Assessment of surface relief and short cracks under cyclic creep in a type 316LN austenitic stainless steel

Formation of surface relief and short cracks under cyclic creep (stress-controlled fatigue) in type 316LN stainless steel was studied at temperatures ranging from ambient to 923 K using scanning electron microscopy technique. The surface topography and crack distribution behaviour under cyclic creep were found to be strong functions of testing temperature due to the difference in strain accumulation. At 823 K, surface relief mainly consisted of fine slip markings due to negligible accumulation of strain as a consequence of dynamic strain ageing (DSA) which led to an increase in the cyclic life. Persistent slip markings (PSM) with distinct extrusions containing minute cracks were seen to prevail in the temperature range 873–923 K, indicating a higher slip activity causing higher strain accumulation in the absence of DSA. Besides, a large number of secondary cracks (both transgranular and intergranular) which were partially accentuated by severe oxidation, were observed. Extensive cavitation-induced grain boundary cracking took place at 923 K, which coalesced with PSM-induced transgranular cracks resulting in failure dominated by creep that in turn led to a drastic reduction in cyclic life. Investigations on the influence of stress rate were also carried out which underlined the presence of DSA at 823 K. At 923 K, lowering the stress rate caused further strengthening of the contribution from creep damage marked by a shift in the damage mechanism from cyclic slip to diffusion.     

A novel and facile synthesis of 3,5-Disubstituted isothiozoles under metal free conditions using acetophenones and dithioesters

Abstract

A facile and conveniently simple new protocol is devised for the synthesis of 3,5-disubstituted and annulated isothiozoles under transition metal and catalyst free conditions utilizing easily available acetophenones, dithioesters and NH₄OAc. This strategy involves C=O and C=S functionalization via sequential imine formation followed by intra molecular cyclization and aerial oxidation forming consecutive C?N and S?N bonds respectively in one pot. This protocol offers a low cost, user friendly, straight forward and widely applicable approach to 3,5-disubstituted isothiazoles.     

Isolation of novel azadirachtins H and I by high-performance liquid chromatography

Summary A high-performance liquid chromatographic procedure for the isolation of azadirachtins A, B, D, H and I is described. While azadirachtins A, B, and D are already known, azadirachtins H and I have been isolated for the first time from neem kernels.     

Fluorophilicity of alkyl and polyfluoroalkyl nicotinic acid ester prodrugs

The fluorophilicity of a series of hydrocarbon and fluorocarbon-functionalized nicotinic acid esters (nicotinates) is measured from their partitioning behavior (log K_p) in the biphasic solvent system of perfluoro(methylcyclohexane) (PFMC) and toluene. The chain length of the hydrocarbon or fluorocarbon alkyl group of the ester ranges from one to twelve carbon atoms. Knowledge of the fluorophilicity of these solutes is relevant to the design of these prodrugs for fluorocarbon-based drug delivery. The experimental log K_p values range from −1.72 to −3.40 for the hydrocarbon nicotinates and −1.64 to 0.13 for the fluorinated nicotinates, where only the prodrug with the longest fluorinated chain (2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctyl nicotinic acid ester) partitions preferentially into the fluorinated phase (log K_p = 0.13). Predictions of the partition coefficients using solubility parameters calculated from group contribution techniques or molecular dynamics simulation are in reasonable agreement for the perhydrocarbon nicotinates and short chained perfluorinated nicotinates (≈0.3-39% deviation). Significant deviations from experimental partition coefficients (greater than 100%) are observed for the longest chain perfluoroalkyl nicotinates.     

Possible violation of the spin-statistics relation for neutrinos: checking through future galactic supernova

We use the detection of neutrinos from a future galactic type-II supernova event in a water Cerenkov detector like Super-Kamiokande to constrain the possible violation of spin-statistics by neutrinos resulting in their obeying a mixed statistics instead of Fermi–Dirac.     

Solid phase synthesis of combinatorial libraries using anhydrides as templates

A simple and general approach to the synthesis of chemical libraries based on a universal anhydride template allows the preparation of large number of compounds. Various cyclic/acyclic amines, primary/secondary amines, differentially protected bifunctional amines were used as nucleophiles to react with anhydrides. The free carboxylic acid generated was then coupled with solid-bound amines. The facile and rapid generation of compounds through this multi-component assembly can be accomplished in a combinatorial parallel synthesis. This revised version was published online in August 2006 with corrections to the Cover Date.     

Site-specific fluorescent labeling of nascent proteins on the translating ribosome

As newly synthesized proteins emerge from the ribosome, they interact with a variety of cotranslational cellular machineries that facilitate their proper folding, maturation, and localization. These interactions are essential for proper function of the cell, and the ability to study these events is crucial to understanding cellular protein biogenesis. To this end, we have developed a highly efficient method to generate ribosome-nascent chain complexes (RNCs) site-specifically labeled with a fluorescent dye on the nascent polypeptide. The fluorescent RNC provides real-time, quantitative information on its cotranslational interaction with the signal recognition particle and will be a valuable tool in elucidating the role of the translating ribosome in numerous biochemical pathways.     

Theoretical prediction of spectroscopic constants of 1-alkoxy radicals

Spectroscopic constants for the conformers of the 1-alkoxy radicals were computed by ab initio and density functional methods. These parameters include ground and excited state rotational constants, harmonic frequencies, and and excitation energies. Elements of the electronic spin–molecular rotation tensor have also been predicted for the ground electronic state utilizing a simple transformation. The transformation employed the experimentally observed spin-rotation tensor of the ethoxy radical as a reference and the calculated rotational constants of the ethoxy radical and the investigated 1-alkoxy radicals. The predicted spectroscopic parameters are in good agreement with the experimental ones where available, and found to be useful parameters for assigning the rotationally resolved spectral bands to given conformers.