Thermal history and enthalpy relaxation of an interpenetrating network polymer with exceptionally broad relaxation time distribution

Differential scanning calorimetry (DSC) of an interpenetrating network polymer of composition 25% polyurethane–75% poly(methyl methacrylate) shows a slowly increasing heat capacity, instead of the usual glass transition endotherm, whose onset temperature is not clearly discernible. On aging of the polymer at several temperatures between 193 and 333 K, an endothermic peak is observed whose onset is in the vicinity of the respective temperature of aging. The area under these peaks increases with increasing aging time at a fixed temperature. The effects are attributed to a very broad distribution of relaxation times, which may be represented by either a sum of discrete structural relaxation times of local network arrangement or by a nonexponential relaxation function which is equivalent to a distribution of relaxation times. In either view the vitrified state of the polymer can be envisaged as containing local structures whose own T_gs extend over a wide range of temperature. Aging decreases the enthalpy and produces an endothermic region which resembles an increase in C_p on heating because of relaxation of that local structure. The interpretation is supported by simulation of DSC scans in which the distribution of relaxation times is assumed to be exceptionally broad and in which aging introduced at several temperatures over a wide range produces endothermic effects (or regions of DSC scans) qualitatively similar to those observed for the interpenetrating network polymer. © 1994 John Wiley & Sons, Inc.     

Oxidation of alkanes by Ph4PHSO5 catalyzed by manganese(III) porphyrins. A study of the factors determining alcohol and ketone formation

As reported in previous papers, the oxidation of ethylbenzene with Ph₄PHSO₅ catalyzed by Mn(TMP)Cl in the presence of nitrogen bases in 1,2-dichloroethane homogeneous solution affords fair yields (up to 80%) of oxygenated products. Acetophenone is the major product together with minor amounts of 1-phenylethanol ([ketone]/[alcohol]6). In this paper we report further observations concerning this system. In particular we find that a similar products distribution is observed when soluble Co(II) or Fe(II) species, i.e. acetylacetonate derivatives, are used instead of the manganese porphyrin. On the other hand for these compounds, which are catalysts of radical reactions, the product distribution is determined by a remarkably larger reactivity of the alcohol initially formed compared with that of the alkane (k_R–OH/k_R–H200). The product distribution for the Mn(TMP)Cl catalysis cannot be rationalized on the same basis. Direct experiments show that the reactivity of the two substrates is similar (k_R–OH/k_R–H2–6) thus suggesting that a mechanism different from the simple radical hydrogen atom abstraction is taking place. The dependence of the chemioselectivity of hydrocarbon oxidation on the nature of the manganese porphyrin employed and of a number of additives indicates that the product distribution is mainly determined by the relevance of the association of the alcohol intermediate to the catalyst prior to the second oxidation step leading to ketone. Two different rho Hammett's values are obtained for ethylbenzenes oxidation depending on the method employed for the measurement of reaction rates, i.e. by separate or by competitive experiments thus providing further mechanistic information on the association of the substrates to the oxo-species.     

Short-time synthesis of SBA-15 using various silica sources

A short-time synthesis of SBA-15 is reported by using two different silica sources, sodium metasilicate (Na2SiO3(9)H2O) and tetraethyl orthosilicate (TEOS). The SBA-15 samples obtained from both silica sources were highly ordered as evidenced by SAXS spectra showing five reflection peaks characteristic for p6mm symmetry group. While the surface areas of these samples were similar, the pore volume of the sample prepared from TEOS was slightly larger than that from sodium metasilicate. However, the latter exhibited higher microporosity and thicker pore walls. It was shown that a significant reduction of time of the self-assembly step from 24 to 2 h had no detrimental influence on the quality of SBA-15 materials.     

On the self-consistency requirement in the low density expansion of the optical potential in nuclear matter

We critically discuss the choice of the auxiliary potential U which is introduced in the low density expansion of the mass operator M(k, w). This choice is related to the analytical properties of M(k, w) in the complex w-plane and we take due account of momentum conservation in the intermediate states appearing in the diagrams associated with M(k, w). We also provide a computation of the one-hole line, rearrangement and renormalization contributions to the optical potential, of the hole state spectral function and of the momentum distribution in nuclear matter. We use a real auxiliary potential which is self-consistent up to the order considered here, i.e. which takes into account the rearrangement and the renormalization corrections. Rearrangement is treated rigorously. The dependence of the obtained results on the choice of the nucleon-nucleon interaction, namely the Hamman-Ho Kim one in our calculation, is discussed.     

The Influence of solvent and crown polyethers on the nucleophilic reactivity of potassium tert-Butylperoxide,potassium tert-Butoxide,and some other oxygen bases

The rates of reaction of t-BuOOK, t-BuOK, n-BuOOK, and p-MeC₆H₄OKwith p-nitrophenyl diphenylphosphinate 1 and with p-nitrophenyl benzoate 2 have been measured in toluene both in the absence and in the presence of crown polyether dicyclohexyl-18-crown-6 3a . The rates of nucleophilic displacementon 1 by HOO^?, t-BuOO^?, and some “nonalpha” oxyanions in water have also been determined. Solvent transfer from water to toluene results in increasing the nucleophilic reactivity of the t-butyl hydroperoxide anion. Rate ratios Q_Qa are given which allow one to estimate the enhanced reactivity of t-BuOO^? (an α-nucleophile) compared to oxygen nucleophiles of comparable base strength toward 1 and 2 . These are for substrate 1 , Q_α (water) ? 6.5 and Q_α (toluene) ? 2.7; for substrate 2 , Q_α (water) ? 5.5 and Q_α (toluene) ? 5. The hypothesis is advanced that solvation is not a major factor in determining the α-effect of the t-butylhydroperoxide anion.     

How do concentration and dosage of the contrast agent affect the signal change in perfusion-weighted magnetic resonance imaging? A computer simulation

In this study we investigated the effect of varying both concentration and dosage of an intravenously administered MR contrast agent on the concentration-time curve in brain tissue. Aside from injection time and injection rate, our model considers the distribution of transit-time between injection site and brain but it is independent from pulse rate, heart volume or other circulation parameters. The width of the transit-time distribution and the concentration-time course in the brain were computed according to indicator dilution theory. We found that increasing the dosage of the administered contrast agent raises the maximum concentration of the agent in the brain, particularly if the injection time is short. Increasing the concentration of the agent (at fixed dosage and injection rate) also increases maximum concentration in the brain capillaries, particularly if the injection time is long. This increase, however, is less than that achieved by raising the dosage.     

An automated method for volumetric quantification of magnetization transfer of the brain

Cerebral white matter damages can be detected and characterized using magnetization transfer (MT) imaging. In this study a fully automated method of measuring and analyzing the MT of the whole human brain is presented and assessed. A 3D-FLASH sequence with off-resonance RF pulse was optimized for fast, volumetric MT measurements. The postprocessing software developed for this purpose includes a SPM99-based segmentation algorithm, a visualization tool, and a histogram-based MT parameter analysis. The reproducibility of the method was tested with phantom measures and in studies on nine healthy volunteers. Small variances (0-1.6%) and therefore, a high reproducibility of MT parameter measurements were found in vitro, slightly higher variances in volunteer investigations (0.7-4.0%). With our technique, we expect to be able to better recognize and follow up the progression of white matter diseases. Due to the high reproducibility, this volumetric approach is specifically suitable for longitudinal MT studies.