Environmental exposure enhances the internalization of microplastic particles into cells.

Microplastic particles ubiquitously found in the environment are ingested by a huge variety of organisms. Subsequently, microplastic particles can translocate from the gastrointestinal tract into the tissues likely by cellular internalization. The reason for cellular internalization is unknown, since this has only been shown for specifically surface-functionalized particles. We show that environmentally exposed microplastic particles were internalized significantly more often than pristine microplastic particles into macrophages. We identified biomolecules forming an eco-corona on the surface of microplastic particles, suggesting that environmental exposure promotes the cellular internalization of microplastics. Our findings further indicate that cellular internalization is a key route by which microplastic particles translocate into tissues, where they may cause toxicological effects that have implications for the environment and human health.

Excited state dynamics and conformations of a Cu(ii)-phthalocyanine-perylenebisimide dyad.

We investigate the excited state dynamics and the conformations of a new molecular donor-bridge-acceptor system, a Cu(ii)-phthalocyanine (CuPc) covalently linked via a flexible aliphatic spacer to a perylenebisimide (PBI). We performed time-resolved polarization anisotropy and pump-probe measurements in combination with molecular dynamics simulations. Our data suggest the existence of three conformations of the dyad: two more extended, metastable conformations with centre-of-mass distances >1 nm between the PBI and CuPc units of the dyad, and a highly stable folded structure, in which the PBI and CuPc units are stacked on top of each other with a centre-of-mass distance of 0.4 nm. In the extended conformations the dyad shows emission predominantly from the PBI unit with a very weak contribution from the CuPc unit. In contrast, for the folded conformation the PBI emission of the dyad is strongly quenched due to fast energy transfer from the PBI to the CuPc unit (3 ps) and subsequent intersystem-crossing (300 fs) from the first excited singlet state of CuPc unit into its triplet state. Finally, the CuPc triplet state is deactivated non-radiatively with a time constant of 25 ns.

The role of colloidal plasmonic nanostructures in organic solar cells.

Plasmonic particles can contribute via multiple processes to the light absorption process in solar cells. These particles are commonly introduced into organic solar cells via deposition techniques such as spin-coating or dip-coating. However, such techniques are inherently challenging to achieve homogenous surface coatings as they lack control of inter-particle spacing and particle density on larger areas. Here we introduce interface assisted colloidal self-assembly as a concept for the fabrication of well-defined macroscopic 2-dimensional monolayers of hydrogel encapsulated plasmonic gold nanoparticles. The monolayers showed a pronounced extinction in the visible wavelength range due to localized surface plasmon resonance with excellent optical homogeneity. Moreover this strategy allowed for the investigation of the potential of plasmonic monolayers at different interfaces of P3HT:PCBM based inverted organic solar cells. In general, for monolayers located anywhere underneath the active layer, the solar cell performance decreased due to parasitic absorption. However with thick active layers, where low hole mobility limited the charge transport to the top electrode, the plasmonic monolayer near that electrode spatially redistributed the light and charge generation close to the electrode led to an improved performance. This work systematically highlights the trade-offs that need to be critically considered for designing an efficient plasmonically enhanced organic solar cell.

Unravelling the conformations of di-(perylene bisimide acrylate) by combining time-resolved fluorescence-anisotropy experiments and molecular modelling.

We compare the results from time-resolved fluorescence anisotropy experiments and molecular modelling on perylene bisimide acrylate dimers which allows us to connect the observed spectral signatures unambiguously with the non-stacked and two (parallel and anti-parallel) stacked conformations. For the parallel stacked conformation the experimental data can be reproduced quantitatively using a model that assumes structural relaxation in the electronically excited state of the stacked aggregate. For the non-stacked conformation we find quantitative agreement between experiment and modelling only if a fast hopping of the electronic excitation between the perylene bisimide subunits is taken into account.

Fluorescence quenching of substituted polyperylene with functionalized polythiophenes.

The present investigation focuses the influence of polythiophene i) containing hetero aromatic structures and ii) containing mesogenic groups towards the photoluminescence properties of substituted polyperylene (PPE). The structural contribution towards the optical properties was individually discussed. The photoluminescence of PPE was quenched to the maximum level (30%) when it was blended with polythiophene with mesogenic groups containing longer alkyl spacer. Results of the same blend in solid-state shows 85% of PL quenching.

Characterization of the adsorption of Ru-bpy dyes on mesoporous TiO2 films with UV-Vis, Raman, and FTIR spectroscopies.

In the present work the adsorption of a new dye, [Ru(dcbpyH(2))(2)(bpy-TPA(2))](PF(6))(2), and the well-known (Bu(4)N)(2)[Ru(dcbpyH)(2)(NCS)(2)] complex on mesoporous anatase films were investigated to clarify the role of the carboxylate groups in the anchoring process of the dyes on the semiconductor surface. For this purpose UV-vis, Raman, resonance Raman, and ATR-FTIR spectroscopies have been used. The results of the Raman experiments at different excitation wavelengths demonstrate that photoinduced charge-transfer processes take place efficiently between the adsorbate and the substrate. Moreover, this is the first time that the Raman spectrum of a Ru-bpy dye (in this case, the dye N719) adsorbed on TiO(2) has been obtained without the resonance condition, only by means of SERS enhancement. The coordination of both complexes on the TiO(2) paste films is proposed to occur via bidentate or bridging linkage.

Influence of the solvent on the surface-enhanced raman spectra of ruthenium(II) bipyridyl complexes.

In the present work a new dye, [Ru(dcbpyH2)2(bpy-TPA2)](PF6)2, and the well-known (Bu4N)2[Ru(dcbpyH)2(NCS)2] complex were investigated. The electronic transitions of both dyes showed solvatochromic shifts due to specific interactions of the ligands with the solvent molecules. The surface-enhanced Raman (SER) spectra of the dyes dissolved in water, ethanol, and acetonitrile were measured in silver and gold colloidal solutions. The results demonstrate that the dyes were adsorbed on the metallic nanoparticles in different ways for different solvents. It was also found that in the gold colloid, the aqueous solutions of both dyes did not produce any SERS signal, whereas in ethanolic solution the SERS effect was very weak. Deprotonation, H-bonding, and donor-acceptor interactions seem to determine these different behaviors. Our results indicate the important role of the charge-transfer mechanism in SERS.