The nucleophilic, phosphine-catalyzed thiol-ene click reaction and convergent star synthesis with RAFT-prepared homopolymers

The synthesis of 3-arm star polymers from reversible addition-fragmentation chain transfer (RAFT)-prepared precursor homopolymers in combination with thiol-ene click chemistry is described. Homopolymers of n-butyl acrylate and N,N-diethylacrylamide were prepared with 1-cyano-1-methylethyl dithiobenzoate and 2,2′-azobis(2-methylpropionitrile) yielding materials with polydispersity indices (M_w/M_n) ≤ 1.18 and controlled molecular weights as determined by a combination of NMR spectroscopy, size exclusion chromatography (SEC), and matrix assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF MS). Subsequent one-pot reaction of homopolymer, hexylamine (HexAM), dimethylphenylphosphine (DMPP), and trimethylolpropane triacrylate (TMPTA) results in cleavage of the thiocarbonylthiol end-group (by HexAM) of the homopolymer yielding a macromolecular thiol that undergoes DMPP-initiated thiol-Michael addition to TMPTA yielding 3-arm star polymers. The presence of DMPP is demonstrated to serve an important second role in effectively suppressing the presence of any polymeric disulfide as determined by SEC. Such phosphine-mediated thiol-ene reactions are shown to be extremely rapid, as verified by a combination of FTIR and NMR spectroscopies, with complete consumption of the CC bonds occurring in a matter of min. MALDI-TOF MS and SEC were used to verify the formation of 3-arm stars. A broadening in the molecular weight distribution (M_w/M_n ∼ 1.35) was observed by SEC that was attributed to the presence of residual homopolymer and possibly 2-arm stars formed from trimethylolpropane diacrylate impurity. Interestingly, the MALDI analysis also indicated the presence of 1- and 2-arm species most likely formed from the fragmentation of the parent 3-arm star during analysis. Finally, a control experiment verified that the consumption of CC bonds does not occur via a radical pathway.     

Spatial ecology of reintroduced walleye (Sander vitreus) in Hamilton Harbour of Lake Ontario

Many coastal embayments in the Laurentian Great Lakes have been subjected to extensive human physical modification and pollution that has led to the loss of freshwater biodiversity. For example, Hamilton Harbour is a large coastal embayment situated at the western end of Lake Ontario, with a long history of industrial and urban development that has resulted in the loss and degradation of aquatic habitat and the extirpation of several fish species. To restore the fish community in Hamilton Harbour, several attempts have been made to increase apex predator biodiversity by reintroducing native walleye (Sander vitreus). To assess how reintroduced (i.e., stocked) walleye use Hamilton Harbour, we used acoustic telemetry to characterize the residency of individuals within the boundaries of the harbour as well as their seasonal space use, with a focused interest on the spring spawning period. During the 1?yr tracking period tagged walleye spent an average of 357?days (range 135–365?days) within the harbour. Most individuals (12/15) remained within the harbour during the entire spring spawning period, and over half of the tagged fish departed (n?=?7) at the end of summer and beginning of fall. Core use areas appeared to gradually shift more easterly as the seasons progressed from winter to summer. Results from this study indicate that stocked fish are resident within Hamilton Harbour for most of the year, including the reproductive period, which suggests that stocking efforts to re-establish walleye populations may be an effective restoration strategy if recruitment is successful.     

Analogues of the thrombin receptor tethered-ligand enhance mesangial cell proliferation

Thrombin stimulates cytosolic calcium mobilization and tritiated thymidine incorporation in rat glomerular mesangial cells. This effect may be mediated by a thrombin receptor similar to the receptor found in human platelets. In order to test this possibility, a series of analogues of the thrombin receptor peptide, SFLL-RNPNDKYEPF, was evaluated for their effects on mesangial cells. Analogues of the thrombin receptor peptide containing five, six, seven and 14 amino acids were as efficacious as thrombin with respect to calcium mobilization and thymidine incorporation, although they were significantly less potent. The dissimilarity in potency between thrombin and the thrombin receptor peptides is consistent with the kinetics of the proposed mechanism of action of the enzyme, since the cleavage by thrombin of its receptor results in a tethered ligand which is at a relatively high concentration compared to the free peptides in solution. Those thrombin receptor peptide analogues which showed decreased activity in platelets were tested in mesangial cells. Removal of serine at position one, N-acetylation, or replacement of the phenylalanine at position two with alanine resulted in analogues which were inactive in stimulating mesangial cell proliferation or calcium mobilization. In addition, those analogues which had no stimulatory effects in mesangial cells were not antagonists of SFLLRN-mediated calcium mobilization and thymidine incorporation in mesangial cells.     

Simulations for parallel processing of ultrasound reflection-mode tomography with applications to two-phase flow measurement

An evaluation of the application of a parallel-processing array to the measurement of two-phase flow, such as bubbly oil flow through a pipe, in real-time is described. Pulse-echo ultrasound tomography is used to generate a cross-sectional image of the flow that forms the basis for the deduction of flow parameters, such as the void fraction. The tomographic algorithm used is backprojection adapted for execution on an array of parallel-processing devices. It is shown that real-time reconstruction is feasible using the concepts of parallel processing. Different sensor arrangements were investigated by computer simulation. It is shown that a special multisegment sensor results in a significant improvement in signal-to-noise ratio and image quality and that the reconstructed image benefits from the concurrent activation of multiple receivers per transmitted pulse. The findings may also be useful for nondestructive testing and medical applications.     

Catalysis of H2, CO and alkane oxidation–combustion over Pt/Silica catalysts: evidence of coupling and promotion

Results are presented on the oxidative–combustion reactions of H₂, CO, methane and propane over polycrystalline-powdered silica-supported catalysts containing Pt (and possibly oxide promoters, e.g. MnO₂, etc.) and the coupling of different combustion processes and also heterogeneous–homogeneous reactions. The Pt/silica catalysts appear to mature with use. Catalysed combustions take place, as expected, at far lower temperatures and with smaller activation energies than the homogeneous reactions. The role of added or intermediate (i.e. produced by alkane partial oxidation or steam reforming) H₂ in accelerating and lowering the temperatures of catalysed alkane combustions and hence minimising NO_x emission is considered with regard to the dispersion of the Pt, as is bifurcative–hysteretic combustion in the catalysed reaction, prevalent for CO, but less certain for H₂ or alkanes. CO decelerates the catalysed combustion of hydrogen on supported Pt (and may also do this for alkane combustion). Whether the acceleration due to intermediate H₂ in alkane combustion exceeds the deceleration due to intermediate CO remains to be seen, but it may be that the water–gas shift reaction moves the advantage to H₂. Further study by in situ methods will be needed to optimise and understand this coupling so that it can be used to maximise efficient alkane-catalysed combustion with minimum NO_x production. This should also lead to higher turnover numbers (which are at present quite low for propane-catalysed combustion).     

A Novel Maleimide Photoinitiator System

1. Introruction The continued growth of UV curing as an industrial process is a driving force for the development of new photoinitiators with improved photosensitivity and curing speed An example of this has been the development of N-substituted maleimides as photoinitiators for the free-radical polymerizations of acrylate, vinyl ether and styryloxy monomers[1-5].     

Associations Between Message Features and Subjective Evaluations of the Sensation Value of Antidrug Public Service Announcements

The effective targeting of high sensation-seeking adolescents, who are most at risk for drug abuse, requires the creation of high sensation value messages. Whereas previous research has focused on subjective reactions of receivers as the primary way to define message sensation value (MSV), we conceptualize message sensation value as the formal and content features (audio, visual, and format) of a message that contribute to subjective message sensation evaluations. The three objectives of this study were (a) to identify message design features that would aid in the development of effective prevention messages targeting high sensation seekers, (b) to develop an objective measure of message sensation value based on formal and content features of messages, and (c) to determine whether high message sensation value messages were associated with higher subjective evaluations of message sensation value. In the present study, 418 undergraduates each viewed 10 PSAs selected at random from a pool of 109 PSAs that had been previously coded for message sensation value. Analyses provide support for the central hypothesis of the study, indicating that perceived message sensation value is at least in part a product of the formal and content features of a PSA.     

A Transactional Model of Parent-Infant Interactions in Alcoholic Families.

This study examined the transactional nature of parent-infant interactions over time among alcoholic and nonalcoholic families. The sample consisted of 222 families assessed at 12, 18, and 24 months of child age. Results indicated that infant behavior did not influence parental behavior across time, but parental behavior was longitudinally predictive of infant behavior during play interactions. Higher paternal alcohol consumption at 12 months was longitudinally predictive of negative parental behavior at 24 months. Other significant risk factors included marital conflict, fathers' depression, and fathers' education. Results highlight the nested nature of risk in alcoholic families and the direction of influence from parent to child during interactions and suggest that 1 pathway to risk among these children is through negative parent-infant interactions. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

The kinetics of vinyl acrylate photopolymerization

The photopolymerization of vinyl acrylate has been investigated using real-time FTIR. The acrylate and vinyl groups exhibit different polymerization kinetics with the acrylate functionality polymerizing at a much faster rate. Vinyl acrylate not only self-initiates its own free-radical polymerization, but also photoinitiates the polymerization of mono- and difunctional acrylates. Kinetic studies using a model monomer system indicate that it is essential for the acrylate and vinyl group to be part of the same molecule in order to function as an effective initiator for acrylate polymerization.     

Kinetics analysis and physical properties of photocured silicate-based thiol-ene nanocomposites: The effects of vinyl POSS ene on the polymerization kinetics and physical properties of thiol-triallyl ether networks

The kinetics and thermal/physical properties of the trithiol-TAE (triallyl ether) system were measured with respect to increasing polyoligomeric silsesquioxane (POSS) concentrations in order to understand how the presence of POSS nanoparticles affects network formation at low loadings. Vinyl POSS monomer (vPOSS-Bu₄) with both vinyl and carboxylate pendant groups was synthesized via a thermally initiated, free-radical reaction to improve the compatibility of the inorganic particles with the trithiol and triallyl ether comomoners. Chemically modified vPOSS-Bu₄ particles were incorporated into the trithiol-TAE polymer networks by a thiol-ene free-radical photopolymerization at molar concentrations of 0, 1, and 5 ene mol%. The polymerization rates were analyzed using real-time FTIR and photo-DSC. The polymerization rates showed no significant changes with increasing vPOSS-Bu₄ concentration. Thermal analyses of the films by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) demonstrated that thermal stability improves without affecting T _g as the POSS concentration increased. Additionally, scratch resistance increased and flame spread decreased markedly with increasing POSS concentration for concentrations up to 5 mol% vPOSS-Bu₄.