Impact of reductive cleavage of an intramolecular disulfide bond containing cationic gemini surfactant in monolayers and bilayers

The properties of a novel disulfide-bond-containing gemini surfactant bis[N,N-dimethyl-N-hexadecyl-N-(2-mercaptoethyl)ammonium bromide] disulfide (DSP) were studied using a Langmuir balance, supported monolayers, differential scanning calorimetry, giant vesicles, and LUVs. In 150 mM NaCl the cmc for DSP was 7.5 microM whereas that of the monomer N,N-dimethyl-N-hexadecyl-N-(2-mercaptoethyl)ammonium bromide (MSP) was 12.1 microM. Both surfactants exhibited single endotherms upon DSC, with peak temperatures Tm at 21.7 and 20.1 degrees C for DSP and MSP, respectively. The endotherm for MSP was significantly broader indicating less cooperative melting. Both in monolayers and in vesicles reductive cleavage of the disulfide bond of DSP could be obtained by glutathione (GSH). For Langmuir films of DSP the addition of GSH into the subphase led to a decrease in surface pressure pi as well as surface dipole potential psi. Although the cleavage by GSH was significantly slower in the presence of a charge saturating concentration of DNA, it did not prevent the reaction. The resulting monomers detached from supported monolayers, leading to loss of affinity of the surface for DNA. Disruption of giant vesicles containing DSP within approximately 30 s following a local injection of GSH was observed, revealing membrane destabilization.     

Role of the spacer stereochemistry on the aggregation properties of cationic gemini surfactants

The preparation and characterization of three stereoisomeric cationic gemini surfactants, 2,3-dimethoxy-1,4-bis(N-hexadecyl-N,N-dimethylammonio)butane dibromide, are described. The aggregation properties have been studied by fluorescence, electrical conductivity, and quasi-elastic light scattering. A conformational study of the surfactant headgroups has been performed by molecular mechanics calculations to investigate the effect of the stereogenic centers on the surfactant molecular shape and therefore on the different organizations of the monomers in the aggregates. Results show that the stereochemistry of the spacer strongly influences the aggregation behavior of the diasteromeric gemini in water.     

Synthesis, multiphase characterization, and helicity control in chiral DACH-linked oligothiophenes

A new class of chiral oligothiophenes is described. Mono-, bi-, ter-, and quarterthiophenes have been linked to enantiopure trans-1,2-cyclohexanediamine (DACH) via diamino or diimino moieties. The stereochemistry of DACH, the type of linker, and oligothiophene size determine the conformational flexibility of these molecules and consequently their molecular and supramolecular helicity in solution and in the solid state. The case of diaminobis(bithiophene), which inverts helicity and shows chiral amplification in the transition from solution to film, is described in detail. Based on the combined use of circular dichroism in solution and in the solid state, single-crystal/thin-film X-ray diffraction, and polarized optical microscopy, a working mechanism has been proposed to explain this unexpected behavior.     

Determination of nitrite, nitrate, and glucose-6-phosphate in muscle tissues and cured meat by IC/MS

The endogenous nitrate concentration in fresh meat and the residual nitrate and nitrite contents after curing are related to food quality and safety. Most ion chromatography (IC) methods suffer from interferences, especially in fresh meat samples, in which the endogenous nitrate content is low, and in cured meat products, in which other nitrogenous compounds can interfere with the separation of inorganic anions. One of the major classes of interfering compounds in fresh meat are sugar phosphates, which originate from glycolysis during the conversion of muscle glycogen to lactic acid. Nitrate can be separated from interfering compounds with a high-capacity anion-exchange column that was manufactured for use with hydroxide eluents (i.e., hydroxide-selective). This column has a different selectivity than traditional IC columns that use carbonate eluents and facilitates the determination of nitrate in both fresh and cured meats. Nitrate was detected by both suppressed conductivity measurement and mass spectrometry (MS). The identifications of nitrate and glucose-6-phosphate were confirmed by MS detection. The described IC/MS method is robust, sensitive to nitrate concentrations as low as 0.10 mg/kg, and can determine sugar phosphates that are useful for monitoring meat freshness. We successfully used this method to determine nitrate in nearly 100 muscle tissues and cured meat samples.     

Double Vivaldi antenna for wireless optical networks on chip

In this paper we present a double plasmonic Vivaldi antenna for on-chip optical wireless communication. The proposed antenna is a two-element broadside array fed by a silicon waveguide. The designs of the power splitter and of the hybrid Si-plasmonic coupler used for antenna excitation are described in detail. The array radiation characteristics are optimized through Finite Difference Time Domain simulations and the performance of a point-to-point link is evaluated. The proposed double Vivaldi array increases the gain of 3 dB with respect to a single antenna, improving the received power on a link of 6 dB when the double antenna is used for both transmitting and receiving sections.     

Analysis of Nonlinear Poro-Elastic and Poro-Visco-Elastic Models

We consider the initial and boundary value problem for a system of partial differential equations describing the motion of a fluid–solid mixture under the assumption of full saturation. The ability of the fluid phase to flow within the solid skeleton is described by the permeability tensor, which is assumed here to be a multiple of the identity and to depend nonlinearly on the volumetric solid strain. In particular, we study the problem of the existence of weak solutions in bounded domains, accounting for non-zero volumetric and boundary forcing terms. We investigate the influence of viscoelasticity on the solution functional setting and on the regularity requirements for the forcing terms. The theoretical analysis shows that different time regularity requirements are needed for the volumetric source of linear momentum and the boundary source of traction depending on whether or not viscoelasticity is present. The theoretical results are further investigated via numerical simulations based on a novel dual mixed hybridized finite element discretization. When the data are sufficiently regular, the simulations show that the solutions satisfy the energy estimates predicted by the theoretical analysis. Interestingly, the simulations also show that, in the purely elastic case, the Darcy velocity and the related fluid energy might become unbounded if indeed the data do not enjoy the time regularity required by the theory.     

Vertical link solutions for multilayer optical-networks-on-chip topologies

This paper presents two different approaches that may allow the optical interconnection between superposed levels of multilayer photonic circuits as, for example, in optical-networks-on-chip. The first configuration is based on multi-mode interference devices, while the second one exploits multiple stacked directional couplers. The issues concerning the analytical and numerical design of such devices are discussed, together with a performance analysis in terms of efficiency and footprint.     

Molecular dynamics reveal that isoDGR-containing cyclopeptides are true αvβ3 antagonists unable to promote integrin allostery and activation

Ain't got that swing(-out): The cyclopeptide isoDGR is emerging as a new αvβ3 integrin binding motif. Agreement between the results of computational and biochemical studies reveals that isoDGR-containing cyclopeptides are true αvβ3 integrin antagonists that block αvβ3 in its inactive conformation (see scheme). isoDGR-based ligands may give αvβ3 antagonists without paradoxical effects.     

Analysis of a unilateral contact problem taking into account adhesion and friction

In this paper, we investigate a contact problem between a viscoelastic body and a rigid foundation, when both the effects of the (irreversible) adhesion and of the friction are taken into account. We describe the adhesion phenomenon in terms of a damage surface parameter according to Frémond?s theory, and we model unilateral contact by Signorini conditions, and friction by a nonlocal Coulomb law. All the constraints on the internal variables as well as the contact and the friction conditions are rendered by means of subdifferential operators, whence the highly nonlinear character of the resulting PDE system. Our main result states the existence of a global-in-time solution (to a suitable variational formulation) of the related Cauchy problem. It is proved by an approximation procedure combined with time discretization.