Magnetic and transport properties of UPd2Sb

A new compound UPd₂Sb was prepared and studied by means of X-ray diffraction, magnetization, electrical resistivity, magnetoresistivity, thermoelectric power and specific heat measurements. The phase crystallizes with a cubic structure of the MnCu₂Al-type (s.g. ). It orders antiferromagnetically at T_N=55 K and exhibits a modified Curie-Weiss behaviour with reduced effective magnetic moment at higher temperatures. The electrical resistivity behaves in a manner characteristic of systems with strong electronic correlations, showing Kondo effect in the paramagnetic region and Kondo-like response to the applied magnetic field. The Seebeck coefficient exhibits a behaviour expected for scattering of conduction electrons on a narrow quasiparticle band near the Fermi energy. The low-temperature electronic specific heat in UPd₂Sb is moderately enhanced being about 81 mJ/mol K².     

Onsite hybridization between Ce 4f and 5d states as the indicator of the transition from Kondo insulator to metallic state in CeRhSb

We discuss and determine the conditions under which a Kondo-insulator phase is stable. We show for CeRhSb that the dependence of the onsite hybridization energy Vdf between the Ce 5d and Ce 4f states on the number of valence electrons or the unit cell volume is decisive for the hybridization Kondo gap formation. We also propose the method for determining the energy Vdf from the ab initio calculations. This approach supplies an accurate Kondo-insulator-metal transition in agreement with the recent experimental data.     

Model of prison riots

We present a model of a prison with two types of inmates. One (recidivists) is a better organized and has more influence on the formation of opinions, whereas the second one is more susceptible to the influence of internal and external pressure. We study, via computer simulations, the interplay between well-organized minority and the rest and how the final decision, like e.g. starting a riot, depends on such factors as: fraction of recidivists, their initial support of the riot and possibility of contacts among cells. We find that, as expected, the riot is more likely to start if there is more recidivists favoring it at the beginning. The influence of external factors (media) turned out to have a larger impact on the second group of prisoners. Contrary to a common practice, we show that in order to prevent riots it might be better not to block the inter-cell contacts.     

Computational study of the deamination reaction of cytosine with H2O and OH-

The mechanism for the deamination reaction of cytosine with H(2)O and OH(-) to produce uracil was investigated using ab initio calculations. Optimized geometries of reactants, transition states, intermediates, and products were determined at RHF/6-31G(d), MP2/6-31G(d), and B3LYP/6-31G(d) levels and for anions at the B3LYP/6-31+G(d) level. Single-point energies were also determined at B3LYP/6-31+G(d), MP2/GTMP2Large, and G3MP2 levels of theory. Thermodynamic properties (DeltaE, DeltaH, and DeltaG), activation energies, enthalpies, and free energies of activation were calculated for each reaction pathway that was investigated. Intrinsic reaction coordinate analysis was performed to characterize the transition states on the potential energy surface. Two pathways for deamination with H(2)O were found, a five-step mechanism (pathway A) and a two-step mechanism (pathway B). The activation energy for the rate-determining steps, the formation of the tetrahedral intermediate for pathway A and the formation of the uracil tautomer for pathway B, are 221.3 and 260.3 kJ/mol, respectively, at the G3MP2 level of theory. The deamination reaction by either pathway is therefore unlikely because of the high barriers that are involved. Two pathways for deamination with OH(-) were also found, and both of them are five-step mechanisms. Pathways C and D produce an initial tetrahedral intermediate by adding H(2)O to deprotonated cytosine which then undergoes three conformational changes. The final intermediate dissociates to product via a 1-3 proton shift. Deamination with OH(-), through pathway C, resulted in the lowest activation energy, 148.0 kJ/mol, at the G3MP2 level of theory.     

Folding Behavior of Polypeptides. A Monte Carlo Study of Simplified Models

A simple model of polypeptide chains was designed and studied. The chains were constructed on a flexible [310] lattice and consisted of united atoms located at the position of alpha carbons. Each united atom represented amino acid residues of two kinds: hydrophilic and hydrophobic. The sequence of the residues was assumed to be characteristic for α- and β-type of proteins. The force field used consisted of the long-range contact potential between polymer segments, the short range repulsion, and the local potential preferring conformational states characteristic for α-helices and β-strands. The Monte Carlo simulations of this model were carried out using the replica exchange technique coupled with the histogram method. The influence of temperature and the local potential on the size and internal structure of collapsed low temperature chains were studied. Thermodynamics of these systems consisting mainly of α and β secondary structures were determined. The properties of the coil-to-globule transition were presented and compared with other theoretical predictions and simulation results.     

High frequency faradaic rectification voltammetry at microelectrodes

An experimental setup for carrying out faradaic rectification measurements at micrometer-sized electrodes under potential control is described. A new method of data analysis is proposed that allows the determination of the standard rate constant and the electron-transfer coefficient of a fast charge transfer process without knowing the impedance of the microelectrode. This method is based on the frequency dependence of the shape of the faradaic rectification voltammograms (i.e., the average width of the peaks and the ratio of the peak heights) rather than on the magnitude of the faradaic rectification signal. The method was tested in the determination of heterogeneous electron transfer kinetics of Fe(CN)6(3-/4-) and Ru(NH3)6(2+/3+) in aqueous solutions on a platinum microelectrode (12.5 microm in radius) and ferrocene/ferrocinum redox couple in a dimethylformamide solution on a gold microelectrode (12.5 microm in radius).     

Lectin-carbohydrate affinity measured using a quartz crystal microbalance

The association of two molecules is described by two parameters, association equilibrium and association rate constants, which are characteristic for a given type of interaction. Usually, they are determined for interacting molecules dissolved in solution. However, for many applications one type of molecules is immobilized on a substrate, which may influence the binding kinetics. The studied complex of concanavalin A and carboxypeptidase Y belongs to the lectin-carbohydrate type of interaction involving the recognition of oligosaccharide moieties. The concanavalin A was immobilized on a gold electrode of quartz crystal, while carboxypeptidase Y was added to a buffer (Tris-buffered saline). The constants describing the association of the investigated molecules were determined on the basis of measurements performed using a quartz crystal microbalance in liquid. The obtained values were (0.59+/-0.01)x10(6) M(-1) for the association equilibrium constant and (5.6+/-0.1)x10(4) M(-1)s(-1) for the association rate constant. The saturation binding experiment gave another value of the association constant, (2.7+/-0.02)x10(6) M(-1). The comparison of obtained values with previously published ones verifies that the molecule orientation and binding site accessibility for specific ligands could influence the association equilibrium constant value. The presented measurements demonstrate the ability of a quartz crystal microbalance to detect and to evaluate the association process occurring between molecules.     

Modulation of calcium oxalate monohydrate crystallization by citrate through selective binding to atomic steps

The majority of human kidney stones are composed primarily of calcium oxalate monohydrate (COM) crystals. Thus, determining the molecular modulation of COM crystallization by urinary constituents is crucial for understanding and controlling renal stone disease. A comprehensive molecular-scale view of COM shape modification by citrate, obtained through a combination of in situ atomic force microscopy and molecular modeling, is presented here. We find that while the most important factors determining binding strength are coordination between COO- groups on citrate and Ca ions in the lattice, as well as H-bonds formed between the OH group of citrate and an oxalate group, the nonplanar geometry of the steps provides the most favorable environment due to the ability of the step-edge to accommodate all Ca-COO- coordinations with minimal strain. However, binding to all steps and terraces on the (010) face is much less favorable than on the (101) face due to electrostatic repulsion between oxalate and COO- groups. For example, the maximum binding energy, -166.5 kJ mol(-1), occurs for the [101] step on the (101) face, while the value for the [021] step on the (010) face is only -56.9 kJ mol(-1). This high selectivity leads to preferential binding to steps on the (101) face that pins step motion. Yet anisotropy in interaction strength on this face drives anisotropic changes in step kinetics that are responsible for shape modification of macroscopic COM crystals. Thus, the molecular scale growth kinetics and the bulk crystal habit are fully consistent with the simulations.     

pi-Conjugated conjoined double helicene via a sequence of three oxidative CC- and NN-homocouplings

Dimerization of planarized diamine 2 using benzoyl peroxide gave dihydrazine 1 in about 70% yield; that is, three dehydrogenations (one CC- and two NN-homocouplings) and two ring closures were attained in one synthetic step. Dihydrazine 1 may be viewed as a chiral pi-conjugated conjoined double helicene, with two homochiral [5]helicene-like fragments, annelated in their mid-sections. A relatively high barrier of approximately 35 kcal mol-1 for inversion of configuration for one of the [5]helicene-like helices in 1 was found.     

Nucleation-controlled multiphase transitions

Thermodynamics and kinetics of phase transitions in multiphase systems have been discussed. Thermodynamically admissible transitions have been identified and transition kinetics described in terms of the extended Kolmogoroff-Avrami-Evans model. Different combinations of transitions have been described as directed graphs. Graph nodes represented individual phases, graph edges--transitions. Superposition of parallel transitions in various mother phases, simultaneous transition of the same mother phase into different target phases, and successive (chain) transitions have been analyzed. Detailed solutions for a three-phase system consisting of one liquid phase and two polymorphic solid phases have been presented.