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  1. Free, publicly-accessible full text available January 24, 2025
  2. Free, publicly-accessible full text available January 24, 2025
  3. Two-dimensional infrared (2D IR) spectroscopy, infrared pump–infrared probe spectroscopy, and density functional theory calculations were used to study vibrational relaxation by ring and carbonyl stretching modes in a series of methylated xanthine derivatives in acetonitrile and deuterium oxide (heavy water). Isotropic signals from the excited symmetric and asymmetric carbonyl stretch modes decay biexponentially in both solvents. Coherent energy transfer between the symmetric and asymmetric carbonyl stretching modes gives rise to a quantum beat in the time-dependent anisotropy signals. The damping time of the coherent oscillation agrees with the fast decay component of the carbonyl bleach recovery signals, indicating that this time constant reflects intramolecular vibrational redistribution (IVR) to other solute modes. Despite their similar frequencies, the excited ring modes decay monoexponentially with a time constant that matches the slow decay component of the carbonyl modes. The slow decay times, which are faster in heavy water than in acetonitrile, approximately match the ones observed in previous UV pump–IR probe measurements on the same compounds. The slow component is assigned to intermolecular energy transfer to solvent bath modes from low-frequency solute modes, which are populated by IVR and are anharmonically coupled to the carbonyl and ring stretch modes. 2D IR measurements indicate that the carbonyl stretching modes are weakly coupled to the delocalized ring modes, resulting in slow exchange that cannot explain the common solvent-dependence. IVR is suggested to occur at different rates for the carbonyl vs ring modes due to differences in mode-specific couplings and not to differences in the density of accessible states.

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  4. Catechol-based materials possess diverse properties that are especially well-suitable for redox-based bioelectronics. Previous top-down, systems-level property measurements have shown that catechol-polysaccharide films ( e.g. , catechol-chitosan films) are redox-active and allow electrons to flow through the catechol/quinone moieties via thermodynamically-constrained redox reactions. Here, we report that catechol-chitosan films are also photothermally responsive and enable near infrared (NIR) radiation to be transduced into heat. When we simultaneously stimulated catechol-chitosan films with NIR and redox inputs, times-series measurements showed that the responses were reversible and largely independent. Fundamentally, these top-down measurements suggest that the flow of energy through catechol-based materials via the redox-based molecular modality and the electromagnetic-based optical modality can be independent. Practically, this work further illustrates the potential of catecholic materials for bridging bio-device communication because it enables communication through both short-range redox modalities and long-range electromagnetic modalities. 
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  6. DNA strands are polymeric ligands that both protect and tune molecular-sized silver cluster chromophores. We studied single-stranded DNA C4AC4TC3XT4 with X = guanosine and inosine that form a green fluorescent Ag106+ cluster, but these two hosts are distinguished by their binding sites and the brightness of their Ag106+ adducts. The nucleobase subunits in these oligomers collectively coordinate this cluster, and fs time-resolved infrared spectra previously identified one point of contact between the C2–NH2 of the X = guanosine, an interaction that is precluded for inosine. Furthermore, this single nucleobase controls the cluster fluorescence as the X = guanosine complex is ∼2.5× dimmer. We discuss the electronic relaxation in these two complexes using transient absorption spectroscopy in the time window 200 fs–400 µs. Three prominent features emerged: a ground state bleach, an excited state absorption, and a stimulated emission. Stimulated emission at the earliest delay time (200 fs) suggests that the emissive state is populated promptly following photoexcitation. Concurrently, the excited state decays and the ground state recovers, and these changes are ∼2× faster for the X = guanosine compared to the X = inosine cluster, paralleling their brightness difference. In contrast to similar radiative decay rates, the nonradiative decay rate is 7× higher with the X = guanosine vs inosine strand. A minor decay channel via a dark state is discussed. The possible correlation between the nonradiative decay and selective coordination with the X = guanosine/inosine suggests that specific nucleobase subunits within a DNA strand can modulate cluster–ligand interactions and, in turn, cluster brightness. 
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  8. Abstract

    Eumelanin is a brown-black biological pigment with sunscreen and radical scavenging functions important to numerous organisms. Eumelanin is also a promising redox-active material for energy conversion and storage, but the chemical structures present in this heterogeneous pigment remain unknown, limiting understanding of the properties of its light-responsive subunits. Here, we introduce an ultrafast vibrational fingerprinting approach for probing the structure and interactions of chromophores in heterogeneous materials like eumelanin. Specifically, transient vibrational spectra in the double-bond stretching region are recorded for subsets of electronic chromophores photoselected by an ultrafast excitation pulse tuned through the UV-visible spectrum. All subsets show a common vibrational fingerprint, indicating that the diverse electronic absorbers in eumelanin, regardless of transition energy, contain the same distribution of IR-active functional groups. Aggregation of chromophores diverse in oxidation state is the key structural property underlying the universal, ultrafast deactivation behavior of eumelanin in response to photoexcitation with any wavelength.

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  9. The ability to characterize and control the energy and charge transfer events triggered by the photoexcitation of molecules and materials is of fundamental importance to many fields, including the sustainable capture and conversion of solar energy. This article summarizes the papers that were presented and discussed at the recent Faraday discussion meeting on ultrafast photoinduced energy and charge transfer. Ultrafast laser spectroscopy and theory were at the center of discussions on photoinduced phenomena in biological and nanoscale systems of interacting absorbers. Many of the questions that motivate this field of science have occupied scientists for many decades, as a look back to a Faraday discussion meeting that took place 60 years earlier reveals. 
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  10. Here, we investigate the photochemistry of a catechol : o-quinone heterodimer as a model system for uncovering the photoprotective roots of eumelanin. 
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