Synthesis and characterisation of low density porous polymers by reversible addition-fragmentation chain transfer (RAFT)

PolyHIPE foams with densities of 0.05–0.1 g cm^?3 have been prepared by the polymerisation of the continuous phase of high internal phase emulsions (HIPEs). The internal aqueous phase in HIPE occupies more than 74 % of the total volume, which leads to highly porous and open-cell morphologies. In this paper a method of preparing polyHIPE foams by using reversible addition-fragmentation chain transfer (RAFT) polymerisation has been investigated. Polystyrene-co-polymethyl methacrylate (PS-co-PMMA) has been studied and by using a variety of characterisation methods, it was possible to compare the polyHIPEs prepared by the conventional free radical polymerisation (FRP) to those by RAFT polymerisation. Scanning electron microscopy images have confirmed the presence of a cellular polyHIPE structure. PS-co-PMMA polyHIPEs made by RAFT have significantly narrower molecular weight distribution with values for the polydispersity index (PDI) for PS-co-PMMA between 1.46 and 2.08 compared to 4.68 observed by FRP. The effects of different concentrations of the RAFT agent on structure, glass transition temperature (T _g) and PDI of PS-co-PMMA polyHIPE foams are presented.     

A correlation for burn time of aluminum particles in the transition regime

A study of the combustion times for aluminum particles in the size range of 3–11 μm with oxygen, carbon dioxide, and water vapor oxidizers at high temperatures (>2400 K), high pressures (4–25 atm), and oxidizer composition (15–70% by volume in inert diluent) in a heterogeneous shock tube has generated a correlation valid in the transition regime. The deviation from diffusion limited behavior and burn times that could otherwise be accurately predicted by the widely accepted Beckstead correlation is seen, for example, in particles below 20 μm, and is evidenced by the lowering of the diameter dependence on the burn time, a dependence on pressure, and a reversal of the relative oxidizer strengths of carbon dioxide and water vapor. The strong dependence on temperature of burn time that is seen in nano-Al is not observed in these micron-sized particles. The burning rates of aluminum in these oxidizers can be added to predict an overall mixture burnout time adequately. This correlation should extend the ability of modelers to predict combustion rates of particles in solid rocket motor environments down to particle diameters of a few microns.     

Structural characterization of ß-amyloid oligomer-aggregates by ion mobility mass spectrometry and electron spin resonance spectroscopy

Formation and accumulation of fibrillar plaques and aggregates of ß-amyloid peptide (Aß) in brain have been recognized as characteristics of Alzheimer’s disease (AD). Oligomeric aggregates of Aß are considered critical intermediates leading to progressive neurodegeneration; however, molecular details of the oligomerization and aggregation pathway and the structures of Aß-oligomers are hitherto unclear. Using an in vitro fibril formation procedure of Aß(1–40), ß-amyloid aggregates were prepared and insoluble aggregates separated from soluble products by centrifugation. In this study, ion mobility mass spectrometry (IM-MS) was applied in combination with electron paramagnetic resonance spectroscopy (EPR) to the identification of the components of Aß-oligomers, and to their structural and topographical characterization. The formation of Aß-oligomers and aggregates was monitored by gel electrophoresis, and Aß-oligomer bands were identified by in-gel tryptic digestion and matrix-assisted laser desorption ionization–mass spectrometry (MALDI-MS) to consist predominantly of Aß(1–40) peptide. First, ion mobility-MS studies of soluble Aß-aggregates prepared by incubation for 5 days were performed on a quadrupole time-of-flight mass spectrometer and revealed (1) the presence of at least two different conformational states, and (2), the formation of Met-35 oxidized products. For estimation of the size of Aß-aggregates using EPR spectroscopy, a modified Aß(1–40) peptide containing an additional N-terminal cysteine residue was prepared, and a 3-(2-iodoacetamido)-2,2,5,5-tetramethyl-1-pyrrolidinyloxy radical spin label derivative (IPSL) was coupled by S-alkylation. The EPR spectra of the spin-labeled Cys-Aß(1–40) oligomers were matched with spectra simulations using a multi-component simulation strategy, resulting in complete agreement with the gel electrophoresis results.     

Giant excitonic Zeeman splittings in colloidal Co2+ -doped ZnSe quantum dots

Colloidal Co(2+):ZnSe diluted magnetic semiconductor quantum dots (DMS-QDs) were prepared by the hot injection method and studied spectroscopically. Ligand-field electronic absorption and magnetic circular dichroism (MCD) spectra confirm homogeneous substitutional speciation of Co(2+) in the ZnSe QDs. Absorption spectra collected at various times throughout the syntheses reveal that dopants are absent from the central cores of the QDs but are incorporated at a constant concentration during nanocrystal growth. The undoped cores are associated with dopant exclusion from the ZnSe critical nuclei. Analysis of low-temperature electronic absorption and MCD spectra revealed excitonic Zeeman splitting energies (DeltaE(Zeeman)) of these Co(2+):ZnSe QDs that were substantially smaller than anticipated from bulk Co(2+):ZnSe data. This reduction in DeltaE(Zeeman) is explained quantitatively by the absence of dopants from the QD cores, where dopant-exciton overlap would be greatest. Since dopant exclusion from nucleation appears to be a general phenomenon for DMS-QDs grown by direct chemical methods, we propose that DeltaE(Zeeman) will always be smaller in colloidal DMS-QDs grown by such methods than in the corresponding bulk materials.     

Structural and molecular evolutionary analysis of Agouti and Agouti-related proteins

Agouti (ASIP) and Agouti-related protein (AgRP) are endogenous antagonists of melanocortin receptors that play critical roles in the regulation of pigmentation and energy balance, respectively, and which arose from a common ancestral gene early in vertebrate evolution. The N-terminal domain of ASIP facilitates antagonism by binding to an accessory receptor, but here we show that the N-terminal domain of AgRP has the opposite effect and acts as a prodomain that negatively regulates antagonist function. Computational analysis reveals similar patterns of evolutionary constraint in the ASIP and AgRP C-terminal domains, but fundamental differences between the N-terminal domains. These studies shed light on the relationships between regulation of pigmentation and body weight, and they illustrate how evolutionary structure function analysis can reveal both unique and common mechanisms of action for paralogous gene products.     

Thiamine models and perspectives on the mechanism of action of thiamine-dependent enzymes

Thiamine dependent enzymes catalyze ligase and lyase reactions near a carbonyl moiety. Chemical models for these reactions serve as useful tools to substantiate a detailed mechanism of action. This tutorial review covers all such studies performed thus far, emphasizing the role of each part around the active site and the conformation of the cofactor during catalysis.     

SmartPhantom--an fMRI simulator

Many informatics tools have emerged to process the voluminous and complex data generated by functional magnetic resonance imaging (fMRI). The interpretation of fMRI exams is largely determined by these tools. However, their performance is hard to evaluate because there is no independent means of calibration. A novel fMRI calibration system called SmartPhantom has been developed to simulate functional blood oxygen level dependent (BOLD) imaging. SmartPhantom contains a quadrature radio frequency coil, comprising two perpendicular planar loops that can be externally activated or deactivated. The system is able to produce reasonably uniform signal enhancements in a calibration sample surrounded by the two loops during an MRI scan. The enhancement is controlled well in both magnitude and predefined timing and produces BOLD-like signals. Characteristics of SmartPhantom are discussed in detail, followed by a comparison of fMRI informatics tools. Two fMRI data sets are acquired with the SmartPhantom. One with high signal-to-noise ratio provides the calibration. Another with lower SNR is input into three software packages (BrainVoyager, FSL and Statistical Parametric Mapping 2) for data preprocessing and statistical analysis. Results from the three packages are compared in both sensitivity of detecting the activation and correlation between the predicted activation and calibration.     

Self-assembling of In(Ga)As/GaAs quantum dots on (N11) substrates: the (311)A case

We have investigated the In(Ga)As island formation, in the Stranski-Krastanov growth mode, on (311)A GaAs substrates. The surface topography of InAs and InGaAs strained epilayers was studied by contact microscopies. The different substrate affects the overgrown island shape. In(Ga)As grown on (311)A gives rise to quantum wire-like islands. Quantum dots (QDs), but with highly anisotropic shapes, are the outcomes of InAs deposition. QD samples were also characterized by photoluminescence (PL) measurements. Correlation between optical and morphological properties was observed.