Utility of Squaraine Dyes for Dye-Sensitized Photocatalysis on Water or Carbon Dioxide Reduction

Red light-sensitized squaraine (SQ) dyes were developed and incorporated into dye-sensitized catalysts (DSCs) with the formula of SQ/TiO2/Cat, and their efficacies were evaluated in terms of performance on either water or carbon dioxide reduction. Pt nanoparticles or fac-[Re­(4,4′-bis-(diethoxyphosphorylmethyl)-2,2′-bipyridine)­(CO)3Cl] were used as each catalytic center within the DSC frame of SQ/TiO2/Pt (Type I) or SQ/TiO2/Re­(I) (Type II). In order to convey the potential utility of SQ in low energy sensitization, the following catalytic reductions were carried out under selective lower energy irradiation (>500 nm). Type I and II showed different catalytic performances, primarily due to the choice of solvent for each catalytic condition: hydrogenation was carried out in H2O, but CO2 reduction in dimethylformamide (DMF), and SQ was more stable in aqueous acid conditions for hydrogen generation than CO2 reduction in DMF. A suspension of Type I in 3 mL water containing 0.1 M ascorbic acid (pH = 2.66) resulted in efficient photocatalytic hydrogen evolution, producing 37 μmol of H2 for 4 h. However, in photocatalysis of Type II (SQ/TiO2/Re­(I)) in 3 mL DMF containing 0.1 M 1,3-dimethyl-2-phenyl-1,3-dihydrobenzimidazole, the TiO2-bound SQ dyes were not capable of working as a low energy sensitizer because SQ was susceptible to dye decomposition in nucleophilic DMF conditions, resulting in DSC deactivation for the CO2 reduction. Even with the limitation of solvent, the DSC conditions for the utility of SQ have been established: the anchoring group effect of SQ with either phosphonic acid or carboxylic acid onto the TiO2 surface; energy alignment of SQ with the flat band potentials (Efb) of TiO2 semiconductors and the reduction power of electron donors; and the wavelength range of the light source used, particularly when >500 nm

Highly Selective and Durable Photochemical CO₂ Reduction by Molecular Mn(I) Catalyst Fixed on a Particular Dye-Sensitized TiO₂ Platform

A Mn­(I)-based hybrid system (OrgD-|TiO2|-MnP) for photocatalytic CO2 reduction is designed to be a coassembly of Mn­(4,4′-Y2-bpy)­(CO)3Br (MnP; Y = CH2PO­(OH)2) and (E)-3-[5-(4-(diphenylamino)­phenyl)-2,2′-bithiophen-2′-yl]-2-cyanoacrylic acid (OrgD) on TiO2 semiconductor particles. The OrgD-|TiO2|-MnP hybrid reveals persistent photocatalytic behavior, giving high turnover numbers and good product selectivity (HCOO– versus CO). As a typical run, visible-light irradiation of the hybrid catalyst in the presence of 0.1 M electron donor (ED) and 0.001 M LiClO4 persistently produced HCOO– with a >99% selectivity accompanied by a trace amount of CO; the turnover number (TONformate) reached ∼250 after 23 h of irradiation. The product selectivity (HCOO–/CO) was found to be controlled by changing the loading amount of MnP on the TiO2 surface. In situ FTIR analysis of the hybrid during photocatalysis revealed that, at low Mn concentration, the Mn–H monomeric mechanism associated with HCOO– formation is dominant, whereas at high Mn concentration, CO is formed via a Mn–Mn dimer mechanism

ESRRA (estrogen related receptor alpha) is a critical regulator of intestinal homeostasis through activation of autophagic flux via gut microbiota

The orphan nuclear receptor ESRRA (estrogen related receptor alpha) is critical in mitochondrial biogenesis and macroautophagy/autophagy function; however, the roles of ESRRA in intestinal function remain uncharacterized. Herein we identified that ESRRA acts as a key regulator of intestinal homeostasis by amelioration of colonic inflammation through activation of autophagic flux and control of host gut microbiota. Esrra-deficient mice presented with increased susceptibility to dextran sodium sulfate (DSS)-induced colitis with upregulation of intestinal inflammation. In addition, esrra-null mice had depressed AMP-activated protein kinase phosphorylation (AMPK), lower levels of TFEB (transcription factor EB), and accumulation of SQSTM1/p62 (sequestosome 1) with defective mitochondria in intestinal tissues. Esrra-deficient mice showed distinct gut microbiota composition and significantly higher microbial diversity than wild-type (WT) mice. Cohousing or fecal microbiota transplantation from WT mice to Esrra-deficient mice ameliorated DSS-induced colitis severity. Importantly, patients with ulcerative colitis (UC) had significantly decreased ESRRA expression in intestinal mucosal tissues that correlated with disease activity, suggesting clinical relevance of ESRRA in UC. Taken together, our results show that ESRRA contributes to intestinal homeostasis through autophagy activation and gut microbiota control to protect the host from detrimental inflammation and dysfunctional mitochondria. Abbreviations: ABX, antibotics; AMPK, AMP-activated protein kinase; ATP5A1, ATP synthase, H+ transporting, mitochondrial F1 complex, alpha subunit 1; BECN1, beclin1, autophagy related, CCL, C-C motif chemokine ligand; CD, Crohn disease; CLDN, claudin; COX4I1, cytochrome c oxidase subunit 4I1; cKO, conditional knockout; cWT, conditional wild-type; CXCL, C-X-C motif chemokine ligand; DAI, disease activity index; DSS, dextran sodium sulfate; EGFP, enhanced green fluorescent protein; ESRR, estrogen related receptor; ESRRA, estrogen related receptor alpha; Esrra+/+, Esrra wild type; esrra–/-, esrra homozygous knockout; FMT, fecal microbiota transplantation; GABARAP, gamma-aminobutyric acid receptor associated protein; GSEA, gene set enrichment analysis; IBD, inflammatory bowel disease; IL, interleukin; KO, knockout; LAMP1, lysosomal-associated membrane protein 1; LCN2, lipocalin 2; LEfSe, linear discriminant analysis (LDA) effect size; LPS, lipopolysachharide; MAP1LC3/LC3, microtubule associated protein 1 light chain 3; NDUFAB1, NADH: ubiquinone oxidoreductase subunit AB1; OCLN, occludin; OUT, operational taxonomic unit; OXPHOS, oxidative phosphorylation; PCoA, principal coordinate analysis; PPARGC1A, PPARG coactiva- tor 1 alpha; PRKAA, 5’-AMP-activated protein kinase catalytic subunit alpha; PTGS2/COX2, prostaglandin-endoperoxide synthase 2; RAB7, member RAS oncogene family; SDHB, succinate dehydrogenase complex, subunit B, iron sulfur (Ip); SQSTM1/p62, sequestosome 1; S100A9, S100 calcium binding protein A9 (calgranulin B); TCA, tricarboxylic acid; TFEB, transcription factor EB; TNF, tumor necrosis factor; UC, ulcerative colitis; UCP2, uncoupling protein 2 (mitochondrial, proton carrier); UQCRC1, ubiquinol-cytochrome c reductase core protein 1; UVRAG, UV radiation resistance associated gene; Vil1, villin; VPS11, VPS11, CORVET/HOPS core sub-unit; WT, wild type.</p

Additional file 4 of Host phylogeny, habitat, and diet are main drivers of the cephalopod and mollusk gut microbiome

Additional file 4. Supplementary Table S3. Basic information on the acheived from previous studies

Additional file 3 of Host phylogeny, habitat, and diet are main drivers of the cephalopod and mollusk gut microbiome

Additional file 3. Supplementary Table S2. Topological measures in oligotypes-based network analyses

Additional file 5 of Host phylogeny, habitat, and diet are main drivers of the cephalopod and mollusk gut microbiome

Additional file 5. Code and Scripts

Additional file 2 of Host phylogeny, habitat, and diet are main drivers of the cephalopod and mollusk gut microbiome

Additional file 2. Supplementary Table S1. Basic information on the cephalopod hosts

Additional file 1 of Host phylogeny, habitat, and diet are main drivers of the cephalopod and mollusk gut microbiome

Additional file 1. Fig. S1: Alpha diversity indices of the cephalopod gut microbiota. (a) Number of observed species. (b) Chao1 index. (c) Shannon diversity. (d) Faith’s PD. The letters above the whisker indicate significant differences (p  1% are shown; those with an abundance of < 1% are classified as “Others.” Abbreviations: Cutt, cuttlefish; Bek, beka squid; Ins, Inshore squid; Jap, Japanese flying squid; Whip, whiparm squid; Comm, common octopus. Fig. S4: Distribution of core genera of cephalopods. Boxplot diagram of (a) Mycoplasma, (b) Photobacterium, (c) Alivibrio, (d) Acrobacter, and (e) Psychrilyobacter. The letters above the whisker indicate significant differences (p < 0.05) among groups (Mann–Whitney U test). Abbreviations: Cutt, cuttlefish; Bek, beka squid; Ins, Inshore squid; Jap, Japanese flying squid; Whip, whiparm squid; Comm, common octopus. Fig. S5: Comparisons of intra-order host COI similarity and microbial variation of Octopoda and other orders. Host similarity was calculated with pairwise COI sequence comparison. Microbial variation was calculated based on binary Jaccard distance. Asterisks indicate significant differences according to two-tailed Mann–Whitney U tests. *p < 0.05, **p < 0.01; ***p < 0.001. Fig. S6. Distributions of Photobacterium and Mycoplasma OTUs and oligotypes in cephalopod gut microbiomes. The distributions of 97% clustered OTUs assigned to Photobacterium and Mycoplasma (a–b) are compared with re-clustered oligotypes and generated using the MED pipeline with aligned sequence reads that originally matched to Photobacterium and Mycoplasma by the QIIME 1.9.1 pipeline. Fig. S7: Phylogenetic trees of Photobacterium and Mycoplasma based on oligotypes (maximum likelihood tree with 1000 bootstrap replicates and the GTR + Gamma model). Bar graphs are color-coded to show the proportions of oligotypes assigned to Photobacterium (a) and Mycoplasma (b) in each cephalopod species. Abbreviations: Cutt, cuttlefish; Bek, beka squid; Ins, Inshore squid; Jap, Japanese flying squid; Whip, whiparm squid; Comm, common octopus. Fig. S8. Beta-diversity analysis for cephalopod species using the Bray–Curtis index. Principal coordinates analysis (PCoA) of Bray–Curtis between cephalopod samples. The colors of the dots in the PCoA represent the host cephalopod species and their orders. (b–c) Comparisons of intra- and inter-specific (b) and intra- and inter-order (c) microbial variation based on the Bray–Curtis dissimilarity. Asterisks indicate significant differences according to two-tailed Mann–Whitney U tests. *p < 0.05, **p < 0.01; ***p < 0.001. Abbreviations: Cutt, cuttlefish; Bek, beka squid; Ins, Inshore squid; Jap, Japanese flying squid; Whip, whiparm squid; Comm, common octopus. Fig. S9. Linear regression analysis with the slope of the regression line. Correlation between body weight and relative abundance of Mycoplasma (a) was positive and significant, but body weight and relative abundance of Photobacterium (b) was negative but not significant. Fig. S10. Boxplot diagram of the relative abundance for the phyla (a) Tenericutes, (b) Proteobacteria, and genera (c) Mycoplasma, and (d) Photobacterium. The letters above the whisker indicate significant differences (p < 0.05) among groups (Mann–Whitney U test). Fig. S11. Beta-diversity analysis for mollusk and fish using the binary Jaccard and Bray–Curtis indices. PCoA plots with (a) binary Jaccard and (b) Bray–Curtis indices show different distribution patterns. The colors of the dots, centroids and ellipses in the PCoAs represent the group that each host belongs to