utilized in a study. With the upconverted higher energy photons, we demonstrate the induction of photochemical (cleaving) reactions that enable the local release of specific dyes as a model system near the implant. The modified ECoG electrodes can be implanted in brain tissue to act as an uncaging system that releases small amounts of substance while simultaneously measuring the evoked neural response upon light activation. In this paper, several technological challenges like the surface modification of UCNPs, the immobilization of particles on the implantable platform, and measuring the stability of integrated UCNPs in in vitro and in vivo conditions are addressed in detail. Besides the chemical, mechanical, and optical characterization of the ready-to-use devices, the effect of nanoparticles on the original electrophysiological function is also evaluated. The results confirm that silicone-based brain–machine interfaces can be efficiently complemented with UCNPs to facilitate local model drug release. Full article

This paper explores a novel synthesis and characterization of silica-coated gold nanorods (AuNRs) embedding a highly emissive cyclometalated iridium(III) complex, denoted as Ir₁. We investigate the optical properties and the interplay between the metal compound and gold plasmon, observing how the emission of Ir₁ incorporated into the nanoparticles shows two emission bands, one in the blue and the other in the green-orange range of the visible spectrum. To obtain a clearer picture of what we were observing, we synthesized analogous nanosystems, from which it was possible to highlight the effect of different features. Based on what we observed, we proposed that the fraction of the iridium(III) complex in direct contact with the surface of the gold nanoparticle undergoes a “demixing” of the excited state, which, for cyclometalated iridium complexes, is generally considered a mixed LC+MLCT state. This preliminary study sheds light on the complexity of the “talking” between a fluorophore and a plasmonic system, highlighting the importance of considering the emitter typology when modeling such systems. Full article

Electrochemical water splitting, a sustainable method for hydrogen production, faces the challenge of slow oxygen evolution reaction (OER) kinetics. Iridium oxide (IrO₂) is widely regarded as the most effective catalyst for OER due to its excellent properties. Compared to nanoparticles, IrO₂ thin films exhibit significant advantages in OER, including a uniform and stable catalytic interface and excellent mechanical strength. This paper reviews recent advancements in one-step deposition techniques for the preparation of IrO₂ thin films and their application in OER. Additionally, it analyzes the advantages and disadvantages of various methods and the latest research achievements, and briefly outlines the future trends and applications. Full article

Three different iridium(III) complexes, labelled as Ir1–Ir3, each bearing a unique anchoring moiety (diethyl [2,2′-bipyridine]-4,4′-dicarboxylate, tetraethyl [2,2′-bipyridine]-4,4′-diylbis(phosphonate), or [2,2′-biquinoline]-4,4′-dicarboxylic acid), were synthesized to serve as photosensitizers. Their electrochemical and photophysical characteristics were systematically investigated. ERP measurements were employed to elucidate the impact of the anchoring groups on the photocatalytic hydrogen generation performance of the complexes. The novel iridium(III) complexes were integrated with platinized TiO₂ (Pt–TiO₂) nanoparticles and tested for their ability to catalyze hydrogen production under visible light. A H₂ turnover number (TON) of up to 3670 was obtained upon irradiation for 120 h. The complexes with tetraethyl [2,2′-bipyridine]-4,4′-diylbis(phosphonate) anchoring groups were found to outperform those bearing other moieties, which may be one of the important steps in the development of high-efficiency iridium(III) photosensitizers for hydrogen generation by water splitting. Additionally, toxicological analyses found no significant difference in the toxicity to luminescent bacteria of any of the present iridium(III) complexes compared with that of TiO₂, which implies that the complexes investigated in this study do not pose a high risk to the aquatic environment compared to TiO₂. Full article

Preparing high-performance oxygen evolution reaction (OER) catalysts with low precious metal loadings for water electrolysis applications (e.g., for green hydrogen production) is challenging and requires electrically conductive, high-surface-area, and stable support materials. Combining the properties of stable TiO₂ with those of active iridium oxide, we synthesized highly active electrodes for OER in acidic media. TiO₂ powders (both commercially available Degussa P-25^® and hydrothermally prepared in the laboratory from TiOSO₄, either as received/prepared or following ammonolysis to be converted to titania black), were decorated with IrO₂ by UV photodeposition from Ir(III) aqueous solutions of varied methanol scavenger concentrations. TEM, EDS, FESEM, XPS, and XRD measurements demonstrate that the optimized version of the photodeposition preparation method (i.e., with no added methanol) leads to direct deposition of well-dispersed IrO₂ nanoparticles. The electroactive surface area and electrocatalytic performance towards OER of these catalysts have been evaluated by cyclic voltammetry (CV), Linear Sweep Voltammetry (LSV), and Electrochemical Impedance Spectroscopy (EIS) in 0.1 M HClO₄ solutions. All TiO₂-based catalysts exhibited better mass-specific (as well as intrinsic) OER activity than commercial unsupported IrO₂, with the best of them (IrO₂ on Degussa P-25^® ΤiO₂ and laboratory-made TiO₂ black) showing 100 mAmg_Ir⁻¹ at an overpotential of η = 243 mV. Chronoamperometry (CA) experiments also proved good medium-term stability of the optimum IrO₂/TiO₂ electrodes during OER. Full article

A highly sensitive and selective electrogenerated chemiluminescence (ECL) biosensor was developed for the determination of matrix metalloproteinase 3 (MMP-3) in serum via the target-induced cleavage of an oligopeptide. One ECL probe (named as Ir-peptide) was synthesized by covalently linking a new cyclometalated iridium(III) complex ([(3-pba)₂Ir(bpy-COOH)](PF₆)) (3-pba = 3-(2-pyridyl) benzaldehyde, bpy-COOH = 4′-methyl-2,2′-bipyridine-4-carboxylic acid) with an oligopeptide (CGVPLSLTMGKGGK). An ECL biosensor was fabricated by firstly casting Nafion and gold nanoparticles (AuNPs) on a glassy carbon electrode and then self-assembling both of the ECL probes, 6-mercapto-1-hexanol and zwitterionic peptide, on the electrode surface, from which the AuNPs could be used to amplify the ECL signal and Ir-peptide could serve as an ECL probe to detect the MMP-3. Thanks to the MMP-3-induced cleavage of the oligopeptide contributing to the decrease in ECL intensity and the amplification of the ECL signal using AuNPs, the ECL biosensor could selectively and sensitively quantify MMP-3 in the concentration range of 10–150 ng·mL⁻¹ and with both a limit of quantification (26.7 ng·mL⁻¹) and a limit of detection (8.0 ng·mL⁻¹) via one-step recognition. In addition, the developed ECL biosensor showed good performance in the quantization of MMP-3 in serum samples, with a recovery of 92.6% ± 2.8%–105.6% ± 5.0%. An increased level of MMP-3 was found in the serum of rheumatoid arthritis patients compared with that of healthy people. This work provides a sensitive and selective biosensing method for the detection of MMP-3 in human serum, which is promising in the identification of patients with rheumatoid arthritis. Full article

The efficacy of electrodes that are chronically implanted and used in the context of deep brain stimulation (DBS) for the treatment of neurological disorders critically depends on stable impedance. Platinum–iridium electrodes were coated with laser-generated platinum nanoparticle colloids (PtNPs) via electrophoretic deposition using pulsed direct currents (DC-EPD). Uncoated electrodes were used as controls. In vitro, electrodes were stimulated for four weeks in a 0.9% NaCl solution. For the in vivo (rats) study, coated electrodes were implanted in the left and uncoated control electrodes in the right subthalamic nucleus (STN). After two weeks of recovery, electrodes were stimulated for four weeks. Impedance measurements were conducted after each week of stimulation, both in vivo and in vitro. NP-coating resulted in a significant and long-lasting reduction in electrode impedance (p < 0.05) over four weeks of in vitro stimulation. Despite an initial increase in impedance after intracranial implantation, the impedance of the NP-coated electrodes was also reduced during in vivo stimulation over four weeks. NP-coated electrodes had a lower fluctuation of impedance during stimulation compared to uncoated electrodes both in vitro and in vivo (p < 0.05). Laser-generated PtNPs applied to electrodes by pulsed DC-EPD lead to lower and more stable electrode impedance during chronic stimulation, with the potential to enhance the performance of DBS systems during chronic use. Full article

The novel class of fluids known by nanofluids is composed of colloidal suspensions of solid nanoparticles dispersed in a base fluid. When the solid nanoparticles are made of noble metals they can be named as noble metals nanofluids or noble nanofluids for short. This review attempts to offer a comprehensive survey along with a critical analysis of the noble metals nanofluids and their hybrids. Hence, the nanofluids having gold, silver, palladium, platinum, iridium, among others, nanoparticles are overviewed, giving emphasis to their superior thermophysical characteristics, stability, synthesis easiness, and potential applications. This work summarizes the published research findings about the noble metal nanofluids including the synthesis methods, heat transfer underlying mechanisms, and their performance evaluation in heat transfer and thermal energy storage purposes. This work intends also to provide practical insights in applications like Concentrated Solar Power systems, transformers, heat exchangers and heat pipes, cooling of electronics, among others. Also, it is highlighted the impact of the different formulations, temperature and pH values, and surfactants in the thermal conductivity, specific heat, and viscosity of these nanofluids. Besides, the interactions between the metal nanostructures and the base fluid molecules as viscosity and thermal conductivity determiners are discussed. Finally, the limitations, challenges, and prospects of the noble nanofluids are addressed such as their scalability and investment cost in large-scale applications. Full article

The present work reports on the synthesis and characterization of iridium (Ir)-based nanohybrids with variable chemical compositions. More specifically, highly stable polyvinylpyrrolidone (PVP) nanohybrids of the PVP-IrO₂ and PVP-Ir/IrO₂ types, as well as non-coated Ir/IrO₂ nanoparticles, are synthesized using different synthetic protocols and characterized in terms of their chemical composition and morphology via X-ray photoelectron spectroscopy (XPS) and scanning transmission electron microscopy (STEM), respectively. Furthermore, their nonlinear optical (NLO) response and optical limiting (OL) efficiency are studied by means of the Z-scan technique, employing 4 ns laser pulses at 532 and 1064 nm. The results demonstrate that the PVP-Ir/IrO₂ and Ir/IrO₂ systems exhibit exceptional OL performance, while PVP-IrO₂ presents very strong saturable absorption (SA) behavior, indicating that the present Ir-based nanohybrids could be strong competitors to other nanostructured materials for photonic and optoelectronic applications. In addition, the findings denote that the variation in the content of IrO₂ nanoparticles by using different synthetic pathways significantly affects the NLO response of the studied Ir-based nanohybrids, suggesting that the choice of the appropriate synthetic method could lead to tailor-made NLO properties for specific applications in photonics and optoelectronics. Full article

In this work, approaches to the formation of multifunctional film heterostructures based on noble metals for the modification of the surface of implant materials (titanium alloy TiAl₆V₄ and carbon-fiber-reinforced polyetheretherketone CFR-PEEK) are developed. Such heterostructures consist of continuous layers of platinum (Pt) or iridium (Ir) and antibacterial components on their surface, namely silver (nanoparticles or discontinuous films) and gold (nanoparticles). Chemical or physical gas-phase deposition methods were used for their preparation. The influence of the concentration and form of the antibacterial component on the antibacterial activity and in vivo biocompatibility of the film structures was evaluated for the first time. Differences in the dynamics of silver dissolution depending on Ag concentration in the sample and the type of bottom surface (the noble metal layer = Ir, Pt or TiAl₆V₄) surfaces allowed us to better understand the nature of the antibacterial action against Staphylococcus aureus and Pseudomonas aeruginosa (S. aureus and P. aeruginosa) of Ag/M heterostructures. From in vivo histological studies using rats, the best biocompatibility was shown by the Ag/M heterostructure with a prolonged release of the low fraction of antibacterial component (Ag). Full article

Owing to multiple physicochemical properties, the combination of hybrid elemental compositions of nanoparticles can be widely utilized for a variety of applications. To combine pristine tellurium nanorods, which act as a sacrificing template, with another element, iridium–tellurium nanorods (IrTeNRs) were synthesized via the galvanic replacement technique. Owing to the coexistence of iridium and tellurium, IrTeNRs exhibited unique properties, such as peroxidase-like activity and photoconversion. Additionally, the IrTeNRs demonstrated exceptional colloidal stability in complete media. Based on these properties, the IrTeNRs were applied to in vitro and in vivo cancer therapy, allowing for the possibility of multiple therapeutic methodologies. The enzymatic therapy was enabled by the peroxidase-like activity that generated reactive oxygen species, and the photoconversion under 473, 660 and 808 nm laser irradiation induced cancer cell apoptosis via photothermal and photodynamic therapy. Full article

The limitations of current treatment strategies for cancer management have prompted a significant shift in the research and development of new effective strategies exhibiting higher efficacy and acceptable side effects. In this direction, nanotheranostics has gained significant interest in recent years, combining the diagnostic and therapeutic capabilities of nanostructures for efficient disease diagnosis, treatment, and management. Such nano-assisted platforms permit the site-specific release of bioactive cargo in a controlled fashion while permitting non-invasive real-time in situ monitoring. A plethora of materials has been developed as pharmacologically relevant nanoformulations for theranostic applications ranging from metallic to lipid and polymer-based composite systems, with each offering potential opportunities and its own limitations. To improve advancements with better clarity, the main focus of this review is to highlight the recent developments focusing on using different noble metal nanoparticles (noble MNPs) as cancer nanotheranostic agents, highlighting their properties, advantages, and potential modifications for their successful utilization in personalized medicine. The advantage of using noble metals (not all, but those with an atomic number ≥76) over metal NPs is their tendency to provide additional properties, such as X-ray attenuation and near-infrared activity. The combination of these properties translates to noble MNPs for therapeutic and diagnostic applications, independent of the need for additional active molecules. Through this review, we highlighted the potential application of all noble MNPs and the limited use of osmium, iridium, palladium, rhodium, and ruthenium metal NSs, even though they express similar physicochemical characteristics. The literature search was limited by PubMed, full-text availability, and studies including both in vitro and in vivo models. Full article

Nonlinear optical phenomena enable novel photonic and optoelectronic applications. Especially, metallic nanoparticles and thin films with nonlinear optical properties offer the potential for micro-optical system integration. For this purpose, new nonlinear materials need to be continuously identified, investigated, and utilized for nonlinear optical applications. While noble-metal nanoparticles, nanostructures, and thin films of silver and gold have been widely studied, iridium (Ir) nanoparticles and ultrathin films have not been investigated for nonlinear optical applications yet. Here, we present a combined theoretical and experimental study on the linear and nonlinear optical properties of iridium nanoparticles deposited via atomic layer deposition (ALD). Linear optical constants, such as the effective refractive index and extinction coefficient, were evaluated at different growth stages of nanoparticle formation. Both linear and nonlinear optical properties of these Ir ALD coatings were calculated theoretically using the Maxwell Garnett theory. The third-order susceptibility of iridium nanoparticle samples was experimentally investigated using the z-scan technique. According to the experiment, for an Ir ALD coating with 45 cycles resulting in iridium nanoparticles, the experimentally determined nonlinear third-order susceptibility is about χ_Ir⁽³⁾ = (2.4 − i2.1) × 10⁻¹⁷ m²/V² at the fundamental wavelength of 700 nm. The theory fitted to the experimental results predicts a 5 × 10⁶-fold increase around 230 nm. This strong increase is due to the proximity to the Mie resonance of iridium nanoparticles. Full article

Four iridium(III) dyes functionalized with aldehyde functional group in the cyclometalating (C^N) ligands, bearing either diethyl [2,2′-bipyridine]-4,4′-dicarboxylate or tetraethyl [2,2′-bipyridine]-4,4′-diylbis(phosphonate) anchoring groups, coded as Ir1–Ir4, are synthesized and explored as photosensitizers. The synthetic route is described and all of the complexes are characterized with respect to their electrochemical and photophysical properties. Density functional theory (DFT) calculation was used to gain insight into the factors responsible for the photocatalytic properties of Ir1–Ir4 as effective photosensitizers for photocatalytic hydrogen generation. Relative to common iridium(III) dyes, such as [Ir(ppy)₂(dcbpy)]⁺ (ppy = 2-phenylpyridine), the absorption spectra of our dyes are broader, which is attributed to the extended π-conjugation in their C^N ligands. All of the new iridium(III) dyes were used as photosensitizers for visible-light driven hydrogen production by attaching to platinized TiO₂ nanoparticles (Pt–TiO₂) in the presence of sacrificial electron donor (SED) of ascorbic acid (AA) in a purely aqueous solution. A H₂ turnover number (TON) up to 5809 was demonstrated for 280 h irradiation. Complexes with tetraethyl [2,2′-bipyridine]-4,4′-diylbis(phosphonate) anchoring groups were found to outperform those with classical diethyl [2,2′-bipyridine]-4,4′-dicarboxylate, which may be one of the important steps in developing high-efficiency iridium(III) photosensitizers in water splitting hydrogen generation. Full article