Synthetic enantiopure aziridinomitosenes: preparation, reactivity, and DNA alkylation studies

An enantiocontrolled route to aziridinomitosenes had been developed from l-serine methyl ester hydrochloride. The tetracyclic target ring system was assembled by an internal azomethine ylide cycloaddition reaction based on silver ion-assisted intramolecular oxazole alkylation and cyanide-induced ylide generation via a labile oxazoline intermediate (62 to 66). Other key steps include reductive detritylation of 26, methylation of the N-H aziridine 56, oxidation of the sensitive cyclohexenedione 68 to quinone 70, and carbamoylation using Fmoc-NCO. Although the aziridinomitosene tetracycle is sensitive, a range of protecting group manipulations and redox chemistry can be performed if suitable precautions are taken. A study of DNA alkylation by the first C-6,C-7-unsubstituted aziridinomitosene 11a has been carried out, and evidence for DNA cross-link formation involving nucleophilic addition to the quinone subunit is described.     

Iodometric determination of ferricyan in the presence of copper,silver, cadmium and zinc

Ferricyan can be determined in the presence of copper, silver and cadmium by addition of potassium ferrocyanide, filtration of the ferrocyanides of copper, silver and cadmium formed in this reaction, and titration of the potassium ferricyanide contained in the filtrate. In the case of silver, the ferricyan can also be determined without filtration by addition of potassium iodide and titration of the ferricyanide. In the case of zinc, potassium, ferrocyanide is added and without filtration the ferricyanide titrated.     

μ+ depolarization inAlGd alloys

The ⁺ depolarization rate in diluteAlGd alloys containing 50 and 450 atomic ppm Gd was measured in a transverse field of 80 Oe over the temperature range 6–300 K. For both alloys, A increased dramatically above 200 K, reaching values of 0.69 and 0.93 s^–1, respectively, near room temperature. The results are interpreted as providing evidence for a thermally-activated trapping mechanism.This work was supported by the U.S. Department of Energy.     

Computer analysis of two-dimensional images in the Zernike phase contrast method for hard X rays

The problems of the numerical simulation of two-dimensional images in the Zernike phase contrast method in hard X rays are analyzed. Calculations are performed for experimental conditions typical of third-generation synchrotron radiation sources (ESRF, APS, Spring-8, etc.). Schemes are considered where the focusing elements are a refracting lens and a zone plate and the phase-shifting element is situated at the point of the source image. It is shown that the refracting lens allows better resolution than the zone plate. A technique similar to ptychography can be successfully applied to improve the quality of the images obtained by the Zernike phase contrast method.     

Theory of an X-ray interferometer in the form of an array of planar compound refractive lenses

The results of theoretical analysis of the interference pattern created by an X-ray multilens interferometer in the case of an arbitrary number of planar compound refractive lenses are presented. The full widths at half maximum of the resonance peaks in the transverse and longitudinal directions relative to the direction of synchrotron radiation are calculated at distances corresponding to the fractional Talbot effect. A relation between the widths is shown to exist that is very close to the width relation in the case of focusing by a single lens. A difference between the fractional and full Talbot effects is discussed, and the necessary conditions for the transverse and longitudinal coherence of radiation are analyzed, the satisfaction of which guarantees that undistorted interference peaks will be observed experimentally.     

Energy Scaling Laws for Conically Constrained Thin Elastic Sheets

We investigate low-energy deformations of a thin elastic sheet subject to a displacement boundary condition consistent with a conical deformation. Under the assumption that the displacement near the sheet’s center is of order h|logh|, where h?1 is the thickness of the sheet, we establish matching upper and lower bounds of order h ²|logh| for the minimum elastic energy per unit thickness, with a prefactor determined by the geometry of the associated conical deformation. These results are established first for a 2D model problem and then extended to 3D elasticity.     

Self-Assembling Catalytic Peptide Nanomaterials Capable of Highly Efficient Peroxidase Activity

The self-assembly of short peptides gives rise to versatile nanomaterials capable of promoting efficient catalysis. We have shown that short, seven-residue peptides bind hemin to produce functional catalytic materials which display highly efficient peroxidation activity, reaching a catalytic efficiency of 3×10⁵ m ⁻¹ s⁻¹. Self-assembly is essential for catalysis as non-assembling controls show no activity. We have also observed peroxidase activity even in the absence of hemin, suggesting the potential to alter redox properties of substrates upon association with the assemblies. These results demonstrate the practical utility of self-assembled peptides in various catalytic applications and further support the evolutionary link between amyloids and modern-day enzymes.     

Hydrogen and deuterium diffusion in non-stoichiometric spinel

High pressure/temperature annealing experiments are used to determine diffusivities of H⁺ and D⁺ in non-stoichiometric spinel, a low-pressure analogue for nominally anhydrous minerals in Earth’s mantle. Data are fitted to the following Arrhenius law: Diffusivity (m²/s)?=?4?±?1?×?10^?12 exp(?54?±?2 kJ?mol^?1/RT). At low temperatures, H⁺ and D⁺ diffusion in non-stoichiometric spinel is charge balanced by flux of O vacancies, with infrared data consistent with protonation of both octahedral and tetrahedral O–O edges in non-stoichiometric spinel, and additional fine structure due to Mg–Al mixing and/or coupling of structurally incorporated H⁺ with cation vacancies. Absence of changes in the fine structure of O–H absorption bands indicates that H⁺ can become locally coupled and uncoupled to other defects during bulk diffusion. As such, proton conductivity in spinel group minerals, arising from faster flux of uncoupled H⁺, can only be calculated from H⁺ mobility data if the extent of defect coupling is constrained.