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Hybrid complexes incorporating synthetic Mn-porphyrins into an artificial four-helix bundle domain of bacterial reaction centers created a system to investigate new electron transfer pathways. The reactions were initiated by illumination of the bacterial reaction centers, whose primary photochemistry involves electron transfer from the bacteriochlorophyll dimer through a series of electron acceptors to the quinone electron acceptors. Porphyrins with diphenyl, dimesityl, or fluorinated substituents were synthesized containing either Mn or Zn. Electrochemical measurements revealed potentials for Mn(III)/Mn(II) transitions that are ~ 0.4 V higher for the fluorinated Mn-porphyrins than the diphenyl and dimesityl Mn-porphyrins. The synthetic porphyrins were introduced into the proteins by binding to a four-helix bundle domain that was genetically fused to the reaction center. Light excitation of the bacteriochlorophyll dimer of the reaction center resulted in new derivative signals, in the 400 to 450 nm region of light-minus-dark spectra, that are consistent with oxidation of the fluorinated Mn(II) porphyrins and reduction of the diphenyl and dimesityl Mn(III) porphyrins. These features recovered in the dark and were not observed in the Zn(II) porphyrins. The amplitudes of the signals were dependent upon the oxidation/reduction midpoint potentials of the bacteriochlorophyll dimer. These results are interpreted as photo-induced charge-separation processes resulting in redox changes of the Mn-porphyrins, demonstrating the utility of the hybrid artificial reaction center system to establish design guidelines for novel electron transfer reactions. 

Abstract This paper presents a new empirical model, called the cumulative storm impact index (CSII), that quantifies the impact of coastal storms on sandy beaches. The new model utilizes user‐defined storm data to incorporate both individual storm magnitude and the cumulative effect of successive storms into an index, which is a proxy for beach erosion at a given time. Applying this model to long‐term water‐level data from a Virginia tide gauge showed that the greatest storm impact resulted not from the larger individual storms, such as the Ash Wednesday nor'easter of 1962, the “Perfect Storm” of 1991, or Hurricane Sandy of 2012, but rather from especially stormy winter seasons that occurred during the twenty‐first century. Additionally, the CSII model uncovered a trend—not detectable by single storm impact analyses—toward greater storm impacts, which began c. 1980 and continued to the present day. Finally, comparative analyses using wave power as a storm index shows CSII can capture decadal or seasonal scale storminess. We expect this model to have utility in many areas of the coastal sciences and engineering, including developing holistic response models, quantifying erosion potential at other locations, and managing coastal ecosystems.