Stable silica gel-bound crown ethers. Selective separation of metal ions and a potential for separations of amine enantiomers

Silica gel-bound crown ethers and aza macrocycles have been synthesized with the attaching arm connected to the carbon framework of the macrocycles. The interactions of these bound macrocycles with cations are almost identical to those involving the analogous free macrocycles. This has allowed for predictable cation separation, concentration, and removal processes to be performed on a small scale. Quantum mechanical calculations and NMR measurements indicate that similarly bound chiral macrocycles will be capable of use in separating chiral organic amines.Dedicated to the memory of Professor James J. Christensen who died on 5 September 1987.     

Conducting polymer membranes for low activity potentiometric ion sensing

Conducting polymer (CP) films, used as ion-sensing membranes under open circuit potentiometric conditions, are usually characterised with rather high detection limit, in the range of 10⁻⁴-10⁻⁵ mol dm⁻³. This effect is unfavourable, not only from the point of view of CP applications in potentiometry as ion sensitive membranes, but also when these materials are used as ion-to-electron transducers (solid contacts) for ion-selective electrodes. The theoretical considerations presented underline the crucial role of spontaneous processes of polymer charging/discharging—the source of observed high detection limit of sensors comprising CP layer under zero current conditions. Although the mechanism of occurring process is different from that observed for plastic, solvent polymeric based ion-selective electrodes, the ultimate result—alteration of activity of electrolyte at the membrane/solution interface leading to elevation of the detection limit—is the same.The method of estimation of parameters characterising spontaneous charge transfer processes is presented. The values obtained can be used to calculate the resulting polymer/solution interface activity of electrolyte ions, thus the detection limit of CP membrane can be theoretically predicted.A method of lowering of the detection limit of conducting polymer membranes, applying galvanostatic polarisation to compensate the spontaneous process of polymer charging/discharging, is presented.The experimental results obtained for poly(pyrrole), poly(N-methylpyrrole) and poly(3,4-ethylenedioxythiophene) are in good accordance with predictions of the presented model.     

Electrochemical Characteristics of Discrete,Uniform, and Monodispersed Hollow Mesoporous Carbon Spheres in Double‐Layered Supercapacitors

Core–shell‐structured mesoporous silica spheres were prepared by using n‐octadecyltrimethoxysilane (C18TMS) as the surfactant. Hollow mesoporous carbon spheres with controllable diameters were fabricated from core–shell‐structured mesoporous silica sphere templates by chemical vapor deposition (CVD). By controlling the thickness of the silica shell, hollow carbon spheres (HCSs) with different diameters can be obtained. The use of ethylene as the carbon precursor in the CVD process produces the materials in a single step without the need to remove the surfactant. The mechanism of formation and the role played by the surfactant, C18TMS, are investigated. The materials have large potential in double‐layer supercapacitors, and their electrochemical properties were determined. HCSs with thicker mesoporous shells possess a larger surface area, which in turn increases their electrochemical capacitance. The samples prepared at a lower temperature also exhibit increased capacitance as a result of the Brunauer–Emmett–Teller (BET) area and larger pore size.     

Evaluation of liquid-vapour density profiles of associating fluids: A density-functional approach

The structure of liquid-gas interface of associating Lennard-Jones particles is studied using the density-functional theory and the Monte Carlo simulation. The model with one bonding site per particle is considered. It is shown that the considered version of the density functional is quite successful in predicting the gas-liquid density profile.     

Counter-Ion Influence on Polypyrrole Potentiometric pH Sensitivity

The pH sensitivity of conducting polymer films is an important issue from the sensor design point of view. The doping and supporting electrolyte anions effect on the potentiometric sensitivity and response time of polypyrrole (PPy) electrodes towards changes of solution pH were studied. It was found that (i) the response of PPy doped by easily exchangeable common anions (Cl^–, NO₃ ^–, ClO₄ ^–) in their solutions (KCl, KNO₃, NaClO₄) is slow. In contrast, (ii) polypyrrole films deposited in the presence of weak acid anions (phthalates, oxalates, salicylates) were characterised by instantaneous responses in the above mentioned solutions. On the basis of electrochemical experiments (open circuit potential vs. time dependencies, cyclic voltammetry, EQCM), the observed differences were attributed to different mechanisms of pH sensitivity of tested films. The long response times are related to the incorporation of the solution ions into the film in order to compensate charges created due to protonation. On the other hand, if the ion-exchange is hindered as in the case of (ii), instantaneous open circuit responses are observed due to polarisation of the oxidised polymer layer, analogously to the metal electrode. Moreover, for these films the internal pH buffering within the polymer membrane will weaken the pH change effect.The mechanisms were confirmed in the course of studying the pH effect in solutions containing anions easily (KCl, NaClO₄, KNO₃) or hardly exchangeable with polypyrrole (K₂SO₄, sodium poly(4-styrenesulphonate) solutions) acidified with H₂SO₄.     

A numerical model of multimode fiber PON frequency response

Frequency response of passive optical network (PON) based on multimode fibers is investigated. The network comprises fibers, connectors and splitters/couplers. It is shown that due to mode filtering at splitters, the frequency response is different for different network nodes in otherwise symmetrical network.     

Chern-Simons states at genus one

We present a rigorous analysis of the Schrödinger picture quantization for theSU(2) Chern-Simons theory on 3-manifold torusxline, with insertions of Wilson lines. The quantum states, defined as gauge covariant holomorphic functionals ofsu(2)-connections on the torus, are expressed by degree 2k theta-functions satisfying additional conditions. The conditions are obtained by splitting the space of semistablesu(2)-connections into nine submanifolds and by analyzing the behavior of states at four codimension 1 strata. We construct the Knizhnik-Zamolodchikov-Bernard connection allowing to compare the states for different complex structures of the torus and different positions of the Wilson lines. By letting two Wilson lines come together, we prove a recursion relation for the dimensions of the spaces of states which, together with the (unproven) absence of states for spins>1/2 level implies the Verlinde dimension formula.     

Effect of interferents present in the internal solution or in the conducting polymer transducer on the responses of ion-selective electrodes

The effect of interferents present on the opposite side of the Pb²⁺-selective membrane has been studied for both internal solution and all-solid-state sensors with a conducting polymer (CP) transducer. For interferents with moderate selectivity coefficients (sodium cations) present in the internal solution or in the CP transducer phase, super-Nernstian responses were obtained. For sensors containing strongly discriminated interferents (lithium ions), however, responses typical of conventional electrodes are observed, despite the low activity of primary ions on the opposite side of the membrane. This effect is attributed to hindered incorporation of interfering ions into the membrane, which also impairs the long term stability of the potential. Because of the relatively small absolute amounts of interferents in the transducer of all-solid-state sensors, their exchange for primary ions occurs quickly. Thus, transformation of the sensor to one with a micromolar detection limit and high potential stability is observed.      

Determinants,Grassmanniannians and Elliptic Boundary Problems for the Dirac Operator

We study the relations between different determinants of the Dirac operator over a manifold with boundary considered as sections of a holomorphic line bundle over the Grassmannian of boundary conditions of Atiyah–Patodi–Singer type.     

Colorimetric and fluorimetric pH sensing using polydiacetylene embedded within PVC-PCL nanofibers

The applicability of model polydiacetylenes (PDAs) in hydrogen ions sensitive optodes was tested. Nanofibers mats were electrospun using a mixture of polyvinyl chloride (PVC) and polycaprolactone (PCL) together with 10, 12-tricosadiynoic acid (TCDA) or 10,12-pentacosadiynoic acid (PCDA). After the polymerization the mats were applied in colorimetric and fluorimetric pH sensors. The PDAs were formed by photopolymerization with a UV lamp (254 nm), resulting in a change of mats color from white to dark blue. The morphology of both fiber mats is similar (SEM images), and the average diameters of fibers were estimated as equal to 228±73 and 248±61 nm for TCDA and PCDA, respectively. As the pH increases, the color of the fiber mat changes from blue to red and the process can be followed visually. The result obtained by computer image analysis showed a sigmoidal increase in the intensity of red and a decrease in the intensity of blue color with increasing pH. A similar sigmoidal response is observed for the dependence of the emission intensity on the pH. Changes in the recorded signal occur in the pH range from 7 to 8.5 or from 8 to 9.5 for mats with TCDA and PCDA, respectively. Both readout modes can be successfully used for pH sensing with proposed nanofibrous mats in the range of pH close to the physiological pH range.