3,6,9,12,15,18,21-Heptaoxatetracos-23-yn-1-ol

The derivatized 19- and 20-membered macrocyclic thio crowns 3,6,9,12,15,18-hexathianonadecanol C(13)H(26)OS(6) (19-aneS6-OH) (1) and 3,6,9,13,16,19-hexathiacycloicosanol C(14)H(28)OS(6) (20-aneS6-OH) (2) have been synthesized by [1 + 1] cyclization in about 30% yield. The ligands 1 and 2 react readily at room temperature with different silver(I) salts in water and in organic solvents to form in quantitative yields the complexes [Ag(19-aneS6-OH)](+) (3) and [Ag(20-aneS6-OH)](+) (4) for which crystals of X-ray quality were grown by slow diffusion of diethylether into methanol. [Ag(19-aneS6-OH)][CF(3)SO(3)] crystallizes in the triclinic space group P&onemacr; with Z = 2, a = 10.760(1), b = 10.853(2) and c = 11.326(2)Å, and alpha = 78.73(1), beta = 73.47(1), and gamma = 74.99(1) degrees. [Ag(20-aneS6-OH)][BF(4)] also crystallizes in the triclinic space group P&onemacr; with Z = 4. The unit cell constants were determined with a = 10.076(4), b = 10.525(3), and c = 22.135(8)Å, alpha = 93.32(2), beta = 102.43(2), and gamma = 100.32(2) degrees. The complex cations [Ag(19-aneS6-OH)](+) and [Ag(20-aneS6-OH)](+) are coordinated through only four sulfur atoms; thus, a distorted tetrahedral coordination geometry is exhibited. In addition we found a highly asymmetric Ag-S bond lengths distribution throughout all complex cations. The stability constants of [Ag](+) with 1 and 2 and, for comparison with [18-aneS6] (5), have been determined in methanol by potentiometric [Ag](+) measurements. Log K values for the formation of 3, 4, and [Ag(18-aneS6](+) (6) are 12.04 +/- 0.19, 11.49 +/- 0.15, and 12.67 +/- 0.13 respectively. Owing to a comparable macrocyclic effect, the similar log K values are reasonable but, since 6 coordinates octahedrally, not expected. (1)H and (13)C NMR investigations at various temperatures give evidence for fluxional coordinative behavior between all six sulfur atoms in solution. Consequently [Ag(19-aneS6-OH)](+), [Ag(20-aneS6-OH)](+), and [Ag(18-aneS6](+) seem to exhibit principally the same solution structures although the solid structures are very different.

Blue-green microalga Spirulina platensis (SP) gained more attention for its antioxidant and/or anti-inflammatory properties magnifying its beneficial effects as a feed additive and for cosmetic and biomedical applications. This study was performed to examine the impact of SP on the cutaneous wound and burn healing and to develop an understanding of the correlation between the sequelae of wound healing and the molecular expression patterns of wound healing-related genes as angiogenic basic fibroblast growth factor (bFGF) and vascular endothelial growth factor (VEGF) and fibrosis-related genes as transforming growth factor-β (TGF-β) and α-smooth muscle actin (α-SMA) in rat wound models. To achieve these goals, two experiments were performed on 32 Wister male rats that were divided into 4 groups of 8 rats each. Each experiment was represented by 2 groups; the control group (CG) and the Spirulina group (SG). A full-thickness wound (1.5 × 1.5 cm) and burn wound (2 × 2 cm) were made on the back of each generally anaesthetized rat and the areas of wound and burn were measured on days of 0, 3, 6, 9, 12, and 15 and 0, 3, 6, 9, 12, 15, 18, and 21 post-wound and post-burn respectively. In both experiments, SP was topically applied on the backs of wounded and burned rats in Spirulina treated groups. The phases of wound granulation tissues were detected histopathologically. Immunohistochemistry was used to determine the expressions of (TGF-B1) and (VEGF). Furthermore, the relative quantification of gene expression was implemented using the (bFGF), (VEGF), (TGF-Ɓ1), and (α-SMA) as target genes. Histopathological examination revealed inflammatory cell infiltration, angiogenesis, epithelialization, and extracellular matrix deposition and wound contraction in SG as compared to CG in both experiments. Immunohistochemistry results showed a significant improvement in the VEGF and TGF-β1 expression levels of SG in both experiments. Interestingly, SG in both experiments revealed upregulation of angiogenic genes (bFGF and VEGF) and downregulation of fibrotic genes (TGF-β1 and α-SMA). In conclusion, our findings suggest that the topically applied Spirulina promoted wound healing. Thus, SP can be used as a biomedical application to treat various skin wounds and may reveal a potential molecular basis for future promising antifibrotic agents against scar formation.

Vitamin D signaling is important for intestinal homeostasis. An increase in vitamin D receptors in immune cells can modulate cell phenotype and cytokine secretion. Cytokines regulate both pro- (interleukin 17; IL-17) and anti-inflammatory (IL-10) responses triggered by external stimuli. Inflammation in intestinal tissues can disrupt the structure and the remodeling of epithelial tight junction complexes, thus, compromising the protective barrier. The objective of the study was to determine the impact of dietary supplementation with 25-hydroxycholecalciferol (25OHD3), a hydroxylated metabolite of vitamin D, on intestinal cytokine abundance and epithelial barrier integrity over time in broilers. A randomized complete block design experiment was conducted to evaluate the effect of dietary 25OHD3 inclusion on relative protein expression of the cytokines, IL-17 and IL-10, and tight junction proteins, Zona Occludens 1 (ZO-1), and Claudin-1 (CLD-1), in broiler chicken duodenum and ileum from 3 to 21 days post-hatch. On day 0, male chicks (n = 168) were randomly assigned to raised floor pens. Experimental corn-soybean meal-based treatments were as follows: (1) a common starter diet containing 5,000 IU of D3 per kg of feed (VITD3) and (2) a common starter diet containing 2,240 IU of D3 + 2,760 IU of 25OHD3 per kg of feed (25OHD3) fed from days 0 to 21. On days 3, 6, 9, 12, 15, 18, and 21, 12 birds per treatment were euthanized to collect tissue samples for quantitative, multiplex, and fluorescent Western blot analysis. Target proteins were quantified using Image Quant TL 8.1 and expressed relative to total protein. Feeding 25OHD3 post-hatch decreased ileal IL-10 (anti-inflammatory) protein expression in 21-day-old broilers compared with VITD3 only (P = 0.0190). Broilers fed only VITD3 post-hatch had greater IL-17 (pro-inflammatory) protein expression in the ileum at 18 and 21 days-of-age (P = 0.0412) than those that fed 25OHD3. Dietary inclusion of 25OHD3 lowered the abundance of key inflammatory cytokines in the ileum of young broilers.