Ion Transport Through Nanopores and the Effects of Pore Wall-Ion Interaction.

Ion transport inside nanopores is affected by the physicochemical interactions between the ions and the internal pore wall, offering novel opportunities useful for nanopore-based applications. Here we demonstrate that the transport of Fe(CN)63-/4- is influenced by the pore wall-ion interactions in sub-10 nm pore channels of a mesoporous zirconia film (MZF) formed on an electrode based on cyclic voltammetric (CV) studies. At pH lower than the point of zero charge of zirconia, the pore wall is positively charged, enabling it to exert attractive interaction with the negatively charged analyte ions. Moreover, experimental data indicate that the attractive interaction strongly favors the more highly charged Fe(CN)64- ions over the Fe(CN)63- ions. These effects affect the ion transport through the MZF nanopore channels, which is manifested by a number of different sets of data, including the positive shift of the reduction potential, the disparity between the CV curves of the anodic and cathodic sweeps, and the splitting of the single pair of redox peaks into two pairs when the electrical double layer thickness is increased by reducing the concentration of the supporting electrolyte. Each of these observations can be explained by the wall-ion interactions. Our findings may lead to further explorations into the transport of redox ions that interact differently with the pores and into the development of novel applications based on nanopores.

Investigation of porosity and heterojunction effects of a mesoporous hematite electrode on photoelectrochemical water splitting.

In this paper, we report the porosity and heterojunction effects of hematite (α-Fe2O3) on the photoelectrochemical (PEC) water splitting properties. The worm-like mesoporous hematite thin films (MHFs) with a pore size of ~9 nm and a wall thickness of ~5 nm were successfully obtained through the self-assembly process. MHFs formed on FTO showed much better PEC properties than those of nonporous hematite thin films (NP-HF) owing to the suppression of charge recombination. The PEC data of MHFs under front and back illumination conditions indicated that the porous structure allows the diffusion of electrolyte deep inside the MHF increasing the number of holes to be utilized in the water oxidation reaction. A heterojunction structure was formed by introducing a thin layer of SnO2 (~15 nm in thickness) between the MHF and FTO for a dramatically enhanced PEC response, which is attributed to the efficient electron transfer. Our spectroscopic and electrochemical data show that the SnO2 layer functions as an efficient electron transmitter, but does not affect the recombination kinetics of MHFs.

Bactericidal activity of immobilized silver nanoparticles on silica substrates with different sizes.

Hybrid particles with immobilized silver nanoparticles (AgNPs) receive a lot of attention due to their excellent antibacterial activity with the prevention of inherent aggregation of AgNPs. In this study, serial sized silica substrate particles (231, 401, and 605 nm) and their corresponding hybrid particles with AgNPs (~ 30 nm) are prepared, with detailed bactericidal images of the corresponding particles at various times. Their bactericidal activity is elucidated for both Gram-positive Streptococcus agalactiae and Gram-negative Escherichia coli CN13, which show the size of 0.8 µm × 0.9 µm and 1.3 µm × 1.8 µm, respectively. There is a large difference in the bactericidal activity between the smallest (231 nm, 3-log10 reduction) and larger (401 and 605 nm, 6-log10 reduction) silica substrates, whereas there is hardly a difference between the latter. Their effective total surface area (ETSA) is considered important for their bactericidal activity, based on the nearly equal large ETSA of the well-dispersed two larger silica substrates and the much smaller ETSA of the agglomerated smallest substrates. Submicron-sized pits appear on the bacterial membrane by direct contact with the hybrid particles, implicating the importance of ETSA. Still, further research is needed with much different silica substrate sizes to fully elucidate the impact of the silica substrate on the bactericidal activity of immobilized AgNPs.

Disinfection of waterborne viruses using silver nanoparticle-decorated silica hybrid composites in water environments.

Silver nanoparticles (AgNPs) have been reported as an effective alternative for controlling a broad-spectrum of pathogenic viruses. We developed a micrometer-sized silica hybrid composite decorated with AgNPs (AgNP-SiO2) to prevent the inherent aggregation of AgNPs, and facilitated their recovery from environmental media after use. The production process had a high-yield, and fabrication was cost-effective. We evaluated the antiviral capabilities of Ag30-SiO2 particles against two model viruses, bacteriophage MS2 and murine norovirus (MNV), in four different types of water (deionized, tap, surface, and ground). MNV was more susceptible to Ag30-SiO2 particles in all four types of water compared to MS2. Furthermore, several water-related factors, including temperature and organic matter content, were shown to affect the antimicrobial capabilities of Ag30-SiO2 particles. The modified Hom model was the best-fit disinfection model for MNV disinfection in the different types of water. Additionally, this study demonstrated that the effects of a certain level of physical obstacles in water were negligible in regards to the use of Ag30-SiO2 particles. Thus, effective use of AgNPs in water disinfection processes can be achieved using our novel hybrid composites to inactivate various waterborne viruses.

Inactivation of influenza A virus via exposure to silver nanoparticle-decorated silica hybrid composites.

Influenza A virus (IFV-A) is one of the main cause of seasonal flu and can infect various of host species via the reassortment of segmented RNA genomes. Silver nanoparticles (AgNPs) have been known as excellent antiviral agent against IFV. However, the use of free AgNPs has several major drawbacks, including the inherent aggregation among AgNPs and unwanted cytotoxic or genotoxic damages for human body via inhalation or ingestion. In this study, we assessed the efficacy of our novel ~ 30-nm-diameter AgNP-decorated silica hybrid composite (Ag30-SiO2; ~ 400 nm in diameter) for IFV-A inactivation. Ag30-SiO2 particles can inhibit IFV-A effectively in a clear dose-dependent manner. However, when real-time RT-PCR assay was used, merely 0.5-log10 reduction of IFV-A was observed at both 5 and 20 °C. Moreover, even after 1 h of exposure to Ag30-SiO2 particles, more than 80% of hemagglutinin (HA) damage and 20% of neuraminidase (NA) activities had occurred, and the infection of Madin-Darby Canine Kidney (MDCK) cells by IFV-A was reduced. The results suggested that the major antiviral mechanism of Ag30-SiO2 particles is the interaction with viral components located at the membrane. Therefore, Ag30-SiO2 particles can cause nonspecific damage to various IFV-A components and be used as an effective method for inactivating IFV-A.

Peptide-Programmable Nanoparticle Superstructures with Tailored Electrocatalytic Activity.

Biomaterials derived via programmable supramolecular protein assembly provide a viable means of constructing precisely defined structures. Here, we present programmed superstructures of AuPt nanoparticles (NPs) on carbon nanotubes (CNTs) that exhibit distinct electrocatalytic activities with respect to the nanoparticle positions via rationally modulated peptide-mediated assembly. De novo designed peptides assemble into six-helix bundles along the CNT axis to form a suprahelical structure. Surface cysteine residues of the peptides create AuPt-specific nucleation site, which allow for precise positioning of NPs onto helical geometries, as confirmed by 3-D reconstruction using electron tomography. The electrocatalytic model system, i.e., AuPt for oxygen reduction, yields electrochemical response signals that reflect the controlled arrangement of NPs in the intended assemblies. Our design approach can be expanded to versatile fields to build sophisticated functional assemblies.

Disinfection of various bacterial pathogens using novel silver nanoparticle-decorated magnetic hybrid colloids.

Silver nanoparticles (AgNPs) have long been considered a powerful disinfectant for controlling pathogenic microorganisms. However, AgNPs might have adverse effects on both human health and our ecosystems due to their potential cytotoxicity and the difficulty in recovering them after their release into the environment. In this study, we characterized the antimicrobial efficacy caused by a novel micrometer-sized magnetic hybrid colloid (MHC) containing 7, 15, or 30nm sized monodispersed AgNPs (AgNP-MHCs), which can be re-collected from the environment using simple procedures, such as a magnet or centrifugation. We evaluated the antibacterial capabilities of AgNP-MHCs against target bacteria (Legionella pneumophila, Bacillus subtilis, Escherichia coli, and Clostridium perfringens) and compared them with the inactivation efficacy of AgNPs ~30nm in diameter (nAg30s). Among the different AgNP-MHCs composites evaluated, Ag30-MHCs had the greatest antibacterial effect. After 1h of exposure, more than a 4-log10 reduction of L. pneumophila and 6-log10 reduction of B. subtilis was achieved by 4.6×109particles/mL of Ag30-MHCs and Ag30-MHC-Ls. In addition, Ag30-MHC-Ls maintained their strong antibacterial capabilities under anaerobic conditions. Our results indicate that AgNP-MHCs can be considered excellent tools for controlling waterborne bacterial pathogens, with a minimal risk of release into the environment.

Nature-Inspired Construction of Two-Dimensionally Self-Assembled Peptide on Pristine Graphene.

Peptide assemblies have received significant attention because of their important role in biology and applications in bionanotechnology. Despite recent efforts to elucidate the principles of peptide self-assembly for developing novel functional devices, peptide self-assembly on two-dimensional nanomaterials has remained challenging. Here, we report nature-inspired two-dimensional peptide self-assembly on pristine graphene via optimization of peptide-peptide and peptide-graphene interactions. Two-dimensional peptide self-assembly was designed based on statistical analyses of >104 protein structures existing in nature and atomistic simulation-based structure predictions. We characterized the structures and surface properties of the self-assembled peptide formed on pristine graphene. Our study provides insights into the formation of peptide assemblies coupled with two-dimensional nanomaterials for further development of nanobiocomposite devices.

Prompt and synergistic antibacterial activity of silver nanoparticle-decorated silica hybrid particles on air filtration.

There is a significant need for materials that promptly exhibit antimicrobial activity upon contact. The large-scale fabrication of monodisperse silver nanoparticle (AgNP)-decorated silica (AgNP@SiO2) hybrid particles, and their prompt and synergistic antibacterial activity against both the Gram-negative bacteria Escherichia coli and the Gram-positive bacteria Staphylococcus epidermidis on air filtration units are presented. Monodisperse aminopropyl-functionalized silica colloids (406 nm) were used as a support material and were hybridized with AgNPs using a seeding, sorting-out, and growing strategy with Ag seeds (1-2 nm) into ∼30 nm AgNPs, successfully yielding 51 g of AgNP@SiO2 hybrid particles. Medium filter samples (glass fiber material, 4 × 4 cm2) were coated with AgNP@SiO2 particles and tested for antibacterial efficacy. SEM characterization of the bacterial morphology suggested prompt and synergistic antibacterial activity against both classes of bacteria. Moreover, antibacterial efficacies >99.99% for both bacteria were obtained using a filter sample with a coating areal density of 1 × 108 particles per cm2. Solutions of AgNP@SiO2 at 1.3% were stable even after 8 months. The hybrid particle AgNP@SiO2 and the air filter system coated with the particles are expected to be useful for future green environment applications.

Mesoporous zirconia thin films with three-dimensional pore structures and their application to electrochemical glucose detection.

Mesoporous zirconia thin films (MZFs) were synthesized using zirconium hydroxide sol particles and a structure directing agent, Pluronic F127 (PEO106PPO70PEO106, EO = ethylene oxide, PO = propylene oxide). By controlling the F127/Zr ratio, we obtained two distinct MZFs with one in the Fmmm structure and the other in the P63/mmc structure. The pore structures of these films were characterized by low-angle X-ray diffraction, grazing incidence small-angle X-ray scattering, electron microscopy, and N2 sorption measurement. The Fmmm structure has interconnected pores and the P63/mmc structure has less accessible pores. The MZFs were functionalized with glucose oxidase (GOx) and were studied for their potentials as an electrochemical sensor for glucose. The GOx-functionalized MZF electrodes show high sensitivity to glucose in a broad range of glucose concentration of 0.025 - 6.8 mM, which can be attributed to their biocompatibility providing a favorable microenvironment for GOx immobilization and to their 3D pore structures with good accessibility of pores.

Synthesis of a CdSe-graphene hybrid composed of CdSe quantum dot arrays directly grown on CVD-graphene and its ultrafast carrier dynamics.

We report the original fabrication and performance of a photocurrent device that uses directly grown CdSe quantum dots (QDs) on a graphene basal plane. The direct junction between the QDs and graphene and the high quality of the graphene grown by chemical vapor deposition enables highly efficient electron transfer from the QDs to the graphene. Therefore, the hybrids show large photocurrent effects with a fast response time and shortened photoluminescence (PL) lifetime. The PL lifetime quenching can be explained as being due to the efficient electron transfer as evidenced by femtosecond transient absorption spectroscopy. These hybrids are expected to find applications in flexible electronics and optoelectronic devices.