Biochemistry
Department of Chemistry, University of California, Davis, One Shields Avenue, Davis, California 95616, United States.
Published: October 2020
In this report, we compare the femtosecond to nanosecond primary reverse photodynamics (P → P) of eight tetrapyrrole binding photoswitching cyanobacteriochromes in the canonical red/green family from the cyanobacterium . Three characteristic classes were identified on the basis of the diversity of excited-state and ground-state properties, including the lifetime, photocycle initiation quantum yield, photointermediate stability, spectra, and temporal properties. We observed a correlation between the excited-state lifetime and peak wavelength of the electronic absorption spectrum with higher-energy-absorbing representatives exhibiting both faster excited-state decay times and higher photoisomerization quantum yields. The latter was attributed to both an increased number of structural restraints and differences in H-bonding networks that facilitate photoisomerization. All three classes exhibited primary Lumi-G intermediates, with class II and III representatives evolving to a secondary Meta-G photointermediate. Class II Meta-G intermediates were orange absorbing, whereas class III Meta-G had structurally relaxed, red-absorbing chromophores that resemble their dark-adapted P states. Differences in the reverse and forward reaction mechanisms are discussed within the context of structural constraints.
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http://dx.doi.org/10.1021/acs.biochem.0c00454 | DOI Listing |
Background: Total shoulder arthroplasty frequently is performed in patients with a history of shoulder surgery. The purpose of this study was to evaluate clinical outcomes after primary shoulder arthroplasty in patients with a history of nonarthroplasty shoulder surgery, and whether certain modifiable risk factors (MRFs) were negatively associated with final outcome measures. The secondary purpose was to determine if costs or complications were higher in patients with prior shoulder surgery.
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