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.     

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).     

High-intensity lasers as radiation sources

In the last decade or so, an evolution in experimental relativistic laser-plasma physics has led to highly sophisticated lasers which are now capable of generating ultra-short pulses and can be focused to intensities in excess of 10²¹ W cm^-2. The laser interaction with solid or gas targets can generate collimated beams of highly energetic electrons, protons and ions. These high-intensity laser systems, therefore, turn out to be versatile and powerful sources of radiation and high-energy particles, without recourse to large-scale facilities such as nuclear reactors or particle accelerators. The potential to induce various kinds of nuclear reactions with laser-induced radiation fields has been demonstrated at several laboratories in recent years. The present paper lays out a comprehensive overview of nuclear reactions induced by high-intensity laser matter interactions. Mechanisms for electron, proton and ion acceleration, in addition to secondary bremsstrahlung, positron and neutron production, are addressed, with a focus on the types of nuclear reactions that are possible and potential applications. Discussion of the extrapolation of these processes and applications to the next generation of table-top lasers under construction is also presented.     

Insertion Reactions of Neutral Phosphidozirconocene Complexes as a Convenient Entry into Frustrated Lewis Pair Territory

Neutral phosphidozirconocene complexes [Cp₂Zr(PR₂)Me] (Cp=cyclopentadienyl; 1a : R=cyclohexyl (Cy); 1b : R=mesityl (Mes); 1c : R=tBu) undergo insertion into the Zr?P bond by non‐enolisable carbonyl building blocks (O=CR′R′′), such as benzophenone, aldehydes, paraformaldehyde or CO₂, to give [Cp₂Zr(OCR′R′′PR₂)Me] ( 3 – 7 ). Depending on the steric bulk around P, complexes 3 – 7 react with B(C₆F₅)₃ to give O‐bridged cationic zirconocene dimers that display typical frustrated Lewis pair (FLP)/ambiphilic ligand behaviour. Thus, the reaction of {[Cp₂Zr(μ‐OCHPhPCy₂)][MeB(C₆F₅)₃]}₂ ( 10a ) with chalcone results in 1,4 addition of the Zr⁺/P FLP, whereas the reaction of {[Cp₂Zr(μ‐OCHFcPCy₂)][MeB(C₆F₅)₃]}₂ ( 11a ; Fc=(C₅H₄)CpFe) with [Pd(η³‐C₃H₅)Cl]₂ yields the unique Zr?Fe?Pd trimetallic complex 13a , which has been characterised by XRD analysis.     

Separation and characterisation of caprolactam-formaldehyde reaction products

Methylolation and condensation products formed in caprolactam-formaldehyde reaction mixtures have been identified using nuclear magnetic resonance (NMR) and mass spectrometry (MS). Previously unreported side-products were also detected. All of the reaction products were separated by micellar electrokinetic chromatography (MEKC) and high performance liquid chromatography (HPLC), and the separation parameters, such as efficiency and distribution constants, obtained in the two techniques were compared. For quantification, the response factors for the monomers were determined using standard calibration and hydrolysis, whilst those for the condensation products were deduced from the values of the monomers. The accurate determination of the response factors was confirmed by checking the mass balance of a known mixture.     

Microscopic description of low-energy neutron scattering by nuclei

The Bloch and Gillet shell-model formalism extended to continuum states is applied to lowenergy neutron scattering by nuclei. It is shown that complete antisymmetrization leads in the r-representation to corrective terms which yield important corrections to the scattering lengths. Calculations are performed within a model restricted configuration space for the target nuclei ¹²C, ¹³C, ¹⁶O, ¹⁷O and ⁴⁰Ca. We predict values for the spin-dependent scattering amplitude for ¹³C and ¹⁷O. The antisymmetrization problem in the case of a large configuration mixing is studied for the ¹⁹F target nucleus. The resonant effects of the compound nucleus are then very important and the results become very sensitive to the configuration space and the interaction parameters.