THEORETICAL AND EXPERIMENTAL STUDIES OF STRESS DISTRIBUTION IN WEDGE-SHAPED GRANULAR HEAPS

The present work explains the statics of self-weight transmission restricted to a long prismatic heap inclined at an angle of repose and symmetrically formed on a rigid base. The closure of polarized principal axes with the mobilized state of stress along the slope surface is employed by imposing the orientation of principal stresses on the equilibrium equations. Comparisons were made with calculations based on the finite element method using an elastic model. Moreover, experiments on sand heaps deposited on a rectangular rigid base were conducted to validate the theoretical study. The measured pressure profile generally agreed well with theoretical results.     

C3-symmetric trisimidazoline-catalyzed enantioselective bromolactonization of internal alkenoic acids

A method for conducting enantioselective bromolactonization reactions of trisubstituted alkenoic acids, using the C(3)-symmetric trisimidazoline 1 and 1,3-dibromo-5,5-dimethyl hydantoin as a bromine source, has been developed. The process generates chiral δ-lactones that contain a quaternary carbon. The results of studies probing geometrically different olefins show that (Z)-olefins rather than (E)-olefins are favorable substrates for the process. The method is not only applicable to acyclic olefin reactants but can also be employed to transform cyclic trisubstituted olefins into chiral spirocyclic lactones. Finally, the synthetic utility of the newly developed process is demonstrated by its application to a concise synthesis of tanikolide, an antifungal marine natural product.     

Adsorption and disruption of lipid bilayers by nanoscale protein aggregates

Nanoparticles taken into biological systems can have biological impacts through their interactions with cell membranes, accompanied by protein adsorption onto the nanoparticle surfaces, forming a so-called protein corona. Our current research aims to demonstrate that nanoscale protein aggregates behave like such nanoparticles with regard to the interaction with lipid membranes. In this study, the adsorption and disruption of the lipid membranes by protein aggregates were investigated using amyloid fibrils and nanoscale thermal aggregates of lysozyme. Both types of protein aggregates had disruptive effects on the negatively charged liposomes, similar to polycationic nanoparticles. Interestingly, adsorption of liposomes on the amyloid fibrils preceding disruption occurred even if the net charge of the liposome was zero, suggesting the importance of hydrophobic interactions in addition to electrostatic interactions. The results of the present study provide new insights into the biological impacts of nanoparticles in vivo.     

High-pressure synthesis, crystal structure, and electromagnetic properties of CdRh2O4: an analogous oxide of the postspinel mineral MgAl2O4

The postspinel mineral MgAl(2)O(4) exists only under the severe pressure conditions in the subducted oceanic lithosphere in the Earth's deep interior. Here we report that its analogous oxide CdRh(2)O(4) exhibits a structural transition to a quenchable postspinel phase under a high pressure of 6 GPa at 1400 °C, which is within the general pressure range of a conventional single-stage multianvil system. In addition, the complex magnetic contributions to the lattice and metal nonstoichiometry that often complicate investigations of other analogues of MgAl(2)O(4) are absent in CdRh(2)O(4). X-ray crystallography revealed that this postspinel phase has an orthorhombic CaFe(2)O(4) structure, thus making it a practical analogue for investigations into the geophysical role of postspinel MgAl(2)O(4). Replacement of Mg(2+) with Cd(2+) appears to be effective in lowering the pressure required for transition, as was suggested for CdGeO(3). In addition, Rh(3+) could also contribute to this reduction, as many analogous Rh oxides of aluminous and silicic minerals have been quenched from lower-pressure conditions.     

Probing the 3-D Structure,Dynamics, and Stability of Bacterial Collagenase Collagen Binding Domain (apo- versus holo-) by Limited Proteolysis MALDI-TOF MS

Pairing limited proteolysis and matrix-assisted laser desorption/ionization-time of flight mass spectrometry (MALDI-TOF MS) to probe clostridial collagenase collagen binding domain (CBD) reveals the solution dynamics and stability of the protein, as these factors are crucial to CBD effectiveness as a drug-delivery vehicle. MS analysis of proteolytic digests indicates initial cleavage sites, thereby specifying the less stable and highly accessible regions of CBD. Modulation of protein structure and stability upon metal binding is shown through MS analysis of calcium-bound and cobalt-bound CBD proteolytic digests. Previously determined X-ray crystal structures illustrate that calcium binding induces secondary structure transformation in the highly mobile N-terminal arm and increases protein stability. MS-based detection of exposed residues confirms protein flexibility, accentuates N-terminal dynamics, and demonstrates increased global protein stability exported by calcium binding. Additionally, apo- and calcium-bound CBD proteolysis sites correlate well with crystallographic B-factors, accessibility, and enzyme specificity. MS-observed cleavage sites with no clear correlations are explained either by crystal contacts of the X-ray crystal structures or by observed differences between Molecules A and B in the X-ray crystal structures. The study newly reveals the absence of the βA strand and thus the very dynamic N-terminal linker, as corroborated by the solution X-ray scattering results. Cobalt binding has a regional effect on the solution phase stability of CBD, as limited proteolysis data implies the capture of an intermediate-CBD solution structure when cobalt is bound.     

High-pressure synthesis, crystal structure, and properties of BiPd2O4 with Pd2+ and Pd4+ ordering and PbPd2O4

BiPd(2)O(4) and PbPd(2)O(4) were synthesized at high pressure of 6 GPa and 1500 K. Crystal structures of BiPd(2)O(4) and PbPd(2)O(4) were studied with synchrotron X-ray powder diffraction. BiPd(2)O(4) is isostructural with PbPt(2)O(4) and crystallizes in a triclinic system (space group P1, a = 5.73632(4) ?, b = 6.02532(5) ?, c = 6.41100(5) ?, α = 114.371(1)°, β = 95.910(1)°, and γ = 111.540(1)° at 293 K). PbPd(2)O(4) is isostructural with LaPd(2)O(4) and BaAu(2)O(4) and crystallizes in a tetragonal system (space group I4(1)/a, a = 5.76232(1) ?, and c = 9.98347(2) ? at 293 K). BiPd(2)O(4) shows ordering of Pd(2+) and Pd(4+) ions, and it is the third example of compounds with ordered arrangements of Pd(2+) and Pd(4+) in addition to Ba(2)Hg(3)Pd(7)O(14) and KPd(2)O(3). In PbPd(2)O(4), the following charge distribution is realized Pb(4+)Pd(2+)(2)O(4). PbPd(2)O(4) shows a structural phase transition from I4(1)/a to I2/a at about 240 K keeping basically the same structural arrangements (space group I2/a, a = 5.77326(1) ?, b = 9.95633(2) ?, c = 5.73264(1) ?, β = 90.2185(2)° at 112 K). BiPd(2)O(4) is nonmagnetic while PbPd(2)O(4) exhibits a significant temperature-dependent paramagnetic moment of 0.46μ(B)/f.u. between 2 and 350 K. PbPd(2)O(4) shows metallic conductivity, and BiPd(2)O(4) is a semiconductor between 2 and 400 K.     

Walker 4-manifolds with proper almost complex structures

It is shown that a Walker 4-manifold, endowed with a canonical neutral metric depending on three arbitrary functions, admits a specific almost complex structure (called proper) and an associated opposite almost complex structure. We study when these two almost complex structures are integrable and when the corresponding Kähler forms are symplectic. The conditions for the canonical neutral metric to be Kähler imply that the three arbitrary functions in the metric are all harmonic with respect to two coordinate variables, and we obtain a useful method of constructing indefinite Kähler 4-manifolds. Petean’s example of a nonflat indefinite Kähler–Einstein 4-manifold is a special case of this construction.     

Muonium desorption to vacuum from hot iridium surface

Slow muonium (Mu) emission from the surface of iridium (Ir) foil has been observed in vacuum above \sim1200\ K with a yield of 5(1)% Mu per incident muon stopped in the foil. The relative Mu signal was found to be thermally activated with E_a=1.86(1)\ eV. Analysis of the time‐differential evolution of Mu in vacuum at T_Ir=1580\ K showed that the trapping rate of positive muons during diffusion in the bulk Ir was nearly zero. In situ measurements of the surface of Ir with X‐ray photoelectron spectroscopy verified that the main source of impurities in the 99.9%‐Ir was molybdenum (Mo). This revised version was published online in August 2006 with corrections to the Cover Date.