Control of the block copolymer morphology in templated epoxy thermosets

It has been found that by the addition of low concentrations of an amphiphilic block copolymer to an epoxy resin, novel disordered morphologies can be formed and preserved through curing. This article will focus on characterizing the influence of the block copolymer and casting solvent on the templated morphology achieved in the thermoset sample. The ultimate goal of this work is to determine the parameters that would control the microphase morphology produced. Epoxy resins blended with a series of amphiphilic block copolymers based on hydrogenated polyisoprene (polyethylene-alt-propylene or PEP) and polyethylene oxide (PEO), specifically, were investigated. In this article, the cure-induced order–order phase transition from the spherical to wormlike micelle morphology will also be discussed. It is proposed that the formation of the wormlike micelle structure from the spherical micelle structure is similar to the phase transition behavior that occurs in dilute block copolymer solutions as a function of the influence of the solvent on micelle morphology. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 3338–3348, 2007     

Theories of mathematics education: European perspectives, commentaries and viable research directions

We briefly comment on different perspectives on (1) the role of mathematics education theories, (2) the issue of plurality and healthy heterogeneity versus consolidation; (3) underlying inquiry systems or the implicit role of philosophy in theories of mathematics education. This paper also outlines developments within the European research scene on theory usage in mathematics education research, which complement the discussion at the 29th PME research forum in Melbourne.     

Numerical Modeling of Solitons in a Low Birefringent Optical Fiber

A numerical investigation, based on the split-step Fourier transform algorithm of all optical switching of solitons in a low birefringent optical fiber is presented. The numerical algorithm is described in detail. This revised version was published online in August 2006 with corrections to the Cover Date.     

Solution and solid-state NMR characterization of poly(p-phenylene terephthalamide)

NMR spectroscopy has been used to characterize poly(p-phenylene terephthalamide) in the solid state and in solution in sulfuric acid. Solid-state ¹³C NMR spectra illustrate that the chain structure is highly ordered in the solid state and is of lower symmetry than in solution. Solid-state ¹³C and ¹H NMR results show that only very limited motion takes place over the temperature range of ?170 to +200°C. High-resolution NMR spectra can be observed only in very dilute isotropic solutions because it is the overall rotational motion of the polymer, not segmental motion, that averages the nuclear spin interactions to their isotropic values. These results demonstrate that previous solution NMR studies that were interpreted as reflecting the presence of isotropic and anisotropic high-molecular-weight polymer phases over a wide range of concentrations actually are representative of polymer degradation.     

Selected-area growth of carbon nanotubes by the combination of focused ion beam and chemical vapor deposition techniques.

In this article, we report a technique for growing carbon nanotubes in a more controllable fashion, which enables us to synthesize nanotubes directly in various forms of designed patterns. This nanofabrication process is based on a combination of focused ion beam (FIB) and chemical vapor deposition (CVD) techniques. In this process, arrays of conductive patterns were first deposited on silicon substrates by directing a gaseous compound (C(9)H(16)Pt) via the capillary needle-sized nozzles within a FIB system. The substrates were then coated with catalyst and further modified by the FIB to localize the position of the catalyst. Finally, the growth of carbon nanotubes on the designed substrates was carried out by CVD of hydrocarbon gases. This fabrication technique has the advantage of positioning carbon nanotubes in selected locations. This may open up opportunities for the direct synthesis of carbon nanotubes onto almost any substrate material, thus allowing fabrication of carbon nanotube-based devices.     

Second Dissociation Constant of Bis-[(2-hydroxyethyl)amino]acetic Acid (BICINE) and pH of Its Buffer Solutions from 5 to 55 °C

The values of the second dissociation constant, K ₂, and related thermodynamic quantities of the ampholyte bis[(2-hydroxyethyl)amino]acetic acid (BICINE) have been determined at temperatures from 5 to 55 ^∘C. The pH values of six equimolal buffer solutions, and four buffer solutions having ionic strengths (I = 0.16 mol⋅kg⁻¹) similar to those in blood plasma, have been evaluated at 12 temperatures from 5 to 55 ^∘C using the Bates–Guggenheim convention. The liquid junction potentials (E _j ) between the buffer solutions of BICINE and saturated KCl solution of the calomel electrode at 25 and 37 ^∘C have been estimated by measurement with a flowing junction cell. These values of E _j have been used to ascertain the operational pH values at 25 and 37 ^∘C. The pK ₂ values at 25 and 37 ^∘C are 8.333 and 8.156, respectively. The thermodynamic quantities associated with the second acid dissociation have been calculated from the values of pK ₂ as a function of temperature. The zwitterionic buffer BICINE was shown to be useful as a pH standard in the region close to that of blood serum.     

Nonexponential Fluorescence Decay of 7-Azatryptophan Induced in a Peptide Environment

7-Azatryptophan is an alternative to tryptophan as an optical probe of protein structure and dynamics. 7-Azatryptophan is synthetically incorporated into an octapeptide (NAc-Lys-Ala-Cys-Pro-7-azatryptophan-Asn-Cys-Asp-NH₂) that mimics the active site of potato chymotrypsin inhibitor II, which is known to be a strong inhibitor of α-chymotrypsin. The synthetic octapeptide retains some of this inhibitory activity. This is the first compound containing the 7-azaindole chromophore to display a nonexponential fluorescence decay (well fit to two exponentials) in water when fluorescence is collected over the entire emission band. The effect of external quenchers on the fluorescence decay is monitored and seen to differ markedly for the two components. These results are discussed in terms of the solvation of the 7-azaindole chromophore itself, which promotes or impedes excited-state tautomerization. The fluorescence quenching of free indole and 7-azaindole are compared. The fluorescence quenching of octapeptides containing both chromophores is also compared. It is the thesis of this article that the nonexponential fluorescence decay of the 7-azatryptophan-containing octapeptide is a consequence of excited-state tautomerization of the 7-azaindole chromophore. This tautomerization is suggested to be promoted by solvent reorganization induced by the peptide backbone or by direct interactions of the 7-azaindole with neighboring amino acid side chains.     

Ammonium hexafluorosilicate salts

The preparation and characterization of the ammonium hexafluorosilicate salts, 2[R]⁺ [SiF₆]²⁻ (where R=piperidinium (2), methylammonium (3), quinolinium (4), acridinium (5), 2,2,6,6-tetramethylpiperidinium (6), and propylammonium (7)) is described.The salts were prepared from the reaction of the corresponding alkylammonium fluoride with silica gel. The compounds were characterized by NMR, IR, mass spectrometry and in the case of 1 (piperidinium fluoride), 2-4 by X-ray crystallography. Compounds 1-3 crystallize in the orthorhombic crystal system (space groups Iba2, Fdd2, and Pnnm, respectively), with Z=8, 14, and 4, respectively. Compound 4 crystallizes in the triclinic space group P-1, with Z=2. Compounds 1-4 exhibit hydrogen bonding.