Modification of Cyclodextrins for Use as Artificial Enzymes

The magical powers of enzymes have been attributed to their ability to bind specific substrates and catalyze reactions of the bound substrate. Artificial enzymes synthetically mimic the binding and the catalytic site to produce molecules that are not only smaller in size but also potentially have similar activity to the real enzymes. The main objective of our research is to create artificial redox enzymes by using cyclodextrins as binding sites and attaching flavin derivatives as the catalytic site. We have developed a strategy to attach a catalytic site to cyclodextrin exclusively at the 2-, 3- or the 6-position. The evaluation of the artificial enzyme in which flavin is attached to the 2-position gives a 647-fold acceleration factor. Although this is modest compared to those of real enzymes (which can have acceleration factors of a trillion), the artificial enzymes allow us to understand the elements that contribute to the incredible catalytic power of enzymes.     

Mitochondrial targeting of selective electron scavengers: synthesis and biological analysis of hemigramicidin-TEMPO conjugates

Synthetic hemigramicidin S-peptidyl TEMPO conjugates are effectively delivered into cells and mitochondria, where they act as electron scavengers and exert protection against apoptosis. Our delivery approach is based on the use of specific structural signaling features recognizable by cells as mitochondria targeting sequences and offers considerable therapeutic anti-apoptotic potential.     

Morphological evidence for surface pre-melting on Si(1 1 1)

We present what we believe to be the first morphological evidence for the occurrence of surface pre-melting on the Si(1 1 1) surface. Our results complement the extensive previous evidence from diffraction and ion scattering techniques for the presence of pre-melted (liquid-like) layers on Si(1 1 1) below the bulk melting temperature and also suggest how atomic steps are involved in the initiation of such layers. Our results are based on atomic force microscopy studies of morphologies that are preserved when surfaces are annealed in a range of high temperatures and then rapidly cooled to room temperature for observation. A unique feature of the experiments is the use of specially prepared atomically flat or very low step density surfaces; this allows us to see how the liquid-like morphologies are associated with the steps and also allows the high temperature structures to survive the cooling process without being absorbed into the steps which normally would exist on a surface vicinal to (1 1 1). Quenched-in structures ascribed to pre-melting also act as sinks for diffusing ‘excess’ adatoms generated by the (1 × 1) to (7 × 7) transition and this leads to the formation of dendritic islands.     

Universal behaviour of scattering amplitudes for scattering from a plane in an average rough surface for small grazing angles

Abstract

It is shown that for scattering from a plane in an average rough surface, the scattering cross section of the range of small grazing angles of the scattered wave demonstrates a universal behaviour. If the angle of incidence is fixed (in general it should not be small), the diffusive component of the scattering cross section for the Dirichlet problem is proportional to θ² where θ is the (small) angle of elevation, and for the Neumann problem it does not depend on θ. For the backscattering case these dependences correspondingly become θ⁴ and θ°. The result is obtained from the structure of the equations that determine the scattering problem rather than by use of an approximation.     

Formulation of rough-surface scattering theory in terms of phase factors and approximate solutions based on this formulation

Abstract

This paper presents the formulation of rough-surface scattering theory in which the bounded phase shift factors, ζ(r, α) ζ exp[iαζ(r)], replace the elevation, ζ(r). Both the Dirichlet and the Neumann problems are considered. The integral equations for secondary surface sources are obtained that contain only this phase function in their kernels.

The Neumann (iterative) series for the solutions of the integral equations thus derived are functional Taylor series in powers of L(r, α), not in powers of ζ. If we expand L(r, α) in these series in powers of ζ(r), we obtain the standard perturbation theory series. Thus, the new formulation corresponds to the partial summation of the perturbation series.

Using the Neumann series, we obtain several uniform (with respect to αζ) approximate solutions that contain, as limiting cases, Bragg scattering, the Kirchhoff approximation, and most known advanced approximations.

In the case of random surface z = ζ(r), these new expansions contain the function ζ(r) only in the exponents, and, therefore, the result of averaging can be expressed only in terms of the characteristic functions of the multivariate probability distribution of elevations.     

Secondary-Ion Mass Spectrometry Images Cardiolipins and Phosphatidylethanolamines at the Subcellular Level

Millions of diverse molecules constituting the lipidome act as important signals within cells. Of these, cardiolipin (CL) and phosphatidylethanolamine (PE) participate in apoptosis and ferroptosis, respectively. Their subcellular distribution is largely unknown. Imaging mass spectrometry is capable of deciphering the spatial distribution of multiple lipids at subcellular levels. Here we report the development of a unique 70 keV gas-cluster ion beam that consists of (CO₂)_n⁺(n>10 000) projectiles. Coupled with direct current beam buncher-time-of-flight secondary-ion mass spectrometry, it is optimized for sensitivity towards high-mass species (up to m/z 3000) at high spatial resolution (1 μm). In combination with immunohistochemistry, phospholipids, including PE and CL, have been assessed in subcellular compartments of mouse hippocampal neuronal cells and rat brain tissue.