Solution viscosity behavior of polystyrene-based cationic ionomers. Effects of ion content and solvent

Dilute-solution viscosities of polystyrene-based cationic ionomers containing ammonio or phosphonio groups were measured in several solvents. In polar solvents with dielectric constant (ε_r) beyond 10, the ionomers showed a typical polyelectrolyte behavior, indicating that a large part of ionic groups were dissociated into ions. In nonpolar solvents with low ε_r, the reduced viscosity of the ionomers linearly decreased with a decreasing ionomer concentration. At low polymer concentrations, every ionomer gave a reduced viscosity lower than that of the corresponding chloromethylated polystyrene. With an increasing ion content, the intrinsic viscosity progressively decreased if the nonpolar solvents had a low acceptor number (A_N), such as toluene or tetrahydrofran (THF). In the halogenated solvents with high A_N value, such as chloroform, however, the intrinsic viscosity was hardly dependent on the ion content. This indicates that the intramolecular aggregation among the ionic groups is inhibited in the halogenated solvents due to a strong anion solvation. An addition of a protic solvent to a nonpolar solvent eliminates the aggregation between ionic groups and leads to polyelectrolyte behavior. © 1994 John Wiley & Sons, Inc.     

Blaschke-Süss type theorems for closed plane curves

A C¹-class of plane closed curves is considered, which contains all ovals and rosettes. This class is divided into some subclasses for which greatest lower bounds of numbers of antipodal and arc-antipodal sets are determined.     

PHOTOOXYGENATION OF METHYL LINOLEATE SENSITIZED BY PORPHYRINS AND DYES IN ACETONITRILE SOLUTION AND AQUEOUS EMULSION SYSTEMS

Photooxygenation reaction of an unsaturated fatty acid ester, methyl linoleate (methyl 9- cis. 12- cis -octadecadienoate, ML-H), sensitized by porphyrins and several types of dyes has been studied in aqueous emulsion and acetonitrile solution under air at 40°C. The oxygen (O₂) uptake proceeded slowly in the absence of sensitizers upon irradiation of an aqueous emulsion and an acetonitrile solution of ML-H (20 m M ) at ℷ_ex > 290 nm (11.4 and 6.1 μmol h^-1, respectively). The rate of O₂ uptake was enhanced by a catalytic amount (0.1 m M ) of porphyrins and dyes; hematoporphyrin (HP), zinc tetrakis(N-methyl-4-pyridiniumyi)porphyrin (ZnTMPyP), methylene blue (MB), rose bengal (RB), acridine orange (AO), and acriflavine (AF). In both systems, the sensitized photooxidation of ML-H by O₂ proceeded equimolarly to produce isomeric mixture of C9 and C13 hydroperoxides having the trans,cis and trans,trans conjugated diene configurations, independent of the types of the sensitizers used. The yield ratio of trans,trans/ trans,cis products in the MB-sensitized photooxygenation in acetonitrile and aqueous emulsion were almost equal (0.32 and 0.35. respectively). The sensitizing activity of the sensitizers, as measured by the quantum yield of O₂ uptake, increased in the order: MB (≃ 0) < ZnTMPyP < RB < HP < AF < AO in the aqueous emulsion and AO < AF < HP < RB = MB in the acetonitrile solution. The order in homogeneous acetonitrile solution was interpreted by the sensitizing ability of the dyes to produce singlet oxygen, while that in heterogeneous aqueous emulsion was correlated to the lipophilicity of dyes as well as the singlet-oxygen-producing ability.     

An introduction to molecular spintronics

We review the progress and future possibilities in the emerging area of molecular spintronics. We first provide an overview of the different transport regimes in which electronic nanodevices can operate, then briefly overview the important characteristics of molecular magnetic materials that can be useful for application in spintronics and we eventually present several schemes to include such systems into spintronic nanodevices. We hightlight the importance of a chemical approach to the area, and in the last section we showcase some approaches to the creation of hybrids made of carbon nanostructures and molecular magnets, which are gaining increasing attention.     

Semicontinuous Emulsion Polymerization of Vinyl Acetate. Part I. Homopolymerization with Poly-(Vinyl Alcohol) and Nonionic Coemulsifier

The semicontinuous emulsion polymerization of vinyl acetate has been studied. Poly(vinyl alcohol) as a protective colloid and ethoxylated cetyl alcohol as a coemulsifier were used. The conversion and particle diameter were affected by the stirring speed and the coemulsifier distribution between initial reactor charge and continuously introduced monomer. The amount of unreacted monomer oscillates with time.     

Modelo numérico del comportamiento histerético de uniones entre forjados reticulares y pilares de fachada

Waffle-flat-plate structures have been widely used for residential and office buildings in the South of Europe between the seventies and nineties of the last century. These buildings were designed with old seismic codes and its vulnerability needs to be evaluated to determine whether they need to be seismic retrofitted or not. This article proposes a simple model that represents the moment transfer between plate and column, for existing exterior connections loaded in the direction normal to the building façade. The model takes into account singularities of existing waffle-flat-plate structures such as the concentration of reinforcement in the direction of the joints, and the existence of punching shear reinforcement. The model consists of frame elements for the columns and shell elements for the slabs, both connected with flexural and torsion hinges. The strength of the flexural hinges is obtained by estimating the portion of longitudinal reinforcement of the plate that transfers directly the unbalanced moment to the column by flexure. The yielding deformations of the flexural and torsion hinges are estimated with simple expressions. The ductility of the flexural hinges is taken from FEMA 356, while infinite ductility is adopted for the torsional hinges in accordance with previous experimental studies. It is shown that the proposed model provides a good approximation of the experimental response of the connection under monotonically increasing lateral displacements, in terms of stiffness, strength and ductility.     

Synthesis of All Stereoisomers of Monomeric Spectomycin A1/A2 and Evaluation of Their Protein SUMOylation-Inhibitory Activity

A synthetic methodology to access all possible stereoisomers of spectomycin A1 (SMA1) and A2 (SMA2) has been established through late-stage diversification. The key reaction for the construction of all four diastereomers is an intramolecular cyclization based on the umpolung of π-allyl palladium species with bis(pinacolato)diborane (B₂(pin)₂). Silyl group assisted direct benzylic oxidation of each isomer enabled construction of the fragile β-hydroxytetralone skeleton to provide the SMAs. The relative and absolute stereochemistry of SMA2 was also determined, and the absolute stereochemistry of SMA1 was extrapolated based on the optical rotation of SMA2. The axial chirality of SMAs is discussed based on circular dichroism spectra and DFT calculations, and it is concluded that the M isomer is predominant in solution. Biochemical assessment of all isomers in vitro revealed that the C9 hydroxyl group and dimeric structure were both important for protein SUMOylation-inhibitory activity.     

Operation and preventive maintenance scheduling for containerships: Mathematical model and solution algorithm

This paper considers the problem of determining operation and maintenance schedules for a containership equipped with various subsystems during its sailing according to a pre-determined navigation schedule. The operation schedule, which specifies working time of each subsystem, determines the due-date of each maintenance activity and the maintenance schedule specifies the actual start time of each maintenance activity. The main constraints are subsystem requirements, workforce availability, working time limitation, and inter-maintenance time. To represent the problem mathematically, a mixed integer programming model is developed. Then, due to the complexity of the problem, we suggest a heuristic algorithm that minimizes the sum of earliness and tardiness between the due-date and the actual start time for each maintenance activity. Computational experiments were done on various test instances and the results are reported. In particular, a case study was done on a real instance and a significant amount of improvement is reported over the experience based conventional method.