Screening of pi-basic naphthalene and anthracene amplifiers for pi-acidic synthetic pore sensors

Synthetic ion channels and pores attract current attention as multicomponent sensors in complex matrixes. This application requires the availability of reactive signal amplifiers that covalently capture analytes and drag them into the pore. pi-Basic 1,5-dialkoxynaphthalenes (1,5-DAN) are attractive amplifiers because aromatic electron donor-acceptor (AEDA) interactions account for their recognition within pi-acidic naphthalenediimide (NDI) rich synthetic pores. Focusing on amplifier design, we report here the synthesis of a complete collection of DAN and dialkoxyanthracene amplifiers, determine their oxidation potentials by cyclic voltammetry, and calculate their quadrupole moments. Blockage experiments reveal that subtle structural changes in regioisomeric DAN amplifiers can be registered within NDI pores. Frontier orbital overlap in AEDA complexes, oxidation potentials, and, to a lesser extent, quadrupole moments are shown to contribute to isomer recognition by synthetic pores. Particularly important with regard to practical applications of synthetic pores as multianalyte sensors, we further demonstrate that application of the lessons learned with DAN regioisomers to the expansion to dialkoxyanthracenes provides access to privileged amplifiers with submicromolar activity.     

Rheological properties of asphalt/SBS/clay blends

The effect of the addition of clay as a third component in polymer modified asphalts has been investigated. After a preliminary investigation on the binary asphalt/clay and polymer/clay blends, the tertiary blends were prepared by adding the clay and polymer to the asphalt, either separately or in the form of a premixed master batch. Intercalated nanocomposites with comparable interlayer distances and glass transition temperatures were obtained in both cases. However, the results show that the mixing procedure significantly affected the final rheological properties. The master curves built in the linear viscoelastic range and represented in both the frequency and the temperature domains help to visualize and evaluate such differences.     

Enolate Stabilization by Anion–π Interactions: Deuterium Exchange in Malonate Dilactones on π‐Acidic Surfaces

Of central importance in chemistry and biology, enolate chemistry is an attractive topic to elaborate on possible contributions of anion–π interactions to catalysis. To demonstrate the existence of such contributions, experimental evidence for the stabilization of not only anions but also anionic intermediates and transition states on π‐acidic aromatic surfaces is decisive. To tackle this challenge for enolate chemistry with maximal precision and minimal uncertainty, malonate dilactones are covalently positioned on the π‐acidic surface of naphthalenediimides (NDIs). Their presence is directly visible in the upfield shifts of the α‐protons in the ¹H NMR spectra. The reactivity of these protons on π‐acidic surfaces is measured by hydrogen–deuterium (H–D) exchange for 11 different examples, excluding controls. The velocity of H–D exchange increases with π acidity (NDI core substituents: SO₂R>SOR>H>OR>OR/NR₂>SR>NR₂). The H–D exchange kinetics vary with the structure of the enolate (malonates>methylmalonates, dilactones>dithiolactones). Moreover, they depend on the distance to the π surface (bridge length: 11–13 atoms). Most importantly, H–D exchange depends strongly on the chirality of the π surface (chiral sulfoxides as core substituents; the crystal structure of the enantiopure (R,R,P)‐macrocycle is reported). For maximal π acidity, transition‐state stabilizations up to ?18.8 kJ mol^?1 are obtained for H–D exchange. The Brønsted acidity of the enols increases strongly with π acidity of the aromatic surface, the lowest measured pK_a=10.9 calculates to a ΔpK_a=?5.5. Corresponding to the deprotonation of arginine residues in neutral water, considered as “impossible” in biology, the found enolate–π interactions are very important. The strong dependence of enolate stabilization on the unprecedented seven‐component π‐acidity gradient over almost 1 eV demonstrates quantitatively that such important anion–π activities can be expected only from strong enough π acids.     

Ground states of a nonlinear curl-curl problem in cylindrically symmetric media

We consider the nonlinear curl-curl problem \({\nabla\times\nabla\times U + V(x) U= \Gamma(x)|U|^{p-1}U}\) in \({\mathbb{R}^3}\) related to the Kerr nonlinear Maxwell equations for fully localized monochromatic fields. We search for solutions as minimizers (ground states) of the corresponding energy functional defined on subspaces (defocusing case) or natural constraints (focusing case) of \({H({\rm curl};\mathbb{R}^3)}\). Under a cylindrical symmetry assumption corresponding to a photonic fiber geometry on the functions V and \({\Gamma}\) the variational problem can be posed in a symmetric subspace of \({H({\rm curl};\mathbb{R}^3)}\). For a defocusing case \({{\rm sup} \Gamma < 0}\) with large negative values of \({\Gamma}\) at infinity we obtain ground states by the direct minimization method. For the focusing case \({{\rm inf} \Gamma > 0}\) the concentration compactness principle produces ground states under the assumption that zero lies outside the spectrum of the linear operator \({\nabla \times \nabla \times +V(x)}\). Examples of cylindrically symmetric functions V are provided for which this holds.     

Voltametric,Amperometric, and Chronopotentiometric Determination of Submicromolar Concentrations of Carboxin

New procedures for the determination of pesticide carboxin were developed using differential pulse voltammetry, HPLC with amperometric detection and chronopotentiometry at carbon paste electrode and reticulated vitreous carbon electrode, respectively. Developed procedures based on electrochemical oxidation of carboxin were successfully applied on the determination of carboxin in the model samples of drinking and river water. Limits of detection in samples of river water were in 10^?7 mol L^?1 concentration range for all procedures and electrodes used. All developed procedures proved to be sensitive, accurate and, due to the resistance of the electrode to the passivation, also simple to handle.     

Synthetic pores with sticky pi-clamps

In this report, we describe design, synthesis, evaluation and molecular dynamics simulations of synthetic multifunctional pores with pi-acidic naphthalenediimide clamps. Experimental evidence is provided for the formation of unstable but inert, heterogeneous and acid-insensitive dynamic tetrameric pores that are sensitive to base and ionic strength. Blockage experiments reveal that the introduction of aromatic electron donor-acceptor interactions provides access to the selective recognition of pi-basic intercalators within the pore. This breakthrough is important for the application of synthetic pores as multianalyte sensors.     

Self-organization of water in lithium/nitrobenzene system

The effect of lithium ion on the ordering of water in water-saturated nitrobenzene has been probed by 2H NMR, diffusion ordered spectroscopy and neutron scattering. It was shown that increased water concentration in LiClO4/wet nitrobenzene results in the formation of a metastable solvatomer with mixed water and nitrobenzene character, Li+(W/NB). This species is shown to decay over hours to two solvatomers, one dominated by nitrobenzene Li+(NB) and the other dominated by water Li+(W). To confirm the assignment of these solvation states, diffusion ordered deuterium NMR spectroscopy has been used to elucidate the hydrodynamic radii of these solvatomers. Neutron scattering yields vibrational spectroscopy information that shows how addition of lithium to the nitrobenzene/water system results in relatively slow self-organization of the water environment (hours).     

Voltammetric determination of aminobiphenyls at a boron-doped nanocrystalline diamond film electrode

Voltammetric behavior of 2-aminobiphenyl, 3-aminobiphenyl, and 4-aminobiphenyl at a boron-doped nanocrystalline diamond film electrode was investigated using cyclic voltammetry and differential pulse voltammetry. Optimum conditions have been found for the determination of those genotoxic substances by differential pulse voltammetry at the above given electrode in the concentration range of 2 × 10⁻⁷ to 1 × 10⁻⁵ mol/L.     

Finite difference Poisson-Boltzmann electrostatic calculations: Increased accuracy achieved by harmonic dielectric smoothing and charge antialiasing

A common problem in the calculation of electrostatic potentials with the Poisson-Boltzmann equation using finite difference methods is the effect of molecular position relative to the grid. Previously a uniform charging method was shown to reduce the grid dependence substantially over the point charge model used in commercially available codes. In this article we demonstrate that smoothing the charge and dielectric values on the grid can improve the grid independence, as measured by the spread of calculated values, by another order of magnitude. Calculations of Born ion solvation energies, small molecule solvation energies, the electrostatic field of superoxide dismutase, and protein-protein binding energies are used to demonstrate that this method yields the same results as the point charge model while reducing the positional errors by several orders of magnitude. © 1997 by John Wiley & Sons, Inc.