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.

The High-Spin Heme bL Mutant Exposes Dominant Reaction Leading to the Formation of the Semiquinone Spin-Coupled to the [2Fe-2S]+ Cluster at the Qo Site of Rhodobacter capsulatus Cytochrome bc1

Cytochrome bc1 (mitochondrial complex III) catalyzes electron transfer from quinols to cytochrome c and couples this reaction with proton translocation across lipid membrane; thus, it contributes to the generation of protonmotive force used for the synthesis of ATP. The energetic efficiency of the enzyme relies on a bifurcation reaction taking place at the Qo site which upon oxidation of ubiquinol directs one electron to the Rieske 2Fe2S cluster and the other to heme bL. The molecular mechanism of this reaction remains unclear. A semiquinone spin-coupled to the reduced 2Fe2S cluster (SQo-2Fe2S) was identified as a state associated with the operation of the Qo site. To get insights into the mechanism of the formation of this state, we first constructed a mutant in which one of the histidine ligands of the iron ion of heme bLRhodobacter capsulatus cytochrome bc1 was replaced by asparagine (H198N). This converted the low-spin, low-potential heme into the high-spin, high-potential species which is unable to support enzymatic turnover. We performed a comparative analysis of redox titrations of antimycin-supplemented bacterial photosynthetic membranes containing native enzyme and the mutant. The titrations revealed that H198N failed to generate detectable amounts of SQo-2Fe2S under neither equilibrium (in dark) nor nonequilibrium (in light), whereas the native enzyme generated clearly detectable SQo-2Fe2S in light. This provided further support for the mechanism in which the back electron transfer from heme bL to a ubiquinone bound at the Qo site is mainly responsible for the formation of semiquinone trapped in the SQo-2Fe2S state in R. capusulatus cytochrome bc1.

Interrogation of O-ATRP Activation Conducted by Singlet and Triplet Excited States of Phenoxazine Photocatalysts

Organocatalyzed ATRP (O-ATRP) is a growing field exploiting organic chromophores as photoredox catalysts (PCs) that engage in dissociative electron transfer (DET) activation of alkyl halide initiators following absorption of light. Characterizing DET rate coefficients (<i>k_act</i>) and photochemical yields across various reaction conditions and PC photophysical properties will inform catalyst design and efficient use during polymerization. The studies described herein consider a class of phenoxazine PCs where synthetic handles of core-substitution and <i>N</i>-aryl substitution enable tunability of the electronic and spin character of the catalyst excited state as well as DET reaction driving force ( ). Using Stern-Volmer quenching experiments through variation of diethyl 2-bromo-2-methylmalonate (DBMM) initiator concentration, collisional quenching is observed. Eight independent measurements of <i>k_act</i>are reported as a function of for four PCs: four triplet reactants and four singlets with <i>k_act</i> values ranging from 1.1´10⁸ M^-1s^-1 where DET itself controls the rate to 4.8´10⁹ M^-1s^-1 where diffusion is rate limiting. This overall data set, as well as a second one inclusive of five literature values from related systems, is readily modeled with only a single parameter of reorganization energy under the frameworks of adiabatic Marcus electron transfer theory and Marcus-Savéant theory of DET. The results provide a predictive map where <i>k_act</i> can be estimated if is known and highlight that DET in these systems appears insensitive to PC reactant electronic and spin properties outside of their impact on driving force. Next, on the basis of measured <i>k_act</i> values in selected PC systems and knowledge of their photophysics, we also consider activation yields specific to the reactant spin states as the DBMM initiator concentration is varied. In <i>N</i>-naphthyl-containing PCs characterized by near-unity intersystem crossing, the T₁ is certainly an important driver for efficient DET. However, at DBMM concentrations common to polymer synthesis, the S₁ is also active and drives 33% of DET reaction events. Even in systems with low yields of ISC, such as in <i>N</i>-phenyl-containing PCs, reaction yields can be driven to useful values by exploiting the S₁ under high DBMM concentration conditions. Finally, we have quantified photochemical reaction quantum yields, which take into account potential product loss processes after electron-transfer quenching events. Both S₁ and T₁ reactant states produce the PC^·+ radical cation with a common yield of 71%, thus offering no evidence for spin selectivity in deleterious back electron transfer. The sub-unity PC^·+ yields suggest that some combination of solvent (DMAc) oxidation and energy-wasting back electron transfer is likely at play and these pathways should be factored in subsequent mechanistic considerations.

Interrogation of O-ATRP Activation Conducted by Singlet and Triplet Excited States of Phenoxazine Photocatalysts

Organocatalyzed ATRP (O-ATRP) is a growing field exploiting organic chromophores as photoredox catalysts (PCs) that engage in dissociative electron transfer (DET) activation of alkyl halide initiators following absorption of light. Characterizing DET rate coefficients (<i>k_act</i>) and photochemical yields across various reaction conditions and PC photophysical properties will inform catalyst design and efficient use during polymerization. The studies described herein consider a class of phenoxazine PCs where synthetic handles of core-substitution and <i>N</i>-aryl substitution enable tunability of the electronic and spin character of the catalyst excited state as well as DET reaction driving force ( ). Using Stern-Volmer quenching experiments through variation of diethyl 2-bromo-2-methylmalonate (DBMM) initiator concentration, collisional quenching is observed. Eight independent measurements of <i>k_act</i>are reported as a function of for four PCs: four triplet reactants and four singlets with <i>k_act</i> values ranging from 1.1´10⁸ M^-1s^-1 where DET itself controls the rate to 4.8´10⁹ M^-1s^-1 where diffusion is rate limiting. This overall data set, as well as a second one inclusive of five literature values from related systems, is readily modeled with only a single parameter of reorganization energy under the frameworks of adiabatic Marcus electron transfer theory and Marcus-Savéant theory of DET. The results provide a predictive map where <i>k_act</i> can be estimated if is known and highlight that DET in these systems appears insensitive to PC reactant electronic and spin properties outside of their impact on driving force. Next, on the basis of measured <i>k_act</i> values in selected PC systems and knowledge of their photophysics, we also consider activation yields specific to the reactant spin states as the DBMM initiator concentration is varied. In <i>N</i>-naphthyl-containing PCs characterized by near-unity intersystem crossing, the T₁ is certainly an important driver for efficient DET. However, at DBMM concentrations common to polymer synthesis, the S₁ is also active and drives 33% of DET reaction events. Even in systems with low yields of ISC, such as in <i>N</i>-phenyl-containing PCs, reaction yields can be driven to useful values by exploiting the S₁ under high DBMM concentration conditions. Finally, we have quantified photochemical reaction quantum yields, which take into account potential product loss processes after electron-transfer quenching events. Both S₁ and T₁ reactant states produce the PC^·+ radical cation with a common yield of 71%, thus offering no evidence for spin selectivity in deleterious back electron transfer. The sub-unity PC^·+ yields suggest that some combination of solvent (DMAc) oxidation and energy-wasting back electron transfer is likely at play and these pathways should be factored in subsequent mechanistic considerations.

Effect of TiO2 Photoanodes Morphology and Dye Structure on Dye-Regeneration Kinetics Investigated by Scanning Electrochemical Microscopy

The dye regeneration in dye-sensitized solar cells (DSSCs) is improved by optimizing the charge separation at the level of the sensitized semiconductor treatment of the mesoporous electrode by TiCl4 that passivates the surface for back electron transfer reactions. The dye-regeneration kinetics is analyzed for DN216- and D358-sensitized porous TiO2 electrodes with and without a TiCl4 treatment by means of scanning electrochemical microscopy (SECM). Different mass transport limitation of the [Co(bpy)3]3+ mediator through the porous electrode is found for the comparison of the structurally similar dyes but cannot be detected for the thin layer introduced by the TiCl4 treatment. Phototransient measurements are conducted directly in the SECM cell without any intermediated sample manipulation. The results from those measurements corroborate the findings from steady state SECM measurements.

Triphenylphosphine-catalyzed Alkylative Iododecarboxylation with Lithium Iodide under Visible Light

Photoactivation of an electron donor–acceptor encounter complex in an organic solvent cage, a phenomenon that has been described in Mulliken theory, has been known for decades, but it has not been employed as a photoactivation step in the design of photocatalysis for organic synthesis until recent years. We report herein an iododecarboxylation reaction that applies this concept for photoactivation by using a catalyst to facilitate electron transfer and to suppress back electron transfer in the photoexcited state. Under irradiation of 456 nm blue light-emitting diodes, PPh3 catalyzes the iododecarboxylation of aliphatic carboxylic acid-derived N-(acyloxy)phthalimide with lithium iodide as iodine source. The reaction delivers primary, secondary, and bridgehead tertiary alkyl iodides in acetone solvent, and the alkyl iodide products were easily used to generate C–N, C–O, C–F, and C–S bonds to allow various decarboxylative transformations without using transition-metal or organic dye-based photocatalysts. This protocol is applicable to redox-active esters derived from various natural products and pharmaceuticals.

Overcoming Back Electron Transfer Facilitates the Implementation of Electron Donor-Acceptor Complexes in Catalysis

Electron donor-acceptor (EDA) complexes can controllably generate radicals under mild conditions through selective photoexcitation events. However, unproductive reactivity from fast deactivation of the photoexcited complexes through back electron transfer has slowed the development of EDA complexes in synthetic methodology. Here, we disclose the study of EDA complexes derived from 2-methoxynaphthalene donor and acylated ethyl isonicotinate <i>N</i>-oxide acceptor that undergo a fast N–O bond fragmentation event upon photoexcitation. This reaction design not only overcomes the limitations of back electron transfer but also enables the regeneration of the donor species, representing a rare example EDA photochemistry in a catalytic regime. The synthetic utility is demonstrated through visible light-driven radical trifluoromethylation and Minisci alkylation reactions. The scalability of the EDA complex promoted reaction evidenced by the successful multigram-scale trifluoromethylation of methyl N-Boc pyrrole-2-carboxylate in a continuous flow manifold.