Surface enhanced resonance Raman and luminescence on plasmon active nanostructured cavities

Presented here are studies of the impact of excitation angle on surface enhanced Raman and luminescence spectroscopy of dye immobilised on a plasmon active nanocavity array support. Results show that both Raman and luminescence intensities depend on the angle of incidence consistent with the presence of cavity supported plasmon modes. Dependence of scattering or emission intensity with excitation angle occurs over the window of observation

Controlled side-by-side assembly of gold nanorods and dye molecules into polymer-wrapped SERRS-active clusters

The controlled side-by-side assembly of gold nanorods in solution together with Raman reporter dye molecules to create small SERRS-active clusters stabilised by a surrounding polymer layer is demonstrated. This promising new class of nanotags offers several advantages over spherical nanoparticles for bioimaging and is of potential importance for a wide range of plasmon-enhanced spectroscopies and can also serve as building blocks for more complex solution-phase nanostructures

Water splitting with polyoxometalate-treated photoanodes: Enhancing performance through sensitizer design

Visible light driven water oxidation has been demonstrated at near-neutral pH using photoanodes based on nanoporous films of TiO2, polyoxometalate (POM) water oxidation catalyst [{Ru4O4(OH)2(H2O)4}(γ-SiW10O36)2]10- (1), and both known photosensitizer [Ru(bpy)2(H4dpbpy)]2+ (P2) and the novel crown ether functionalized dye [Ru(5-crownphen)2(H2dpbpy)] (H22). Both triads, containing catalyst 1, and catalyst-free dyads, produce O2 with high faradaic efficiencies (80 to 94%), but presence of catalyst enhances quantum yield by up to 190% (maximum 0.39%). New sensitizer H22 absorbs light more strongly than P2, and increases O2 quantum yields by up to 270%. TiO2-2 based photoelectrodes are also more stable to desorption of active species than TiO2-P2: losses of catalyst 1 are halved when pH > TiO2 point-of-zero charge (pzc), and losses of sensitizer reduced below the pzc (no catalyst is lost when pH < pzc). For the triads, quantum yields of O2 are higher at pH 5.8 than at pH 7.2, opposing the trend observed for 1 under homogeneous conditions. This is ascribed to lower stability of the dye oxidized states at higher pH, and less efficient electron transfer to TiO2, and is also consistent with the 4th 1-to-dye electron transfer limiting performance rather than catalyst TOFmax. Transient absorption reveals that TiO2-2-1 has similar 1st electron transfer dynamics to TiO2-P2-1, with rapid (ps timescale) formation of long-lived TiO2(e-)-2-1(h+) charge separated states, and demonstrates that metallation of the crown ether groups (Na+/Mg2+) has little or no effect on electron transfer from 1 to 2. The most widely relevant findings of this study are therefore: (i) increased dye extinction coefficients and binding stability significantly improve performance in dye-sensitized water splitting systems; (ii) binding of POMs to electrode surfaces can be stabilized through use of recognition groups; (iii) the optimal homogeneous and TiO2-bound operating pHs of a catalyst may not be the same; and (iv) dye-sensitized TiO2 can oxidize water without a catalyst

A Coupled Cavity Micro Fluidic Dye Ring Laser

We present a laterally emitting, coupled cavity micro fluidic dye ring laser, suitable for integration into lab-on-a-chip micro systems. The micro-fluidic laser has been successfully designed, fabricated, characterized and modelled. The resonator is formed by a micro-fluidic channel bounded by two isosceles triangle mirrors. The micro-fluidic laser structure is defined using photo lithography in 10 microns thick SU-8 polymer on a glass substrate. The micro fluidic channel is sealed by a glass lid, using PMMA adhesive bonding. The laser is characterized using the laser dye Rhodamine 6G dissolved in ethanol or ethylene glycol as the active gain medium, which is pumped through the micro-fluidic channel and laser resonator. The dye laser is optically pumped normal to the chip plane at 532 nm by a pulsed, frequency doubled Nd:YAG laser and lasing is observed with a threshold pump pulse energy flux of around 55 micro-Joule/square-milimeter. The lasing is multi-mode, and the laser has switchable output coupling into an integrated polymer planar waveguide. Tuning of the lasing wavelength is feasible by changing the dye/solvent properties.Comment: Accepted for Microelectronic Engineerin

Optofluidic random laser

An active disordered medium able to lase is called a random laser (RL). We demonstrate random lasing due to inherent disorder in a dye circulated structured microfluidic channel. We consistently observe RL modes which are varied by changing the pumping conditions. Potential applications for on-chip sources and sensors are discussed.Comment: 3 pages, 4 figure

Hexagonal microlasers based on organic dyes in nanoporous crystals

Molecular sieves, such as nanoporous AlPO_4-5, can host a wide variety of laser active dyes. We embedded pyridine 2 molecules as a representative of a commercially available dye which fits into the channel pores of the host matrix. Many efficient dye molecules, such as rhodamines, do not fit into the pores. But the amount of encapsulated dyes can be increased by modifying the structure of the dyes such that they match the host templates. The resulting microlasers have properties that depend on size and shape of the microresonators, and we discuss a model for microscopic hexagonal ring resonators. In terms of pump needed to reach lasing threshold molecular sieve microlasers are comparable to VCSELs. For dyes which fit into the pores we observed a partial regeneration of photo-induced damage.Comment: 10 pages, 16 figure

Impact of Quenching Failure of Cy Dyes in Differential Gel Electrophoresis

Background: Differential gel electrophoresis (DIGE) is a technology widely used for protein expression analysis. It is based on labelling with fluorescent Cy dyes. In comparative fluorescence gel electrophoresis experiments, however, unspecific labelling using N-hydroxy-succinimide-ester-based labelling protocols was recently detected. Cross-talk was observed due to failure of the quenching process. Here, the impact of this effect for DIGE experiments was investigated. Methodology/Principal Findings: Experiments to test quenching efficiency were performed in replicate using Escherichia coli lysate. Parameters such as the amount of dye and quencher were varied. Labelling and quenching were reversed in one experiment. Differences in protein spot volumes due to limited quenching were determined. For some spots twice the volume was detected underscoring the importance of proper control of silencing of active dye. Conclusions/Significance: It could be demonstrated that uncontrolled labelling increased protein spot volume, even doubling it in some cases. Moreover, proteins responded differently to the protocol. Such unpredictable and unspecific processes are not acceptable in protein regulation studies so that it is necessary to validate the correct amount of quencher for individual samples before the DIGE experiment is performed. Increase of the concentration of lysine, which is used as quencher, from 10 mM to 2500 mM, was sufficient to silence the dye. Alternatively, active dye molecules can be removed by filtration

Acid-Labile Traceless Click Linker for Protein Transduction

Intracellular delivery of active proteins presents an interesting approach in research and therapy. We created a protein transduction shuttle based on a new traceless click linker that combines the advantages of click reactions with implementation of reversible pH-sensitive bonds. The azidomethyl-methylmaleic anhydride (AzMMMan) linker was found compatible with different click chemistries, demonstrated in bioreversible protein modification with dyes, polyethylene glycol, or a transduction carrier. Linkages were stable at physiological pH but reversible at the mild acidic pH of endosomes or lysosomes. We show that pH-reversible attachment of a defined endosome-destabilizing three-arm oligo(ethane amino)amide carrier generates an effective shuttle for protein delivery. The cargo protein nlsEGFP, when coupled via the traceless AzMMMan linker, experiences efficient cellular uptake and endosomal escape into the cytosol, followed by import into the nucleus. In contrast, irreversible linkage to the same shuttle hampers nuclear delivery of nlsEGFP which after uptake remains trapped in the cytosol. Successful intracellular delivery of bioactive ß-galactosidase as a model enzyme was also demonstrated using the pH-controlled shuttle system