Combined antenna and localized plasmon resonance in Raman scattering from Random arrays of silver-coated, vertically aligned multiwalled carbon nanotubes

The electric field enhancement associated with detailed structure within novel optical antenna nanostructures is modeled using the surface integral equation technique in the context of surface-enhanced Raman scattering (SERS). The antennae comprise random arrays of vertically aligned, multi-walled carbon nanotubes dressed with highly granular Ag. Different types of "hot-spot" underpinning the SERS are identified, but contrasting characteristics are revealed. Those at the outer edges of the Ag grains are antenna driven with field enhancement amplified in antenna antinodes while intergrain hotspots are largely independent of antenna activity. Hot-spots between the tops of antennae leaning towards each other also appear to benefit from antenna amplification.

Effect of resonance frequency, power input, and saturation gas type on the oxidation efficiency of an ultrasound horn

The sonochemical oxidation efficiency (eta(ox)) of a commercial titanium alloy ultrasound horn has been measured using potassium iodide as a dosimeter at its main resonance frequency (20 kHz) and two higher resonance frequencies (41 and 62 kHz). Narrow power and frequency ranges have been chosen to minimise secondary effects such as changing bubble stability, and time available for radical diffusion from the bubble to the liquid. The oxidation efficiency, eta(ox), is proportional to the frequency and to the power transmitted to the liquid (275 mL) in the applied power range (1-6 W) under argon. Luminol radical visualisation measurements show that the radical generation rate increases and a redistribution of radical producing zones is achieved at increasing frequency. Argon, helium, air, nitrogen, oxygen, and carbon dioxide have been used as saturation gases in potassium iodide oxidation experiments. The highest eta(ox) has been observed at 5 W under air at 62 kHz. The presence of carbon dioxide in air gives enhanced nucleation at 41 and 62 kHz and has a strong influence on eta(ox). This is supported by the luminol images, the measured dependence of eta(ox). on input power, and bubble images recorded under carbon dioxide. The results give insight into the interplay between saturation gas and frequency, nucleation, and their effect on eta(ox). (C) 2010 Elsevier B.V. All rights reserved.

The assimilation and chronic effects of sub-lethal concentrations of Endosulfan on condition and spawning in the common mussel Mytilus edulis

The rate of uptake of Endosulfan by Mytilus edulis L. exposed to pesticide concentrations of 0.1, 0.5, and 1.0 mg/l, and its subsequent elution on removal to clean sea water, was investigated. Higher residue levels were recorded for mussels exposed to higher concentrations of the pesticide, but concentration factors were reduced. There was a rapid initial fall in tissue residue levels on transfer to clean sea water due, it is suggested, to elution of Endosulfan adsorbed on particulate matter assimilated in the gut. The spawning period was prolonged at higher concentrations and, at 1.0 mg/l, the onset of spawning was delayed, possibly due to interference with gamonic action. At 0.1 mg/l, the minor protraction of the spawning period may reflect the effect of experimental tank conditions. No seasonal trend was obvious, and there was an exaggeration of the expected fall in condition in mussels exposed to higher concentrations of Endosulfan. In controls, the expected seasonal trend was reduced.

Resonance Raman and surface-enhanced resonance Raman studies of polymer-modified electrodes which mimic heme enzymes

Iron-5,10,15,20-tetraphenylporphyrin (FeTPP) has been incorporated into films of a coordinating hydrogel polymer support medium, poly(gamma-ethyl-L-glutamate) (PEG) functionalised with imidazole pendant arms (PEG-Im), and studied in situ on silver electrodes using a combination of both resonance Raman (RR) and surface-enhanced resonance Raman (SERR) spectroscopy. The SERR spectra give information on the portion of the film close to the electrode surface while RR spectra probe the

Resonance Raman probing of the interaction between dipyridophenazine complexes of Ru(II) and DNA

Resonance Raman (RR) spectroscopy has been used to probe the interaction between dipyridophenazine (dppz) complexes of ruthenium(II), [Ru(L)(2)(dppz)](2+) (L = 1,10-phenanthroline (1) and 2,2-bipyridyl (2)), and calf-thymus DNA. Ground electronic state RR spectra at selected probe wavelengths reveal enhancement patterns which reflect perturbation of the dppz-centered electronic transitions in the UV-vis spectra in the presence of DNA. Comparison of the RR spectra recorded of the short-lived MLCT excited states of both complexes in aqueous solution with those of the longer-lived states of the complexes in the DNA environment reveals changes to excited state modes, suggesting perturbation of electronic transitions of the dppz ligand in the excited state as a result of intercalation. The most prominent feature, at 1526 cm(-1), appears in the spectra of both 1 and 2 and is a convenient marker band for intercalation. For 1, the excited state studies have been extended to the A and A enantiomers. The marker band appears at the same frequency for both but with different relative intensities. This is interpreted as reflecting the distinctive response of the enantiomers to the chiral environment of the DNA binding sites. The results, together with some analogous data for other potentially intercalating complexes, are considered in relation to the more general application of time-resolved RR spectroscopy for investigation of intercalative interactions of photoexcited metal complexes with DNA.

Time-resolved resonance Raman spectroscopy

Vibrational Raman spectroscopy is now widely recognized as a useful technique for chemical analysis. It has become increasingly popular for the characterization of stable species since the technology which underpins Raman measurements has matured. Time-resolved Raman spectroscopy has also become established as an excellent method for the characterization of transient chemical species but it is not so widely applied. However, the technical advances which have reduced the cost and increased the reliability of conventional: Raman systems can also be exploited in studies of transient species. In some cases it is just as straightforward to record the Raman-spectra of a short-lived transient species as it is to monitor a more stable sample. This raises the possibility of routinely adding time-domain Raman measurements to more conventional Raman techniques, increasing the selectivity of the analysis while retaining its ability to provide spectral information which is characteristic of the species under investigation.

Time-resolved resonance Raman scattering of triplet state anthracene in supercritical CO2

The first report of time-resolved resonance Raman (TR(3)) scattering in a supercritical fluid is presented. TR(3) spectra of the lowest triplet excited state (T-1) of anthracene in supercritical (SC) CO2 have been obtained over the pressure range 90-500 bar. These data have been complemented by conventional flash photolysis measurements of the excited state lifetime, transient absorbance difference, and fluorescence spectra over a similar pressure range. The spectroscopic data show systematic changes with increasing pressure; the Delta A spectra of the TI state recorded at two different temperatures display a red shift with increasing fluid pressure, which is in agreement with earlier work carried out over a smaller range of pressures. Similar shifts in the fluorescence are also observed. The vibrational frequencies of the T-1 state of anthracene are found to be relatively insensitive to applied pressure; indeed, the transient bands are readily identified by comparison with resonance Raman (RR) spectra of the T-1 state in cyclohexane solution. Small but well-defined shifts to lower cm(-1) with increasing pressure are observed in some of the vibrational bands of SC COE. The most marked change in the excited state Raman spectra is that the intensity of the T-1 anthracene features, relative to those of CO2, increases with applied pressure. The information which each of the above spectroscopic methods gives on the question of how pressure changes affect the structure and local environment of the excited state probe molecule in the SCF is discussed. Possible explanations for the observed increase in RR band intensities in terms of increased resonance Raman enhancement arising from the spectral shifts and/or the increased solubility of anthracene in CO2 with increasing pressure are also considered.

Resonance-Raman probing of the interaction between dipyridophenazine complexes of ruthenium(II) and DNA

The resonance-Raman spectroscopic technique is an effective probe of the interaction between dipyridophenazine (dppz) complexes of ruthenium(II) and calf-thymus DNA, providing evidence that DNA addition results in changes to electronic transitions of the intercalating dppz ligand in both ground and excited states.