Publications

Bone comprises a complex structure of primarily collagen, hydroxyapatite and water, where each hierarchical structural level contributes to its strength, ductility and toughness. These properties, however, are degraded by irradiation, arising from medical therapy or bone-allograft sterilization. We provide here a mechanistic framework for how irradiation affects the nature and properties of human cortical bone over a range of characteristic (nano to macro) length-scales, following x-ray exposures up to 630 kGy. Macroscopically, bone strength, ductility and fracture resistance are seen to be progressively degraded with increasing irradiation levels. At the micron-scale, fracture properties, evaluated using insitu scanning electron microscopy and synchrotron x-ray computed micro-tomography, provide mechanistic information on how cracks interact with the bone-matrix structure. At sub-micron scales, strength properties are evaluated with insitu tensile tests in the synchrotron using small-/wide-angle x-ray scattering/diffraction, where strains are simultaneously measured in the macroscopic tissue, collagen fibrils and mineral. Compared to healthy bone, results show that the fibrillar strain is decreased by ∼40% following 70 kGy exposures, consistent with significant stiffening and degradation of the collagen. We attribute the irradiation-induced deterioration in mechanical properties to mechanisms at multiple length-scales, including changes in crack paths at micron-scales, loss of plasticity from suppressed fibrillar sliding at sub-micron scales, and the loss and damage of collagen at the nano-scales, the latter being assessed using Raman and Fourier Transform Infrared spectroscopy and a fluorometric assay.

Abstract not Available.

Type Iax supernovae (SN Iax) are the largest known class of peculiar white dwarf supernovae, distinct from normal Type Ia supernovae (SN Ia). The unique properties of SN Iax, especially their strong photospheric lines out to extremely late times, allow us to model their optical spectra and derive physical parameters for the long-lasting photosphere. We present an extensive spectral timeseries, including 21 new spectra, of SN Iax 2014dt from +11 to +562 days after maximum light. We are able to reproduce the entire timeseries with a self-consistent, nearly unaltered deflagration explosion model from Fink et al. (2014) using TARDIS, an open-source radiative transfer code (Kerzendorf & Sim 2014; Kerzendorf et al. 2023). We find that the photospheric velocity of SN 2014dt slows its evolution between +64 and +148 days, which closely overlaps the phase when we see SN 2014dt diverge from the normal spectral evolution of SN Ia (+90 to +150 days). The photospheric velocity at these epochs, ~400$-$1000 km s$^{-1}$, may demarcate a boundary within the ejecta below which the physics of SN Iax and normal SN Ia differ. Our results suggest that SN 2014dt is consistent with a weak deflagration explosion model that leaves behind a bound remnant and drives an optically thick, quasi-steady-state wind creating the photospheric lines at late times. The data also suggest that this wind may weaken at epochs past +450 days, perhaps indicating a radioactive power source that has decayed away.

Sum frequency generation (SFG) vibrational spectroscopy has been used to study the influence of the ionic strength of a solution on the interfacial structure of a model amphiphilic peptide. The ionic strength of the solution is controlled by changing the salt concentration of the solution. This peptide (called LK14) contains 14 amino acids and is composed of hydrophobic leucine (L) and hydrophilic lysine (K) residues. LK14 is shown to be an α helix in solution at high ionic strength and a random coil at low ionic strength. On a hydrophilic silica surface, an N−H mode from LK14 is observed at high ionic strength that is no longer observed when the peptide is adsorbed at low ionic strengths. Instead, a strong interfacial water signal is measured at low ionic strength conditions. The N−H mode that appears at high salt concentrations is seen only when the peptide has a stable secondary structure. On a hydrophobic polystyrene surface, C−H modes are observed that are independent of the ionic strength of the solution. However, the intensity of the water modes observed upon peptide adsorption increases with decreasing ionic strength. In contrast, in the absence of peptide (i.e., the polystyrene/buffer interface), there is no change in the intensity of the water modes with changing ionic strength. This implies that C−H modes observed on hydrophobic surfaces in peptide SFG studies are independent of the secondary structure of the biomolecule in solution and that the adsorption of a peptide can induce ordering of interfacial water molecules.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

We report a catalyst for intermolecular hydroamination of vinylarenes that is substantially more active for this process than catalysts published previously. With this more reactive catalyst, we demonstrate that additions of amines to vinylarenes and dienes occur in the presence of potentially reactive functional groups, such as ketones with enolizable hydrogens, free alcohols, free carboxylic acids, free amides, nitriles, and esters. The catalyst for these reactions is generated from [Pd(eta(3)-allyl)Cl](2) (with or without added AgOTf) or [Pd(CH(3)CN)(4)](BF(4))(2) and Xantphos (9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene), which generates complexes with large P-Pd-P bite angles. Studies on the rate of the C-N bond-forming step that occurs by attack of amine on an eta(3)-phenethyl and an eta(3)-allyl complex were conducted to determine the effect of the bite angle on the rate of this nucleophilic attack. Studies on model eta(3)-benzyl complexes containing various bisphosphines showed that the nucleophilic attack was faster for complexes containing larger P-Pd-P bite angles. Studies of substituted unsymmetrical and unsubstituted symmetrical model eta(3)-allyl complexes showed that nucleophilic attack on complexes ligated by Xantphos was faster than on complexes bearing ligands with smaller bite angles and that nucleophilic attack on unsymmetrical allyl complexes with larger bite angle ligands was faster than on unsymmetrical allyl complexes with smaller bite angle ligands. However, monitoring of catalytic reactions of dienes by (31)P NMR spectroscopy showed that the concentration of active catalyst was the major factor that controlled rates for reactions of symmetrical dienes catalyzed by complexes of phosphines with smaller bite angles. The identity of the counterion also affected the rate of attack: reactions of allylpalladium complexes with chloride counterion occurred faster than reactions of allylpalladium complexes with triflate or tetrafluoroborate counterion. As is often observed, the dynamics of the allyl and benzyl complexes also depended on the identity of the counterion.