Studying electron transfer through alkanethiol self-assembled monolayers on a hanging mercury drop electrode using potentiometric measurements

A new approach based on measuring the change of the open-circuit potential (OCP) of a hanging mercury drop electrode (HMDE), modified with alkanethiols of different chain length conducted in a solution containing a mixture of Ru(NH3)6(2+) and Ru(NH3)6(3+) is used for studying electron transfer across the monolayer. Following the time dependence of the OCP allowed the extraction of the kinetic parameters, such as the charge transfer resistance (R(ct)) and the electron transfer rate constant (k(et)), for different alkanethiol monolayers. An electron tunneling coefficient, beta, of 0.9 A(-1) was calculated for the monolayers on Hg.     

The fundamental group of the complement of the branch curve of the second Hirzebruch surface

In this paper we prove that the Hirzebruch surface F_2,(2,2) embedded in supports the conjecture on the structure and properties of fundamental groups of complement of branch curves of generic projections, as laid out in [M. Teicher, New Invariants for surfaces, Contemp. Math. 231 (1999) 271–281]. We use the regeneration from [M. Friedman, M. Teicher, The regeneration of a 5-point, Pure and Applied Mathematics Quarterly 4 (2) (2008) 383–425. Fedor Bogomolov special issue, part I], the van Kampen theorem and properties of -groups [M. Teicher, On the quotient of the braid group by commutators of transversal half-twists and its group actions, Topology Appl. 78 (1997) 153–186], where is a quotient of the braid group B_n, for n=16.     

The fundamental group of the complement of the branch curve of ℂℙ1 × T

Denoting by T the complex projective torus, we can embed the surface CP^1 × T in CP^5. In this paper we compute the fundamental group of the complement of the branch curve of this surface. Since the embedding is not ＂ample enough＂, the embedded surface does not belong to the classes of surfaces where the fundamental group is virtually solvable： a property which holds for these groups for ＂ample enough＂ embeddings. On the other hand, as it is the first example of this computation for non simply-connected surfaces, the structure of this group （as shown in this paper） give rise to the extension of the conjecture regarding the structure of those fundamental groups of any surface.     

Impact of membrane cholesterol content on the resistance of vesicles to surfactant attack

Vesicle leakage experiments were carried out to establish how cholesterol content regulates membrane permeability as induced by surfactant exposure. Vesicles containing up to 50% cholesterol were examined. Four different surfactants were chosen as membrane perturbants, including nonoxynol-9 which is commonly used in spermicidal formulations. As part of this study, we establish that the extrusion procedure commonly used to fabricate unilamellar vesicles does not unintentionally alter the desired composition of these model membrane systems. The kinetics of the leakage process is well characterized by a single exponential rate of release, similar to the form seen in the absence of membrane cholesterol. Our leakage experiments show that membranes become more resistant toward surfactant attack, in direct proportion with cholesterol content. This rise in resistance is surfactant specific. Above 30%, all membranes show positive deviation from the linear increase in resistance with increasing cholesterol content. Two other sterols, dihydrocholesterol and coprostanol, were also found to increase membrane resistance and behaved similarly despite a key difference in molecular structure. A peculiar leakage response was observed when membranes were exposed to the surfactant sodium dodecyl sulfate (SDS) above its critical micelle concentration. Our findings support the hypothesis that SDS micelles solubilize phospholipid molecules, creating a membrane with higher cholesterol content that is extremely resistant to perturbation.     

Small-angle neutron scattering from aqueous dispersions of single-walled carbon nanotubes with pluronic F127 and poly(vinylpyrrolidone)

Amphiphilic block copolymers are excellent dispersants for single-walled carbon nanotubes (SWCNT) in aqueous environments, where their noncovalent attachments do not affect the π chemical bonding. In this small-angle neutron scattering (SANS) study, we investigate whether the coverage of Pluronic F127 polymers around the CNTs depends on the solution concentration in the range of 1-6% (w/w). The observations indicate that at these concentrations the SWCNT surface is fully saturated at about 14 chains per unit length of 100 ?. Furthermore, we seek to verify whether the unusual effect observed in a previous study by contrast variation, interpreted as being due to a dense hydration layer around the polymer chains, also appears using a homopolymer (polyvinylpyrrolidone - PVP) that does not contain poly(ethylene oxide) (PEO) units. The SANS patterns showed again a minimal intensity value at much higher solvent composition (75% D(2)O) than the expected value of 29% D(2)O. The minimum scattering curve exhibited a nearly q(-1) power law at small angles, an indication of rodlike entities. A model of a CNT thin bundle with loosely adsorbed polymer chains around it (core-chains) was reasonably well fitted to the data. The polymer chains are assumed to be surrounded by a water layer with a slightly higher density than bulk water, having partial selectivity for D(2)O.     

Analogues of uracil nucleosides with intrinsic fluorescence (NIF-analogues): synthesis and photophysical properties

Uridine cannot be utilized as fluorescent probe due to its extremely low quantum yield. For improving the uracil fluorescence characteristics we extended the natural chromophore at the C5 position by coupling substituted aromatic rings directly or via an alkenyl or alkynyl linker to create fluorophores. Extension of the uracil base was achieved by treating 5-I-uridine with the appropriate boronic acid under the Suzuki coupling conditions. Analogues containing an alkynyl linker were obtained from 5-I-uridine and the suitable boronic acid in a Sonogashira coupling reaction. The uracil fluorescent analogues proposed here were designed to satisfy the following requirements: a minimal chemical modification at a position not involved in base-pairing, resulting in relatively long absorption and emission wavelengths and high quantum yield. 5-((4-Methoxy-phenyl)-trans-vinyl)-2'-deoxy-uridine, 6b, was found to be a promising fluorescent probe. Probe 6b exhibits a quantum yield that is 3000-fold larger than that of the natural chromophore (Φ 0.12), maximum emission (478 nm) which is 170 nm red shifted as compared to uridine, and a Stokes shift of 143 nm. In addition, since probe 6b adopts the anti conformation and S sugar puckering favored by B-DNA, it makes a promising nucleoside analogue to be incorporated in an oligonucleotide probe for detection of genetic material.