Elucidating Protein Involvement in the Stabilization of the Biogenic Silver Nanoparticles.

Silver nanoparticles (AgNPs) have been broadly used as antibacterial and antiviral agents. Further, interests for green AgNP synthesis have increased in recent years and several results for AgNP biological synthesis have been reported using bacteria, fungi and plant extracts. The understanding of the role and nature of fungal proteins, their interaction with AgNPs and the subsequent stabilization of nanosilver is yet to be deeply investigated. Therefore, in an attempt to better understand biogenic AgNP stabilization with the extracellular fungal proteins and to describe these supramolecular interactions between proteins and silver nanoparticles, AgNPs, produced extracellularly by Aspergillus tubingensis-isolated as an endophytic fungus from Rizophora mangle-were characterized in order to study their physical characteristics, identify the involved proteins, and shed light into the interactions among protein-NPs by several techniques. AgNPs of around 35 nm in diameter as measured by TEM and a positive zeta potential of +8.48 mV were obtained. These AgNPs exhibited a surface plasmon resonance (SPR) band at 440 nm, indicating the nanoparticles formation, and another band at 280 nm, attributed to the electronic excitations in tryptophan, tyrosine, and/or phenylalanine residues in fungal proteins. Fungal proteins were covalently bounded to the AgNPs, mainly through S-Ag bonds due to cysteine residues (HS-) and with few N-Ag bonds from H2N- groups, as verified by Raman spectroscopy. Observed supramolecular interactions also occur by electrostatic and other protein-protein interactions. Furthermore, proteins that remain free on AgNP surface may perform hydrogen bonds with other proteins or water increasing thus the capping layer around the AgNPs and consequently expanding the hydrodynamic diameter of the particles (~264 nm, measured by DLS). FTIR results enabled us to state that proteins adsorbed to the AgNPs did not suffer relevant secondary structure alteration upon their physical interaction with the AgNPs or when covalently bonded to them. Eight proteins in the AgNP dispersion were identified by mass spectrometry analyses. All these proteins are involved in metabolic pathways of the fungus and are important for carbon, phosphorous and nitrogen uptake, and for the fungal growth. Thereby, important proteins for fungi are also involved in the formation and stabilization of the biogenic AgNPs.

Critical assessment of enhancement factor measurements in surface-enhanced Raman scattering on different substrates.

The SERS enhancement factor (SERS-EF) is one of the most important parameters that characterizes the ability of a given substrate to enhance the Raman signal for SERS applications. The comparison of SERS intensities and SERS-EF values across different substrates is a common practice to unravel the performance of a given substrate. In this study, it is shown that such a comparison may lack significance if we compare substrates of very distinct nature and optical properties. It is specifically shown that the SERS-EF values for static substrates (e.g. immobilized metallic nanostructures) cannot be compared to those of dynamic ones (e.g. colloidal metal nanoparticle solutions), and that the optical properties for the latter show strong dependence on the metal-molecule interaction dynamics. The most representative experimental results concerning the dynamic substrates have been supported by generalized Mie theory simulations, which are tools used to describe the substrate complexity and the microscopic information not usually taken into account.

Rapid synthesis of hollow Ag-Au nanodendrites in 15 seconds by combining galvanic replacement and precursor reduction reactions.

Metallic nanomaterials displaying hollow interiors as well as sharp tips/branches at their surface (such as hollow nanodendrites) are attractive, because these features enable higher surface-to-volume ratios than their solid and/or rounded counterparts. This paper describes a simple strategy for the synthesis of Ag-Au nanodendrites in 15 s using Ag nanospheres prepared in a previous synthetic step as seeds. Our approach was based on the utilization of Ag nanospheres as seeds for Au deposition by a combination of galvanic replacement reaction between Ag and AuCl4(-)(aq) and AuCl4(-)(aq) reduction using hydroquinone in the presence of polyvinylpyrrolidone (PVP) as a stabilizer and water as the solvent. The produced Ag-Au nanodendrites presented monodisperse sizes, and their surface morphologies could be tuned as a function of growth time. Owing to their hollow interiors and sharp tips, the Ag-Au nanodendrites performed as effective substrates for surface-enhanced Raman scattering (SERS) detection of 4-MPy (4-mercaptopyridine) and R6G (rhodamine 6G) as probe molecules. We believe that the approach described herein can serve as a protocol for the fast and one-step synthesis of Ag-Au hollow nanondendrites with a wide range of sizes, compositions, and surface morphologies for applications in SERS and catalysis.

Cu nanoparticles enable plasmonic-improved silicon photovoltaic devices.

This work examines the effect of copper nanoparticles (Cu NPs) on the photocurrent efficiency of silicon photovoltaic (Si PV) devices. An optimized synthesis of stable Cu NPs is reported together with a procedure for their immobilization on the Si PV surface. A comprehensive analysis of the photocurrent and power dependence of the Cu NPs surface coverage and size is presented. A decrease in photoconversion was observed for wavelengths shorter than ~500 nm, due to the Cu interband absorption. In the low surface coverage limit, where the level of aggregation was found to be low, the surface plasmon resonance absorption dominates leading to a modest effect on the photocurrent response. As the number of aggregates increased with the surface coverage, the photocurrent efficiency also increased, and a maximum enhancement power conversion of 16% was found for a 54 ± 6 NPs per µm(2) PV cell. This enhancement was attributed to SPR light scattering and trapping into the Si PV device. Higher surface coverage yielded numerous aggregates which acted as a bulk coating and caused a decrease in both photocurrent and power measurements.

Probing dynamic generation of hot-spots in self-assembled chains of gold nanorods by surface-enhanced Raman scattering.

Further progress in the applications of self-assembled nanostructures critically depends on developing a fundamental understanding of the relation between the properties of nanoparticle ensembles and their time-dependent structural characteristics. Following dynamic generation of hot-spots in the self-assembled chains of gold nanorods, we established a direct correlation between ensemble-averaged surface-enhanced Raman scattering and extinction properties of the chains. Experimental results were supported with comprehensive finite-difference time-domain simulations. The established relationship between the structure of nanorod ensembles and their optical properties provides the basis for creating dynamic, solution-based, plasmonic platforms that can be utilized in applications ranging from sensing to nanoelectronics.