Proton-induced grain boundary segregation in stainless steel

Abstract

A technique is developed which addresses the problem of irradiation assisted stress corrosion cracking of stainless steels in light water reactors using high energy protons to induce grain boundary segregation. These results represent the first grain boundary segregation measurements in bulk produced by proton irradiation of stainless steel. The technique allows the study of grain boundary composition with negligible sample activation, short irradiation time, rapid sample turnaround and at minimal cost. Scanning Auger electron microscopy is used to obtain grain boundary composition measurements of irradiated and unirradiated samples of ultra high purity (UHP) type 304L stainless steel and UHP type 304L steels with the additions of phosphorus (UHP + P) and sulphur (UHP + S). Results show that irradiation of all three alloys causes significant Ni segregation to the grain boundary and Cr and Fe away from it. Irradiation of the UHP + P alloy also results in segregation of P at the grain boundary from 5.3 to 8.7 at %, over 80 times the bulk value. No radiation-induced grain boundary segregation of S was measured in the UHP + S alloy. Results also indicate that the presence of P or S may enhance radiation-induced segregation of major alloying elements at the boundary. Comparison of irradiated and unirradiated regions of the UHP + P alloy indicate that while a prior thermal treatment segregates P to the grain boundary to 5.3 at %, the major element concentrations at the grain boundary are completely different from those under irradiation.     

Enantioselective Friedel-Crafts reaction of acylpyrroles with glyoxylates catalyzed by BINOL-Ti(IV) complexes

We report the first efficient enantioselective Friedel-Crafts hydroxyalkylation of pyrroles having one electron-withdrawing group at the α, β or N-positions with alkyl glyoxylates catalyzed by readily available chiral BINOL-Ti(IV) complexes (1-5 mol %). The reaction regioselectively led to the desired pyrrole-hydroxyacetic acid derivatives with good yields (70-96%) and enantiomeric excesses up to 96%, and is applicable in multigram scale with low loading of the catalyst (1 mol %).     

Quantum Monte Carlo study of the CO interaction with a dimer model surface for Cr(110)

The chemisorption of CO on a Cr (110) surface is investigated using the quantum Monte Carlo method in the diffusion Monte Carlo (DMC) variant and a model Cr₂CO cluster. The present results are consistent with the earlier ab initio HF study with this model that showed the tilted/near-parallel orientation as energetically favoured over the perpendicular arrangement. The DMC energy difference between the two orientations is larger (1.9 eV) than that computed in the previous study. The distribution and reorganization of electrons during CO adsorption on the model surface are analysed using the topological electron localization function method that yields electron populations, charge transfer and clear insight on the chemical bonding that occurs with CO adsorption and dissociation on the model surface.     

Characterization of aromatic-thiol π-type hydrogen bonding and phenylalanine-cysteine side chain interactions through ab initio calculations and protein database analyses

In this study, the aromatic-thiol π hydrogen bonding and phenylalanine-cysteine side chain interactions are characterized through both molecular orbital calculations on a C₆H₆-HSCH₃ model complex and database analyses of 609 X-ray protein structures. The aromatic-thiol π hydrogen bonding interaction can achieve a stabilization energy of 2.60 kcal mol^?1, and is stronger than the already documented aromatic-hydroxyl and aromatic-amino hydrogen bonds. However, the occurrence of the aromatic-thiol hydrogen bond is rather rare in proteins. This is because most of the thiol groups participate in the formation of either disulphide bonds or stronger S—H…O (or N) ‘normal’ hydrogen bonds in a protein environment. Interactions between the side chains of phenylalanine and cysteine residues are characterized as the phenyl(Phe)(HSCH₂-)(Cys) interaction. The bonding energy for such interactions is approximately 3.71 kcal mol-¹ and is achieved in a geometric arrangement with an optimal phenyl(Phe)-(HS-)(Cys) π-type hydrogen bonding interaction. The interaction is very sensitive to the orientation of the two lone electron pairs on the sulphur atom relative to the π electron cloud of the phenyl ring. Accordingly, the interaction configurations that can accomplish a significant bonding energy exist only within a narrow configurational space. The database analysis of 609 experimental X-ray protein structures demonstrates that only 268 of the 1620 cysteine residues involve such phenylalanine-cysteine side chain interactions. Most of these interactions occur in the form of π (aromatic)-lone pair(sulphur) attractions, and correspond to a bonding energy less than 1.5 kcal mol^?1. A few were identified as the aromatic-thiol hydrogen bond with a bonding energy of 2.0–3.6 kcal mol^?1.     

The mass spectrum of glycine

Irreproducibilities in the measurements of isotopic abundance in ¹⁵N labelled glycine have been related to the complex nature of chemical processes occurring during the evaporation of glycine prior to ionization.     

A Non-linear Singular Perturbation Problem Arising in the Study of Chemical Flow Reactors

This paper presents a method of obtaining the complete asymptoticsolution of boundary value problems of the form for x [0,1] where b(x) is strictly positive andfor small and positive. Physically, the problem arises in determiningthe steady-state concentration of a substance in a chemicalflow reactor. A "two-variable" expansion procedure is used.