Role of orbital symmetry in transition metal promoted ring opening reactions of methylenecyclopropanes and cyclobutenes

Transition metals catalyse a variety of organic reactions, of which the ring opening of strained ring organic molecules generated a lot of interest. Theoreticians predicted a metal orbital catalysed pathway, which involved concerted bond breaking and bond forming. On the other hand experimentalists were able to show that the reaction was not proceeding through a concerted pathway by intercepting the intermediates involved. There remained, however, two ring systems methylenecyclopropanes and cyclobutenes—whose reactions with metal complexes seemed to be of a concerted nature. An analysis of the reactions of different metal complexes with these ring systems and the theoretical predictions provide a rationale for understanding these reactions.

Topological phases, Majorana modes and quench dynamics in a spin ladder system

We explore the salient features of the `Kitaev ladder', a two-legged ladder version of the spin-1/2 Kitaev model on a honeycomb lattice, by mapping it to a one-dimensional fermionic p-wave superconducting system. We examine the connections between spin phases and topologically non-trivial phases of non-interacting fermionic systems, demonstrating the equivalence between the spontaneous breaking of global Z(2) symmetry in spin systems and the existence of isolated Majorana modes. In the Kitaev ladder, we investigate topological properties of the system in different sectors characterized by the presence or absence of a vortex in each plaquette of the ladder. We show that vortex patterns can yield a rich parameter space for tuning into topologically non-trivial phases. We introduce and employ a new topological invariant for explicitly determining the presence of zero energy Majorana modes at the boundaries of such phases. Finally, we discuss dynamic quenching between topologically non-trivial phases in the Kitaev ladder and, in particular, the post-quench dynamics governed by tuning through a quantum critical point.

Spontaneous generation of optical activity in urea inclusion compounds vis-a-vis current theories

A novel test of recent theories of the origin of optical activity has been designed based on the inclusion of certain alkyl 2-methylhexanoates into urea channels.

Structure of tri-1-naphthylborane-benzene (1/1) complex, c30h21b.c6h6

M r= 470.46, rhombohedral, R3, a =8.710(4)A, a=91.10(3) o, V= 660.4 (9) A 3, Z= 1,D m= 1.170 (flotation in KI solution), D x=1.183 Mg m -a, Mo Kct, 2 = 0.7107/~,, /t =0.033 mm -1, F(000) - 248.0, T= 293 K, R -- 4.6%(481 unique reflections). The molecule has C a symmetry and is propeller shaped, the angle of twist about the B-C bond being 41.5 (7) °. The space group being chiral, this is yet another example of spontaneous resolution. The results of a thermal-motion analysis are discussed.

Technicolor

The need for reexamination of the standard model of strong, weak, and electromagnetic interactions is discussed, especially with regard to 't Hooft's criterion of naturalness. It has been argued that theories with fundamental scalar fields tend to be unnatural at relatively low energies. There are two solutions to this problem: (i) a global supersymmetry, which ensures the absence of all the naturalness-violating effects associated with scalar fields, and (ii) composite structure of the scalar fields, which starts showing up at energy scales where unnatural effects would otherwise have appeared. With reference to the second solution, this article reviews the case for dynamical breaking of the gauge symmetry and the technicolor scheme for the composite Higgs boson. This new interaction, of the scaled-up quantum chromodynamic type, keeps the new set of fermions, the technifermions, together in the Higgs particles. It also provides masses for the electroweak gauge bosons W± and Z0 through technifermion condensate formation. In order to give masses to the ordinary fermions, a new interaction, the extended technicolor interaction, which would connect the ordinary fermions to the technifermions, is required. The extended technicolor group breaks down spontaneously to the technicolor group, possibly as a result of the "tumbling" mechanism, which is discussed here. In addition, the author presents schemes for the isospin breaking of mass matrices of ordinary quarks in the technicolor models. In generalized technicolor models with more than one doublet of technifermions or with more than one technicolor sector, we have additional low-lying degrees of freedom, the pseudo-Goldstone bosons. The pseudo-Goldstone bosons in the technicolor model of Dimopoulos are reviewed and their masses computed. In this context the vacuum alignment problem is also discussed. An effective Lagrangian is derived describing colorless low-lying degrees of freedom for models with two technicolor sectors in the combined limits of chiral symmetry and large number of colors and technicolors. Finally, the author discusses suppression of flavor-changing neutral currents in the extended technicolor models.

Restoration of symmetry by radiative corrections

It is shown using an explicit model that radiative corrections can restore the symmetry of a system which may appear to be broken at the classical level. This is the reverse of the phenomenon demonstrated by Coleman and Weinberg. Our model is different from theirs, but the techniques are the same. The calculations are done up to the two-loop level and it is shown that the two-loop contribution is much smaller than the one-loop contribution, indicating good convergence of the loop expansion.

Sterochemical studies on cyclic peptides-VIII. Conformational analysis of hydrogen bonded cyclohexaglycyl molecule with a centre of inversion symmetry

A study on the conformational aspects of cyclo-hexaglycyl having inversion symmetry has been made. The cyclic backbone has been assumed to have two internal 4→1 types of NH... O hydrogen bonds. This molecule has been found to take up two types of conformations designated asA* andB* having nearly the same energy values. The theoretical conformations have been compared with the conformations of cyclohexaglycyl hemihydrate observed in the crystal structure. Two molecules with an approximate inversion symmetry are close to the conformation of the typeB* and two other molecules with exact inversino symmetry correspond nearly to the typesB* andA*. comparison with the theoretically possible conformations of cyclohexaglycyl molecule with 2-fold symmetry has been made. The preference of inversion symmetry and preferred ranges ofψ for glycyl molecules is discussed.

Cellular Automata Models of Traffic Behavior in Presence of Speed Breaking Structures

In this article, we study traffic flow in the presence of speed breaking structures. The speed breakers are typically used to reduce the local speed of vehicles near certain institutions such as schools and hospitals. Through a cellular automata model we study the impact of such structures on global traffic characteristics. The simulation results indicate that the presence of speed breakers could reduce the global flow under moderate global densities. However, under low and high global density traffic regime the presence of speed breakers does not have an impact on the global flow. Further the speed limit enforced by the speed breaker creates a phase distinction. For a given global density and slowdown probability, as the speed limit enforced by the speed breaker increases, the traffic moves from the reduced flow phase to maximum flow phase. This underlines the importance of proper design of these structures to avoid undesired flow restrictions.

Transcriptional activation of the Escherichia coli bgl operon: negative regulation by DNA structural elements near the promoter

The bgl operon of Escherichia coil is transcriptionally inactive in wild-type cells. DNA insertion sequences (IS) constitute a major class of spontaneous mutations that activate the cryptic bgl promoter. In an attempt to study the molecular mechanism of activation mediated by insertion sequences, transcription of the bgl promoter was carried out in vitro. Stimulation of transcription is observed when a plasmid containing an insertionally activated bgl promoter is used as a template in the absence of proteins other than RNA polymerase. Deletions that remove sequences upstream of the bgl promoter, and insertion of a 1.2 kb DNA fragment encoding resistance to kanamycin, activate the promoter. Point mutations within a region of dyad symmetry upstream of the promoter, which has the potential to extrude into a cruciform structure under torsional stress, also lead to activation, Introduction of a sequence with dyad symmetry, upstream of an activated bgl promoter carrying a deletion of upstream sequences, results in a fourfold reduction in transcription, These results suggest that the cryptic nature of the bgl promoter is because of the presence of DNA structural elements near the promoter that negatively affect transcription.

Spontaneous and reversible self-assembly of a polypeptide fragment of insulin-like growth factor binding protein-2 into fluorescent nanotubular structures

In this communication, we report the spontaneous and reversible in vitro self-assembly of a polypeptide fragment derived from the C-terminal domain of Insulin-like Growth Factor Binding Protein (IGFBP-2) into soluble nanotubular structures several micrometres long via a mechanism involving inter-molecular disulfide bonds and exhibiting enhanced fluorescence.

Possible high-temperature superconducting state with a d plus id pairing symmetry in doped graphene

Motivated by a suggestion in our earlier work [G. Baskaran, Phys. Rev. B 65, 212505 (2002)], we study electron correlation driven superconductivity in doped graphene where on-site correlations are believed to be of intermediate strength. Using an extensive variational Monte Carlo study of the repulsive Hubbard model and a correlated ground state wave function, we show that doped graphene supports a superconducting ground state with a d+id pairing symmetry. We estimate superconductivity reaching room temperatures at an optimal doping of about 15%-20%. Our work suggests that correlations can stabilize superconductivity even in systems with intermediate coupling.

Two elementary proofs of the Wigner theorem on symmetry in quantum mechanics

In quantum theory, symmetry has to be defined necessarily in terms of the family of unit rays, the state space. The theorem of Wigner asserts that a symmetry so defined at the level of rays can always be lifted into a linear unitary or an antilinear antiunitary operator acting on the underlying Hilbert space. We present two proofs of this theorem which are both elementary and economical. Central to our proofs is the recognition that a given Wigner symmetry can, by post-multiplication by a unitary symmetry, be taken into either the identity or complex conjugation. Our analysis often focuses on the behaviour of certain two-dimensional subspaces of the Hilbert space under the action of a given Wigner symmetry, but the relevance of this behaviour to the larger picture of the whole Hilbert space is made transparent at every stage.

Cubic and ultimate groups of complete symmetry

It is shown that the systems of definite actions described by polar and axial tensors of the second rank and their combinations during the superposition of their elements of complete symmetry with the elements of complete symmetry of the "grey" cube, result in 11 cubic crystallographical groups of complete symmetry. There are 35 ultimate groups (i.e., the groups having the axes of symmetry of infinite order) in complete symmetry of finite figures. 14 out of these groups are ultimate groups of symmetry of polar and axial tensors of the second rank and 24 are new groups. All these 24 ultimate groups are conventional groups since they cannot be presented by certain finite figures possessing the axes of symmetry {Mathematical expression}. Geometrical interpretation for some of the groups of complete symmetry is given. The connection between complete symmetry and physical properties of the crystals (electrical, magnetic and optical) is shown.

The change of complete symmetry of the crystals during the phase transitions in ferroelectrics and ferromagnetics

The extension of the superposition principle of the symmetries (P. Curie principle of symmetry) for the case of complete symmetry is given. The enumeration of all crystallographical groups of complete symmetry is presented, the number of elements having complete symmetry for each class of the crystals being indicated. The change of complete symmetry of the crystals under the phase transitions is obtained by superimposing the elements of complete symmetry of polar or axial vectors on the one hand, and the elements of complete symmetry of the crystals on the other. The tables of complete symmetry changes for the cubic, rhombic, monoclinic and triclinic crystals during the ferroelectric and ferromagnetic phase transitions are given.

Generation of Cationic Two-Coordinate Group-13 Ligand Systems by Spontaneous Halide Ejection: Remarkably Nucleophile-Resistant (Dimethylamino)borylene Complexes

Spontaneous ejection of chloride from a three-coordinate boron Lewis acid can be effected by employing very electron rich metal substituents and leads to the formation of a sterically unprotected terminal (dimethylamino)borylene complex that has a short metal-boron bond and remarkable resistance to attack by nucleophilic and protic reagents.