Water‐soluble/dispersible carbazole‐containing random and block copolymers by nitroxide‐mediated radical polymerisation

A series of carbazole‐containing water‐dispersible poly(acrylic acid)‐b‐(9‐(4‐vinylbenzyl)‐9H‐carbazole) block copolymers (poly(AA)‐b‐poly(VBK)) and water‐soluble poly(methacrylic acid‐ran‐(9‐(4‐vinylbenzyl)‐9H‐carbazole)) (poly(MAA‐ran‐VBK)) random copolymers were synthesised in a controlled manner (i.e. low polydispersities $(\overline {M_{{\rm w}} } /\overline {M_{n} } < 1.3)$ by nitroxide‐mediated polymerisation (NMP) using an SG1‐based alkoxyamine initiator, BlocBuilder. Poly(AA)‐b‐poly(VBK) block copolymers were most easily accessed by using poly(AA) in its protected form as the macroinitiator for the 9‐(4‐vinylbenzyl)‐9H‐carbazole (VBK) block. Controlled polymerisation of MAA was accomplished using an excess of 10 mol.% SG1 relative to BlocBuilder with VBK as controlling co‐monomer (initial molar feed content f_VBK,0 = 0.03–0.20) in dimethylformamide at 80°C. Poly(MAA‐ran‐VBK) copolymers with a final VBK molar composition of F_VBK < 0.30 resulted in water‐soluble copolymers. In addition, as macroinitiators, poly(MAA‐ran‐VBK)s were sufficiently pseudo‐living to reinitiate a second batch of monomer (90 mol.% methyl methacrylate with styrene) in organic solvent and by ab initio, surfactant‐free emulsion polymerisation. In both cases, low polydispersity, amphiphilic block copolymers resulted $(\overline {M_{{\rm w}} } /\overline {M_{{\rm n}} } < 1.3)$ . © 2012 Canadian Society for Chemical Engineering     

A 3D EFFECT IN THE WEDGE ADHESION TEST: APPLICATION OF SPECKLE INTERFEROMETRY

The wedge test is of considerable use for evaluating adhesion between two bonded rigid substrates. In its (usual) static form, release of elastic strain energy is equated to effective adhesion energy during crack growth. However, the test is usually treated as two-dimensional. In fact, it is really three-dimensional due to anticlastic bending effects of the bent beam(s) during crack propagation.

We studied a composite material/epoxy/aluminium alloy system and observed a curved crack front during propagation. This leads to doubt as to the value of crack length to be inserted in the adhesion energy formula. In addition, by using the highly sensitive technique of speckle interferometry, it was possible to study anticlastic bending effects in a quantitative manner. Far from the crack front, agreement between theory and experimental is good, yet work remains to be done to understand the zone near the fracture zone.     

Multivalent Interactions between an Aromatic Helical Foldamer and a DNA G‐Quadruplex in the Solid State

Quinoline‐based oligoamide foldamers have been identified as a potent class of ligands for G‐quadruplex DNA. Their helical structure is thought to target G‐quadruplex loops or grooves and not G‐tetrads. We report a co‐crystal structure of the antiparallel hairpin dimeric DNA G‐quadruplex (G₄T₄G₄)₂ with tetramer 1 —a helically folded oligo‐quinolinecarboxamide bearing cationic side chains—that is consistent with this hypothesis. Multivalent foldamer–DNA interactions that modify the packing of (G₄T₄G₄)₂ in the solid state are observed.     

Characterization of anisotropic gas permeability and thermomechanical properties of highly textured porous alumina

Porous alumina with a highly textured microstructure was fabricated by pulse electric current sintering (PECS) using alumina platelets. Highly oriented porous alumina with a porosity of 3%–50% was obtained by a pressure-controlled method of PECS. The properties of the highly textured porous alumina were measured in two directions. The nitrogen gas permeance and thermal conductivity at room temperature were higher in the direction along the platelet length due to the higher continuity of pores and the connectivity of alumina platelets, respectively. The anisotropy of the thermal conductivity at room temperature was investigated and explained by the effect of grain size of platelets as well as morphology and orientation of pores. The bending strength was higher with the loading direction along the platelet thickness. The thermal shock strength was clearly different in the two directions. The difference in the thermal shock strength was investigated by the measurement of properties and thermal stress analysis.     

Computational studies of the gramicidin channel

Ion channels are highly specific membrane-spanning protein structures which serve to facilitate the passage of selected ions across the lipid barrier. In the past decade, molecular dynamics simulations based on atomic models and realistic microscopic interactions with explicit solvent and membrane lipids have been used to gain insight into the function of these complex systems. These calculations have considerably expanded our view of ion permeation at the microscopic level. This Account will mainly focus on computational studies of the gramicidin A channel, one of the simplest and best characterized molecular pore.     

Interaction between dietary protein and fat in triglyceride metabolism in the rat: Effects of soy protein and menhaden oil

The objective of the present study was to determine the mechanisms by which dietary proteins interact with dietary lipids in the regulation of triglyceridemia in rats. Male Sprague-Dawley rats (n=56) were subjected to 28-d experimental diets containing different combinations of proteins (20% w/w) and lipid sources (14% w/w): (i) casein-menhaden oil, (ii) casein-beef tallow, (iii) soy protein-menhaden oil, and (iv) soy protein-beef tallow. Significant protein-lipid interactions were observed on triglyceridemia and hepatic cholesterol in fasted rats. The combination of casein and beef tallow was associated with high plasma TG and hepatic cholesterol concentrations, which were reduced by substitution either of soy for casein or of menhaden oil for beef tallow. Therefore, triglyceridemia and liver cholesterol remained low with soy protein feeding, independently of the lipid source, as well as with menhaden oil feeding, regardless of the protein source. The menhaden oil diets reduced plasma cholesterol, hepatic TG, and TG secretion compared with beef tallow diets independently of the dietary protein source. Modifying the source of dietary proteins and lipids had no effect on post-heparin plasma lipoprotein lipase activity. These results demonstrate that soy protein can lower rat triglyceridemia relative to casein when associated with beef tallow consumption, whereas menhaden oil can attenuate hypertriglyceridemia when rats are fed casein. The data further suggest that part of the hypotriglyceridemic effect of soy protein in the rat may be mediated by reduced hepatic lipid synthesis, as is the case for menhaden oil.     

Molten core fabrication of bismuth germanium oxide Bi4Ge3O12 crystalline core fibers

Optical fibers possessing a crystalline oxide core have significant potential for novel and useful electro‐ or nonlinear‐optic waveguides. Presently, however, their utility suffers from the slow speed and limited cladding materials afforded by conventional crystal‐fiber‐growth techniques. Described herein is the development of single phase bismuth germanium oxide crystalline core fibers using conventional glass fiber drawing. More specifically, fibers were fabricated and evaluated based on 2 embodiments of the molten core method. In a first approach, a Bi₄Ge₃O₁₂ single crystal was employed as the precursor and sleeved inside a borosilicate glass cladding. In the second approach, additional Bi₂O₃ was included along with the Bi₄Ge₃O₁₂ precursor single crystal. Glass clad fibers drawn from the precursor Bi₄Ge₃O₁₂ single crystal resulted in a polycrystalline core with various crystal morphologies (line‐like, dendrite‐like, and uniform grains) as will be discussed, while fibers drawn from the Bi₄Ge₃O₁₂ single crystal surrounded by Bi₂O₃ resulted in a more homogeneous microstructure. The eulytine crystal structure was crystallized using both approaches, with the formation of a secondary crystal phase using the second approach. More particularly, this work aims at showing that single phase and phase pure crystalline oxide core optical fibers can be achieved using conventional glass fiber draw processes, although further optimization is necessary for obtaining single crystalline core fibers.     

Nitroxide‐mediated synthesis of styrenic‐based segmented and tapered block copolymers using poly(lactide)‐functionalized TEMPO macromediators

Poly(styrene)‐poly(lactide) (PS‐PLA), poly (tert‐butyl styrene)‐poly(lactide) (PtBuS‐PLA) diblocks, and poly(tert‐butyl styrene)‐poly(styrene)‐poly(lactide) (PtBuS‐PS‐PLA) segmented and tapered triblocks of controlled segment lengths were synthesized using nitroxide‐mediated controlled radical polymerization. Well‐defined PLA‐functionalized macromediators derived from hydroxyl terminated TEMPO (PLA_T) of various molecular weights mediated polymerizations of the styrenic monomers in bulk and in dimethylformamide (DMF) solution at 120–130°C. PS‐PLA and PtBuS‐PLA diblocks were characterized by narrow molecular weight distributions (polydispersity index (M_w/M_n) < 1.3) when using the PLA_T mediator with the lowest number average molecular weight M_n= 6.1 kg/mol while broader molecular weight distributions were exhibited (M_w/M_n = 1.47‐1.65) when using higher molecular weight mediators (M_n = 7.4 kg/mol and 11.3 kg/mol). Segmented PtBuS‐PS‐PLA triblocks were initiated cleanly from PtBuS‐PLA diblocks although polymerizations were very rapid with PS segments ～ 5–10 kg/mol added within 3–10 min of polymerization at 130°C in 50 wt % DMF solution. Tapering from the PtBuS to the PS segment in semibatch mode at a lower temperature of 120°C and in 50 wt % DMF solution was effective in incorporating a short random segment of PtBuS‐ran‐PS while maintaining a relatively narrow monomodal molecular weight distribution (M_w/M_n ≈ 1.5). © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008