Secondary mechanical relaxation effects in some cycloalkyl side groups containing polymers

Summary The dynamic mechanical properties at acoustic and low-ultrasonic frequencies (6–60 kHz) have been determined in polycyclopentylmethacrylate (PCPMA), polycyclohexylmethacrylate (PCHMA), polycyclohepthylmethacrylate (PCHpMA), polycyclooctylmethacrylate (PCOcMA), polycyclohexylacrylate (PCHA), polyvinylhexahydrobenzoate (PVHHBz), polyvinylcyclohexylether (PVCHE) and polyvinylcyclohexane (PVCH) Measurements were carried out by an electrostatic method (flexural vibrations) over the temperature range 60 °K to room temperature. All polymers, except for polyvinylcyclohexane, exhibit a γ-relaxation, connected with internal motion of the cycloalkyl ring, whose activation parameters depend exclusively on the nature of the ring. PVCHMA, PVCHA, PVHHBz, PVCHE and PVCH exhibit a further secondary relaxation effect (δ-process) at lower temperature, whose position on the temperature scale, strength (peak height) and activation parameters depend on the nature of the units to which the cyclohexyl ring is attached. The δ-process is attributed to some complex motion of the whole cyclohexyl ring, involving oscillatory rotation of the same around simple bonds which link it to the backbone chain. Contrarily to the δ-process of the phenyl side group containing polymers, the δ-process of the polymers here examined seems to be more sensibly dependent on intramolecuar effects.

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Zusammenfassung Es wurden die dynamischen Eigenschaften im akustischen und im Bereich langsamer Ultraschallfrequenzen (6–60 kHz) untersucht für Polycyclopentylmethacrylat (PCPMA), Polycyclohexylmethacrylat (PCHMA), Polycycloheptylmethacrylat (PCHpMA), Polycyclooctylmethacrylat (PCOcMA), Polycyclohexylacrylat (PCHA), Polyvinylhexahydrobenzoat (PVHHBz) Polyvinylcyclohexyl?ther (PVCHE) und Polyvinylcyclohexan (PVCH). Die Untersuchungen wurden mit einer elektrostatischen Methode (Biegeschwingung) über den Temperaturbereich von 60 °K bis Raumtemperatur durchgeführt. Alle Polymeren, au?er Polyvinylcyclohexanen, zeigen eine γ-Relaxation verbunden mit internen Bewegungen des Cycloalkylrings, deren Aktivierungsparameter wesentlich von der Natur des Rings abh?ngen. PVCHMA, PVCHA, PVHHBz, PVCHE und PVCH zeigen einen weiteren sekund?ren Relaxationseffekt (δ-Proze?) bei tieferen Temperaturen, dessen Lage in der Temperaturskala, St?rke (Peakh?he) und Aktivierungsparameter von der Natur der Einheiten abh?ngen, an welchen der Cyclohexylring h?ngt. Der δ- Proze? wird irgendeiner komplexen Bewegung des ganzen Cyclohexylrings zugeschrieben, eingeschlossen oszillatorische Rotation desselben um die Einfachbindung, die ihn mit der Hauptkette verbindet. Anders als der δ-Proze? der Phenylseitengruppen enthaltenden Polymerenketten scheint der hier untersuchte δ-Proze? emfindlicher von intramolekularen Effekten abzuh?ngen.

     

High-throughput assay of rotenone in olive oil using atmospheric pressure chemical ionization tandem mass spectrometry

A high-throughput method is presented for the determination of rotenone in contaminated matrices. The procedure involves atmospheric pressure chemical ionization tandem mass spectrometry with a triple-quadrupole instrument and the use as internal standard of a cycloadduct derivative of rotenone itself. The method was applied to the evaluation of the decay of rotenone in olives and olive oil at various times after exposure to the contaminant.     

4‐Fluoro‐2‐(phospho­no­methyl)­benzene­sulfonic acid monohydrate

The title compound, C₇H₈FO₆PS·H₂O, contains both phospho­nic and sulfonic acid functionalities. An extensive network of O—H?O hydrogen bonds is present in the crystal structure. The three acidic protons are associated with the phospho­nate group. Two protons experience typical hydrogen‐bond contacts with the sulfonate‐O atoms, while the third has a longer covalent bond of 1.05 (3) Å to the phospho­nate‐O atom and a short hydrogen‐bond contact of 1.38 (3) Å to the water O atom (all O—H?O angles are in the range 162–175°). The sulfonate group is positioned so that one S—O bond is nearly coplanar with the phenyl ring [torsion angle O—S—C—C ?8.6 (2)°]. The phospho­nate group is oriented approximately perpendicular to the ring [torsion angle P—C—C—C 99.2 (2)°] with one P—O bond anti to the benzyl C—C bond. The mol­ecules pack in layers in the b–c plane with the water mol­ecules in between adjacent pairs of inverted layers.     

Ternary Hybrid γ‐Fe2O3/CrVI/Amine Oxidase Nanostructure for Electrochemical Sensing: Application for Polyamine Detection in Tumor Tissue

Dichromate binds to surface‐active maghemite nanoparticles (SAMNs) to form a stable core–shell nanostructures (SAMN@Cr^VI). The hybrid was characterized by Mössbauer spectroscopy, high‐angle annular dark‐field imaging, electron energy‐loss spectroscopy, and electrochemical techniques, which revealed a strong interaction of dichromate with the nanoparticle surface. Electrochemical characterization showed lower charge‐transfer resistance, better electrochemical performance, and more reversible electrochemical behavior with respect to naked SAMNs. Moreover, SAMN@Cr^VI is an excellent electrocatalyst for hydrogen peroxide reduction. Furthermore, an enzyme, namely, bovine serum amine oxidase (BSAO: EC 1.4.3.6), was immobilized on SAMN@Cr^VI by self‐assembly to give a ternary hybrid nanostructured catalyst for polyamine oxidation (SAMN@Cr^VI‐BSAO). SAMN@Cr^VI‐BSAO was applied for the development of a reagentless, fast, inexpensive, and interference‐free polyamine biosensor, which was successfully exploited for the discrimination of tumorous tissue from healthy tissue in human crude liver extracts.     

A geometric mass‐preserving redistancing scheme for the level set function

In this paper we describe and evaluate a geometric mass‐preserving redistancing procedure for the level set function on general structured grids. The proposed algorithm is adapted from a recent finite element‐based method and preserves the mass by means of a localized mass correction. A salient feature of the scheme is the absence of adjustable parameters. The algorithm is tested in two and three spatial dimensions and compared with the widely used partial differential equation (PDE)‐based redistancing method using structured Cartesian grids. Through the use of quantitative error measures of interest in level set methods, we show that the overall performance of the proposed geometric procedure is better than PDE‐based reinitialization schemes, since it is more robust with comparable accuracy. We also show that the algorithm is well‐suited for the highly stretched curvilinear grids used in CFD simulations. Copyright © 2010 John Wiley & Sons, Ltd.     

Heat conduction in a cylinder crossed by an electric current with skin effect

The steady periodic temperature distribution in an infinitely long solid cylinder crossed by an alternating current is evaluated. First, the time dependent and non-uniform power generated per unit volume by Joule effect within the cylinder is determined. Then, the dimensionless temperature distribution is obtained by analytical methods in steady periodic regime. Dimensionless tables which yield the amplitude and the phase of temperature oscillations both on the axis and on the surface of copper or nichrome cylindrical electric resistors are presented.

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Wärmeleitung in einem stromdurchflossenen Zylinder unter Berücksichtigung des Skin-Effektes

Zusammenfassung Es wird die periodische Temperaturverteilung für den eingeschwungenen Zustand in einem unendlich langen, von Wechselstrom durchflossenen Vollzylinder ermittelt. Zuerst erfolgt die Bestimmung der zeitabhängigen, nichgleichförmigen Energiefreisetzung pro Volumeneinheit des Zylinders infolge Joulescher Wärmeentwicklung und anschließend die Ermittlung der quasistationären Temperaturverteilung auf analytischem Wege. Amplitude und Phasenverzögerung der Temperaturschwingungen werden für die Achse und die Oberfläche eines Kupfer- oder Nickelchromzylinders tabellarisch in dimensionsloser Form mitgeteilt.

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Nomenclature A integration constant introduced in Eq. (2) - ber, bei Thomson functions of order zero - Bi Biot numberhr ₀/ - c speed of light in empty space - c ₁,c ₂ integration constants introduced in Eq. (46) - c _p specific heat at constant pressure - E electric field - E _z component ofE alongz - E time independent part ofE, defined in Eq. (1) - f function ofs and defined in Eq. (11) - g function ofs and defined in Eq. (37) - h convection heat transfer coefficient - H magnetic field - i imaginary uniti=(–1)^1/2 - I electric current - I _eff effective electric currentI _eff=I/2^1/2 - Im imaginary part of a complex number - J _n Bessel function of first kind and ordern - J electric current density - q _g power generated per unit volume - time average of the power generated per unit volume - time averaged power per unit length - r radial coordinate - R electric resistance per unit length - r ₀ radius of the cylinder - Re real part of a complex number - s dimensionless radial coordinates=r/r ₀ - s, s integration variables - t time - T temperature - time averaged temperature - T _f fluid temperature outside the boundary layer - time average of the surface temperature of the cylinder - u, functions ofs, and defined in Eqs. (47) and (48) - W Wronskian - x position vector - x real variable - Y _n Bessel function of second kind and ordern - z unit vector parallel to the axis of the cylinder - z axial coordinate - · modulus of a complex number - equal by definition Greek symbols amplitude of the dimensionless temperature oscillations - electric permittivity - dimensionless temperature defined in Eq. (16) - ₀, ₁, ₂ functions ofs defined in Eq. (22) - thermal conductivity - dimensionless parameter=(2)^1/2 - magnetic permeability - ₀ magnetic permeability of free space - function of defined in Eq. (59) - dimensionless parameter=c _p/() - mass density - electric conductivity - dimensionless time=t - phase of the dimensionless temperature oscillations - function ofs:= ₁+i ₂ - angular frequency - dimensionless parameter=()^1/2 r ₀     

The effect of buoyancy forces on laminar convection with viscous dissipation in a vertical channel

The interaction of the viscous dissipation effect with the presence of buoyancy forces is investigated for laminar-flow heat transfer in a parallel-plate vertical channel. One of the channel walls is considered as isothermal with a prescribed temperature, while the other wall is considered as insulated. The velocity field is assumed to be parallel. The velocity field, the temperature field and the Nusselt number are obtained by a perturbation series method which employs the ratio between the Grashof number and the Reynolds number as the perturbation parameter. The radius of convergence of the perturbation series is estimated. Received on 10 December 1997