Conformational properties of cylindrical rod brushes consisting of a flexible polystyrene main chain and poly(n-hexyl isocyanate) (PHIC) rod side chains have thoroughly been studied by static light and small-angle X-ray scattering (SAXS) in tetrahydrofuran (THF) at 25 °C. These rod brushes were prepared by radical homopolymerization of 4-vinylbenzyloxy-ended PHIC macromonomers (1) (VB-HIC-N s , where N s is the weight-averaged degree of polymerization of HIC and in a range from 21 to 80) in n-hexane at 60 °C. The mean-square cross-sectional radius of gyration (〈R c 2 〉 0 ) of the brush at an infinite dilution is determined by SAXS measurement and rationalized as a function of N s . The experimental value of 〈R c 2 〉 0 gradually increases with N s but above N s higher than 20 increases to follow the scaling law of 〈R c 2 〉 0 ∝ N s 0.87 . The experimental N s dependence of 〈R c 2 〉 0 is compared to that from the wormlike comb model whose main and side chains have different stiffness parameters. The molecular weight dependence of z-averaged mean-square radius of gyration (〈R g 2 〉 z ) of the brush is determined and analyzed in terms of the wormlike cylinder model taking into account the end effects. The parameters characteristic of the rod brush in THF solution, such as the main chain stiffness parameter (λ M -1 ), the molecular weight per unit contour length (M L ), and the excluded-volume strength (B), are determined and rationalized as a function of the contour length of the side rod. The polystyrene main chain stiffness of the rod brush remarkably increases by the densely located rod side chains to follow the scaling law of λ M -1 ∝ N s 1 . The backbone stiffness of the rod brush is higher than that of the flexible brush consisting of flexible polystyrene side chains with the corresponding contour length. A single rod brush of poly(VB-HIC-47) deposited on a mica surface is observed by the scanning force microscopy to reasonably demonstrate the cylindrical rod brushes.
Wingless proteins, termed Wnt, are involved in embryonic development, blood cell differentiation, and tumorigenesis. In mammalian hematopoiesis, Wnt signaling is essential for stem-cell homeostasis and lymphocyte differentiation. Recent studies have suggested that these molecules are associated with cardiovascular diseases, rheumatoid arthritis, and osteoarthritis. Furthermore, Wnt5a signaling is essential for the general inflammatory response of human macrophages. Periodontitis is a chronic inflammatory disease caused by gram-negative periodontopathic bacteria and the resultant host immune response. Periodontitis is characterized by loss of tooth-supporting structures and alveolar bone resorption. There have been no previous reports on Wnt5a expression in periodontitis tissue, and only few study reported the molecular mechanisms of Wnt5a expression in LPS-stimulated monocytic cells. Using RT-PCR, we demonstrated that Wnt5a mRNA expression was up-regulated in chronic periodontitis tissue as compared to healthy control tissue. P. gingivalis LPS induced Wnt5a mRNA in the human monocytic cell line THP-1 with a peak at 4 hrs after stimulation. P. gingivalis LPS induced higher up-regulation of Wnt5a mRNA than E. coli LPS. The LPS receptors TLR2 and TLR4 were equally expressed on the surface of THP-1 cells. P. gingivalis LPS induced IκBα degradation and was able to increase the NF-κB binding activity to DNA. P. gingivalis LPS-induced Wnt5a expression was inhibited by NF-κB inhibitors, suggesting NF-κB involvement. Furthermore, IFN-γ synergistically enhanced the P. gingivalis LPS-induced production of Wnt5a. Pharmacological investigation and siRNA experiments showed that STAT1 was important for P. gingivalis LPS-induced Wnt5a expression. These results suggest that the modulation of Wnt5a expression by P. gingivalis may play an important role in the periodontal inflammatory process and serve a target for the development of new therapies.
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