Oxidative stress-dependent inflammatory diseases represent a major concern for the population's health worldwide. Biocompatible nanomaterials with enzymatic properties could play a crucial role in the treatment of such pathologies. In this respect, platinum nanoparticles (PtNPs) are promising candidates, showing remarkable catalytic activity, able to reduce the intracellular reactive oxygen species (ROS) levels and impair the downstream pathways leading to inflammation. This review reports a critical overview of the growing evidence revealing the anti-inflammatory ability of PtNPs and their potential applications in nanomedicine. It provides a detailed description of the wide variety of synthetic methods recently developed, with particular attention to the aspects influencing biocompatibility. Special attention has been paid to the studies describing the toxicological profile of PtNPs with an attempt to draw critical conclusions. The emerging picture suggests that the material per se is not causing cytotoxicity, while other physicochemical features related to the synthesis and surface functionalization may play a crucial role in determining the observed impairment of cellular functions. The enzymatic activity of PtNPs is also summarized, analyzing their action against ROS produced by pathological conditions within the cells. In particular, we extensively discuss the potential of these properties in nanomedicine to down-regulate inflammatory pathways or to be employed as diagnostic tools with colorimetric readout. A brief overview of other biomedical applications of nanoplatinum is also presented.
In recent years, the use of nanomaterials as biomimetic enzymes has attracted great interest. In this work, we show the potential of biocompatible platinum nanoparticles (Pt NPs) as antioxidant nanozymes, which combine abundant cellular internalization and efficient scavenging activity of cellular reactive oxygen species (ROS), thus simultaneously integrating the functions of nanocarriers and antioxidant drugs. Careful toxicity assessment and intracellular tracking of Pt NPs proved their cytocompatibility and high cellular uptake, with compartmentalization within the endo/lysosomal vesicles. We have demonstrated that Pt NPs possess strong and broad antioxidant properties, acting as superoxide dismutase, catalase, and peroxidase enzymes, with similar or even superior performance than natural enzymes, along with higher adaptability to the changes in environmental conditions. We then exploited their potent activity as radical scavenging materials in a cellular model of an oxidative stress-related disorder, namely human Cerebral Cavernous Malformation (CCM) disease, which is associated with a significant increase in intracellular ROS levels. Noteworthily, we found that Pt nanozymes can efficiently reduce ROS levels, completely restoring the cellular physiological homeostasis.
Gold nanoparticles protected by a binary mixture of thiolate molecules have a ligand shell that can spontaneously separate into nanoscale domains. Complex morphologies arise in such ligand shells, including striped, patchy, and Janus domains. Characterization of these morphologies remains a challenge. Scanning tunneling microscopy (STM) imaging has been one of the key approaches to determine these structures, yet the imaging of nanoparticles' surfaces faces difficulty stemming from steep surface curvature, complex molecular structures, and the possibility of imaging artifacts in the same size range. Images obtained to date have lacked molecular resolution, and only domains have been resolved. There is a clear need for images that resolve the molecular arrangement that leads to domain formation on the ligand shell of these particles. Herein we report an advance in the STM imaging of gold nanoparticles, revealing some of the molecules that constitute the domains in striped and Janus gold nanoparticles. We analyze the images to determine molecular arrangements on parts of the particles, highlight molecular "defects" present in the ligand shell, show persistence of the features across subsequent images, and observe the transition from quasi-molecular to domain resolution. The ability to resolve single molecules in the ligand shell of nanoparticles could lead to a more comprehensive understanding of the role of the ligand structure in determining the properties of mixed-monolayer-protected gold nanoparticles.
Poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) brushes have been grown by surface-initiated atom transfer radical polymerization (SI-ATRP) from a polyanionic macroinitiator adsorbed at the sapphire-water interface, and neutron reflectivity has been used to characterize the structures and pH response of the brushes. The polymer brushes are well-described by Gaussian density profiles with an additional thin, dense layer close to the solid-liquid interface for the thicker brushes at pH 7 and 9, which produces a spike in the density profile. The spike in the distribution accounts for less than 5% of the polymer and disappears as the brushes swell at pH 3. The observed swelling behavior has been used in combination with the predictions of scaling theory and previous experimental measurements to determine the grafted density of PDMAEMA chains.
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