Mesophase behaviour of 2,5-dibenzoyloxy-p-benzoquinone derivatives and tetrahydrobenzene tetraesters

The synthesis of 2,5-dibenzoyloxy-p-benzoquinone derivatives, their products after reduction and tetraesters from tetrahydroxybenzene prepared from those products is described. Their phase behaviour was investigated by differential scanning calorimetry and polarizing microscopy and is discussed in terms of their detailed structure.     

Physical aging of a polyetherimide: Creep and DSC measurements

Creep and differential scanning calorimetry (DSC) measurements have been used to study the physical aging behavior of a polyetherimide. Isothermal aging temperatures ranged from 160°C to T_g with aging times ranging from 10 min to 8 days. The only measurable effect of physical aging on the short-time creep curves is a shift of the creep compliance to longer times. Andrade plots of the compliance versus the cube root of time are linear at short times with the slope β decreasing with increasing aging time to a constant value once equilibrium is reached. Log β³ is related directly to the degree to which the creep curves shift to longer times with physical aging, and is used in this work as a measure of physical aging. A reduced curve of log β³ versus log aging time is obtained for the aging temperatures investigated by appropriate vertical and horizontal shifts. The enthalpy change during aging increases linearly with the logarithm of the aging time, t_a, leveling off at equilibrium at values which increase with decreasing aging temperature. Hence, both nonequilibrium and equilibrium temperature shift factors can be calculated from the DSC data. Good agreement is observed between the equilibrium temperature shift factors obtained from the creep and DSC data. The temperature dependence of the nonequilibrium temperature shift factors is found to be an order of magnitude smaller than that of the equilibrium shift factors. The time scales to reach equilibrium for enthalpy and for mechanical measurements are found to be the same within experimental error. © 1995 John Wiley & Sons, Inc.     

The effect of crystallinity on chain mobility and free volume in the amorphous regions of a miscible polycarbonate/polyester blend

Homopolymers and blends of polycarbonate/ThermX have been investigated by differential scanning calorimetry, dynamic mechanical analysis, density measurements, and positron annihilation lifetime spectroscopy. The study focuses on the chain mobility and free volume in the amorphous miscible regions of the blends and how this mobility and free volume are affected by increasing crystallinity. It is proposed that judicious annealing, which results in increasing crystallinity (while avoiding ageing or transesterification), induces a constraint on the amorphous region leading to an increase in T_g and coalescence of free volume sites. © 1994 John Wiley & Sons, Inc.     

Synthesis and structural characterization of acetatobis(triphenylphosphine)dicarbonylmanganese(I), (CH3CO2)Mn(CO)2[P(C6H5)3]2: An organometallic complex containing a chelating acetate ligand

The accidental but intriguing synthesis of acetatobis(triphenylphosphine)dicarbonylmanganese(I), (CH₃CO₂)Mn(CO)₂[P(C₆H₅)₃]₂, has been accomplished by the reaction of NaMn(CO)₅ with (CH₃)₃SiCl followed by the addition of triphenylphosphine and acetic acid. A three-dimensional single-crystal X-ray diffraction analysis has shown an octahedral-like molecule containing a symmetrically oxygen-chelating acetate group, the first such group to be reported in a metal carbonyl complex. The two triphenylphosphine ligands occupy mutually trans positions with the two carbonyl ligands possessing the remaining cis sites in the octahedral complex. The compound crystallizes with four molecules in a monoclinic unit cell of space group symmetry $\text{P}\text{2}{}_1\text{c}$ and of dimensions a = 17.744(2) Å, b = 9.692(1) Å, c = 20.004(2) Å, and β = 106.195(4)°. The relatively long MnO(acetate) bond lengths [2.066(6) and 2.069(7) Å] and the relatively short MnCO bond lengths [1.701(12) and 1.760(13) Å] and the relatively short MnP(C₆H₅)₃ bond lengths [2.260(3) and 2.275(3) Å], compared to the corresponding MnCO and MnP(C₆H₅)₃ bond lengths in other manganese carbonyl triphenylphosphine complexes, are rationalized on the basis that the acetate ligand in this molecule functions primarily as a σ-donor.     

Détermination des modèles d'imperfections de différentes variétés allotropiques du sulfure cuivreux (digénite cubique,chalcocite hexagonale “haute et basse température”, chalcocite orthorhombique)

From the study of the CuCuBrCu_2?εSC solid cell in the range of cubic digenite and “high temperature” hexagonal chalcocite we have deduced the laws of variation of the deviation from stoichiometry and the holes concentration with the equilibrium partial pressure of sulfur (δ and p are found to be proportional to ). The electronic model corresponding to the formation of associations (V^×_CuV′_Cu) in the presence of neutral vacancies V^×_Cu allows one to explain these laws. In the low temperature range (range of “low temperature” hexagonal chalcocite and orthorhombic chalcocite) the study of thermal variations of Hall coefficient permits us to propose the following models: (a) the deviation from stoichiometry of the “low temperature” hexagonal chalcocite is due to the simple ionized vacancies V′_Cu; (b) the deviation from stoichiometry of the orthorhombic chalcocite is due to the vacancies V′_Cu and to the associations (V^×_CuV^×_Cu).     

Microelectrode for potassium ions based on a neutral carrier and comparison of its characteristics with a cation exchanger sensor

A potassium-selective liquid-membrane microelectrode based on valinomycin is described. Tip diameters of about 2 μm as well as high discrimination against Na⁺, H₃O⁺, acetylcholine and some other quaternary ammonium ions, allow the intracellular measurement of potassium ion activity changes. The inherently high membrane resistance of the neutral carrier-based microelectrodes is reduced by adding a lipophilic charge carrier to the valinomycin. Results are compared with those of classical microelectrodes.     

Über sechsgliedrige Heterocyclen mit Phosphor-, Stickstoff- und Schwefelatomen im Ring

Cyclic sulphurylphosphazochloride (I: formula see ?Inhaltsübersicht”?) reacts with ammonia or methylamine forming the. tetramide(II) and (III), respectively, and with aniline or dimethylamine forming the diamide (IV) resp. (V). The synthesis of the diphenyl derivative (VI) is achieved starting from C₆H₅? PCl₄. (II) gives with PCl₅ the ionic compound (VII).     

CH2CHOH2+ + PN: a proton-transfer triple play

Quantum chemical calculations are used to explore the proton-transfer reactivity of O-protonated vinyl alcohol, CH2CHOH2+, with phosphorus nitride, PN. This reaction is relevant to the chemical evolution of interstellar clouds, since O-protonated vinyl alcohol has been postulated (and tentatively identified) as a product of the association reaction between interstellar H3O+ and C2H2, while PN is the most widespread and abundant phosphorus-containing molecule seen in astrophysical environments. Furthermore, the reaction exhibits an unusual mechanistic feature, namely, an extended "proton-transport catalysis" mechanism, which we characterize here as a "proton-transfer triple play". The reaction proceeds initially by proton transfer from CH2CHOH2+ to PN, then from PNH+ to CH2CHOH, and finally from CH3CHOH+ to PN, where the emphasized atom indicates the resultant site of protonation/deprotonation. Thus, the ultimate overall bimolecular proton-transfer reaction is expected to occur as CH2CHOH2+ + PN --> CH3CHO + PNH+; that is, the apparent favored product channel exhibits not only proton transfer but also keto/enol tautomerization. The triple-play mechanism can be rationalized in terms of the proton affinities of vinyl alcohol, acetaldehyde, and phosphorus nitride, which here are satisfactorily reproduced by high-level ab initio calculations. Other neutrals with a proton affinity appropriate for the possible triple-play mechanism converting CH2CHOH2+ to CH3CHO are also identified, with a view to encouraging experimental investigation of this mechanism.