Microwave Effects Due to Anionic or Cationic Initiators in Emulsion Polymerization Reactions

Summary: Emulsion polymerization reactions were performed under microwave irradiation and conventional heating using anionic or cationic initiators and surfactants. Microwave irradiation promoted higher reaction rates for both initiators and surfactants, in comparison with the conventional heating. The effect of high power microwave irradiation was studied using a method of cycles of heating and cooling, where rapid polymerization reactions were obtained. In the reactions with anionic initiator and surfactant, a decrease in the particle diameters was observed with microwave heating, and even smaller particles were obtained using high power microwave irradiation. Moreover, the decrease in the particle size was acompanied by an increase in the polymer molecular weight. On the other hand, these effects were not observed for reactions with cationic initiator and surfactant.     

Kinetics and Molecular Weight Development of Dithiolactone‐Mediated Radical Polymerization of Styrene

Calculations of polymerization kinetics and molecular weight development in the dithiolactone‐mediated polymerization of styrene at 60 °C, using 2,2′‐azobisisobutyronitrile (AIBN) as initiator and γ‐phenyl‐γ‐butirodithiolactone (DTL1) as controller, are presented. The calculations were based on a polymerization mechanism based on the persistent radical effect, considering reverse addition only, implemented in the PREDICI® commercial software. Kinetic rate constants for the reverse addition step were estimated. The equilibrium constant (K = k_add/k_‐add) fell into the range of 10⁵–10⁶ L · mol^?1. Fairly good agreement between model calculations and experimental data was obtained.

     

Graphs of transportation polytopes

This paper discusses properties of the graphs of 2-way and 3-way transportation polytopes, in particular, their possible numbers of vertices and their diameters. Our main results include a quadratic bound on the diameter of axial 3-way transportation polytopes and a catalogue of non-degenerate transportation polytopes of small sizes. The catalogue disproves five conjectures about these polyhedra stated in the monograph by Yemelichev et al. (1984). It also allowed us to discover some new results. For example, we prove that the number of vertices of an m×n transportation polytope is a multiple of the greatest common divisor of m and n.     

Stable equivariant abelianization, its properties, and applications

Let G be a finite group. For a based G-space X and a Mackey functor M, a topological Mackey functor is constructed, which will be called the stable equivariant abelianization of X with coefficients in M. When X is a based G-CW complex, is shown to be an infinite loop space in the sense of G-spaces. This gives a version of the RO(G)-graded equivariant Dold-Thom theorem. Applying a variant of Elmendorf's construction, we get a model for the Eilenberg-Mac Lane spectrum HM. The proof uses a structure theorem for Mackey functors and our previous results.     

Synthesis, photochemistry, and electrochemistry of single-wall carbon nanotubes with pendent pyridyl groups and of their metal complexes with zinc porphyrin. Comparison with pyridyl-bearing fullerenes

A soluble, functionalized Py-SWNT has been synthesized and characterized by solution (1)H and (13)C NMR, FT-Raman, and electron microscopy. Experimental data indicate that Py-SWNT has short tubes with pentyl esters at the tips and pyridyl isoxazolino units along the walls. The synthesis of Py-SWNT is based on a 1,3-dipolar cycloaddition of a nitrile oxide on the SWNT walls, similar to 1,3-dipolar cycloadditions that are common for fullerene functionalization. The resulting Py-SWNT forms a complex with a zinc porphyrin (ZnPor) in a way similar to that reported for pyridyl-functionalized [60]-fullerenes. Formation of this metal-ligand complex was firmly established by a detailed electrochemical study. However, in contrast to the behavior observed for the ZnPor/Py-C(60) complex, photochemical excitation of the complex between ZnPor/Py-SWNT does not lead to electron transfer with the generation of charge-separated states. Fluorescence and laser flash studies indicate that the main process is energy transfer from the singlet ZnPor excited state to the Py-SWNT with observation of emission from Py-SWNT. Triplet ZnPor excited-state quenching by Py-SWNT is only observed in polar solvents such as DMF, but not in benzonitrile.     

Electrostatic attraction between cationic-anionic assemblies with surface compositional heterogeneities

Electrostatics play a key role in biomolecular assembly. Oppositely charged biomolecules, for instance, can be coassembled into functional units, such as DNA and histone proteins into nucleosomes and actin-binding protein complexes into cytoskeleton components, at appropriate ionic conditions. These cationic-anionic coassemblies often have surface charge heterogeneities that result from the delicate balance between electrostatics and packing constraints. Despite their importance, the precise role of surface charge heterogeneities in the organization of cationic-anionic coassemblies is not well understood. We show here that coassemblies with charge heterogeneities strongly interact through polarization of the domains. We find that this leads to symmetry breaking, which is important for functional capabilities, and structural changes, which is crucial in the organization of coassemblies. We determine the range and strength of the attraction as a function of the competition between the steric and hydrophobic constraints and electrostatic interactions.     

How "sticky" are short-range square-well fluids?

The aim of this work is to investigate to what extent the structural properties of a short-range square-well (SW) fluid of range lambda at a given packing fraction eta and reduced temperature T* = kBT/epsilon can be represented by those of a sticky-hard-sphere (SHS) fluid at the same packing fraction and an effective stickiness parameter tau(T*,lambda). Such an equivalence cannot hold for the radial distribution function g(r) since this function has a delta singularity at contact (r = sigma) in the SHS case, while it has a jump discontinuity at r = lambda sigma in the SW case. Therefore, the equivalence is explored with the cavity function y(r), i.e., we assume that [formula: see text]. Optimization of the agreement between y(SW) and y(SHS) to first order in density suggests the choice tau(T*,lambda) = [12(e(1/T* - 1)(lambda - 1)](-1). We have performed Monte Carlo (MC) simulations of the SW fluid for lambda = 1.05, 1.02, and 1.01 at several densities and temperatures T* such that tau(T*,lambda) = 0.13, 0.2, and 0.5. The resulting cavity functions have been compared with MC data of SHS fluids obtained by Miller and Frenkel[J. Phys.: Condens. Matter 16, S4901 (2004)]. Although, at given values of eta and tau, some local discrepancies between y(SW) and y(SHS) exist (especially for lambda = 1.05), the SW data converge smoothly toward the SHS values as lambda-1 decreases. In fact, precursors of the singularities of y(SHS) at certain distances due to geometrical arrangements are clearly observed in y(SW). The approximate mapping y(SW)-->y(SHS) is exploited to estimate the internal energy and structure factor of the SW fluid from those of the SHS fluid. Taking for y(SHS) the solution of the Percus-Yevick equation as well as the rational-function approximation, the radial distribution function g(r) of the SW fluid is theoretically estimated and a good agreement with our MC simulations is found. Finally, a similar study is carried out for short-range SW fluid mixtures.     

Mimicking the atmospheric OH-radical-mediated photooxidation of isoprene: formation of cloud-condensation nuclei polyols monitored by electrospray ionization mass spectrometry

Recently, it has been proposed (M. Claeys et al., Science 2004; 303: 1173) that the atmospheric OH-radical-mediated photooxidation of isoprene is a source of two major secondary organic aerosol (SOA) components, that is, 2-methylthreitol and 2-methylerythritol. These diastereoisomeric tetrols, which were characterized for the first time in the fine size fraction (<2.5 microm aerodynamic diameter) of aerosols collected in the Amazon rain forest during the wet season, were proposed to enhance the capability of the aerosols to act as cloud-condensation nuclei. In the present study, we performed the oxidation of isoprene in aqueous solution under conditions that attempted to mimic atmospheric OH-radical-induced photooxidization, and monitored and characterized on-line the reaction products via electrospray ionization mass (and tandem mass) spectrometry in the negative ion mode. The results show that the reaction of isoprene with photo- or chemically generated hydroxyl radicals indeed yields 2-methyltetrols. Other polyols were also detected, and they may therefore be considered as plausible SOA components eventually formed in normal or more extreme OH-radical-mediated photooxidation of biogenic isoprene.