Design and synthesis of quasi-diastereomeric molecules with unchanging central, regenerating axial and switchable helical chirality via cleavage and formation of Ni(II)–O and Ni(II)–N coordination bonds

9 p.

Recognition of double helical DNA by purine oligonucleotides via triple helix formation

Oligonucleotide-directed triple helix formation is one of the most versatile methods for the sequence specific recognition of double helical DNA. Chapter 2 describes affinity cleaving experiments carried out to assess the recognition potential for purine-rich oligonucleotides via the formation of triple helices. Purine-rich oligodeoxyribonucleotides were shown to bind specifically to purine tracts of double helical DNA in the major groove antiparallel to the purine strand of the duplex. Specificity was derived from the formation of reverse Hoogsteen G•GC, A•AT and T•AT triplets and binding was limited to mostly purine tracts. This triple helical structure was stabilized by multivalent cations, destabilized by high concentrations of monovalent cations and was insensitive to pH. A single mismatched base triplet was shown to destabilize a 15 mer triple helix by 1.0 kcal/mole at 25°C. In addition, stability appeared to be correlated to the number of G•GC triplets formed in the triple helix. This structure provides an additional framework as a basis for the design of new sequence specific DNA binding molecules.

In work described in Chapter 3, the triplet specificities and required strand orientations of two classes of DNA triple helices were combined to target double helical sequences containing all four base pairs by alternate strand triple helix formation. This allowed for the use of oligonucleotides containing only natural 3'-5' phosphodiester linkages to simultaneously bind both strands of double helical DNA in the major groove. The stabilities and structures of these alternate strand triple helices depended on whether the binding site sequence was 5'-(purine)_m (pyrimidine)_n-3' or 5'- (pyrimidine)_m (purine)_n-3'.

In Chapter 4, the ability of oligonucleotide-cerium(III) chelates to direct the transesterfication of RNA was investigated. Procedures were developed for the modification of DNA and RNA oligonucleotides with a hexadentate Schiff-base macrocyclic cerium(III) complex. In addition, oligoribonucleotides modified by covalent attachment of the metal complex through two different linker structures were prepared. The ability of these structures to direct transesterification to specific RNA phosphodiesters was assessed by gel electrophoresis. No reproducible cleavage of the RNA strand consistent with transesterification could be detected in any of these experiments.

Topology of toroidal helical fields in non-circular cross-sectional tokamaks

The ordinary differential magnetic field line equations are solved numerically; the tokamak magnetic structure is studied on Hefei Tokamak-7 Upgrade (HT-7U) when the equilibrium field with a monotonic q-profile is perturbed by a helical magnetic field. We find that a single mode (m, n) helical perturbation can cause the formation of islands on rational surfaces with q = m/n and q = (m +/- 1, +/- 2, +/- 3,...)/n due to the toroidicity and plasma shape (i.e. elongation and triangularity), while there are many undestroyed magnetic surfaces called Kolmogorov-Arnold-Moser (KAM) barriers on irrational surfaces. The islands on the same rational surface do not have the same size. When the ratio between the perturbing magnetic field B-r(r) and the toroidal magnetic field amplitude B(phi)0 is large enough, the magnetic island chains on different rational surfaces will overlap and chaotic orbits appear in the overlapping area, and the magnetic field becomes stochastic. It is remarkable that the stochastic layer appears first in the plasma edge region.

π+ photoproduction at angles from 6° to 90° C.M. and energies from 589 to 1269 MeV

The differential cross section for the reaction γp → π⁺n was measured at 32 laboratory photon energies between 589 and 1269 MeV at the Caltech Synchrotron. At each energy, data have been obtained at typically fifteen π⁺ c.m. angles between 6° and 90°. A magnetic spectrometer was used to detect the π⁺ photo-produced in a liquid hydrogen target. Two Cherenkov counters were used to reject the background of positrons and protons. The data clearly show the presence of a pole in the production amplitude due to the one pion exchange. Moravcsik fits to the 32 angular distributions, including data from another experiment, are presented. The extrapolation of these fits to the pole gives a value for the pion-nucleon coupling constant of 14.5 which is consistent with the accepted value. The second and third pion-nucleon resonances are evident as peaks in the total cross section and as changes in the shape of the angular distributions. At the third resonance there is evidence for both a D5/2 and an F5/2 amplitude. The absence of large variations in the 0° and 180° cross sections implies that the second and third resonances are mostly produced from an initial state with helicity ± 3/2.

Core size scaling of helical-core optical fibres

The mode-area, scaling properties of helical-core optical fibres are numerically studied and the limit of core size for achievable single-mode operation is explored. By appropriate design, helical-core fibres can operate in a single mode with possible scaling up to 300 mu m in core diameter with numerical aperture 0.1.

Spin-helical Dirac states in graphene induced by polar-substrate surfaces with giant spin-orbit interaction: a new platform for spintronics

Spintronics, or spin electronics, is aimed at efficient control and manipulation of spin degrees of freedom in electron systems. To comply with demands of nowaday spintronics, the studies of electron systems hosting giant spin-orbit-split electron states have become one of the most important problems providing us with a basis for desirable spintronics devices. In construction of such devices, it is also tempting to involve graphene, which has attracted great attention because of its unique and remarkable electronic properties and was recognized as a viable replacement for silicon in electronics. In this case, a challenging goal is to lift spin degeneracy of graphene Dirac states. Here, we propose a novel pathway to achieve this goal by means of coupling of graphene and polar-substrate surface states with giant Rashba-type spin-splitting. We theoretically demonstrate it by constructing the graphene@BiTeCl system, which appears to possess spin-helical graphene Dirac states caused by the strong interaction of Dirac and Rashba electrons. We anticipate that our findings will stimulate rapid growth in theoretical and experimental investigations of graphene Dirac states with real spin-momentum locking, which can revolutionize the graphene spintronics and become a reliable base for prospective spintronics applications.

Self-Similarity and helical symmetry in vortex generator flow simulations

According to experimental observations, the vortices generated by vortex generators have previously been observed to be self-similar for both the axial (u(z)) and azimuthal (u(circle minus)) velocity profiles. Further, the measured vortices have been observed to obey the criteria for helical symmetry. This is a powerful result, since it reduces the highly complex flow to merely four parameters. In the present work, corresponding computer simulations using Reynolds-Averaged Navier-Stokes equations have been carried out and compared to the experimental observations. The main objective of this study is to investigate how well the simulations can reproduce the physics of the flow and if the same analytical model can be applied. Using this model, parametric studies can be significantly reduced and, further, reliable simulations can substantially reduce the costs of the parametric studies themselves.