Thermal properties of a disc-like compound benzene-hexa-n-pentanoate: a precursor of a discotic mesogen

The heat capacity of a disk-like compound, benzene-hexa-n-pentanoate (BH5), a precursor of a discotic mesogen, has been measured by adiabatic calorimetry between 13 and 390 K. BH5 showed four different crystalline phases, but no liquid crystalline phase. Molar entropy and transition entropies were determined and compared with those of other homologues (BH6, BH7, and BH8). An odd-even effect with respect to the number of carbon atoms in the alkyl chain was observed for the cumulative entropies of the phase transitions occurring in the solid state. This effect is discussed by comparing with data for the n-alkanes. The molar entropies of the crystalline state, especially below 250 K, exhibited a peculiar 'pairing effect' between BH(2m- 1) and BH(2m), where m is an integer.     

Impedance of a passive iron electrode in a solution containing a reducing agent

Frequency dependences of impedance of a passive iron electrode in 0.5 M Na₂SO₄ solutions with and without 0.01 M K₄[Fe(CN)₆] are obtained by a pulsed method and the Fourier transform. At 1–1000 Hz, the results in 0.5 M Na₂SO₄ satisfactorily agree with our previous results obtained by a lock-in method. With the [Fe(CN)₆]^4- ions present, the impedance decreases faster at lower frequencies. The impedance of the oxide film/solution interface relaxes longer the film impedance. These conclusions are similar to those obtained earlier.Translated from Elektrokhimiya, Vol. 41, No. 1, 2005, pp. 97–101.Original Russian Text Copyright © 2005 by Klyuev, Rotenberg, Batrakov.To the Centennial of B.N. Kabanov.     

Miscibility of a polyarylate with a liquid crystalline copolyester

The miscibility has been investigated for binary blends of a polyarylate (PAr) with a liquid crystalline copolyester of p-hydroxybenzoate and ethylene terephthalate units in a 6/4 molar ratio (PET/PHB). The binary blends were prepared by solution precipitation. The transitions of the PET/PHB have been measured with a rheometrics dynamic spectrometer. The phases in blends have been studied with a differential scanning calorimeter, by ther-mogravimetry and with a polarizing optical microscope. The blends exhibit two glass transitions (T_gs) over the composition range 10–90 wt %. The amorphous PET phase from the PET-PHB is found to be partially miscible with PAr, which leads to a decrease of the PAr T_g. The amount of this partially miscible portion of PET has been estimated by the Couch-man equation. On heat treatment of the blends at 250 to 300°C, transesterficiation takes place, as judged by the shift of the higher of the two T_gs. © 1993 John Wiley & Sons, Inc.     

Motion of a Colloidal Sphere Covered by a Layer of Adsorbed Polymers Normal to a Plane Surface

A combined analytical–numerical study is presented for the slow motion of a spherical particle coated with a layer of adsorbed polymers perpendicular to an infinite plane, which can be either a solid wall or a free surface. The Reynolds number is assumed to be vanishingly small, and the thickness of the surface polymer layer is assumed to be much smaller than the particle radius and the spacing between the particle and the plane boundary. A method of matched asymptotic expansions in a small parameter λ incorporated with a boundary collocation technique is used to solve the creeping flow equations inside and outside the adsorbed polymer layer, where λ is the ratio of the characteristic thickness of the polymer layer to the particle radius. The results for the hydrodynamic force exerted on the particle in a resistance problem and for the particle velocity in a mobility problem are expressed in terms of the effective hydrodynamic thickness (L) of the polymer layer, which is accurate to O(λ²). The O(λ) term forLnormalized by its value in the absence of the plane boundary is found to be independent of the polymer segment distribution and the volume fraction of the segments. The O(λ²) term forL, however, is a sensitive function of the polymer segment distribution and the volume fraction of the segments. In general, the boundary effects on the motion of a polymer-coated particle can be quite significant.     

Self-assembly of a nucleotide-calixarene hybrid in a triangular supramolecule

The self-assembly of a thymine nucleotide-calixarene hybrid (1) in CDCl₃ as a solvent was investigated. FT-IR, ESI-MS, ¹H and DOSY-NMR spectra evidenced that compound 1 (ammonium or sodium salt) self-assembles in a triangular trimeric supramolecule by thymine-thymine hydrogen bonding. The saline form is crucial for the arrangement in the cyclic trimer as the protonation of the nucleotide phosphate groups leads the assembly toward a dimeric species.     

Equation of state for hydrofluorocarbon refrigerant mixtures of HFC-125/143a,HFC-125/134a,HFC-134a/143a and HFC-125/134a/143a

Equations of state (EOSs) in the form of dimensionless Helmholtz free energy have been developed for the binary hydrofluorocarbon (HFC) refrigerant mixtures HFC-125/143a, HFC-125/134a, HFC-134a/143a and for the ternary refrigerant mixture HFC-125/134a/143a in the present work. These EOSs are effective in the temperature and pressure ranges where the experimental measurements covered, i.e., 200 K⩽T⩽413 K, P⩽35 MPa for HFC-125/143a and HFC-125/134a; 243 K⩽T⩽413 K, P⩽17 MPa for HFC-134a/143a and HFC-125/134a/143a. Experimental measurements in both single-phase and two-phase regions are represented by the present EOSs within their estimated uncertainties.     

Mobility of a tackifying resin in a pressure-sensitive adhesive

A detailed study of the mobility of a tackifying resin in a pressure-sensitive adhesive (PSA) has been done for the first time. The objective of this work is to relate changes in adhesive performance with tackifier loading to tackifier mobility. Tackifiers are low-molecular weight resins that improve the overall performance of PSAs. They increase the adhesive tack or the ability to form a bond of measurable strength after brief contact under slight applied pressure. In this study the diffusion of n-butyl ester of abietic acid (n-BEAA) in either polyisoprene (PI) (M_w = 195,000 M_w/M_n ∼ 1.05) or poly(ethylene-propylene) (PEP) (M_w = 40,000 M_w/M_n ∼ 2.30) was measured by Pulsed Gradient Spin Echo-Nuclear Magnetic Resonance (PGSE-NMR) as a function of both tackifier concentration and temperature. The concentration dependence of the tackifier's diffusion coefficient was weak for both systems. The weak variation in mobility with composition for the PI/n-BEAA system was consistent with that system's weak variation in tack with composition. On the other hand, blends of PEP/n-BEAA showed only modest variation in mobility, even though these adhesive systems showed appreciable enhancement of tack at intermediate compositions. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36 : 373–381, 1998     

Recoordination of a metal ion in the cavity of a crown compound: a theoretical study

The absorption spectra of styrylbenzothiazolium dye derivatives were calculated by the time-dependent density functional (TD DFT) method. The dyes of interest were (p-dimethylamino)styrylbenzothiazolium dye and its protonated form as well as aza-15(18)-crown-5(6)-containing dyes and their complexes with alkali (K⁺ and Na⁺) and alkaline-earth (Ca²⁺, Sr²⁺, and Ba²⁺) cations. Several low-lying conformers of the azacrown-containing dyes were considered. The electronic and geometric structures of the excited states responsible for the appearance of the long-wave (π-π*) absorption bands are studied. Complexation causes a hypsochromic shift of the long-wave absorption band correlating with the pyramidality of the crown ether nitrogen in the complex. The interaction of the cation with 3–4 solvent molecules or a counterion (ClO₄ ^?) considerably reduces this shift, especially in the conformers without the metal-nitrogen bond. In some cases, the long-wave absorption band is close to the absorption band of the free dye. Similar results were obtained using the polarizable continuum model of solvation. Excited-state structures of the free model dye and the free azacrown-containing dyes exhibit a tendency to bond alternation. Conversely, the cationic complexes of the crown-containing dyes and the protonated model dye exhibit a tendency to bond equalization in the excited state. The changes in the excited-state geometries of the free dyes and their complexes account for the complexation-induced fluorescence enhancement observed in the experiments.     

Use of a Photovoltaic Receptor in a Phototitrator

Abstract

In phototitrators especially designed to allow operation in ambient light, a photovoltaic device, the Texas Instrument LS 222, may be used instead of the photoresistive diode Texas Instrument 1N2175. This permits elimination of one battery, and a simplier circuit. Construction and performance of the titrator are otherwise identical.     

Transform of a thermogram into a thermogenesis curve by the use of the frequency transfer function of a calorimeter

In calorimeter experiments, we obtain the thermogram y = y(t), temperature variation y(t) as a function of time t, when thermal reaction occurs in the calorimeter reaction cell. For thermokinetic studies, we need to know the calorific power generated in the cell, due to the thermal reaction, as a function of time. By use of the frequency transfer function of the calorimeter, we can calculate numerically the calorific power at any time from numerical analysis of the thermogram without any assumption of analytical form of the transfer function.The method is composed of three steps. (1) Experimental determination of the frequency transfer function G of the calorimeter from numerical analysis of the thermogram which is obtained by applying a constant calorific power in the calorimeter cell. (2) Numerical Laplace transform L[y] = Y of the thermogram which is recorded when the thermal reaction under investigation occurs in the cell. (3) Numerical determination of the calorific power, evolved by the thermal reaction in the cell, by numerical inverse Laplace transform of Y/G.This method is examined in two ways. First, simulation by numerical calculation on a mathematical model calorimeter is done and the accuracy of the method is assured. Second, experiments and numerical analysis on the heat-flow (conduction) type of calorimeter are performed to test the availability of the method.     

Electron Transfer in a Supramolecular Associate of a Fullerene Fragment

Herein, we investigate the association of a fullerene fragment, hemifullerene C₃₀H₁₂, with an electron‐donating bowl‐shaped tetrathiafulvalene derivative (truxTTF). UV/Vis titrations and DFT calculations support formation of the supramolecular complex, for which an association constant of log K_a=3.6±0.3 in CHCl₃ at room temperature is calculated. Remarkably, electron transfer from truxTTF to C₃₀H₁₂ to form the fully charge‐separated species takes place upon irradiation of the associate with light, constituting the first example in which a fullerene fragment mimics the electron‐accepting behavior of fullerenes within a supramolecular complex.     

Coupling of a sheep anti-T3 IgG to a solid phase for a triiodothyronine radioimmunoassay

Optimal conditions for coupling sheep anti-T₃ IgG to a solid phase are presented. We found that the optimal activation of microcrystalline cellulose was achieved with 0.15M 1,1-carbonyldiimidazol (CDI) in acetone. We also found that using a 25 mg/cm³ anti-T₃ IgG solution, in barbitone buffer 0.05M, pH 8.0, we could get a reasonable yield of coupling and a remaining solution of anti-T₃ IgG (first supernatant) with a suitable concentration (10 mg/cm³) for another coupling. The solid phase anti-T₃ obtained in these two couplings present similar characteristics which make possible their use in a total T₃ RIA.     

First Measurement of a Thermochemical Property of a Seaborgium Compound

With only a few atoms of seaborgium (Sg, element 106), in the form of volatile SgO₂Cl₂, it was possible to determine the sublimation enthalpy of this compound using gas chromatography. Furthermore, it was demonstrated that in Group 6 Sg is chemically more similar to W than to Mo.     

1,2-Shift of a Carboxyl Group in a Wagner-Meerwein Rearrangement

On treatment with HSO₃F in SO₂C1F at 0°, 3-hydroxy-2,2-dimethyl-3-phenyl-propionic acid ( 1a ) is transformed into 2-phenyl-3-methyl-2-butenoic acid ( 2a ) (isolated yield: 40–44%). Using monolabelled [3-¹³C]- 1a ( 1a *) and doubly labelled [1,3-¹³C₂]- 1a ( 1a **), the migration of HOOC (or a mechanistically equivalent group) was proved; a cross experiment established the intramolecular character of the rearrangement. By following the reaction at low temperature in an NMR. spectrometer, the formation of intermediates and side products was demonstrated.     

Unexpected formation of a xanthone in the synthesis of a bisbenzoxazole

Recently we reported the synthesis in polyphosphoric acid of a graft copolymer consisting of a rigid-rod poly[benzo(1,2-d;4,5-d′)bisthiazole-2,6-diyl]-1,4-phenylene backbone and flexible poly(oxy-1,3-phenylenecarbonyl-1,4-phenylene) side-chains [1]. However, upon extension of this synthetic approach to the analogous graft copolymer with a poly[benzo(1,2-d:5,4-d′)bisoxazole-2,6-diyl]-1,4-phenylene backbone, we encountered some unexpected results due to methyl group migration. In order to better understand these results, we carried out the synthesis of selected benzothiazole and benzoxazole structures under appropriate reaction conditions. The results are reported in this article.     

Influence of a cooling rate on a structure of PA6

The structure of the plate specimens obtained from the molten PA6 that was cooled at rates between 2 and 2000 °C/min have been studied. The cooling rate of 2000 °C/min did not ensure a complete amorphization of the specimens. The amorphous phase created by supercooling is unstable and at room temperature undergoes a noticeable cold crystallization. The access of water to the specimen from the surrounding air accelerates this process.Variations in the cooling rate of the melt reflect in rearrangement of the amorphous phase of PA6. Owing to the effect of interaction with the crystalline phase, the amorphous regions undergo changes in molecular weight and MWD of the chain segments between junctions in topological regions, temperatures of the glass transition and β-relaxation, compaction, etc.     

Determination of depth of a radionuclide source in a tissue equivalent phantom

Hydrophilic materials which refer to a group of cross-linked polymers originally developed in the 60s to produce soft contact lenses are characterised by an equilibrium water uptake in the range 15–95 % by wet weight when hydrated in water or normal saline solution at 25 °C. This ability to absorb controlled amounts of water makes them suitable human tissue substitutes. Four types of hydrophilic materials of different composition and thickness were placed between a ²²Na calibrated point source and a single LaBr₃: Ce (5 %) detector (Saint-Gobain) at a fixed distance between source and detector. The scatter-to-peak ratio was determined by selecting five scatter angle windows between 25 and 50^° (467–376 keV), at 5^° intervals, to study how the ratio varied with attenuating material, thickness and composition. From photon spectra recorded a ‘best’ estimate of the depth of the source in the hydrophilic material was obtained by finding the most sensitive scattering window. Theoretical and practical models of the source-to-detector geometries are included and discussed.     

Electroluminescence of a bichromophoric molecule with a benzoxyazolylcoumarin and carbazole moiety

The electroluminescent properties of a bichromophoric molecule in which a benzoxyazolylcoumarin and carbazole moiety is combined with 1,2-ethylene linkage, i.e. 3-(2-benzoxyazolyl)-7-[2-(9-carbazolyl)ethoxy]-coumarin (CmCz), were investigated. CmCz exhibits fluorescence of different colors in a solid state and solution. Two types of device were made. One consisted of a vacuum vapor-deposited film of CmCz as an emission layer to utilize fluorescence in the solid state; the second consisted of a spin-cast film doped with CmCz as an emission material to utilize fluorescence in the solution. The device with a vapor-deposited CmCz film between electrodes shows a green emission with a luminance of less than 10⁻² cd/m². The multiple layer device in which the CmCz film was sandwiched between a hole transport layer and electron transport layer showed a green emission whose spectrum is identical to the photoluminescent spectrum in the vapor-deposited CmCz film. A maximum luminance of the multiple layer device is about 5000 cd/m². On the other hand, the devices consisting of a spin-cast film containing a hole transport material, an electron transport material and CmCz showed a blue emission whose spectra are identical to the photoluminescent spectrum of CmCz in chloroform. Luminance of these devices is over 100 cd/m². © 1997 John Wiley & Sons, Ltd.     

Deformation of a Polymer Brush Immersed in a Binary Solvent

An analog of the Alexander‐De Gennes box model is used for the theoretical investigation of an external deformation of polymer brushes in a mixture of two solvents. The basic solvent A and the admixture B are assumed to be highly incompatible (Flory‐Huggins parameter χ_AB = 3.5). The thermodynamics of a polymer in the solvents A and B is described by parameters χ_A and χ_B, χ_A > χ_B. The brush behavior under deformation is investigated with regard to solvent composition and polymer‐solvent interactions. It is shown that in a pre‐binodal range of the solvent composition Φ_B < Φ_B⁰ in the bulk (here Φ_B⁰ is a binodal value) there is such a value of Φ_B = Φ _B* that deformation does not affect solvent composition inside the brush. This invariant quantity Φ _B*, being a function of only thermodynamic parameters, is independent of the brush characteristics, such as grafting density. It is shown that two types of the first‐order phase transitions can arise in the system considered: a compositional phase transition induced by a change in the solvent composition in the bulk, and a deformational phase transition caused by an external deformation of the brush. The value of Φ _B* defines a borderline concentration of the admixture in the bulk; the brush behavior in the ranges 00 ⪇ Φ_B ⪇ Φ _B* and Φ _B* ⪇ Φ_B < Φ_B⁰ are different. If no compositional phase transition occurs in the system, the deformational phase transition should arise under stretching at Φ _B* ⪇ Φ_B. If the compositional phase transition exists, it is realized in the range Φ_B < Φ _B* and causes the deformational phase transition in this concentration range, not only under stretching, but also under compression. Microphase segregation inside the brush is demonstrated for both phase transitions despite overestimation of the brush homogeneity in the box model.     

Formation and redox properties of a complex of phenazine di-N-oxide with a proton

The electrochemical properties of phenazine di-N-oxide (OPO) in acetonitrile solutions in the presence of acids were studied by the method of cyclic voltammetry (CVA). It was shown that OPO forms with a proton a complex having a 2:1 composition, its oxidation and reduction potentials being equal to 1.57 and 0.35 V (saturated calomel electrode), respectively. The same protonated form is also formed in the reaction of OPO^+. with organic substrates, in particular with hydrocarbons and alcohols. The reaction mechanism includes a complexation of OPO^+. with the substrate, followed by splitting off of a hydrogen from the complex by another OPO^+· cation-radical or a proton by the initial OPO. A rapid selective deoxygenation of the protonated form of OPO by iodide ion in acetonitrile in an acid medium has been discovered.Institute of Chemical Physics in Chernogolovka, Russian Academy of Sciences, Chernogolovka 142432. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 4, pp. 845–851, April, 1992.