Properties of solution-grown crystals of fractions of isotactic polypropylene with different degrees of stereoregularity

Solution-grown crystals of fractions of isotactic polypropylene (IPP) with different degrees of stereoregularity have been obtained by isothermal crystallization from α-chloronaphthalene, using a self-seeding technique. Electron micrographs of samples, crystallized under the same undercooling, show that, with decreasing fraction of isotactic pentads, the perfect rectangular shape of the single crystal is lost and the presence of more complex morphologies is increasingly observed. The equilibrium dissolution temperature T_d of IPP fractions, from polymers prepared with a titanium based catalyst, decreases linearly with decreasing percentage of isotactic pentads. An extrapolated value of 171°C is obtained for the equilibrium dissolution temperature of a crystal of IPP with 100% isotactic pentads, i.e., an IPP crystal free of configurational defects. The melting temperature T′_m and the apparent enthalpy of fusion ΔH of crystallized and annealed crystal aggregates have been determined by differential calorimetry. The equilibrium melting temperature T_m also depends greatly upon the isotactic pentad concentration. For 100% concentration the extrapolated value of T_m is 181°C. T_m decreases about 1°C per 1% decrease in the isotactic pentad population. The observed equilibrium melting and dissolution temperature depression does not follow the predictions of the Flory equation for copolymer crystallization. In fact, the effect of decreasing probability of isotactic sequence propagation is to depress T_d and T_m much more rapidly. The apparent enthalpy of fusion of both solution-grown crystals and melt-recrystallized samples decreases with an increase in the number of configurational impurities along the chain. For the most stereoregular fraction the average length of isotactic stereoblocks has been compared with the lamellar thickness of solution-grown lath-shaped single crystals.     

Characterisation by high-performance liquid chromatography-multiple mass spectrometry of intermediate compounds formed from mepanipyrim photoinduced degradation

Mepanipyrim, a widely used pyrimidinic fungicide, has been photocatalytically degraded in aqueous solution on TiO2. The purpose of this study is to artificially produce degradation compounds similar to those formed in the environment. Numerous intermediates have been identified and characterised through a MSn spectra analysis, allowing us to give insight into the early steps of the degradation process. Several concomitant pathways occur concerning both reductive and/or oxidative attacks; the main steps involve the cleavage of triple bond, mono and bihydroxylation of the parent molecule, loss of benzene moiety and/or propynylic chain. All these structures are easily degraded themselves, so that the only species recognised to endure in the investigated times is guanidine. A mechanism of transformation accounting for the identified intermediates is proposed.     

Temperature dependent magnetic anisotropy in metallic magnets from an ab initio electronic structure theory: L1(0)-ordered FePt

Using a first-principles, relativistic electronic structure theory of finite temperature metallic magnetism, we investigate the variation of magnetic anisotropy K with magnetization M in metallic ferromagnets. We apply the theory to the high uniaxial K material, L1(0)-ordered FePt, and find its magnetic easy axis perpendicular to the Fe/Pt layers for all M and K to be proportional to M2 for a broad range of values of M. For small M, near the Curie temperature, the calculations pick out the easy axis for the onset of magnetic order. Our ab initio results for this important magnetic material agree well with recent experimental measurements, whereas the single-ion anisotropy model fails to give the correct qualitative behavior.     

Replacement of benzene with regulators for the catalyzed polymerization of 1,3‐butadiene to high cis‐1,4‐polybutadiene

The polymerization regulators mesitylene and 1,3,5‐trimethoxybenzene were investigated as suitable substitutes for benzene in the cobalt(II) octanoate/diethylaluminum chloride/water‐catalyzed polymerization of 1,3‐butadiene to high cis‐1,4‐polybutadiene. The propagation rates were reduced by 50% with the inclusion of 18 mM mesitylene or 0.17 mM trimethoxybenzene. Mesitylene was found to be an inefficient polymerization regulator because it reduced the propagation rate by a combination of regulation and destruction of the active catalyst complex. Not only did trimethoxybenzene reduce the propagation rate by effective regulation at low concentration, it also increased the percentage activity of cobalt to 200%, indicating that two polymer chains were propagating simultaneously from each active center. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2244–2255, 2001     

Well‐posedness,positivity, and time asymptotics properties for a reaction–diffusion model of plankton communities,involving a rational nonlinearity with singularity

In this work, we consider a reaction–diffusion system, modeling the interaction between nutrients, phytoplankton, and zooplankton. Using a semigroup approach in , we prove global existence, uniqueness, and positivity of the solutions. The nonlinearity is handled by providing estimates in , allowing to deal with most of the functional responses that describe predator/prey interactions (Holling I, II, III, Ivlev) in ecology. The paper finally exhibits some time asymptotic properties of the solutions.     

A new method based on low background instrumental neutron activation analysis for major,trace and ultra-trace element determination in atmospheric mineral dust from polar ice cores

Dust found in polar ice core samples present extremely low concentrations, in addition the availability of such samples is usually strictly limited. For these reasons the chemical and physical analysis of polar ice cores is an analytical challenge. In this work a new method based on low background instrumental neutron activation analysis (LB-INAA) for the multi-elemental characterization of the insoluble fraction of dust from polar ice cores is presented. Thanks to an accurate selection of the most proper materials and procedures it was possible to reach unprecedented analytical performances, suitable for ice core analyses. The method was applied to Antarctic ice core samples. Five samples of atmospheric dust (μg size) from ice sections of the Antarctic Talos Dome ice core were prepared and analyzed. A set of 37 elements was quantified, spanning from all the major elements (Na, Mg, Al, Si, K, Ca, Ti, Mn and Fe) to trace ones, including 10 (La, Ce, Nd, Sm, Eu, Tb, Ho, Tm, Yb and Lu) of the 14 natural occurring lanthanides. The detection limits are in the range of 10⁻¹³–10⁻⁶ g, improving previous results of 1–3 orders of magnitude depending on the element; uncertainties lies between 4% and 60%.     

Donor–acceptor rod–coil block copolymers comprising poly[2,7‐(9,9‐dihexylfluorene)‐alt‐bithiophene] and fullerene as compatibilizers for organic photovoltaic devices

The successful synthesis is described for a donor–acceptor rod–coil block copolymer comprising blocks of poly[2,7‐(9,9‐dihexylfluorene)‐alt‐bithiophene] (F6T2) and polystyrene functionalized with fullerene (PS(C₆₀)) (F6T2‐b‐PS(C₆₀)). This new material was obtained by combining Suzuki polycondensation with radical addition fragmentation chain transfer. The block copolymer was characterized by nuclear magnetic resonance, gel permeation chromatography, and optical spectroscopy methods. Photophysical data for (F6T2‐b‐PS(C₆₀)) and a related block copolymer (F6T2‐b‐PS(PCBM)) (PCBM, phenyl‐C61‐butyric acid methyl ester) are reported and their performance as compatibilizers in bulk heterojunction organic solar cells is assessed. It is demonstrated that the addition of the rod–coil block copolymers to the active layer extends the operational stability of organic photovoltaic devices. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 888–903     

An Arm‐First Approach to Cleavable Mikto‐Arm Star Polymers by RAFT Polymerization

Redox‐cleavable mikto‐arm star polymers are prepared by an “arm‐first” approach involving copolymerization of a dimethacrylate mediated by a mixture of macroRAFT agents. Thus, RAFT copolymerization of the monomers BMA, DMAEMA, and OEGMA, with the disulfide dimethacrylate cross‐linker (DSDMA), bis(2‐methacryloyl)oxyethyl disulfide, mediated by a 1:1:1 mixture of three macroRAFT agents with markedly different properties [hydrophilic, poly[oligo(ethylene glycol) methacrylate]—P(OEGMA)_8–9; cationizable, poly[2‐(dimethylamino)ethyl methacrylate]—P(DMAEMA); hydrophobic, poly(n‐butyl methacrylate)—P(BMA)] provides low dispersity mikto‐arm star polymers. Good control (Đ < 1.3) is observed for the target P(DMAEMA)/P(OEGMA)/P(BMA) (3:3:1) mikto‐arm star, a double hydrophilic P(DMAEMA)/P(OEGMA) (3:3) mikto‐arm star and a hydrophobic P(BMA) homo‐arm star. However, Đ for the target mikto‐arm stars increases with an increase in either the ratio [DSDMA]:[total macroRAFT] or the fraction of hydrophobic P(BMA) macroRAFT agent. The quaternized mikto‐arm star in dilute aqueous solution shows a monomodal particle size distribution and an average size of ≈145 nm.

     

A Leslie-Gower Holling-type II ecoepidemic model

The modified Leslie-Gower and Holling-type II predator-prey model is generalized in the context of ecoepidemiology, with disease spreading only among the prey species. A new feature is introduced, the intraspecific competition of infected prey. All the equilibria are characterized and the existence of a Hopf bifurcation at the coexistence equilibrium is shown.