Chemical applications of group theory and topology

The following procedure is described for investigating the qualitative dynamics of simple chemical systems: 1) A so-called influence diagram is generated representing the relationships between the reference reactants (phase-determining intermediates); 2) This influence diagram is used to generate a truth table indicating possible transitions between state vectors representing the signs of the time derivatives of of the reference reactant concentrations; 3) The truth table is used to determine a state transition diagram representing the flow topology around unstable equilibrium points; 4) The characteristic equation of the adjacency matrix of the influence diagram is solved in order to determine the presence of such unstable equilibrium points. The two types of qualitative dynamics possible for chemical systems containing two reference reactants and one feedback circuit are bifurcation between two attracting regions (bistability) and limit cycle oscillation. However, in two reference reactant systems oscillation requires an additional self-activating loop to generate the unstable equilibrium point required for its realization. Bistability and limit cycle oscillation are also two of the possible types of qualitative dynamics for chemical systems containing three reference reactants. However, chemical systems with three reference reactants and two or more feedback circuits can also contain interlocking limit cycles, which can lead to toroidal oscillations or chaos. The influence diagrams are given for the systems exhibiting these various types of dynamic behavior along with a summary of the important properties of all 729 possible influences for simple chemical systems containing three reference reactants.     

New insights into ethene epoxidation on two oxidized Ag[111] surfaces

Reaction mechanisms and activation energies for the complete conversion of ethene to ethene epoxide on two recently characterized oxidized Ag{111} surfaces have been determined from density functional theory. On both surfaces, epoxidation proceeds through a two-step nonconcerted mechanism via an oxametallacycle intermediate. The key implications are that both surfaces are active and that epoxidation can take place over a wide O coverage regime.     

Nanoclusters of Silicon and Germanium

Synthetic routes for the preparation of Si or Ge nanoclusters as gaseous species, colloids, supported composites, or as unsupported powders are reviewed along with selected characterization data. The optical properties of these and related materials, such as porous Si, are summarized with particular emphasis on photo- or electroluminescence phenomena. Research opportunities related to Si and Ge cluster chemistry are suggested.     

Binding Aedes aegypti densonucleosis virus to ion exchange membranes

Experimental and numerical results for binding Aedes aegypti densonucleosis virus (AeDNV) using anion and cation exchange membranes are presented. AeDNV particles are adsorbed by anion and cation exchange membranes providing the virus particles and membranes are oppositely charged. Q membranes which are strongly basic anion exchangers were the most effective. Dynamic and static capacities for Q membranes were found to be similar. A numerical model is proposed which assumes a log normal pore size distribution. By estimating the required parameters from static binding experiments, the model may be used to calculate the breakthrough curve for virus adsorption.     

Importance of dynamic surface tension to the residual water content of fabrics

At the end of the final spin cycle of the laundry process, the residual moisture content (RMC) of fabric is directly related to the dynamic surface tension of the residual water in the fabric. The LaPlace equation for capillary rise predicts that the capillary rise of solutions in a capillary is proportional to the surface tension at the air-liquid interface. If fabric can be considered to be a large ensemble of capillaries due to interfiber spacing, then the RMC of fabrics will be directly related to the surface tension of residual solution in the fabric. The use of a tailored rinse additive has the potential to decrease the surface tension of solution significantly, thus leading to a decrease in the residual water content of the fabric. It is expected that as the surfactant concentration increases the surface tension decreases. Hence, the RMC of fabrics must decrease with increasing surfactant concentration. However, a peak is observed in the RMC of fabrics before the critical micelle concentration (CMC) is reached. Prior to the CMC, it is proposed that a sudden adsorption of surfactant is occurring on the fabric surface leading to a decrease in bulk monomer concentration. The decrease in free monomer concentration should result in an increase in the equilibrium surface tension of the residual solution leading to a concomitant increase in RMC. Because the dynamic surface tension is measured on a short time scale (on the order of milliseconds), there will be less adsorption of monomer onto the newly created air-liquid interface of the bubbles during the measurement process. This decrease in adsorption should lead to a pronounced increase in the dynamic surface tension. This indeed was observed. The RMC correlates very well with the dynamic surface tension of the residual solution.     

Antiferromagnetic three-dimensional order induced by carboxylate bridges in a two-dimensional network of [Cu3(dcp)2(H2O)4] trimers

A new Cu(II) complex, [Cu(3)(dcp)(2)(H(2)O)(4)](n), with the ligand 3,5-pyrazoledicarboxylic acid monohydrate (H(3)dcp) has been prepared by hydrothermal synthesis, and it crystallizes in the monoclinic space group P2(1)/c with a = 11.633(2) A, b = 9.6005(14) A, c = 6.9230(17) A, beta = 106.01(2) degrees, and Z = 2. In the solid state structure of [Cu(3)(dcp)(2)(H(2)O)(4)](n), trinuclear [Cu(3)(dcp)(2)(H(2)O)(4)] repeating units in which two dcp(3-) ligands chelate the three Cu(II) ions with the central Cu(II) ion, Cu(1) (on an inversion center), link to form infinite 2D sheets via syn-anti equatorial-equatorial carboxylate bridges between Cu(2) atoms in adjacent trimers. These layers are further linked by syn-anti axial-equatorial carboxylate bridging between Cu(1) atoms in adjacent sheets resulting in the formation of a crystallographic 3D network. A detailed analysis of the magnetic properties of [Cu(3)(dcp)(2)(H(2)O)(4)](n) reveals that the dcp(3-) ligand acts to link Cu(II) centers in three different ways with coupling constants orders of magnitude apart in value. In the high temperature region above 50 K, the dominant interaction is strongly antiferromagnetic (J/k(B) = -32 K) within the trimer units mediated by the pyrazolate bridges. Below 20 K, the trimer motif can be modeled as an S = 1/2 unit. These units are coupled to their neighbors by a ferromagnetic interaction mediated by the syn-anti equatorial-equatorial carboxylate bridge. This interaction has been estimated at J(2D)/k(B) = +2.8 K on the basis of a 2D square lattice Heisenberg model. Finally, below 3.2 K a weak antiferromagnetic coupling (J(3D)/k(B) = -0.1 K) which is mediated by the syn-anti axial-equatorial carboxylate bridges between the 2D layers becomes relevant to describe the magnetic (T, H) phase diagram of this material.     

The configurational dependence of binding free energies: A Poisson–Boltzmann study of Neuraminidase inhibitors

The linear finite difference Poisson-Boltzmann (FDPB) equation is applied to the calculation of the electrostatic binding free energies of a group of inhibitors to the Neuraminidase enzyme. An ensemble of enzyme-inhibitor complex conformations was generated using Monte Carlo simulations and the electrostatic binding free energies of subtly different configurations of the enzyme-inhibitor complexes were calculated. It was seen that the binding free energies calculated using FDPB depend strongly on the configuration of the complex taken from the ensemble. This configurational dependence was investigated in detail in the electrostatic hydration free energies of the inhibitors. Differences in hydration energies of up to 7 kcal mol^–1 were obtained for root mean square (RMS) structural deviations of only 0.5 Å. To verify the result, the grid size and parameter dependence of the calculated hydration free energies were systematically investigated. This showed that the absolute hydration free energies calculated using the FDPB equation were very sensitive to the values of key parameters, but that the configurational dependence of the free energies was independent of the parameters chosen. Thus just as molecular mechanics energies are very sensitive to configuration, and single-structure values are not typically used to score binding free energies, single FDPB energies should be treated with the same caution.     

Methodology for the synthesis of the core EFGH rings of diazonamide A

Conversion of substituted 2-oxindoles into 2-thionoindoles followed by Raney nickel desulfurization provides a mild method for synthesizing the core EFGH rings of diazonamide A.