Two-Dimensional Electronic Spectroscopy of Chlorophyll a: Solvent Dependent Spectral Evolution

The interaction of the monomeric chlorophyll Q-band electronic transition with solvents of differing physical-chemical properties is investigated through two-dimensional electronic spectroscopy (2DES). Chlorophyll constitutes the key chromophore molecule in light harvesting complexes. It is well-known that the surrounding protein in the light harvesting complex fine-tunes chlorophyll electronic transitions to optimize energy transfer. Therefore, an understanding of the influence of the environment on the monomeric chlorophyll electronic transitions is important. The Q-band 2DES is inhomogeneous at early times, particularly in hydrogen bonding polar solvents, but also in nonpolar solvents like cyclohexane. Interestingly this inhomogeneity persists for long times, even up to the nanosecond time scale in some solvents. The reshaping of the 2DES occurs over multiple time scales and was assigned mainly to spectral diffusion. At early times the reshaping is Gaussian-like, hinting at a strong solvent reorganization effect. The temporal evolution of the 2DES response was analyzed in terms of a Brownian oscillator model. The spectral densities underpinning the Brownian oscillator fitting were recovered for the different solvents. The absorption spectra and Stokes shift were also properly described by this model. The extent and nature of inhomogeneous broadening was a strong function of solvent, being larger in H-bonding and viscous media and smaller in nonpolar solvents. The fastest spectral reshaping components were assigned to solvent dynamics, modified by interactions with the solute

Enhancing the efficacy of fouling-release coatings against fouling by Mytilus galloprovincialis using nanofillers

Fouling-release (FR) coatings minimise the adhesion strength of fouling organisms. This study describes improved technologies to control the settlement and adhesion of the important fouling organism Mytilus galloprovincialis by incorporating the nanofillers titanium dioxide (TiO2) and carbon nanotubes (CNTs) in polydimethylsiloxane (PDMS) matrices. The incorporation of TiO2 prevented larval settlement when photoactivated with UV light, even at the lowest concentration of the nanofiller (3.75 wt%). Notably, there was 100% mortality of pediveligers exposed to photoactivated TiO2. However, plantigrades initially settled to photoactivated TiO2, but their adhesion strength was significantly reduced on these surfaces in comparison to blank PDMS. In addition, plantigrades had high mortality after 6 h. In contrast to the enhanced antifouling and FR properties of PDMS incorporating TiO2, the incorporation of CNTs had no effect on the settlement and adhesion of M. galloprovincialis