The vibrational Raman optical activity (ROA) spectrum of a polypeptide in a model beta-sheet conformation, that of poly(l-lysine), was measured for the first time, and the alpha-helix --> beta-sheet transition monitored as a function of temperature in H(2)O and D(2)O. Although no significant population of a disordered backbone state was detected at intermediate temperatures, some side chain bands not present in either the alpha-helix or beta-sheet state were observed. The observation of ROA bands in the extended amide III region assigned to beta-turns suggests that, under our experimental conditions, beta-sheet poly(L-lysine) contains up-and-down antiparallel beta-sheets based on the hairpin motif. The ROA spectrum of beta-sheet poly(L-lysine) was compared with ROA data on a number of native proteins containing different types of beta-sheet. Amide I and amide II ROA band patterns observed in beta-sheet poly(L-lysine) are different from those observed in typical beta-sheet proteins and may be characteristic of an extended flat multistranded beta-sheet, which is unlike the more irregular and twisted beta-sheet found in most proteins. However, a reduced isoform of the truncated ovine prion protein PrP(94-233) that is rich in beta-sheet shows amide I and amide II ROA bands similar to those of beta-sheet poly(L-lysine), which suggests that the C-terminal domain of the prion protein is able to support unusually flat beta-sheets. A principal component analysis (PCA) that identifies protein structural types from ROA band patterns provides a useful representation of the structural relationships among the polypeptide and protein states considered in the study.

No abstract

No abstract

-The failure process ahead of a mode I crack advancing in a ductile thin metal plate or sheet produces plastic dissipation through a sequence of deformation steps that include necking well ahead of the crack tip and shear localization followed by a slant fracture in the necked region somewhat closer to the tip. The objective of this paper is to analyze this sequential process to characterize the traction-separation behavior and the associated effective cohesive fracture energy of the entire failure process. The emphasis is on what is often described as plane stress behavior taking place after the crack tip has advanced a distance of one or two plate thicknesses. Tractionseparation laws are an essential component of finite element methods currently under development for analyzing fracture of large scale plate or shell structures. The present study resolves the sequence of failure details using the Gurson constitutive law based on the micromechanics of the ductile fracture process, including a recent extension that accounts for damage growth in shear. The fracture process in front of an advancing crack, subject to overall mode I loading, is approximated by a 2D plane strain finite element model, which allows for an intensive study of the parameters influencing local necking, shear localization and the final slant failure. The deformation history relevant to a cohesive zone for a large scale model is identified and the traction-separation relation is determined, including the dissipated energy. For ductile structural materials, the dissipation generated during necking prior to the onset of shear localization is the dominant contribution; it scales with the plate thickness and is mesh-independent in the present numerical model. The energy associated with the shear localization and fracture is secondary; it scales with the width of the shear band, and inherits the finite element mesh dependency of the Gurson model. The cohesive tractionseparation laws have been characterized for various material conditions.