Can the ebselen derivatives catalyze the isomerization of peroxynitrite to nitrate?

The reaction of ebselen and its derivatives (1-7) with peroxynitrite anion (ONOO(-); PN) has been studied in gas phase and in aqueous, dichloromethane, benzene, and cyclohexane solutions using B3LYP/6-311+G(d,p)//B3LYP/6-311G(d,p) and PCM-B3LYP/6-311+G(d,p)//B3LYP/6-311G(d,p) approaches, respectively. It was shown that the reaction of 2 (R=H) with PN proceeds via 2 + PN --> 2-PN --> 2-TS1 (O-O activation) --> 2-O(NO(2)(-)()) --> 2-SeO + NO(2)(-) pathway with a rate-determining barrier of 25.3 (14.8) kcal/mol at the NO(2)(-) dissociation step (numbers presented without parentheses are enthalpies, and those in parentheses are Gibbs free energies). The NO(3)(-) formation process, starting from the complex 2-O(NO(2)(-)()), requires by (7.9) kcal/mol more energy than the NO(2)(-) dissociation process and is unlikely to compete with the latter. Thus, in the gas phase, the peroxynitrite --> nitrate isomerization catalyzed by complex 2 is unlikely to occur. It is shown that the NO(3)(-) formation process is slightly more favorably than the NO(2)(-) dissociation process for complex 4, with a strongest electron-withdrawing ligand R=CF(3). Therefore, complex 4 (as well as complex 6 with R=OH) is predicted to be a good catalyst for peroxynitrite <--> nitrite isomerization in the gas phase. Solvent effects (a) change the rate-determining step of the reaction 2 + PN from NO(2)(-) dissociation in the gas phase to O-O activation, which occurs with barriers of (13.9), (8.4), (8.4), and (8.2) kcal/mol in water, dichloromethane, benzene, and cyclohexane, respectively, and (b) significantly reduce the NO(2)(-) dissociation energy, while only slightly destabilizing the NO(3)(-) formation barrier, and make the peroxynitrite <--> nitrate isomerization process practically impossible, even for complex 4.     

Ground state and phase transitions in a system of arg-cysteamines self-assembled on a Au(111) crystal surface

The translational and orientation order of arg-cysteamine molecules chemiabsorbed on the Au(111) crystal surface is considered. Couplings between carbon, nitrogen, and hydrogen atoms of the n-alkanethiols are approximated by the Lennard-Jones potential. Moreover, hydrogen bonds between oxygen and nitrogen and dipole-dipole interactions of the dipole moments of different atomic groups are taken into account. It is found that molecules are arranged in a 2 x 2 lattice and have the total symmetry C6 x Z2. The critical temperature of the phase transition to the tilted state Tc1, which breaks the symmetry C6, is estimated to be extremely high. The spontaneous breakdown of the remaining symmetry Z2 leads to the twisted state of the molecules and has the critical temperature Tc2=340 K.     

[C10N2H10][ZnCl(HPO4)]2: A New Templated Zincophosphate Containing Tetrahedral Nets with 63 Topology

The crystal structure of [C₁₀N₂H₁₀][ZnCl(HPO₄)]₂ contains corrugated tetrahedral layers with 6³ topology. Charge balance is achieved by insertion of diprotonated 4,4′‐bipyridine between the layers. Crystal data: monoclinic, P2₁/n (no. 14), a = 4.8832(2) Å, b = 22.673(2) Å, c = 8.1643(4) Å, β = 104.02(1)°; V = 877.0(1) ų; Z = 4; R1 = 0.041 and wR2 = 0.088 for 1836 reflections [I > 2σ(I)]. Tetrahedral layers are also observed in other organo‐ammonium templated compounds. However, their topologies are characterized by 4.8² nets. With the title compound a layered tetrahedral net with 6³‐topology is reported for the first time.     

A convenient approach to λ-phosphinines via interaction of phosphorylated 3-pyrrolidinocrotonitrile with 2-bromoacetophenones

The alkylation of 2-(diphenylphosphino)-3-pyrrolidin-1-ylbut-2-enenitrile with a set of bromoacetophenones has been studied. Cyclization of the phosphonium salts into 6-cyano-3-hydroxy-3-aryl-1,1-diphenyl-5-pyrrolidin-1-yl-1,2,3,4-tetrahydrophosphininium bromides under heating in the presence of catalytic amount of a base is discussed. Starting both from the acyclic and the cyclic phosphonium salts, new types of λ⁵-phosphinines have been synthesized.     

Sol-gel-derived biomaterials of silica and carrageenans

A new precursor, tetrakis(2-hydroxyethyl) orthosilicate (THEOS), introduced by Hoffmann et al. (J. Phys. Chem. B 106 (2002) 1528-1533), was used to synthesize monolithic hybrid biomaterials on the basis of silica and three main types of carrageenans, kappa-, iota-, and lambda-carrageenans. The advantage of THEOS over the currently applied TEOS and TMOS is in its complete solubility in water. This negated the need to add organic solvents, thus excluding a denaturating effect on biopolymers. In their turn, carrageenans introduced into the precursor solution made use of common catalysts unneeded to trigger the sol-gel transition. It was found that they promoted the mineralization, acting as a template for the inorganic component. The kinetics of sol-gel processes, mechanical properties, phase behavior, and structure of novel hybrid biomaterials were studied by dynamic rheology, differential scanning calorimetry, and scanning electron microscopy. The material properties were regulated by both the precursor and carrageenan. The increase of silicate concentration led to a rise in the stiffness and brittleness of the material, whereas the polysaccharide addition made it softer and more elastic. It was shown that the formation and properties of mixed gels were determined by the nature of carrageenan. kappa-Carrageenans brought about shrinkage of hybrid materials that led to water separation, while iota- and lambda-carrageenans did not induce the syneresis. This is in line with the difference in polysaccharide properties when they are in aqueous solutions without silicate. Furthermore, kappa- and iota-carrageenans experienced a thermoreversible phase transition in the hybrid materials owing to the helix-coil transition. This resulted in a step like change in the mechanical properties of mixed systems in the corresponding temperature range. lambda-Carrageenan is a nongelling polysaccharide, which is why the rheological parameters of its hybrid gel were unchanged with the temperature. It was found that the polysaccharides modified the structure of silica-based materials. They transformed a three-dimensional network of connected silica particles into that consisting of crossed fibers.     

Synthesis of new 4-(pyrimidin-4-yl)pyrazol-3-one derivatives

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Endotypes of partial equivalence relations

We classify all partial equivalence relations according to their endotype with respect to endotopisms and compute the cardinalities of endotopism semigroups (strong endotopism monoids, autotopism groups) of partial equivalence relations on a finite set.

     

Mössbauer study of iron in high oxidation states in the K–Fe–O system

Oxidation of metallic iron by potassium superoxide leads to the formation of ferrate(V). Under room temperature this compound is unstable and instantly decomposes by disproportionation mechanism. Grinding the substance into powder accelerates the decomposition process.     

Control of the Lyapunov exponents of dynamical systems in the plane with incomplete observation

Control linear systems in the plane are studied under the assumption of incomplete observation and incomplete control. In this situation ordinary static output controls may fail to stabilize the system. That is why special dynamic output feedback controls with finitely many states (hybrid feedback controls) are applied. Necessary and sufficient conditions are offered that guarantee exponential convergence/divergence of the solutions at an arbitrary rate. It is also shown that the general case can be reduced to two particular cases which are treated in detail.