Organic hybrid of chlorinated polyethylene and hindered phenol. II. Influence of the chemical structure of small molecules on viscoelastic properties

The viscoelastic properties and stabilities of those properties of organic hybrids consisting of chlorinated polyethylene (CPE) and tetrakis[methylene‐3‐(3‐5‐di‐tert‐butyl‐4‐hydroxy phenyl)propionyloxy]methane (AO‐60) and triethylene glycol bis[3‐(3‐tert‐butyl‐4‐hydroxy‐5‐methyl phenyl)propionyloxy] (AO‐70) were investigated. The CPE/AO‐70 hybrids show only one transition, whereas for the CPE/AO‐60 hybrids, one novel relaxation appears above the glass‐transition temperature of CPE. This relaxation on the higher temperature side in the mechanical spectrum for CPE/AO‐60 is associated with the appearance of the AO‐60‐rich phase. Furthermore, the stabilities of the viscoelastic properties and microstructures of the organic hybrids consisting of CPE and multifunctional hindered phenols are dominated by the strength of the intermolecular interaction between CPE and phenols and the conformations of the middle skeletal parts of hindered phenols. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1496–1503, 2000     

Dehydration‐fragmentation mechanism of cathinones and their metabolites in ESI‐CID

Various cathinone‐derived designer drugs (CATs) have recently appeared on the drug market. This study examined the mechanism for the generation of dehydrated ions for CATs during electrospray ionization collision‐induced dissociation (ESI‐CID). The generation mechanism of dehydrated ions is dependent on the amine classification in the cathinone skeleton, which is used in the identification of CATs. The two hydrogen atoms eliminated during the dehydration of cathinone (primary amine) and methcathinone (secondary amine) were determined, and the reaction mechanism was elucidated through the deuterium labeling experiments. The hydrogen atom bonded to the amine nitrogen was eliminated with the proton added during ESI, in both of the tested compounds. This provided evidence that CATs with tertiary amine structures (such as dimethylcathinone and α‐pyrrolidinophenones [α‐PPs]) do not undergo dehydration. However, it was shown that the two major tertiary amine metabolites (1‐OH and 2″‐oxo) of CATs generate dehydrated ions in ESI‐CID. The dehydration mechanisms of the metabolites of α‐pyrrolidinobutiophenone (α‐PBP) belongs to α‐PPs were also investigated. Stable‐isotope labeling showed the dehydration of the 1‐OH metabolite following a simple mechanism where the hydroxy group was eliminated together with the proton added during ESI. In contrast, the dehydration mechanism of the 2″‐oxo metabolite involved hydrogen atoms in three or more locations along with the carbonyl group oxygen, indicating that dehydration occurred via multiple mechanisms likely including the rearrangement reaction of hydrogen atoms. These findings presented herein indicate that the dehydrated ions in ESI‐CID can be used for the structural identification of CATs.     

An experimental study on unsteady turbulent near wake of a rectangular cylinder in channel flow

 Unsteady turbulent near wake of a rectangular cylinder in channel flow has been studied experimentally with a laser Doppler velocimetry (LDV). The time-averaged and phase-averaged statistics were measured for the cylinders having various width-to-height ratios, b/h. It is shown that the turbulent intensities on the centerline of the channel have their maxima near the rear stagnation point of a recirculation region. The contours of coherent vorticity and streamline reproduce clearly the shed vortices from the cylinder observed by the flow visualization. The characteristics of the flow field, which depends on b/h, are discussed and the significant contribution of the coherent structure to the flow field is clarified. Moreover, the turbulent kinetic energy budget has been examined. Received: 19 January 1998/Accepted: 21 July 1998     

Limit of the solutions for the finite horizon problems as the optimal solution to the infinite horizon optimization problems

In this paper, we consider how to construct the optimal solutions for the undiscounted discrete time infinite horizon optimization problems. We present the conditions under which the limit of the solutions for the finite horizon problems is optimal among all attainable paths for the infinite horizon problem under two modified overtaking criteria, as well as the conditions under which it is the unique optimum under the sum-of-utilities criterion. The results are applied to a parametric example of a simple one-sector growth model to examine the impacts of discounting on the optimal path.     

Applications of Clifford’s Geometric Algebra

We survey the development of Clifford’s geometric algebra and some of its engineering applications during the last 15 years. Several recently developed applications and their merits are discussed in some detail. We thus hope to clearly demonstrate the benefit of developing problem solutions in a unified framework for algebra and geometry with the widest possible scope: from quantum computing and electromagnetism to satellite navigation, from neural computing to camera geometry, image processing, robotics and beyond.     

Ultimate tensile behavior of linear polyethylene solids

The influence of the elongation rate and temperature on the ultimate tensile properties of melt‐crystallized linear polyethylene solids was investigated, with a double‐edge‐notched specimen to avoid necking, in which uniform deformation could be assumed throughout the experiment. The data on ultimate properties such as the tensile strength and elongation at break for different temperatures could be superimposed, by shifts along the elongation rate axis, to give a master curve as a function of the time to rupture. The shift factors obtained from the superpositioning of both the tensile strength and ultimate strain took the form of the Williams–Landel–Ferry equation. As a result, the ultimate data provided a failure envelope curve that made it possible to predict rupture times when the tensile tests were conducted under any experimental conditions. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2018–2026, 2002     

Viscoelastic properties of bis(phenyl)fluorene‐based cardo polymers with different chemical structure

Viscoelastic properties of urethane and ester conjugation cardo polymers that contain fluorene group, 9,9‐bis(4‐(2‐hydroxyethoxy)phenyl)fluorene (BPEF), were investigated. As for the urethane‐type cardo polymers containing BPEF in the main chain, it had a high glass‐transition temperature (T_g), which was observed as the α dispersion on viscoelastic measurement, and its temperature depended on the chemical structure of the spacing unit, such as toluene diisocyanate (TDI), 4,4′‐methylene diphenyl diisocyanate (MDI), methylene dicycloexyl diisocyanate (CMDI), and hexamethylene diisocyanate (HDI). Moreover, the T_g of urethane‐type cardo copolymers with various cardo contents increased with an increase of cardo content. Owing to the increase of T_g of cardo polymers, another molecular motion can be measured at the temperature between the α and β dispersion that was assigned to the molecular motion of urethane conjugation unit around 200 K, and it was referred to as the α_sub dispersion. The peak temperature of the α_sub dispersion was influenced by the chemical structure of the spacing unit, but it did not change for the cardo polymer containing the same spacing unit. Consequently, it was deduced that the α_sub dispersion was originated in the subsegmental molecular motions of the cardo polymers. Ester‐type cardo polymer had higher T_g in comparison with noncardo polymer that consisted of dimethyl groups (BPEP) instead of BPEF as well. The α_sub dispersion was also measured at the temperature between the α and β dispersion, which was assigned to the molecular motion of ester conjugation unit, around 220 K. For ester cardo polymer, the γ dispersion was measured in a low‐temperature region around 140 K, and it was due to a small unit motion in the ester‐type cardo polymers, such as ethoxyl unit, ? C₂H₄O? . Moreover, the intensity of the γ dispersion of noncardo polymer was higher than that of cardo polymer, which means the molecular motion was much restricted by the cardo structure of BPEF. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2259–2268, 2005     

Classification of non‐well‐founded sets and an application

A complete list of Finsler, Scott and Boffa sets whose transitive closures contain 1, 2 and 3 elements is given. An algorithm for deciding the identity of hereditarily finite Scott sets is presented. Anti‐well‐founded (awf) sets, i. e., non‐well‐founded sets whose all maximal ∈‐paths are circular, are studied. For example they form transitive inner models of ZFC minus foundation and empty set, and they include uncountably many hereditarily finite awf sets. A complete list of Finsler and Boffa awf sets with 2 and 3 elements in their transitive closure is given. Next the existence of infinite descending ∈‐sequences in Aczel universes is shown. Finally a theorem of Ballard and Hrbá?ek concerning nonstandard Boffa universes of sets is considerably extended.     

Poly(γ-alkyl L-glutamates). II. Optical rotatory dispersion studies in organic solvents

Conformations of a series of poly(γ-alkyl L -glutamates) (ethyl, n-propyl, n-butyl, isobutyl, and isoamyl) were studied by ORD and infrared absorption methods. All except the n-propyl ester were found to be in helical form in nonpolar non-aromatic solvents such as ethyl acetate, chloroform, ethylene dichloride, methylene chloride, carbon tetrachloride, 2-chloroethanol, dimethylformamide, and dioxane. In such cases, the Cotton effects due to the n–π* transition of peptide bonds occurred near 234 mμ and were of a magnitude similar to those found for poly(γ-benzyl L -glutamate) and poly-L -methionine in nonpolar non-aromatic organic solvents. These four polypeptides in aromatic nonpolar solvents, such as benzene, benzyl alcohol, pyridine, and m-cresol, were also found to be in helical form, although the ORD parameters differed considerably from the values in non-aromatic solvents. An essential cause seems to be the interaction of π electrons on peptide bonds with π electrons in the solvents. Helix-coil transitions of these esters in chloroform-dichloroacetic acid mixtures (dichloroacetic acid seems to be a random coil-forming solvent) were expressed by the Shechter-Blout formulation. This was not true, however, for helix–coil transitions in benzyl alcohol–dichloroacetic acid mixtures. The dependence of the helical stability of these polypeptides in chloroform solution upon the side-chain length and upon temperature is discussed.