Revealing the photophysics of gold-nanobeacons via time-resolved fluorescence spectroscopy.

We demonstrate that time-resolved fluorescence spectroscopy is a powerful tool to investigate the conformation states of hairpin DNA on the surface of gold nanoparticles (AuNPs) and energy transfer processes in Au-nanobeacons. Long-range fluorescence quenching of Cy5 by AuNPs has been found to be in good agreement with electrodynamics modeling. Moreover, time-correlated single-photon counting (TCSPC) is shown to be promising for real-time monitoring of the hybridization kinetics of Au-nanobeacons, with up to 60% increase in decay time component and 300% increase in component fluorescence fraction observed. Our results also indicate the importance of the stem and spacer designs for the performance of Au-nanobeacons.

Influence of Ions and pH on the Formation of Solid- and Liquid-like Melanin.

Melanin is a natural pigment with broadband absorption and effective ability to dissipate the energy absorbed. The macromolecular structure of melanin shows a delicate balance between short-range ordered and disordered structures without being a random aggregate. The presence of ions or the variation in pH or ionic strength can alter the self-assembly process which subsequently changes the structure of melanin. To understand these relationships, this study investigates the influence of ions and pH in melanin formation. The types of ions present and pH have a profound influence on the formation and structure of melanin particles, while only minor changes are observed in the absorption and excitation-emission analysis. In some conditions, the formation of discernible particles with significant refractive index contrast is avoided while retaining the spectroscopic characteristics of melanin, leading to liquid-like melanin. These findings identify potential pathways which can be used to manipulate the melanin macromolecular structure while providing the desired spectral properties to enable novel bio-engineering applications.

Toward single-metal-ion sensing by Förster resonance energy transfer.

Here we describe progress toward our objective of detecting single nonfluorescent hydrated metal ions. Single-ion detection represents detection and spectroscopy at the ultimate sensitivity level of approximately 1.6 x 10(-24) M. Achieving this goal would provide a breakthrough in analytical science and allow much more detailed insight into sensor-ion interaction than that available with conventional bulk detection methods. We combine recent advances in confocal microscopy with the sensitivity and the noninvasive nature of fluorescence by analyzing Förster resonance energy transfer between sensor fluorophores and transition metal ions.

Tracking the formation of eumelanin from L-Dopa using coupled measurements.

Melanin plays a crucial role as a pigment all through the animal kingdom. Being a macromolecule just on the divide between an ordered crystalline or a purely amorphous form melanin has proven a challenge to structure-function analysis. Melanin assembles from small molecules much like a jigsaw and much like in a jigsaw the fine detail quickly vanishes in the overall picture. With melanin being first and foremost a photo-active molecule we focus on spectral properties for the characterisation of its structure. We use absorption measurements to illustrate the complex nature of the formation process. To gain a better hold on the formation pathway we use coupled measurements of excitation and emission to identify 'areas of interest' in the excitation-emission matrix (EEM). We then probe one area for characteristic fluorescence lifetimes to track one melanin building block through the formation process. Comparison of the EEMs of L-Dopa derived melanin with natural Sepia melanin shows characteristic differences. We show how the presence of copper ions creates a melanin closer to its natural form.