Semiconductor nanomaterials are often proposed as photocatalysts for wastewater treatment; silica nanomaterials are still largely unexploited because their photocatalytic performances need improvements, especially under visible light. The present study is a proof-of-concept that amorphous silica colloids once submitted to the proper surface modifications change into an efficient photocatalyst even under low-energy illumination source. For this reason, silica-based colloidal nanomaterials, such as bare (SiO2 NPs), aminated (NH2-SiO2 NPs), and Ag NPs-decorated (Ag-SiO2 NPs) silica, are tested as photocatalysts for the degradation of 9-anthracenecarboxylic acid (9ACA), taken as a model aromatic compound. Interestingly, upon irradiation at 313 nm, NH2-SiO2 NPs induce 9ACA degradation, and the effect is even improved when Ag-SiO2 NPs are used. On the other hand, irradiation at 405 nm activates the plasmon of Ag-SiO2 NPs photocatalyst, providing a faster and more efficient photodegradation. The photodegradation experiments are also performed under white light illumination, employing a low-intensity fluorescent lamp, confirming satisfying efficiencies. The catalytic effect of SiO2-based nanoparticles is thought to originate from photo-excitable surface defects and Ag NP plasmons since the catalytic degradation takes place only when the 9ACA is adsorbed on the surface. In addition, the involvement of reactive oxygen species was demonstrated through a scavenger use, obtaining a yield of 17%. In conclusion, this work shows the applicability of silica-based nanoparticles as photocatalysts through the involvement of silica surface defects, confirming that the silica colloids can act as photocatalysts under irradiation with monochromatic and white light. Graphic abstract Silica and Ag-decorated silica colloids photosensitize the formation of Reactive Oxygen Species with 17% efficiencies. ROS are able to oxidase aromatic pollutants chemi-adsorbed on the surface of the colloids. Silica-silver nanocomposites present a photocatalytic activity useful to degrade aromatic compounds.
Scattering-type scanning near-field optical microscopy (s-SNOM) has emerged over the past years as a powerful characterization tool that can probe important properties of advanced materials and biological samples in a label-free manner, with spatial resolutions lying in the nanoscale realm. In this work, we explore such usefulness in relationship with an interesting class of materials: polymer-coated gold nanoparticles (NPs). As thoroughly discussed in recent works, the interplay between the Au core and the polymeric shell has been found to be important in many applications devoted to biomedicine. We investigate bare Au NPs next to polystyrenesulfonate (PSS) and poly(diallyldimethylammonium chloride) (PDDA) coated ones under 532 nm laser excitation, an wavelength matching the surface plasmon band of the custom-synthesized nanoparticles. We observe consistent s-SNOM phase signals in the case of bare and shallow-coated Au NPs, whereas for thicker shell instances, these signals fade. For all investigated samples, the s-SNOM amplitude signals were found to be very weak, which may be related to reduced scattering efficiency due to absorption of the incident beam. We consider these observations important, as they may facilitate studies and applications in nanomedicine and nanotechnology where the precise positioning of polymer-coated Au NPs with nanoscale resolution is needed besides their dielectric function and related intrinsic optical properties, which are also quantitatively available with s-SNOM.
15 April 2021 in The Journal of Physical Chemistry Letters
Different silica-protoporphyrin IX (PpIX) nanocomposites have been synthesized to evaluate the dependence of singlet oxygen production and bacterial inactivation efficiency on the morphology of the nanomaterials. Modulation of the synthetic procedure allowed obtaining silica nanoparticles with different porosity which were characterized by TEM and spectroscopic analysis after PpIX adsorption. Time-resolved phosphorescence measurements on the different nanoporous samples revealed that the porosity of the nanoparticles plays a pivotal role on the singlet oxygen production and release from the nanoparticles. Thus, apart from the expected decay of singlet oxygen outside the silica matrix, a second component has been observed for the porous materials, attributed to the decay of singlet oxygen inside the pores. The relative efficiency of singlet oxygen production resulted to be higher for the sample with the greatest pores volume. The capability of the nanocomposites to inactivate bacteria was tested in vitro on Staphylococcus aureus strain. Interestingly, the efficiency for singlet oxygen production of the nanocomposites and their bacterial inactivation efficiency followed a different trend, indicating that the relative position of the photosensitizer and the superficial properties of the particles affect the antibacterial activity of the overall system.
Nanoscale metal–organic frameworks (NMOFs) exhibit unique properties for drug delivery, including ultrahigh storage capabilities, biocompatibility, biodegradability, and sustained release of encapsulated cargo. However, due to their localized electronic states, MOFs are nonresponsive to external stimuli such as light or magnetic fields. This study investigates the integration of light‐responsive nanoantennas into NMOFs to enhance their application as smart drug delivery nanosystems. By integrating gold bipyramid nanoantennas within ZIF‐8 and NU‐1000 NMOFs, core@shell nanosystems are created with photothermal capabilities. Utilizing cresyl violet as a model drug, the loading and release dynamics of these nanosystems are analyzed, demonstrating controlled drug release under near‐infrared (NIR) light stimulation. Photothermal release studies conducted in living cells reveal the potential of these nanocomposites for spatiotemporal targeted, light‐activated drug delivery. Further evaluation of the NU‐1000 nanocomposite loaded with chemotherapeutics—doxorubicin, carboplatin, and oxaliplatin—in both 2D and 3D cell cultures shows the nanosystem effectiveness in cell internalization and therapeutic NIR activation. The findings demonstrate that the incorporation of stimuli‐responsive elements into NMOFs offers a promising approach for developing advanced drug delivery platforms.
The preparation of tailored nanomaterials able to support cell growth and viability is mandatory for tissue engineering applications. In the present work, silica nanoparticles were prepared by a sol-gel procedure and were then functionalized by condensation of amino groups and by adsorption of silver nanoparticles. Transmission electron microscopy (TEM) imaging was used to establish the morphology and the average dimensions of about 130 nm, which were not affected by the functionalization. The three silica samples were deposited (1 mg/mL) on cover glasses, which were used as a substrate to culture adult human bone marrow-mesenchymal stem cells (hBM-MSCs) and human adipose-derived stem cells (hASCs). The good cell viability over the different silica surfaces was evaluated by monitoring the mitochondrial dehydrogenase activity. The analysis of the morphological parameters (aspect ratio, cell length, and nuclear shape Index) yielded information about the interactions of stem cells with the surface of three different nanoparticles. The data are discussed in terms of chemical properties of the surface of silica nanoparticles.