There is currently a worldwide need to develop efficient photocatalytic materials that can reduce the high-energy cost of common industrial chemical processes. One possible solution focuses on metallic nanoparticles (NPs) that can act as efficient absorbers of light due to their surface plasmon resonance. Recent work indicates that small NPs, when photoexcited, may allow for efficient electron or hole transfer necessary for photocatalysis. Here we investigate the mechanisms behind hot hole carrier dynamics by studying the photodriven oxidation of citrate ions on Au@SiO@Au core-shell NPs. We find that charge transfer to adsorbed molecules is most efficient at higher photon energies but still present with lower plasmon energy. On the basis of these experimental results, we develop a simple theoretical model for the probability of hot carrier-adsorbate interactions across the NP surface. These results provide a foundation for understanding charge transfer in plasmonic photocatalytic materials, which could allow for further design and optimization of photocatalytic processes.
BackgroundMultidrug resistant microorganisms are a growing challenge and new substances that can be useful to treat infections due to these microorganisms are needed. Silver nanoparticle may be a future option for treatment of these infections, however, the methods described in vitro to evaluate the inhibitory effect are controversial.ResultsThis study evaluated the in vitro activity of silver nanoparticles against 36 susceptible and 54 multidrug resistant Gram-positive and Gram-negative bacteria from clinical sources. The multidrug resistant bacteria were oxacilin-resistant Staphylococcus aureus, vancomycin-resistant Enterococcus spp., carbapenem- and polymyxin B-resistant A. baumannii, carbapenem-resistant P. aeruginosa and carbapenem-resistant Enterobacteriaceae. We analyzed silver nanoparticles stabilized with citrate, chitosan and polyvinyl alcohol and commercial silver nanoparticle. Silver sulfadiazine and silver nitrate were used as control. Different methods were used: agar diffusion, minimum inhibitory concentration, minimum bactericidal concentration and time-kill. The activity of AgNPs using diffusion in solid media and the MIC methods showed similar effect against MDR and antimicrobial-susceptible isolates, with a higher effect against Gram-negative isolates. The better results were achieved with citrate and chitosan silver nanoparticle, both with MIC90 of 6.75 μg mL−1, which can be due the lower stability of these particles and, consequently, release of Ag+ ions as revealed by X-ray diffraction (XRD). The bactericidal effect was higher against antimicrobial-susceptible bacteria.ConclusionIt seems that agar diffusion method can be used as screening test, minimum inhibitory concentration/minimum bactericidal concentration and time kill showed to be useful methods. The activity of commercial silver nanoparticle and silver controls did not exceed the activity of the citrate and chitosan silver nanoparticles. The in vitro inhibitory effect was stronger against Gram-negative than Gram-positive, and similar against multidrug resistant and susceptible bacteria, with best result achieved using citrate and chitosan silver nanoparticles. The bactericidal effect of silver nanoparticle may, in the future, be translated into important therapeutic and clinical options, especially considering the shortage of new antimicrobials against the emerging antimicrobial resistant microorganisms, in particular against Gram-negative bacteria.
Multifunctional nanoparticles for biomedical applications have shown extraordinary potential as contrast agents in various bioimaging modalities, near-IR photothermal therapy, and for lighttriggered therapeutic release processes. Over the past several years, numerous studies have been performed to synthesize and enhance MRI contrast with nanoparticles. However, understanding the MRI enhancement mechanism in a multishell nanoparticle geometry, and controlling its properties, remains a challenge. To systematically examine MRI enhancement in a nanoparticle geometry, we have synthesized MRI-active Au nanomatryoshkas. These are Au coresilica layer-Au shell nanoparticles, where Gd(III) ions are encapsulated within the silica layer between the inner core and outer Au layer of the nanoparticle (Gd-NM). This multifunctional nanoparticle retains its strong near-IR Fano-resonant optical absorption properties essential for photothermal or other near-IR light-triggered therapy, while simultaneously providing increased T 1 contrast in MR imaging by concentrating Gd(III) within the nanoparticle. Measurements of Gd-NM revealed a strongly enhanced T 1 relaxivity (r 1 ∼ 24 mM
Engineered nanomaterials have been extensively applied as active materials for technological applications. Since the impact of these nanomaterials on health and environment remains undefined, research on their possible toxic effects has attracted considerable attention. It is known that in humans, for example, the primary site of gold nanoparticles (AuNps) accumulation is the liver. The latter has motivated research regarding the use of AuNps for cancer therapy, since specific organs can be target upon appropriate functionalization of specific nanoparticles. In this study, we investigate the geno and cytotoxicity of two types of AuNps against human hepatocellular carcinoma cells (HepG2) and peripheral blood mononuclear cells (PBMC) from healthy human volunteers. The cells were incubated in the presence of different concentrations of AuNps capped with either sodium citrate or polyamidoamine dendrimers (PAMAM). Our results suggest that both types of AuNps interact with HepG2 cells and PBMC and may exhibit in vitro geno and cytotoxicity even at very low concentrations. In addition, the PBMC were less sensitive to DNA damage toxicity effects than cancer HepG2 cells upon exposure to AuNps.
Engineering a compact, near-infrared plasmonic nanostructure with integrated image-enhancing agents for combined imaging and therapy is an important nanomedical challenge. Recently, we showed that Au@SiO@Au nanomatryoshkas (NM) are a highly promising nanostructure for hosting either T MRI or fluorescent contrast agents with a photothermal therapeutic response in a compact geometry. Here, we show that a near-infrared-resonant NM can provide simultaneous contrast enhancement for both T magnetic resonance imaging (MRI) and fluorescence optical imaging (FOI) by encapsulating both types of contrast agents in the internal silica layer between the Au core and shell. We also show that this method of T enhancement is even more effective for Fe(III), a potentially safer contrast agent compared to Gd(III). Fe-NM-based contrast agents are found to have relaxivities 2× greater than those found in the widely used gadolinium chelate, Gd(III) DOTA, providing a practical alternative that would eliminate Gd(III) patient exposure entirely. This dual-modality nanostructure can enable not only tissue visualization with MRI but also fluorescence-based nanoparticle tracking for quantifying nanoparticle distributions in vivo, in addition to a near-infrared photothermal therapeutic response.
Graphene oxide (GO) with their interesting properties including thermal and electrical conductivity and antibacterial characteristics have many promising applications in medicine. The prevalence of resistant bacteria is considered a public health problem worldwide, herein, GO has been used as a broad spectrum selective antibacterial agent based on the photothermal therapy (PTT)/photodynamic therapy (PDT) effect. The preparation, characterization, determination of photophysical properties of two different sizes of GO is described. In vitro light dose and concentration-dependent studies were performed using Gram-negative Escherichia coli and Gram-positive Staphylococcus aureus bacteria based on the PTT/PDT effect used ultra-low doses (65 mW cm −2 ) of 630 nm light, to achieve efficient bacterial decontamination. The results show that GO and nanographene oxide (nGO) can sensitize the formation of 1 O 2 and allow a temperature rise of 55 • C to 60 • C together nGO and GO to exert combined PTT/PDT effect in the disinfection of gram-positive S. aureus and gram-negative E. coli bacteria. A complete elimination of S. aureus and E. coli bacteria based on GO and nGO is obtained by using a dose of 43-47 J cm −2 for high concentration used in this study, and a dose of around 70 J cm −2 for low dose of GO and nGO. The presence of high concentrations of GO allows the bacterial population of S. aureus and E. coli to be more sensitive to the use of PDT/PTT and the efficiency of S. aureus and E. coli bacteria disinfection in the presence of GO is similar to that of nGO. In human neonatal dermal fibroblast, HDFs, no significant alteration to cell viability was promoted by GO, but in nGO is observed a mild damage in the HDFs cells independent of nGO concentration and light exposure. The unique properties of GO and nGO may be useful for the clinical treatment of disinfection of broad-spectrum antimicrobials. The antibacterial results of PTT and PDT using GO in gram-positive and gram-negative bacteria, using low dose light, allow us to conclude that GO and nGO can be used in dermatologic infections, since the effect on human dermal fibroblasts of this treatment is low compared to the antibacterial effect.
The understanding of the interactions between small molecules and magnetic nanoparticles is of great importance for many areas of bioapplications. Although a large array of studies in this area have been performed, aspects involving the interaction of magnetic nanoparticles with phospholipids monolayers, which can better mimic biological membranes, have not yet been clarified. This study was aimed at investigating the interactions between Langmuir films of dipalmitoyl phosphatidylglycerol and dipalmitoyl phosphatidylcholine, obtained on an aqueous subphase, and magnetic nanoparticles. Sum-frequency generation (SFG) vibrational spectroscopy was used to verify the orientation and molecular conformation and to better understand the interactions between phospholipids and the magnetic nanoparticles. Surface pressure-area isotherms and SFG spectroscopy made it possible to investigate the interaction of these nanomaterials with components of phospholipids membranes at the water surface.
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