Study of rapid stress annealed nano-crystalline Fe74.5Cu1Nb3Si15.5B6 alloy

Rapid stress annealing induced changes in structural and magnetic properties in Fe_74.5Cu₁Nb₃Si_15.5B₆ are reported. Obtained results suggest changes in spin texture with preferred orientation along ribbon axis. Fraction of A site in the DO₃ lattice occupied by Si atoms, increases, with increase of applied stress during annealing. Volume fraction of the nanograins up to 60% (exhibiting quite similar mean grain diameter ～9 nm) is observed. Lattice parameter values suggest that Si content in the nanocrystalline phase is between 14% and 19% and increase of lattice parameter suggests the elongation of the unit cell. Studied stress annealed samples exhibit soft magnetic behavior (coercive field ranging between 4 and 8 Am^???1). Stress annealing reduces permeability whereas anisotropy field increases almost linearly exhibiting the induction of uniaxial and perpendicular to the ribbon axis anisotropy. Obtained stress-induced-anisotropy constant values range between 50 and 2,140 Jm^???3.     

Protein interactions with self-assembled monolayers presenting multimodal ligands: a surface plasmon resonance study

This paper describes the use of surface plasmon resonance (SPR) spectroscopy and self-assembled monolayers (SAMs) to understand the characteristics of surfaces that promote the adsorption of proteins at high ionic strengths (high-salt conditions). We synthesized SAMs presenting different multimodal ligands and determined the influence of surface composition, solution composition, and the nature of the protein on the extent of protein adsorption onto the SAMs. Our results confirm that hydrophobic interactions can contribute significantly to protein adsorption under high-salt conditions. In particular, the extent of protein adsorption under high-salt conditions increased with increasing surface hydrophobicity. The extent of protein adsorption was also influenced by the solution composition and decreased with an increase in the chaotropicity of the anion. The combination of SPR and SAMs is well-suited for studying the interaction of proteins with complex surfaces of relevance to chromatography.     

Control of competing N-H insertion and Wolff rearrangement in dirhodium(II)-catalyzed reactions of 3-indolyl diazoketoesters. synthesis of a potential precursor to the marine 5-(3-indolyl)oxazole martefragin A

Dirhodium(II)-catalyzed reaction of 3-indolyl alpha-diazo-beta-ketoester 25 in the presence of hexanamide results in competing metal carbene N-H insertion and Wolff rearrangement. The corresponding phenyl diazoketoester 32, on the other hand, gives only the product of N-H insertion, suggesting that the indole moiety is more prone to 1,2-rearrangement. The competing processes were investigated in a range of 3-indolyl alpha-diazo-beta-ketoesters (36, 38, 40, 44); these studies established that the Wolff rearrangement could be effectively suppressed by the presence of a strong electron-withdrawing group on the indole nitrogen. Dirhodium(II) catalysts were also more effective than copper or Lewis acid catalysts in favoring the insertion process. The products of N-H insertion, the ketoamides (26, 47, 49, 51, 53), were readily cyclodehydrated to the corresponding 5-(3-indolyl)oxazoles. The N-H insertion/cyclodehydration methodology was used in a formal synthesis of the marine natural product martefragin A. Thus the N-Boc homoisoleucine amide 23, prepared by asymmetric hydrogenation of a dehydro amino acid, underwent N-H insertion with the rhodium carbene derived from the N-nosyl indolyl diazoester 40, followed by cyclodehydration and deprotection to give the 5-(3-indolyl)oxazole martefragin A precursor 75.     

Electric-field-driven deracemization.

We demonstrate, both theoretically and experimentally, that it is possible to use an electric field to drive the formation of macroscopic chiral (conglomerate) domains from an initially homogeneous fluid racemate. Field-induced segregation is exhibited in a fluid smectic liquid-crystal phase of a racemic mesogen, wherein enantiomerically-enriched domains are readily identifiable by their chiral electro-optical response. The sharp field-generated boundaries that form between opposite-handed domains broaden by diffusion in the absence of field, but reform rapidly if the field is switched on again, providing unambiguous evidence for the field-driven physical separation of enantiomers. A mean-field model successfully describes the steady-state and the dynamic evolution of conglomerate formation.     

Enantioconvergent synthesis by sequential asymmetric Horner-Wadsworth-Emmons and palladium-catalyzed allylic substitution reactions

A new method for enantioconvergent synthesis has been developed. The strategy relies on the combination of an asymmetric Horner-Wadsworth-Emmons (HWE) reaction and a palladium-catalyzed allylic substitution. Different alpha-oxygen-substituted, racemic aldehydes were initially transformed by asymmetric HWE reactions into mixtures of two major alpha,beta-unsaturated esters, possessing opposite configurations at their allylic stereocenters as well as opposite alkene geometry. Subsequently, these isomeric mixtures of alkenes could be subjected to palladium-catalyzed allylic substitution reactions with carbon, nitrogen, and oxygen nucleophiles. In this latter step, the respective (E) and (Z) alkene substrate isomers were observed to react with opposite stereospecificity: the (E) alkene reacted with retention and the (Z) alkene with inversion of stereochemistry with respect to both the allylic stereocenter and the alkene geometry. Thus, a single gamma-substituted ester was obtained as the overall product, in high isomeric purity. The method was applied to a synthesis of a subunit of the iejimalides, a group of cytotoxic macrolides.     

Effects of B and P content on structural and magnetic properties of cast iron based amorphous alloys

Mössbauer spectroscopy, DSC and magnetic measurements have been used to study the influence of B and P on structural; magnetic properties and thermal stability of cast iron based alloys. Results reveal that addition of B and P affects appreciably: (1) the crystallization temperature and supercooled liquid region ranging between 690–781 and 53–81 K respectively; (2) the spin texture, disorder and (3) the obtained magnetization parameters. Coercive field values range between 10.09 and 16.37 A/m, with lowest value of 10.09 A/m obtained for Ci_87.82B_12.17. Saturation induction (B _s) values vary between 1.32 and 1.85 T. Highest B _s value of 1.85 T is obtained for the Ci_95.65B_4.32 alloy which is at the edge of glass forming ability, with only 4.32 at.% of boron was added to the cast iron composition. Losses (at 50 Hz and 0.32 kA/m) for the studied samples range between 0.43 and 0.82 W/kg. Lowest losses of 0.43 W/kg was obtained for the Ci_91.3P_4.35B_4.35 alloy. Phosphorous and boron additions, helps in the bulk glass forming ability, suggesting perspective applications of these cheap cast iron based soft magnetic alloys as a substitute of the conventional materials.     

Modelling laser cleaning of low-absorbing substrates: the effect of near-field focussing

A three-dimensional model for laser cleaning of spherical, transparent particles on low-absorbing substrates has been developed. It takes into account near-field focussing of the laser radiation by the particles. The intensity distribution under a particle was found using Mie theory together with the geometrical optics approximation. This permits the estimation of the beam width at the substrate surface and the focal distance of the radiation coming from the spherical particle. These parameters are used to find the distribution of intensity within the low-absorbing substrate from the formula for a focussed Gaussian beam. This is in contrast with most other models of laser cleaning, which assume that all absorption occurs at the surface of the substrate. The energy criterion was used to calculate the threshold fluence. The model predicts threshold fluences of the order of 10³ J/cm² for silica spheres having a diameter of the order of a micron on silica substrates, assuming adhesion by van der Waals force. As this is well above the damage threshold for silica, it effectively predicts that laser cleaning of silica spheres from silica will be impossible. For glass slides the threshold fluence is predicted to be a factor of 10^-4 times smaller than that for silica slides (about 0.1 J/cm²). This is due to the much higher absorption of glass compared to that of silica at 248 nm. PACS 42.62.Cf; 81.65.Cf