From Stimuli-Responsive Polymorphic Organic Dye Crystals to Photoluminescent Cationic Open-Framework Metal Phosphate

Four photoluminescent dye crystals, TPB-<i>n</i> (<i>n</i> = 1–3) and TPCH, have been synthesized in isolation from carbon–carbon coupling of 4,4′-trimethylene-dipyridine (tmdp) in the absence of organic solvent and catalyst via in situ one-pot metal/ligand oxidative-dehydrogenation reactions. Large crystals have been obtained and readily separated from reaction products without the need for purification. Their structures were characterized: TPB and TPCH represent two dissimilar oxidized forms of tmdp dimers; TPCH was less oxidized but accompanied with partial hydrolysis with molecular formula further confirmed by FAB-MASS analysis. They exhibit distinct photoluminescence (PL) with quantum efficiency measured up to 42%. TPB-2 and TPB-3 are two polymorphic dihydrates, stimuli-responsive toward photoluminescence color changes; both can transform to TPB-1 upon gentle heating. Importantly, the three TPB-<i>n</i> crystals establish the first tetrapyridyl-type ligands adapted by metal phosphates to create a cationic luminescent framework, NTHU-12. This study serves as an inspiring route beyond conventional C–C bond formation reactions and has generated four tmdp dimers in isolation. The facile syntheses have resulted in ample production of a rare type of tetrapyridyl ligands, leading to the discovery of the first positively charged hybrid topology in nanoporous solids. The features of the four luminescent tmdp dimers and NTHU-12 embodied in synthesis, structure, and optical property are reported

From Stimuli-Responsive Polymorphic Organic Dye Crystals to Photoluminescent Cationic Open-Framework Metal Phosphate

Four photoluminescent dye crystals, TPB-<i>n</i> (<i>n</i> = 1–3) and TPCH, have been synthesized in isolation from carbon–carbon coupling of 4,4′-trimethylene-dipyridine (tmdp) in the absence of organic solvent and catalyst via in situ one-pot metal/ligand oxidative-dehydrogenation reactions. Large crystals have been obtained and readily separated from reaction products without the need for purification. Their structures were characterized: TPB and TPCH represent two dissimilar oxidized forms of tmdp dimers; TPCH was less oxidized but accompanied with partial hydrolysis with molecular formula further confirmed by FAB-MASS analysis. They exhibit distinct photoluminescence (PL) with quantum efficiency measured up to 42%. TPB-2 and TPB-3 are two polymorphic dihydrates, stimuli-responsive toward photoluminescence color changes; both can transform to TPB-1 upon gentle heating. Importantly, the three TPB-<i>n</i> crystals establish the first tetrapyridyl-type ligands adapted by metal phosphates to create a cationic luminescent framework, NTHU-12. This study serves as an inspiring route beyond conventional C–C bond formation reactions and has generated four tmdp dimers in isolation. The facile syntheses have resulted in ample production of a rare type of tetrapyridyl ligands, leading to the discovery of the first positively charged hybrid topology in nanoporous solids. The features of the four luminescent tmdp dimers and NTHU-12 embodied in synthesis, structure, and optical property are reported

Phosphorylation of Isoflavones by Bacillus subtilis BCRC 80517 May Represent Xenobiotic Metabolism

The soy isoflavones daidzein (DAI) and genistein (GEN) have beneficial effects on human health. However, their oral bioavailability is hampered by their low aqueous solubility. Our previous study revealed two water-soluble phosphorylated conjugates of isoflavones, daidzein 7-<i>O</i>-phosphate and genistein 7-<i>O</i>-phosphate, generated via biotransformation by Bacillus subtilis BCRC80517 cultivated with isoflavones. In this study, two novel derivatives of isoflavones, daidzein 4′-<i>O</i>-phosphate and genistein 4′-<i>O</i>-phosphate, were identified by HPLC-ESI–MS/MS and ¹H, ¹³C, and ³¹P NMR, and their biotransformation roadmaps were proposed. Primarily, isoflavone glucosides were deglycosylated and then phosphorylated predominantly into 7-<i>O</i>-phosphate conjugates with traces of 4′-<i>O</i>-phosphate conjugates. Inevitably, trace quantities of glucosides were converted into 6″-<i>O</i>-succinyl glucosides. GEN was more efficiently phosphorylated than DAI. Nevertheless, the presence of GEN prolonged the time until the exponential phase of cell growth, whereas the other isoflavones showed little effect on cell growth. Our findings provide new insights into the novel microbial phosphorylation of isoflavones involved in xenobiotic metabolism

Additional file 8 of Genome-wide analyses identify novel risk loci for cluster headache in Han Chinese residing in Taiwan

Additional file 8: Supplemental Table 3. GIGSEA Biological Pathway Enrichment in brain tissues. The significant level of empirical P-value was 0.05 and the BayesFactor was 100. Top significantly associated pathways in these tissues that may be relevant to cluster headache were listed in the table. UsedGenes indicates number of gene used in the enrichment estimation of the GIGSEA model

Additional file 6 of Genome-wide analyses identify novel risk loci for cluster headache in Han Chinese residing in Taiwan

Additional file 6: Supplemental Table 2. Meta-analysis of previous studies and the current study for previously reported cluster-associated loci

Additional file 9 of Genome-wide analyses identify novel risk loci for cluster headache in Han Chinese residing in Taiwan

Additional file 9: Supplemental Figure 6. GIGSEA pathway analysis of the genes relevant to cluster headache GWAS variants

Additional file 3 of Genome-wide analyses identify novel risk loci for cluster headache in Han Chinese residing in Taiwan

Additional file 3: Supplemental Figure 2. Principal component analysis (PCA) plot. The horizontal and vertical axes are the first and second dimensions from principal component analysis based on the cluster headache GWAS samples. Blue dots indicate controls and red dots indicate patients

Additional file 7 of Genome-wide analyses identify novel risk loci for cluster headache in Han Chinese residing in Taiwan

Additional file 7: Supplemental Figure 5. eQTL analysis by MetaXca

Additional file 2 of Genome-wide analyses identify novel risk loci for cluster headache in Han Chinese residing in Taiwan

Additional file 2: Supplemental Figure 1. Quantile-quantile plot of the GWAS results of cluster headache

Additional file 4 of Genome-wide analyses identify novel risk loci for cluster headache in Han Chinese residing in Taiwan

Additional file 4: Supplemental Figure 3. Manhattan plot of the discovery cohort (A) and replication cohort (B)