Electrochemical studies of blocking properties of solid supported tethered lipid membranes on gold

The insulating properties of self-assembled thiolipid monolayers and tethered lipid bilayers on polycrystalline gold electrodes were studied by means of cyclic voltammetry (CV). These films were formed by two-step self-assembly processes. Electrochemical measurements of the heterogeneous electron transfer rate constant of different redox couples such as potassium ferrocyanide (K(4)[Fe(CN)(6)]) and dopamine (DP) were used to examine the molecular integrity and structural defects and pinholes within the monolayers. We demonstrate by means of cyclic voltammetry that the bilayer lipid membranes tethered to the gold surface are blocking, stable, yet retaining their dynamic properties and can be used as a model of the cell membrane.     

Hydrogen bonds seal single-molecule capsules

In the presence of methanol the tetrakis(benzoxazines) complex tetramethylammonium cation within the cavity, and the cavity is completely sealed by two intramolecular hydrogen bonds between amide groups. The Cl(-) anion is found external to the cavity. In CHCl(3), Me(4)N(+) is complexed within the cavity, but the Cl(-) anion acts as a stopper in the upper rim of the cavity, hydrogen-bonded to the amide groups. The solution results are supported by single-crystal X-ray structural studies of both the single-molecule molecular capsules, and those stoppered by Cl(-).     

Inverse sodium hydride: a theoretical study

A recent experimental investigation in which a salt containing the unusual charge distribution H(+) and Na(-) was synthesized and characterized prompted us to undertake an ab initio theoretical investigation. In the salt synthesized, the H(+) is bound to the nitrogen center of an amine and the Na(-) alkalide is "blocked" from approaching the protonated amine site by steric constraints of a cage structure. Although one expects that the Na(-) would deprotonate an unprotected R(3)N-H(+) cation, we decided to further explore this issue. Using extended atomic orbital basis sets and M?ller-Plesset and coupled-cluster treatments of electron correlation, we examined the relative stabilities of the prototype (Me)(3)N + NaH, (Me)(3)N + Na(+) + H(-), (Me)(3)N-H(+) + Na(-), and (Me)(3)N-Na(+) + H(-) as well as the ion pair complexes (Me)(3)N-H(+).Na(-) and (Me)(3)N-Na(+).H(-). The primary focus of this effort was to determine whether the high-energy (Me)(3)N-H(+).Na(-) ion pair, which is the analogue of what the earlier workers termed "inverse sodium hydride", might be stable with respect to proton abstraction under any reasonable solvation conditions (which we treated within the polarized continuum model). Indeed, we find that such ion pairs are metastable (i.e., locally geometrically stable with a barrier to dissociation) for solvents having dielectric constants below approximately 2 but spontaneously decompose into their constituent ions for solvents with higher dielectric constants. We suggest that amines with large proton affinities and/or metals with weaker MH bond strengths should be explored experimentally.     

A new approach to the synthesis of porphyrin-fullerene dyads

A new synthetic approach to porphyrin-fullerene dyads utilizing tetraphenylporphyrin (TPP) and three novel reactions (vicarious nucleophilic substitution, metathesis, and [4+2]-cycloaddition to fullerene) is described. 5-(4-Nitrophenyl)-10,15,20-triphenylporphyrin zinc complex reacts with the carbanion of chloromethyl para-tolyl sulphone (which bears a leaving group Cl at the carbanionic center), affording the nucleophilic substitution of hydrogen product containing a CH2SO2Tol group. The product obtained when alkylated with an alkyl halide (bearing an acetylenic function in the terminal position), followed by the cross-enyne metathesis reaction (with the use of an efficient ruthenium catalyst), resulted in the formation of a TPP-diene building block. Its Diels-Alder reaction with C60-fullerene led to the title dyad--a new artificial photosynthetic model. This method opens up the possibility for synthesis of dyads with variable distances between chromophores, depending on the type of the alkyl halides used.     

Static and Dynamic Equilibria in Games With Continuum of Players

This paper is a study of a general class of deterministic dynamic games with an atomless measure space of players and an arbitrary time space. The payoffs of the players depend on their own strategy, a trajectory of the system and a function with values being finite dimensional statistics of static profiles. The players' available decisions depend on trajectories of the system.The paper deals with relations between static and dynamic open-loop equilibria as well as their existence. An equivalence theorem is proven and theorems on the existence of a dynamic equilibrium are shown as consequences.     

Amplification of changes of a thin film's macromolecular structure into macroscopic reaction-diffusion patterns

A reaction-diffusion process induced from a micronetwork geometry amplifies changes in the molecular structure of a thin gel film into macroscopic readout patterns. When the gel undergoes a helix-to-coil phase transition, the patterns formed by RD switch from symmetry-broken to symmetric ones. Theoretical analysis explains how the system reconfigures internally in response to mass transfer between the applied network and the probed film.     

Synthesis of a cisplatin derivative from lithocholic acid

A new steroidal-platinum(II) hybrid compound was synthesized using a simple and efficient methodology. The synthesis was performed by a convergent approach with cross metathesis (CM) as a key step. An olefin derived from lithocholic acid and a vinyl substituted ethylenediamine derived from l-serine were used as chiral building blocks, which were combined in the CM step. The most important advantage of this method was the utilization of l-serine as a cheap, stereoisomerically pure substrate. A steroid with a diamino system in the side chain was subjected to reaction with potassium tetrachloroplatinate to obtain the target platinum(II) complex. Attempts to synthesize similar diamine systems using the asymmetric Strecker reaction were unsuccessful.     

Does a fluorinated Lewis acid catalyst change the molecular mechanism of the decomposition process of nitroethyl carboxylates?

The molecular mechanism of the decomposition reaction of nitroethyl benzoates catalyzed by Lewis acids based on boron element—BH₃ and BF₃—was studied using density functional theory methods. These reactions take place much faster than the uncatalyzed process. However, the presence of fluorinated Lewis acids has a unique influence on the molecular mechanism. In the case of BF₃, a change from a one-step mechanism to a two-step one involving a zwitterionic intermediate is observed.