Ultrafast base rotations mediate a solvent-assisted back-electron transfer in UV-excited DNA single strands

The photochemistry of DNA systems is characterized by the ultraviolet (UV) absorption of π-stacked nucleobases, resulting in exciton states delocalized over several bases. As their relaxation sensitively depends on local stacking conformations, disentangling the ensuing electronic and structural dynamics has remained an experimental challenge, despite their fundamental role in protecting the genome from potentially harmful UV radiation. Here we use transient absorption and transient absorption anisotropy spectroscopy with broadband femtosecond deep-UV pulses (250-360 nm) to resolve the exciton dynamics of UV-excited adenosine single strands under physiological conditions. Due to the exceptional deep-UV bandwidth and polarization sensitivity of our experimental approach, we simultaneously resolve the population dynamics, charge-transfer (CT) character and conformational changes encoded in the UV transition dipoles of the π-stacked nucleotides. Whilst UV excitation forms fully charge-separated CT excitons in less than 0.3 ps, we find that most decay back to the ground state via a solvent-assisted back-electron transfer. This deactivation mechanism is accompanied by a structural relaxation of the photoexcited base-stack, which we identify as an inter-base rotation of the nucleotides. Our results finally complete the exciton relaxation mechanism for adenosine single strands and offer a direct view into the coupling of electronic and structural dynamics in aggregated photochemical systems.

PHOTOPHYSICAL AND PHOTOCHEMICAL SYSTEMS WITH SEMICONDUCTORS FOR THE CONVERSION OF SOLAR ENERGY. A REVIEW

Electrochemical energy sources are an alternative to replace technology based on the burning of fossil fuels. In an elec-trochemical system the potential drop spreads over a very narrow region at an interphase, creating high electric fields.So, there are good technological reasons to study semiconductor / electrolyte interphases. Currently, one of the ways touse renewable resources is through photovoltaic technology that directly converts solar radiation into electrical energy.This technology is manufactured from semiconductors, generally silicon, following an extremely careful and expensivemanufacturing procedure. An option for photovoltaic devices is photoelectrochemical cells.These cells are made bythe contact of a semiconductor electrode with a solution, which can be easily prepared and offers the possibility oflow-cost manufacturing. Understanding how these devices work requires knowledge of the characteristics of semicon-ductors and how these materials behave in contact with an electrolytic solution and under illumination by sunlight. Thepresent work describes, through an updated review, the principles and applications of semiconductor electrodes as themain components in a photoelectrochemical solar cell (PEC), to carry out chemical reactions of technological interest.In addition, the elements that are required for the improvement in the performance and construction of the PEC are discussed.

Revisiting the Concept of Photocatalysis: An Analysis from the Chemical Potentials

<p>A renewed criterion of photochemical free energy is proposed by introducing the concept of absorbed photon chemical potential. The so-called “photocatalytic” and “photosynthetic” processes are both spontaneous reactions in the corresponding physical fields. The misconception towards the classification method according to thermodynamic spontaneity of chemical reactions can be <a></a><a>rectified</a>. In this new vision, the photocatalysts in photochemical systems act as the “mediator” between the reactants and photons (a special reactant) to accelerate the kinetics process, which is exactly what the catalysts does.</p>

Revisiting the Concept of Photocatalysis: An Analysis from the Chemical Potentials

<p>A renewed criterion of photochemical free energy is proposed by introducing the concept of absorbed photon chemical potential. The so-called “photocatalytic” and “photosynthetic” processes are both spontaneous reactions in the corresponding physical fields. The misconception towards the classification method according to thermodynamic spontaneity of chemical reactions can be <a></a><a>rectified</a>. In this new vision, the photocatalysts in photochemical systems act as the “mediator” between the reactants and photons (a special reactant) to accelerate the kinetics process, which is exactly what the catalysts does.</p>

Sustainable hydrogen production from water using tandem dye-sensitized photoelectrochemical cells

If generated from water using renewable energy, hydrogen could serve as a carbon-zero, environmentally benign fuel to meet the needs of modern society. Photoelectrochemical cells integrate the absorption and conversion of solar energy and chemical catalysis for the generation of high value products. Tandem photoelectrochemical devices have demonstrated impressive solar-to-hydrogen conversion efficiencies but have not become economically relevant due to high production cost. Dye-sensitized solar cells, those based on a monolayer of molecular dye adsorbed to a high surface area, optically transparent semiconductor electrode, offer a possible route to realizing tandem photochemical systems for H2 production by water photolysis with lower overall material and processing costs. This review addresses the design and materials important to the development of tandem dye-sensitized photoelectrochemical cells for solar H2 production and highlights current published reports detailing systems capable of spontaneous H2 formation from water using only dye-sensitized interfaces for light capture.