Following the aggregation of amyloid-forming peptides by computer simulations

There is experimental evidence suggesting that the toxicity of neurodegenerative diseases such as Alzheimer's disease may result from the soluble intermediate oligomers. It is therefore important to characterize extensively the early steps of oligomer formation at atomic level. As these structures are metastable and short lived, experimental data are difficult to obtain and they must be complemented with numerical simulations. In this work, we use the activation-relaxation technique coupled with a coarse-grained energy model to study in detail the mechanisms of aggregation of four lys-phe-phe-glu (KFFE) peptides. This is the shortest peptide known to form amyloid fibrils in vitro. Our simulations indicate that four KFFE peptides adopt a variety of oligomeric states (tetramers, trimers, and dimers) with various orientations of the chains in rapid equilibrium. This conformational distribution is consistent with all-atom molecular-dynamics simulations in explicit solvent and is sequence dependent; as seen experimentally, the lys-pro-gly-glu (KPGE) peptides adopt disordered structures in solution. Our unbiased simulations also indicate that the assembly process is much more complex than previously thought and point to intermediate structures which likely are kinetic traps for longer chains.     

LABORATORY TESTING OF RADIANT GAS BURNERS AND ELECTRIC INFRARED EMITTERS

A project focusing on industrial infrared technology was carried out at Hydro-Québec's LTEE laboratory [1], The project required the optimization and use of a special test facility. Seven electric emitters and seven radiant gas burners typically used in the textile and pulp and paper industries were evaluated. Three types of experiments were carried out, providing four types of information: radiant flux maps, radiant efficiency evaluation, transient behavior characterization, and spectral emission characterization. The apparatus and the experimental procedures are described. Results are discussed and are presented in the form of tables and graphs. As the procedure and instruments used within each test were identical, this work furnishes rigorous data and objective information on both electric and gas IR technologies.     

Synthesis of (±)Dehydroxyglaupalol and Analogs

The natural furocoumarin dehydroxyglaupalol and two analogs were prepared by reaction of the appropriate 4-hydroxy-coumarin with 3-chloro-3-methylbutyne in basic medium, followed by catalytic hydrogenation of the exo double bond.     

The Use of 18-Crown-6 As Phase Transfer Catalyst in the Reissert Reaction

Solid-liquid phase transfer of cyanide ion by 18-cro'wn-6 increases the yield of the Reissert reaction and eliminates the undesirable pseudo-base formation.     

GISAXS study of carbon nanotubes grown by CVD

We report a quantitative Grazing Incidence Small Angle X‐ray Scattering (GISAXS) study of a dense film of mutually oriented carbon nanotubes (CNTs) grown by a catalytically‐activated DC HF CCVD process after dispersion of metallic catalytic (Co) islands on SiO₂/Si(100) substrates. The GISAXS pattern analysis is expanded to non‐correlated surface science systems and is based on CNTs density, characteristic lengths, atomic Co dispersion throughout the CNTs and roughnesses of uncorrelated particles. The results are closely compared to SEM and TEM observations. The GISAXS patterns, even dominated by envelope features of disordered objects, provide significant complementary quantitative data about CNTs films. The results underline that cobalt continuously fills the nanotube in the course of the growth and that the CNTs experience a large tendency toward mutual alignment. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Proton radiation tolerance of nanocrystal memories

We report on proton radiation tolerance of Si-nanocrystal (Si-NCs) MOS structures aiming at non-volatile memory applications. Si-NCs were formed by low-energy (1 keV) ion-beam-synthesis within a 9 nm thick SiO₂ layer. A 2-D layer of Si-NCs with 3 nm mean diameter and 10¹² cm⁻² surface density was successfully achieved. After fabrication of Al capacitors, samples with and without Si-NCs were 1.5 and 6.5 MeV proton were irradiated at doses ranging from 1 Mrad (SiO₂) to 120 Mrad (SiO₂). Significant irradiation-dose-dependent shifts are detected in the C–V curves of the NC-MOS cells and programmed cells are found to undergo bit flip. Despite the above, the attainable memory windows after write/erase operations remain unchanged. Retention time characteristics at room temperature for the write and erase states of irradiated and non-irradiated samples reveal that even after an irradiation dose as high as 120 Mrad (SiO₂) the devices still exhibit long time charge storage behavior. We observe that the erase state flat-band voltage decay rate does not depend on the irradiation-dose while the opposite happens for the write state flat-band voltage decay rate which is found to be directly dependent on D_it values giving insight to the physics of the discharging mechanisms.     

Comparison of two methods of measuring wood pyrolysis tar

Two methods for the sampling and analysis of tar produced from wood pyrolysis were compared. The first method used a conventional cold-trapping technique in solvent-filled impingers followed by liquid injection. The second one is a new application of multibed solid-phase adsorbent (SPA) tubes followed by thermal desorption (TD). Both methods are based on gas chromatography (GC) coupled with mass spectrometry (MS). Quantification was performed with a well reproducible GC-MS method with three internal deuterated standards. The SPA/TD method offers several advantages. No solvent is required, the detection levels are improved, and gas chromatography separation is easier. Moreover, sampling time is reduced from about 1h (for the conventional cold-trapping technique in impingers) to a few seconds. No discrimination was observed between the two sampling methods for the 10 quantified compounds (aromatic compounds from benzene to phenanthrene and phenols) except for benzene.     

Synthesis of cationic porphyrin modified amino acids

Derivatives of amino acids bearing a porphyrin moiety on a side chain were synthesized by coupling a porphyrin to a glutamic acid side chain; the utility of these compounds was demonstrated by their use in solid-phase synthesis of a peptide bearing a cationic porphyrin and by studying its DNA-binding properties.     

Coordinatively Unsaturated Amidotitanocene Cations with Inverted σ and π Bond Strengths: Controlled Release of Aminyl Radicals and Hydrogenation/Dehydrogenation Catalysis

Cationic amidotitanocene complexes [Cp₂Ti(NPhAr)][B(C₆F₅)₄] (Cp=η⁵-C₅H₅; Ar=phenyl ( 1 a ), p-tolyl ( 1 b ), p-anisyl ( 1 c )) were isolated. The bonding situation was studied by DFT (Density Functional Theory) using EDA-NOCV (Energy Decomposition Analysis with Natural Orbitals for Chemical Valence). The polar Ti−N bond in 1 a–c features an unusual inversion of σ and π bond strengths responsible for the balance between stability and reactivity in these coordinatively unsaturated species. In solution, 1 a–c undergo photolytic Ti−N cleavage to release Ti(III) species and aminyl radicals ⋅ NPhAr. Reaction of 1 b with H₃BNHMe₂ results in fast homolytic Ti−N cleavage to give [Cp₂Ti(H₃BNHMe₂)][B(C₆F₅)₄] ( 3 ). 1 a–c are highly active precatalysts in olefin hydrogenation and silanes/amines cross-dehydrogenative coupling, whilst 3 efficiently catalyzes amine-borane dehydrogenation. The mechanism of olefin hydrogenation was studied by DFT and the cooperative H₂ activation key step was disclosed using the Activation Strain Model (ASM).     

Design and synthesis of polytripeptide (leuglnpro)n based upon the matrix protein amelogenin

A linear neutral repetitive peptide, (Leu-Gln-Pro)_n (n = 1-100), an analog of the Ca²⁺ ion-binding domain of the matrix protein, amelogenin, has been synthesized. The polypeptide is mostly unordered in trifluoroethanol (TFE) at 25°C and its circular dichroism (CD) spectrum resembles that of the protein itself. In TFE the CD spectrum of (Leu-Gln-Pro)_n reveals that the polypeptide interacts strongly with divalent cations Mg²⁺, Ca²⁺, Sr²⁺, and Ba²⁺ accompanied by conformational rearrangement from a random to a more-ordered one. In the presence of Li⁺, Na⁺ and K⁺ ions no such conformational change has been observed. The CD curves of the complexes suggest the presence of type I β-turns and reinforce the hypothesis that the region Gln₁₁₂-Leu₁₃₈ in amelogenin is the Ca²⁺-binding domain. In the solid state, powder X-ray diffraction suggests that the polymeric (LQP)_n may exist as isolated “rigid rods”.