Modulating the Binding of Polycyclic Aromatic Hydrocarbons Inside a Hexacationic Cage by Anion–π Interactions

We report the template‐directed synthesis of BlueCage⁶⁺, a macrobicyclic cyclophane composed of six pyridinium rings fused with two central triazines and bridged by three paraxylylene units. These moieties endow the cage with a remarkably electron‐poor cavity, which makes it a powerful receptor for polycyclic aromatic hydrocarbons (PAHs). Upon forming a 1:1 complex with pyrene in acetonitrile, however, BlueCage?6 PF₆ exhibits a lower association constant K_a than its progenitor ExCage?6 PF₆. A close inspection reveals that the six PF₆^? counterions of BlueCage⁶⁺ occupy the cavity in a fleeting manner as a consequence of anion–π interactions and, as a result, compete with the PAH guests. This conclusion is supported by a one order of magnitude increase in the K_a value for pyrene in BlueCage⁶⁺ when the PF₆^? counterions are replaced by much bulkier anions. The presence of anion–π interactions is supported by X‐ray crystallography, and confirms the presence of a PF₆^? counterion inside its cavity.     

Boundary condition effects on multiscale analysis of damage localization

The choice of boundary conditions used in multiscale analysis of heterogeneous materials affects the numerical results, including the macroscopic constitutive response, the type and extent of damage taking place at the microscale and the required size of the Representative Volume Element (RVE). We compare the performance of periodic boundary conditions and minimal kinematic boundary conditions applied to the unit cell of a particulate composite material, both in the absence and presence of damage at the particle–matrix interfaces. In particular, we investigate the response of the RVE under inherently non-periodic loading conditions, and the ability of both boundary conditions to capture localization events that are not aligned with the RVE boundaries. We observe that, although there are some variations in the evolution of the microscale damage between the two methods, there is no significant difference in homogenized responses even when localization is not aligned with the cell boundaries.     

Fundamentals of stand‐off Raman scattering spectroscopy for explosive fingerprinting

The fact that a Raman spectrum may be considered the fingerprint of an interrogated target by providing specific information on the particular chemical structures of the molecules present, has boosted the use of Raman spectroscopy for explosives detection in homeland and security applications. Also, the possibility of direct and distant access to suspect targets by stand‐off Raman measurements makes this analytical technique a valuable tool in operational scenarios for security forces. The modest detection power as a result of the well‐known, inherently low efficiency of the Raman scattering requires a careful evaluation of the experimental parameters governing the analytical response of this technique, particularly in respect to the amenable distance to target, the data acquisition speed, and the sources of uncertainty in any given measurement. The present paper highlights the importance of adequate instrumental parameters of the sensor according to the operational scenario when analyzing unknown targets. Raman fingerprints collected from a wide range of high explosives and associated compounds under different analysis conditions and operational scenarios have been evaluated in terms of signal strength, signal‐to‐noise ratio, analytical sensitivity, and signal stability. Copyright © 2012 John Wiley & Sons, Ltd.     

On local search for the generalized graph coloring problem

Given an edge-weighted graph and an integer k, the generalized graph coloring problem is the problem of partitioning the vertex set into k subsets so as to minimize the total weight of the edges that are included in a single subset. We recall a result on the equivalence between Karush-Kuhn-Tucker points for a quadratic programming formulation and local optima for the simple flip-neighborhood. We also show that the quality of local optima with respect to a large class of neighborhoods may be arbitrarily bad and that some local optima may be hard to find.     

Amperometric determination of hydrogen peroxide with a manganese dioxide film-modified screen printed carbon electrode

A carbon thick film electrode modified with an MnO₂-film is investigated as an amperometric detector for hydrogen peroxide in flow-injection analysis (FIA). At an operating potential of +0.48 V vs. Ag/AgCl catalytic oxidation of the analyte is exploited for amperometric monitoring. Experimental parameters, such as pH of the carrier, working potential, flow rate and injection volume, are optimized. The amperometric signals are linearly proportional to the concentration of H₂O₂ in the range from 0.005 to 10 mg/L, showing a detection limit (3σ) of 2.3 μg/L. The method is applied to the determination of H₂O₂ in rain water and to a simple assay to quantify glucose in human plasma. Received: 29 January 1998 / Revised: 4 May 1998 / Accepted: 13 May 1998     

Pyrrolidinium Ionic Liquid Crystals

N‐Alkyl‐N‐methylpyrrolidinium cations have been used for the design of ionic liquid crystals, including a new type of uranium‐containing metallomesogen. Pyrrolidinium salts with bromide, bis(trifluoromethylsulfonyl)imide, tetrafluoroborate, hexafluorophosphate, thiocyanate, tetrakis(2‐ thenoyltrifluoroacetonato)europate(III) and tetrabromouranyl counteranions were prepared. For the bromide salts and tetrabromouranyl compounds, the chain length of the alkyl group C_nH_2n+1 was varied from eight to twenty carbon atoms (n=8, 10–20). The compounds show rich mesomorphic behaviour: highly ordered smectic phases (the crystal smectic E phase and the uncommon crystal smectic T phase), smectic A phases, and hexagonal columnar phases were observed, depending on chain length and anion. This work gives better insight into the nature and formation of the crystal smectic T phase, and the molecular requirements for the appearance of this highly ordered phase. This uncommon tetragonal mesophase is thoroughly discussed on the basis of detailed powder X‐ray diffraction experiments and in relation to the existing literature. Structural models are proposed for self‐assembly of the molecules within the smectic layers. In addition, the photophysical properties of the compounds containing a metal complex anion were investigated. For the uranium‐containing mesogens, luminescence can be induced by dissolving them in an ionic liquid matrix. The europium‐containing compound shows intense red photoluminescence with high colour purity.     

Infrared laser synthesis and properties of magnetic nano‐iron–polyoxocarbosilane composites

Nano‐magnetic, thermally stable iron‐based composites were obtained by a one‐step procedure consisting of continuous‐wave infrared laser‐induced and ethylene‐sensitized co‐pyrolysis of gaseous iron pentacarbonyl and hexamethyldisiloxane in argon. The simultaneously occurring formation of iron from iron pentacarbonyl and that of organosilicon polymer from hexamethyldisiloxane yield iron nanoparticles surrounded by an organosilicon polymer shell. The particles were characterized by spectral analyses, electron microscopy, thermal gravimetry and magnetic measurements. They become superficially oxidized in the atmosphere. Their composition, thermal behaviour and magnetic properties depend on the flow rates of the precursors and the total pressure of the procedure. Magnetization curves, exchange bias H_ex at T = 5 K and AC susceptibility were studied in the temperature range 5–400 K. The values of H_ex verified the observed degree of the particle surface oxidation. The system of the iron nanoparticles is in a ferromagnetic blocked state and the temperature dependence of the coercivity and susceptibility is in accord with the transmission electron microscopy data. Copyright © 2005 John Wiley & Sons, Ltd.     

Time-Reversal and Entropy

There is a relation between the irreversibility of thermodynamic processes as expressed by the breaking of time-reversal symmetry, and the entropy production in such processes. We explain on an elementary mathematical level the relations between entropy production, phase-space contraction and time-reversal starting from a deterministic dynamics. Both closed and open systems, in the transient and in the steady regime, are considered. The main result identifies under general conditions the statistical mechanical entropy production as the source term of time-reversal breaking in the path space measure for the evolution of reduced variables. This provides a general algorithm for computing the entropy production and to understand in a unified way a number of useful (in)equalities. We also discuss the Markov approximation. Important are a number of old theoretical ideas for connecting the microscopic dynamics with thermodynamic behavior.     

Relaxation of Alkali Glass Exposed to an Electron Beam

Binary potassium and rubidium silicate glasses were irradiated with high-energy electrons. The changes induced in the glasses were observed as a decay of alkali X-ray signals with time. The decay curves displayed incubation periods, connected with changes of the transport mechanism. The electron exposures were interrupted relative to the incubation periods, next the glasses were annealed to enable easier relaxations, and successively irradiated again to finish the decay curve. Relaxation, which depends on the point of the decay curve at which exposure is interrupted, is calculated for the glasses. Relaxation was found to depend strongly on the interruption point with regard to the incubation period. The longer irradiation causes worse recovery of the structure during annealing, especially if the irradiation lasts longer than the incubation time. The larger ions and lower concentration also inhibit relaxation.     

Impact of average free‐volume element size on transport in stereoisomers of polynorbornene. I. Properties at 35 °C

This article demonstrates that transport of gases through glassy polymers is significantly influenced not only by the absolute amount but also by the distribution of free volume. Two stereoisomers of polynorbornene with nearly equivalent total free volume, but markedly different average free‐volume sizes, were evaluated. The free‐volume element size was probed with positron annihilation lifetime spectroscopy, wide‐angle X‐ray scattering, gas sorption, and molecular modeling. The permeation, sorption, and diffusion of light gases were measured in each stereoisomer at 35 °C. All analytical techniques indicated that one isomer (labeled as Architecture II) had a larger average free‐volume element size but fewer elements. This isomer also had a very slightly higher bulk density (1.000 vs 0.992 g/cm³ for the other stereoisomer). Architecture II also had gas sorption and diffusion coefficients that were two to three times those of the less dense counterpart. These differences have been attributed to differences in the free‐volume element size available within the polymer matrix. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2185–2199, 2003