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     

Slow quenching for a one-dimensional kinetic Ising model: Residual energy and domain growth

A one-dimensional kinetic Ising model with Glauber dynamics subjected to a slow continuous quench to zero temperature is studied. For a rather general class of cooling schemes, described by a time-dependent temperatureT(t), the mean domain sizeL(t) is calculated along with the residual energye _res (r) as a function of the cooling rater. If the attempt frequency =₀ exp(–/kT), entering into the transition rates, is temperature dependent (i.e., the barrier is non-zero), the asymptotic growth ofL(t) is given byL()–L(t)~exp[–/kT(t)]. For this case the residual energy exhibits a power-law behaviore _res(r) ~r ^{/2(1 + )} forr small, where =4J/ andJ is the nearest neighbor coupling constant. For =0 and for certain cooling schemes the residual energy is zero andL(t)~t1/2, independent ofr.     

Simultaneous analysis of oxidized and reduced glutathione in cell extracts by capillary zone electrophoresis

Glutathione (GSH) and glutathione disulfide (GSSG) levels in cells constitute a thiol redox system. They can be used as an indicator of oxidative stress of the cell. In this study, a capillary zone electrophoresis (CZE) method is described that enables quantitation of GSH and GSSG from cellular extracts. The CZE buffer used was 20 mM ammonium acetate containing 5% (v/v) acetic acid at pH 3.1 in conjunction with a polybrene coated capillary operated in reverse polarity mode. Effects of different acids used to prepare cell samples were investigated on CZE performance. The acids include meta phosphoric acid (MPA), trichloroacetic acid (TCA), phosphoric acid (PA) and sulfosalicylic acid (SSA) and are used to stabilize GSH and GSSG before performing CZE analysis. The method features a limit of detection of 4 microM and a limit of quantitation of 12 microM for both GSSG and GSH and recoveries of 94% for GSH and 100% for GSSG. Quantitative analysis of GSSG and GSH in HaCaT cell extracts (5% SSA, w/v) was performed with this method and changes in the ratio of GSH to GSSG in N-ethylmaleimide treated cell sample was observed by comparing with control cell samples.     

Generalizations of the neumann system a curve-theoretical approach-part I

The following observation, due to E. Trubowitz, illustrates an intimate relationship between spectral theory and Hamiltonian mechanics in the presence of constraints. Let q(s) be a real periodic function such that the Hill operator, has only a finite number g^R of simple eigenvalues. There exist g^R + 1 periodic eigenfunctions x₁,…, x and corresponding eigenvalues a₁,…, a of L such that where y_r = dx_r/ds. The equations Lx_r = a_rx_r, r = 1,…,g_R+1, make up the classical Neumann system, a system of harmonic oscillators constrained to the unit sphere. H. Flaschka obtained similar results about the Neumann system from a more general point of view. His assumption, that there exists an operator of odd order that commutes with L, leads to algebraic curve theory by the method of Krichever and from there to the Neumann formulas above. The familiar Lax pairs, the constants of motion and the quadrics of the Neumann system emerge as consequences of the Riemann-Roch theoreni. The existence of isospectral deformations of L, the Korteweg de-Vries hierarchy of the soliton equations, underlies the complete integrability of the Neumann system. This paper extends Flaschka's techniques, replacing L by an operator of order n 2 2. Higher Neumann systems are defined in a way that leads naturally to interesting symplectic manifolds, Lax pairs and integrals of motion. C. Tomei, using scattering theory, obtained some of our n = 3 formulas.     

A Role for Neuropeptides in UVB-Induced Systemic Immunosuppression

The aim of this study was to investigate the possible role of sensory nerves in UV light-induced systemic immunomodulation. Contact hypersensitivity to the low molecular weight compound picrylchloride was used as a model for cellular immunity that can be suppressed by low (i.e. suberythemal) doses of UV light even after exposure at a distant locus (i.e. systemic immunosuppression). In sensory nerve-depleted mice, achieved by two subcutaneous injections with the neurotoxin capsaicin before the age of 4 weeks, UV light exposure failed to inhibit contact hypersensitivity responses to picrylchloride. This indicates that sensory nerves are at least partially involved in the induction of systemic immunosuppression by UV light. In order to analyze whether sensory neuropeptides, such as calcitonin gene-related peptide (CGRP) and tachykinins, are involved in UV light-induced systemic immunosuppression, mice were pretreated with selective antagonists prior to each UV light exposure. These experiments indicated that CGRP but not the tachykinins plays a crucial role in the UV light-induced systemic immunosuppression.     

Self-assembly of dendrimers by slippage

[reaction: see text] A dendrimer with rotaxane-like characteristics has been assembled under thermodynamic control from complementary wedge-shaped precursors by slippage in CH(2)Cl(2). The driving force for the self-assembly process is the molecular recognition that exists as a result of [N(+)-H.O] and [C-H.O] hydrogen bonds between an NH(2)(+) center in one Fréchet-type benzyl ether wedge and a dibenzo[24]crown-8 unit that links the other two such wedges.     

Gas-phase derivatization of [C3H5]+ ions using tandem mass spectrometry methods A13C labelling study

The study of specifically ¹³C-labelled precursors sheds further light on the gas-phase chemistry of allyl and 2-propenyl cations. It is demonstrated that both species are formed from allyl and 2-propenyl bromide upon 70 eV electron impact ionization without skeletal reorganization. Gas-phase derivatization of the [C₃ H₅]⁺ ions with benzene facilitates, as suggested and observed earlier, the distinction of the two isomers using collision-induced dissociation of the Wheland complexes (or isomers thereof). The ¹³C labelling data clearly demonstrate that 64% of allyl cations survive the derivatization while 36% isomerize to 2-phenylpropyl cations; the latter are also formed via the reaction of 2-propenyl cation with benzene, protonation of α-methylstyrene and water loss from protonated 2-phenyl-2-propanol, respectively. Unimolecular loss of C₂H₄ from protonated allylbenzene proceeds via two competing reaction channels: one involves heterolysis of 1-phenylpropyl cations (～30%); the major pathway (～70%), however, involves decomposition via propylene benzenium ions.