Controlling plasmon propagation and enhancement via reducing agent in wet chemistry synthesized silver nanowires.

Silver nanowires with varying diameters and submillimeter lengths were obtained by changing a reducing agent used during hydrothermal synthesis. The control over the nanowire diameter turns out to play a critical role in determining their plasmonic properties, including fluorescence enhancement and surface plasmon polariton propagation. Advanced fluorescence imaging of hybrid nanostructures assembled of silver nanowires and photoactive proteins indicates longer propagation lengths for nanowires featuring larger diameters. At the same time, with increasing diameter of the nanowires, we measure a substantial reduction of fluorescence enhancement. The results point at possible ways to control the influence of plasmon excitations in silver nanowires by tuning their morphology.

Silver Island Film for Enhancing Light Harvesting in Natural Photosynthetic Proteins.

The effects of combining naturally evolved photosynthetic pigment-protein complexes with inorganic functional materials, especially plasmonically active metallic nanostructures, have been a widely studied topic in the last few decades. Besides other applications, it seems to be reasonable using such hybrid systems for designing future biomimetic solar cells. In this paper, we describe selected results that point out to various aspects of the interactions between photosynthetic complexes and plasmonic excitations in Silver Island Films (SIFs). In addition to simple light-harvesting complexes, like peridinin-chlorophyll-protein (PCP) or the Fenna-Matthews-Olson (FMO) complex, we also discuss the properties of large, photosynthetic reaction centers (RCs) and Photosystem I (PSI)-both prokaryotic PSI core complexes and eukaryotic PSI supercomplexes with attached antenna clusters (PSI-LHCI)-deposited on SIF substrates.

Optical Properties of Submillimeter Silver Nanowires Synthesized Using the Hydrothermal Method.

We report on the synthesis of long silver nanowires using the hydrothermal method, with H2O2 as the reducing agent. Our approach yields nanowires with an average diameter and length of about 100 nm and 160 µm, respectively, reaching the maximum length of 800 µm. Scanning electron microscopy (SEM) measurements revealed the presence of a thick, inhomogeneous poly(vinylpyrrolidone) (PVP) layer covering the nanowires, which with time becomes much more uniform, leading to well-defined extinction peaks in the ultraviolet-visible (UV-Vis) spectra. This change in morphology is evidenced also by the fluorescence enhancement behavior probed using protein complexes. Wide-field and confocal fluorescence microscopy measurements demonstrate strong, 10-fold enhancement of the protein emission intensity, accompanied by a reduction of the fluorescence decay time. In addition, for the aged, one-month-old nanowires, the uniformity of the intensity profile along them was substantially improved as compared with the as-synthesized ones. The results point towards the importance of the morphology of plasmonically active silver nanowires when considering their application in enhancing optical properties or achieving energy propagation over submillimeter distances.

Plasmon-induced absorption of blind chlorophylls in photosynthetic proteins assembled on silver nanowires.

We demonstrate that controlled assembly of eukaryotic photosystem I with its associated light harvesting antenna complex (PSI-LHCI) on plasmonically active silver nanowires (AgNWs) substantially improves the optical functionality of such a novel biohybrid nanostructure. By comparing fluorescence intensities measured for PSI-LHCI complex randomly oriented on AgNWs and the results obtained for the PSI-LHCI/cytochrome c553 (cyt c553) bioconjugate with AgNWs we conclude that the specific binding of photosynthetic complexes with defined uniform orientation yields selective excitation of a pool of chlorophyll (Chl) molecules that are otherwise almost non-absorbing. This is remarkable, as this study shows for the first time that plasmonic excitations in metallic nanostructures can not only be used to enhance native absorption of photosynthetic pigments, but also - by employing cyt c553 as the conjugation cofactor - to activate the specific Chl pools as the absorbing sites only when the uniform and well-defined orientation of PSI-LHCI with respect to plasmonic nanostructures is achieved. As absorption of PSI alone is comparatively low, our approach lends itself as an innovative approach to outperform the reported-to-date biohybrid devices with respect to solar energy conversion.