The polarized infrared spectra of highly oriented crystalline films of polyethylene glycol were measured in the region 3500–400 cm—1. Five parallel bands and eleven perpendicular bands due to the fundamental vibrations were observed in the region 1500–600 cm—1. From the analysis of these bands, the polyethylene glycol chain was found to belong to the dihedral group and have twofold axes intersecting the helix axis at right angles. The structural models of polyethylene glycol were discussed by the use of the equations for the helical parameters (the second paper of this series). The most likely model (TGT) contains seven repeating units and two helical turns per fiber period of 19.25 Å. The internal rotation angles for this model are calculated to be 60° for the C–C bond and 191.5° for the C–O bond. The A1, A2, and E(θ) normal vibrations of polyethylene glycol were calculated by the general method for treating helical polymers (the first paper of this series). The normal vibrations of p-dioxane were also calculated. The modified Urey—Bradley force field was used for the calculations and the potential constants were transferred from polyethylene, dimethyl ether, and propyl alcohol. The frequencies calculated for the TGT model agreed well with the observed frequencies. The potential energy distributions were also calculated and the nature of the infrared bands was elucidated. The far-infrared spectra of crystalline films were also measured in the region 600–50 cm—1 and two parallel bands and two perpendicular bands were observed. The skeletal normal vibrations of the TGT model were also calculated, taking into account the torsional potential field. The torsional constants correspond to a potential barrier of 3 kcal/mole. The calculated frequencies agreed well with the observed, providing substantial support for the TGT model. The infrared bands in the region of 3000 cm—1 were assigned to the C–H stretching modes and the infrared active combination vibrations.

Objectives To evaluate the effect of the microstructure on the Weibull and slow crack growth (SCG) parameters and on the lifetime of three ceramics used as framework materials for fixed partial dentures (FPDs) (YZ - Vita In-Ceram YZ; IZ - Vita In-Ceram Zirconia; AL - Vita In-Ceram AL) and of two veneering porcelains (VM7 and VM9). Methods Bar-shaped specimens were fabricated according to the manufacturer’s instructions. Specimens were tested in three-point flexure in 37°C artificial saliva. Weibull analysis (n=30) and a constant stress-rate test (n=10) were used to determine the Weibull modulus (m) and SCG coefficient (n), respectively. Microstructural and fractographic analyses were performed using SEM. ANOVA and Tukey’s test (α=0.05) were used to statistically analyze data obtained with both microstructural and fractographic analyses. Results YZ and AL presented high crystalline content and low porosity (0.1–0.2%). YZ had the highest characteristic strength (σ0) value (911 MPa) followed by AL (488 MPa) and IZ (423 MPa). Lower σ0 values were observed for the porcelains (68–75 MPa). Except for IZ and VM7, m values were similar among the ceramic materials. Higher n values were found for YZ (76) and AL (72), followed by IZ (54) and the veneering materials (36–44). Lifetime predictions showed that YZ was the material with the best mechanical performance. The size of the critical flaw was similar among the framework materials (34–48 µm) and among the porcelains (75–86 µm). Significance The microstructure influenced the mechanical and SCG behavior of the studied materials and, consequently, the lifetime predictions.

Withaferin A (WA), a major bioactive component of the Indian herb Withania somnifera, induces cell death (apoptosis/necrosis) in multiple types of tumor cells, but the molecular mechanism underlying this cytotoxicity remains elusive. We report here that 2 μM WA induced cell death selectively in androgen-insensitive PC-3 and DU-145 prostate adenocarcinoma cells, whereas its toxicity was less severe in androgen-sensitive LNCaP prostate adenocarcinoma cells and normal human fibroblasts (TIG-1 and KD). WA also killed PC-3 cells in spheroid-forming medium. DNA microarray analysis revealed that WA significantly increased mRNA levels of c-Fos and 11 heat-shock proteins (HSPs) in PC-3 and DU-145, but not in LNCaP and TIG-1. Western analysis revealed increased expression of c-Fos and reduced expression of the anti-apoptotic protein c-FLIP(L). Expression of HSPs such as HSPA6 and Hsp70 was conspicuously elevated; however, because siRNA-mediated depletion of HSF-1, an HSP-inducing transcription factor, reduced PC-3 cell viability, it is likely that these heat-shock genes were involved in protecting against cell death. Moreover, WA induced generation of reactive oxygen species (ROS) in PC-3 and DU-145, but not in normal fibroblasts. Immunocytochemistry and immuno-electron microscopy revealed that WA disrupted the vimentin cytoskeleton, possibly inducing the ROS generation, c-Fos expression and c-FLIP(L) suppression. These observations suggest that multiple events followed by disruption of the vimentin cytoskeleton play pivotal roles in WA-mediated cell death.

No abstract

SynopsisInfrared spectra of polypeptides were measured in the region of 1800-400 cm-1. For the a-helical form, disordered form, and antiparallel-chain &form, amide V bands arising from N-H out-of-plane bending modes were observed at 610-620, around 650, and 700-705 cm-1, respectively, and amide V' bands arising from N-D oubof-plane bending modes were observed at 455-465, around 510, and 515-530 cm-1, respectively. These correlations are useful for conformation diagnoses, particularly for copolyamino-acids or proteins which are not oriented. The nature of low-frequency amide bands are discussed with reference to potential energy distributions calculated for the a-helical form and p form.