A photoproduct of DXCF cyanobacteriochromes without reversible Cys ligation is destabilized by rotating ring twist of the chromophore.

Cyanobacteriochrome photoreceptors (CBCRs) ligate linear tetrapyrrole chromophores via their first (canonical) Cys residue and show reversible photoconversion triggered by light-dependent Z/E isomerization of the chromophore. Among the huge repertoire of CBCRs, DXCF CBCRs contain a second Cys residue within the highly conserved Asp-Xaa-Cys-Phe (DXCF) motif. In the typical receptors, the second Cys covalently attaches to the 15Z-chromophore in the dark state and detaches from the 15E-chromophore in the photoproduct state, whereas atypical ones that lack reversible ligation activity show red-shifted absorption in the dark state due to a more extended π-conjugated system. Moreover, some DXCF CBCRs show blue-shifted absorption in the photoproduct state due to the twisted geometry of the rotating ring. During the process of rational color tuning of a certain DXCF CBCR, we unexpectedly found that twisted photoproducts of some variant molecules showed dark reversion to the dark state, which prompted us to hypothesize that the photoproduct is destabilized by the twisted geometry of the rotating ring. In this study, we comprehensively examined the photoproduct stability of the twisted and relaxed molecules derived from the same CBCR scaffolds under dark conditions. In the DXCF CBCRs lacking reversible ligation activity, the twisted photoproducts showed faster dark reversion than the relaxed ones, supporting our hypothesis. By contrast, in the DXCF CBCRs exhibiting reversible ligation activity, the twisted photoproducts showed no detectable photoconversion. Reversible Cys adduct formation thus results in drastic rearrangement of the protein-chromophore interaction in the photoproduct state, which would contribute to the previously unknown photoproduct stability.

Crystal structures and electrochemical properties of nickel(II) complexes with N,N',N'',S-tetra-dentate Schiff base ligands.

The thiol-ate nickel complexes {2-[({2-[(2-amino-ethyl-κN)(meth-yl)amino-κN]eth-yl}imino-κN)meth-yl]benzene-thiol-ato-κS}nickel(II) chloride, [Ni(C12H18N3S)]Cl (1), and [2-({[2-(piperazin-1-yl-κ2 N 1,N 4)eth-yl]imino-κN}meth-yl)benzene-thiol-ato-κS]nickel(II) hexa-fluoro-phosphate di-chloro-methane monosolvate, [Ni(C13H18N3S)]PF6·CH2Cl2 (2), were synthesized by the reactions of 2-(tert-butyl-thio)-benzaldehyde, tri-amines, and nickel(II) salts. Both complexes have a nickel ion surrounded by an N,N',N'',S-tetra-dentate ligand, forming a square-planar geometry. The terminal N,N-chelating moiety is N,N-di-alkyl-ethane-1,2-di-amine for 1 and 1-alkyl-piperazine for 2. The N-Ni-N bite angle in the terminal N,N-chelate ring in 2 [76.05 (10)°] is much smaller than that in 1 [86.16 (6)°]. Cyclic voltammograms of 1 and 2 in aqueous media indicated that the reduction and oxidation potentials of 2 are more positive than those of 1. The smaller bite angle of the terminal piperazine chelate in 2 reduces the electron-donating ability of the tetra-dentate ligand, resulting in a positive shift of the redox potentials. Both complexes exhibit catalytic activity for proton reduction, and the piperazine moiety in 2 is effective in reducing the overpotential.

Lower promoter activity of the ST8SIA2 gene has been favored in evolving human collective brains.

ST8SIA2 is an important molecule regulating expression of the phenotype involved in schizophrenia. Lowered promoter activity of the ST8SIA2 gene is considered to be protective against schizophrenia by conferring tolerance to psychosocial stress. Here, we examined the promoter-type composition of anatomically modern humans (AMHs) and archaic humans (AHs; Neanderthals and Denisovans), and compared the promoter activity at the population level (population promoter activity; PPA) between them. In AMHs, the TCT-type, showing the second lowest promoter activity, was most prevalent in the ancestral population of non-Africans. However, the detection of only the CGT-type from AH samples and recombination tracts in AH sequences showed that the CGT- and TGT-types, exhibiting the two highest promoter activities, were common in AH populations. Furthermore, interspecies gene flow occurred into AMHs from AHs and into Denisovans from Neanderthals, influencing promoter-type compositions independently in both AMHs and AHs. The difference of promoter-type composition makes PPA unique in each population. East and Southeast Asian populations show the lowest PPA. This results from the selective increase of the CGC-type, showing the lowest promoter activity, in these populations. Every non-African population shows significantly lower PPA than African populations, resulting from the TCT-type having the highest prevalence in the ancestral population of non-Africans. In addition, PPA reduction is also found among subpopulations within Africa via a slight increase of the TCT-type. These findings indicate a trend toward lower PPA in the spread of AMHs, interpreted as a continuous adaptation to psychosocial stress arising in migration. This trend is considered as genetic tuning for the evolution of collective brains. The inferred promoter-type composition of AHs differed markedly from that of AMHs, resulting in higher PPA in AHs than in AMHs. This suggests that the trend toward lower PPA is a unique feature in AMH spread.