Kinetics and Mechanism of Hydrolysis of Benzimidazolylcarbamates

Synthesis of new 2-aminobenzimidazole-1-carbamates was accomplished by carbamoylation of 2-aminobenzimidazole using different substituted phenyl chloroformates. The aqueous hydrolysis of the new compounds was examined in the pH range 1-13 at 25 oC. The evaluated kinetic parameters led to the conclusion that up to pH 4 reaction proceeds by a bimolecular attack of water to the N-protonated substrate. This is the first time this behavior is described for carbamates, and can be ascribed to the higher basicity of the benzimidazolyl moiety when compared with the carbonyl oxygen. For higher values of pH, the results are consistent with a BAc2 mechanism with nucleophilic catalysis, but while between pH 4 and pH 7 water acts as the nucleophile, for pH> 7 the hydroxide ion is the acting species

Phase diagram of two interacting helical states

We consider two coupled time-reversal-invariant helical edge modes of the same helicity, such as would occur on two stacked quantum spin Hall insulators. In the presence of interaction, the low-energy physics is described by two collective modes, one corresponding to the total current flowing around the edge and the other one describing relative fluctuations between the two edges.We find that quite generically, the relative mode becomes gapped at low temperatures, but only when tunneling between the two helical modes is nonzero. There are two distinct possibilities for the gapped state depending on the relative size of different interactions. If the intraedge interaction is stronger than the interedge interaction, the state is characterized as a spin-nematic phase. However, in the opposite limit, when the interaction between the helical edge modes is strong compared to the interaction within each mode, a spin-density wave forms, with emergent topological properties. First, the gap protects the conducting phase against localization by weak nonmagnetic impurities; second, the protected phase hosts localized zero modes on the ends of the edge that may be created by sufficiently strong nonmagnetic impurities

Brain tissue segmentation using q-entropy in multiple sclerosis magnetic resonance images

The loss of brain volume has been used as a marker of tissue destruction and can be used as an index of the progression of neurodegenerative diseases, such as multiple sclerosis. In the present study, we tested a new method for tissue segmentation based on pixel intensity threshold using generalized Tsallis entropy to determine a statistical segmentation parameter for each single class of brain tissue. We compared the performance of this method using a range of different q parameters and found a different optimal q parameter for white matter, gray matter, and cerebrospinal fluid. Our results support the conclusion that the differences in structural correlations and scale invariant similarities present in each tissue class can be accessed by generalized Tsallis entropy, obtaining the intensity limits for these tissue class separations. In order to test this method, we used it for analysis of brain magnetic resonance images of 43 patients and 10 healthy controls matched for gender and age. The values found for the entropic q index were 0.2 for cerebrospinal fluid, 0.1 for white matter and 1.5 for gray matter. With this algorithm, we could detect an annual loss of 0.98% for the patients, in agreement with literature data. Thus, we can conclude that the entropy of Tsallis adds advantages to the process of automatic target segmentation of tissue classes, which had not been demonstrated previously.Coordenacao de Aperfeicoamento de Pessoal de Nivel Superior (CAPES)FAPESPCNP

Nonequilibrium wetting

When a nonequilibrium growing interface in the presence of a wall is considered a nonequilibrium wetting transition may take place. This transition can be studied trough Langevin equations or discrete growth models. In the first case, the Kardar-Parisi-Zhang equation, which defines a very robust universality class for nonequilibrium moving interfaces, with a soft-wall potential is considered. While in the second, microscopic models, in the corresponding universality class, with evaporation and deposition of particles in the presence of hard-wall are studied. Equilibrium wetting is related to a particular case of the problem, it corresponds to the Edwards-Wilkinson equation with a potential in the continuum approach or to the fulfillment of detailed balance in the microscopic models. In this review we present the analytical and numerical methods used to investigate the problem and the very rich behavior that is observed with them.Comment: Review, 36 pages, 16 figure

Exact time-dependent correlation functions for the symmetric exclusion process with open boundary

As a simple model for single-file diffusion of hard core particles we investigate the one-dimensional symmetric exclusion process. We consider an open semi-infinite system where one end is coupled to an external reservoir of constant density $\rho^\ast$ and which initially is in an non-equilibrium state with bulk density $\rho_0$. We calculate the exact time-dependent two-point density correlation function $C_{k,l}(t)\equiv -$ and the mean and variance of the integrated average net flux of particles $N(t)-N(0)$ that have entered (or left) the system up to time $t$. We find that the boundary region of the semi-infinite relaxing system is in a state similar to the bulk state of a finite stationary system driven by a boundary gradient. The symmetric exclusion model provides a rare example where such behavior can be proved rigorously on the level of equal-time two-point correlation functions. Some implications for the relaxational dynamics of entangled polymers and for single-file diffusion in colloidal systems are discussed.Comment: 11 pages, uses REVTEX, 2 figures. Minor typos corrected and reference 17 adde

Disordered Boson Systems: A Perturbative Study

A hard-core disordered boson system is mapped onto a quantum spin 1/2 XY-model with transverse random fields. It is then generalized to a system of spins with an arbitrary magnitude S and studied through a 1/S expansion. The first order 1/S expansion corresponds to a spin-wave theory. The effect of weak disorder is studied perturbatively within such a first order 1/S scheme. We compute the reduction of the speed of sound and the life time of the Bloch phonons in the regime of weak disorder. Generalizations of the present study to the strong disordered regime are discussed.Comment: 27 pages, revte

The critical Ising model via Kac-Ward matrices

The Kac-Ward formula allows to compute the Ising partition function on any finite graph G from the determinant of 2^{2g} matrices, where g is the genus of a surface in which G embeds. We show that in the case of isoradially embedded graphs with critical weights, these determinants have quite remarkable properties. First of all, they satisfy some generalized Kramers-Wannier duality: there is an explicit equality relating the determinants associated to a graph and to its dual graph. Also, they are proportional to the determinants of the discrete critical Laplacians on the graph G, exactly when the genus g is zero or one. Finally, they share several formal properties with the Ray-Singer \bar\partial-torsions of the Riemann surface in which G embeds.Comment: 30 pages, 10 figures; added section 4.4 in version

Singular open book structures from real mappings

We prove extensions of Milnor's theorem for germs with nonisolated singularity and use them to find new classes of genuine real analytic mappings $\psi$ with positive dimensional singular locus \Sing \psi \subset \psi^{-1}(0), for which the Milnor fibration exists and yields an open book structure with singular binding.Comment: more remark