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Eumelanin is a natural pigment found in many organisms that provides photoprotection from harmful UV radiation. As a redox‐active biopolymer, the structure of eumelanin is thought to contain different redox states of quinone, including catechol subunits. To further explore the excited state properties of eumelanin, we have investigated the catechol/o‐quinone redox couple by spectroelectrochemical means, in a pH 7.4 aqueous buffered solution, and using a boron doped diamond mesh electrode. At pH 7.4, the two proton, two electron oxidation of catechol is promoted, which facilitates continuous formation of the unstable o‐quinone product in solution. Ultrafast transient absorption (femtosecond to nanosecond) measurements of o‐quinone species involve initial formation of an excited singlet state followed by triplet state formation within 24 ps. In contrast, catechol in aqueous buffer leads to formation of the semiquinone radical Δt>500 ps. Our results demonstrate the rich photochemistry of the catechol/o‐quinone redox couple and provides further insight into the excited state processes of these key building blocks of eumelanin. [ABSTRACT FROM AUTHOR]

Coumaric acids and flavonoids play pivotal roles in protecting plants against ultraviolet radiation (UVR) exposure. In this work, we focus our photoprotection studies on p-coumaric acid and the flavonoid naringenin chalcone. Photoprotection is well-understood in p-coumaric acid; in contrast, information surrounding photoprotection in naringenin chalcone is lacking. Additionally, and vitally, how these two species work in unison to provide photoprotection across the UV-B and UV-A is unknown. Herein, we employ transient absorption spectroscopy together with steady-state irradiation studies to unravel the photoprotection mechanism of a solution of p-coumaric acid and naringenin chalcone. We find that the excited state dynamics of p-coumaric acid are significantly altered in the presence of naringenin chalcone. This finding concurs with quenching of the p-coumaric acid fluorescence with increasing concentration of naringenin chalcone. We propose a Förster energy transfer mechanism is operative via the formation of dipole-dipole interactions between p-coumaric acid and naringenin chalcone. To our knowledge, this is the first demonstration in plants of a synergic effect between two classes of phenolics to bypass the potentially damaging effects of UVR. [ABSTRACT FROM AUTHOR]

An octanuclear M8L12 coordination cage host (HPEG) in aqueous solution binds neutral electron-accepting guests such as naphthoquinone (NQ) in its central cavity via the hydrophobic effect, and multiple anionic photosensitisers such as Eosin-Y (EY2-) around the exterior surface due to 16+ charge on the complex cation: this is confirmed by both solution titration experiments and X-ray crystallography.  In the three-component assembly HPEG / EY2- / NQ, photoexcitation of EY2- at 525 nm results in ultrafast (ca. 1 ps) photoinduced EY2- ® NQ electron transfer from surface-bound EY2- to cavity-bound NQ (which have been brought into close proximity by their interactions with different sites on the host cage) to give the charge-separated pair EY•- / NQ•-, identified by transient absorption spectroscopy: back-ET results in charge recombination in ≈70 ps.  The assembly of donor and acceptor components via orthogonal interactions using the host cage as a scaffold presents a promising route into spatial control of multiple components in supramolecular arrays for photophysical applications., (© 2025 Wiley‐VCH GmbH.)

Nanofibrous active layers offer hierarchical control over molecular structure, and the size and distribution of electron donor:acceptor domains, beyond conventional organic photovoltaic architectures. This structure is created by forming donor pathways via electrospinning nanofibers of semiconducting polymer, then infiltrating with an electron acceptor. Electrospinning induces chain and crystallite alignment, resulting in enhanced light-harvesting and charge transport. Here, the charge transport capabilities are predicted, and charge separation and dynamics are evaluated in these active layers, to assess their photovoltaic potential. Through X-ray and electron diffraction, the fiber nanostructure is elucidated, with uniaxial elongation of the electrospinning jet aligning the polymer backbones within crystallites orthogonal to the fiber axis, and amorphous chains parallel. It is revealed that this structure forms when anisotropic crystallites, pre-assembled in solution, become oriented along the fiber- a configuration with high charge transport potential. Competitive dissociation of excitons formed in the photoactive nanofibers is recorded, with 95%+ photoluminescence quenching upon electron acceptor introduction. Transient absorption studies reveal that silver nanoparticle addition to the fibers improves charge generation and/or lifetimes. 1 ns post-excitation, the plasmonic architecture contains 45% more polarons, per exciton formed, than the bulk heterojunction. Therefore, enhanced exciton populations may be successfully translated into additional charge carriers., (© 2024 The Author(s). Small published by Wiley‐VCH GmbH.)

Many photoactivated processes involve a change in oxidation state during the reaction pathway and formation of highly reactive photoactivated species. Isolating these reactive species and studying their early-stage femtosecond to nanosecond (fs-ns) photodynamics can be challenging. Here we introduce a combined ultrafast transient absorption-spectroelectrochemistry (TA-SEC) approach using freestanding boron doped diamond (BDD) mesh electrodes, which also extends the time domain of conventional spectrochemical measurements. The BDD electrodes offer a wide solvent window, low background currents, and a tuneable mesh size which minimises light scattering from the electrode itself. Importantly, reactive intermediates are generated electrochemically, via oxidation/reduction of the starting stable species, enabling their dynamic interrogation using ultrafast TA-SEC, through which the early stages of the photoinduced relaxation mechanisms are elucidated. As a model system, we investigate the ultrafast spectroscopy of both anthraquinone-2-sulfonate (AQS) and its less stable counterpart, anthrahydroquinone-2-sulfonate (AH 2 QS). This is achieved by generating AH 2 QS in situ from AQS via electrochemical means, whilst simultaneously probing the associated early-stage photoinduced dynamical processes. Using this approach we unravel the relaxation mechanisms occurring in the first 2.5 ns, following absorption of ultraviolet radiation; for AQS as an extension to previous studies, and for the first time for AH 2 QS. AQS relaxation occurs via formation of triplet states, with some of these states interacting with the buffered solution to form a transient species within approximately 600 ps. In contrast, all AH 2 QS undergoes excited-state single proton transfer with the buffered solution, resulting in formation of ground state AHQS - within approximately 150 ps., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)