Elevation of the glass transition temperature in flexible‐chain semicrystalline polymers

In the idealized two‐phase model of a semicrystalline polymer, the amorphous intercrystalline layers are considered to have the same properties as the fully‐amorphous polymer. In reality, these thin intercrystalline layers can be substantially influenced by the presence of the crystals, as individual polymer molecules traverse both crystalline and amorphous phases. In polymers with rigid backbone units, such as poly(etheretherketone), PEEK, previous work has shown this coupling to be particularly severe; the glass transition temperature (T_g) can be elevated by tens of degrees celsius, with the magnitude of the elevation correlating directly with the thinness of the amorphous layer. However, this connection has not been explored for flexible‐chain polymers, such as those formed from vinyl‐type monomers. Here, we examine T_g in both isotactic polystyrene (iPS) and syndiotactic polystyrene (sPS), crystallized under conditions that produce a range of amorphous layer thicknesses. T_g is indeed shown to be elevated relative to fully‐amorphous iPS and sPS, by an amount that correlates with the thinness of the amorphous layer; the magnitude of the effect is severalfold less than that in PEEK, consistent with the minimum lengths of polymer chain required to make a fold in the different cases. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1198–1204, 2007     

Determination of a double Lie groupoid by its core diagram

In a double groupoid S, we show that there is a canonical groupoid structure on the set of those squares of S for which the two source edges are identities; we call this the core groupoid of S. The target maps from the core groupoid to the groupoids of horizontal and vertical edges of S are now base-preserving morphisms whose kernels commute, and we call the diagram consisting of the core groupoid and these two morphisms the core diagram of S. If S is a double Lie groupoid, and each groupoid structure on S satisfies a natural double form of local triviality, we show that the core diagram determines S and, conversely, that a locally trivial double Lie groupoid may be constructed from an abstractly given core diagram satisfying some natural additional conditions.

In the algebraic case, the corresponding result includes the known equivalences between crossed modules, special double groupoids with special connection (Brown and Spencer), and cat¹-groups (Loday). These cases correspond to core diagrams for which both target morphisms are (compatibly) split surjections.     

Purification of domoic acid from toxic blue mussels (Mytilus edulis) and phytoplankton.

Domoic acid was the primary neurotoxin in blue mussel (Mytilus edulis) that caused poisoning in humans. Further research showed that the algae, Nitzschia pungens, was the source of this toxin. In this study, a method for the extraction and purification of domoic acid from contaminated mussels and phytoplankton was developed. Domoic acid was extracted from these sources by treatment with a mixture of chloroform and methanol (1:2, v/v). The resulting extract was subjected to ultrafiltration through a PM1 Millipore filter, followed by repeated high-performance liquid chromatography on a reversed-phase column. The purity and yield of domoic acid prepared by this method are compared with two previously described methods of extraction. The current method is relatively simple, rapid, and results in improved recovery with comparable purity of domoic acid.     

Determination of colloidally-associated polycyclic aromatic hydrocarbons (PAHs) in fresh water using C18 solid phase extraction disks

A new application of reversed-phase octadecyl (C₁₈) solid phase extraction disks has been developed to separate the colloidally-associated polycyclic aromatic hydrocarbons (PAHs) from those that were truly dissolved in the samples of fresh water. A correction for the retention of small amounts of colloidal material on the C₁₈ disks was required, which would have otherwise lead to minor underestimates in the degree of partitioning between the two phases. Using the humic substance Aldrich Humic Acid (AHA) as a model colloid and the 16 PAHs on the US Enrivonmental Protection Agency priority pollutant list, the partitioning coefficients of the PAHs between the colloidal and truly dissolved phases were shown to be proportional to the hydrophobicity of the PAHs, as measured by their octanol water partition coefficients (K_ow). The values for the partition coefficients obtained (cK_doc′) were similar to those previously reported in the literature using alternative methods, confirming that the technique was producing acceptable results. The technique allows the in situ partitioning of PAHs between the truly dissolved and colloidal phases in fresh water bodies to be determined. It will provide an invaluable cross-check of the laboratory-based methods which often require substantial manipulation of the sample and potentially alter the partitioning between the phases.     

The six semifield planes associated with a semifield flock

In 1965 Knuth (J. Algebra 2 (1965) 182) noticed that a finite semifield was determined by a 3-cube array (a_ijk) and that any permutation of the indices would give another semifield. In this article we explain the geometrical significance of these permutations. It is known that a pair of functions (f,g) where f and g are functions from GF(q) to GF(q) with the property that f and g are linear over some subfield and g(x)²+4xf(x) is a non-square for all x∈GF(q)∗, q odd, give rise to certain semifields, one of which is commutative of rank 2 over its middle nucleus, one of which arises from a semifield flock of the quadratic cone, and another that comes from a translation ovoid of Q(4,q). We show that there are in fact six non-isotopic semifields that can be constructed from such a pair of functions, which will give rise to six non-isomorphic semifield planes, unless (f,g) are of linear type or of Dickson-Kantor-Knuth type. These six semifields fall into two sets of three semifields related by Knuth operations.     

Temperaturmessung

Ohne Zusammenfassung     

N. Charton,A. Feldermann,A. Theis,M. H. Stenzel,T. P. Davis,C. Barner‐Kowollik,Initiator efficiency of 2,2′‐azobis(isobutyronitrile) in bulk dodecyl acrylate free‐radical polymerizations over a wide conversion and molecular weight range (2004) 42(20) 5170–5179

The original article to which this Erratum refers was published in J Polym Sci Part A: Polym Chem (2004) 42(20) 5170–5179. No abstract.     

Asymmetric synthesis of 6-(2′,3′,4′,5′,6′-pentafluorophenyl)-δ-lactones via “allyl”boranes: application for the synthesis of fluorinated analog of key pharmacophore of statin drugs

Asymmetric “allyl”boration of pentafluorobenzaldehyde with various α-pinene based “allyl”boranes provides homoallylic alcohols in high de and ee; the alcohols have been converted into δ-lactones via acryloylation, ring-closing metathesis and hydrogenation. Pentafluorophenyl analog of key pharmacophore of statin drugs has been synthesized using diastereoselective epoxidation and regioselective reduction as key steps.     

Rod–coil block copolymers: An iterative synthetic approach via living free-radical procedures

A modular approach has been developed for the synthesis of rod–coil block copolymers involving the initial preparation of a macroinitiator based on the rod block followed by the growth of the coil segment with living free-radical procedures. The key feature of this strategy is the utilization of an alkoxyamine group from the beginning of the synthesis, which serves as a solubilizing group and ensures that each rod block contains a single initiating fragment. Using this approach permits block copolymers based on insoluble biphenyl ester oligomers to be conveniently prepared with coil segments that range from styrenes to acrylates to 1,3-dienes. The tendency of the rod segments to crystallize is strongly dependent on the weight fraction of the rod segment and the chemical nature of the coil segment. Rod–coil molecules containing at least 25–35 wt % polystyrene or poly(n-butyl acrylate) coil segments show a two-dimensional hexagonal arrangement of rod aggregates, as characterized by transmission electron microscopy and small-angle X-ray scattering. Polyisoprene block copolymers exhibit a lamellar microstructure with short rigid domains in which the rod units lie in an interdigitated smectic C arrangement. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3640–3656, 2003