Sandwich Techniques in flow injection analysis : Part 1. Continuous recalibration techniques for process control

Flow injection methodology based on sample insertion between two different standard solutions used as carrier streams is described. This approach provides a simple system for continuous recalibration in process control; spectrophotometric and ion-selective electrode procedures are outlined.     

Hyperfine characterization of Bi1.9Te0.1SrNb1.9Hf0.1O9

The Aurivillius type oxide Bi_1.9Te_0.1SrNb_1.9Hf_0.1O₉ has been studied by Perturbed Angular Correlations spectroscopy using ¹⁸¹Ta probes. The spin precession curves were measured from room temperature up to 873 K. Two sites are occupied by probes and the temperature dependence of both indicates a continuous phase transition at about 625 K. One site is ordered while the other is disordered. This situation is analyzed in terms of simple models already applied to perovskites. The transition temperature of the solid solution Bi_2−xTe_xSrNb_2−xHf_xO₉ (with 0≤x≤0.5) shows a strong dependence on composition.     

Area orthogonality in normed linear spaces

A new concept of orthogonality in real normed linear spaces is introduced. Typical properties of orthogonality (homogeneity, symmetry, additivity, ...) and relations between this orthogonality and other known orthogonalities (Birkhoff, Boussouis, Unitary-Boussouis and Diminnie) are studied. In particular, some characterizations of inner product spaces are obtained.     

Photonic crystal devices

We developed photochemically controlled photonic crystals which may be useful in novel recordable and erasable memories and/or display devices. These materials can operate in the UV, visible or near IR spectral regions. Information is recorded and erased by exciting the photonic crystal with ∼ 360 nm UV light or ∼ 480 nm visible light. The recorded information is read out by measuring the photonic crystal diffraction wavelength. The active element of the device is an azobenzene functionalized hydrogel which contains an embedded crystalline colloidal array. UV excitation forms cis-azobenzene while visible excitation forms trans-azobenzene. Larger dipole moment of the cis-form results in decrease of the free energy of mixing which causes the hydrogel to swell and to red-shift the photonic crystal diffraction with a 36 s time constant. We also observed fast ms and sub-ms transient dynamics associated with convection due to heating of the medium by UV excitation. Convective motion of the medium stretches the PCCA for about 6 μs within which the convection decays and the elastic restoring force of the PCCA brings back the stretched PCCA to its equilibrium state with 33 μs time constant. Paper presented at the 2nd International Conference on Ionic Devices, Anna University, Chennai, India, Nov. 28–30, 2003.     

Canonical Structure and Symmetries of the Schlesinger Equations

The Schlesinger equations S _(n,m) describe monodromy preserving deformations of order m Fuchsian systems with n + 1 poles. They can be considered as a family of commuting time-dependent Hamiltonian systems on the direct product of n copies of m × m matrix algebras equipped with the standard linear Poisson bracket. In this paper we present a new canonical Hamiltonian formulation of the general Schlesinger equations S _(n,m) for all n, m and we compute the action of the symmetries of the Schlesinger equations in these coordinates.     

Lightly crosslinked,mesomorphic networks obtained through the reaction of dimeric,liquid‐crystalline epoxy–imine monomers and heptanedioic acid

We reacted various dimeric, liquid‐crystalline epoxy–imine monomers, differing in the length of the central aliphatic spacer or the dipolar moments, with heptanedioic acid. The resulting systems showed a liquid‐crystalline phase in some cases, depending on the dimer and on the reaction conditions. The systems were characterized with respect to their mesomorphic properties and then were submitted to dynamic mechanical thermal analysis in both fixed‐frequency and frequency‐sweep modes in the shear sandwich configuration. The arrangement in the liquid‐crystalline phase seemed to be mainly affected both by the polarization of the mesogen and by the reaction temperature, which favored the liquid‐crystalline arrangement when it was lying in the range of stability of the dimer mesophase. In agreement with other recent literature data, dynamic mechanical thermal analysis results suggested that the presence of the mesogen directly incorporated into the main chain increased the lifetimes of the elastic modes both in the isotropic phase and in the liquid‐crystalline phase with respect to side‐chain liquid‐crystalline elastomers and that the time–temperature superposition principle did not hold through the liquid‐crystalline‐to‐isotropic transition. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44:6270–6286, 2006     

Vinyl‐terminated side‐chain liquid‐crystalline polyethers containing mesogenic benzylideneaniline moieties

The synthesis of two vinyl‐terminated side‐chain liquid‐crystalline polyethers containing benzylideneaniline moieties as mesogenic cores was approached in two different ways: by chemically modifying poly(epichlorohydrin) with suitable mesogenic acids or by polymerizing analogous glycidyl ester or glycidyl ether derivatives. In all the conditions tested, the first approach led to materials in which the imine group was hydrolyzed. The second approach led to the desired polymers PG2a and PG2b , but only from the glycidyl ether derivatives and when the initiator was the system that combined polyiminophosphazene base t‐Bu‐P₄ and 3,5‐di‐t‐butylphenol. These polymers were chemically characterized by IR and ¹H and ¹³C NMR spectroscopies. The estimated degrees of polymerization ranged from 30 to 36. The liquid crystalline behavior of the synthesized polymers was studied by differential scanning calorimetry, polarized optical microscopy (POM) and X‐ray diffraction. Both polymers behave like liquid crystals and exhibited a single mesophase, which was recognized as a smectic C mesophase, probably with a bilayer arrangement, i.e., a smectic C₂ mesophase. The crosslinking of both polymers was performed with dicumyl peroxide as initiator, which led to liquid crystalline thermosets. POM and X‐ray diffraction confirmed that the mesophase organization mantained on the crosslinked materials. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1877–1889, 2006     

Time reversal for infinite-dimensional diffusions

Summary In this paper we analize the reversibility of the diffusion property for the solution of certain infinite-dimensional systems of stochastic differential equations. Necessary and sufficient conditions ensuring this reversibility are given. The proofs use the techniques of the stochastic calculus of variations.This work was partly done when the first author was visiting the Centre de Recerca Matemàtica at Barcelona     

Calorimetric approach to tetronic/water interactions

Tetronic^®comprises X-shaped copolymers formed by four poly(propylene oxide) (PPO) andpoly(ethylene oxide) (PEO) block chains bonded to an ethylene diamine centralgroup. Micellization behaviour of three representative Tetronics (T304, T904and T1307) was characterized to gain an insight into the interactions betweenthe copolymer unimers and the state of water in their solutions. The enthalpyof demicellization, recorded at 37°C in an isoperibol microcalorimeter,indicated that the process was in all cases exothermic and the enthalpy rankedin the order T1307≥T904>>T304. Micellization is entropy-driven owing tohydrophobic interactions between the PPO chains.DSC analysisshowed that the crystallization and melting peaks of the free water remainingin T304 and T904 solutions were progressively shifted toward lower temperaturesas the surfactant proportion increased, owing to a colligative effect. Boundwater corresponded to 3 water molecules per EO repeating unit. In the caseof T1307, which has longer PEO chains, a splitting of the melting peak wasobserved, one peak appearing around 0°C due to free water and anotherat –15°C due to interfacial water. As T1307 proportion raised, theenthalpy of the former decreased, whilst the enthalpy of the latter increased.In 40% T1307 solutions, interfacial water overcame the proportion of freewater; there being 1 interfacial and 3 bound water molecules per EO repeatingunit. Gaussian deconvolution of FTIR spectra also enabled to characterizethe evolution of free water as a function of Tetronic proportion. The dependenceof micellization and water interaction behaviour on Tetronics structure shouldbe taken into account to use these copolymers as drug solubilizers and micellarcarriers.     

THE α-OXIDASE SYSTEM OF YOUNG PEA LEAVES (Pisum sativum) AS GENERATOR OF ELECTRONICALLY EXCITED STATES. EXCITATION IN THE DARK UNDER NATURAL CONDITIONS

Abstract. The aerobic oxidation of saturated long chain fatty acids to the lower aldehyde and CO₂ catalyzed by the α-oxidase system of young leaves from germinating Pisum sativum results in concomitant excitation of the chloroplasts or/and fractions present in the α-oxidase preparation. The excitation is attested to by both chlorophyll emission and Hill activity. This is the first case of photobiochemistry without light within a natural system.