Characterization of surface deformation around Vickers indentations in InGaAsP epilayers on InP substrate

The deformation surrounding Vickers indentations on InGaAsP/InP epilayers have been studied in detail. The surface topography was characterized by using atomic force microscopy (AFM). The material pile-up and sink-in regions around the indentation impression was observed for the quaternary InGaAsP/InP epilayers. The sectional analysis mode of the AFM shows the depth profile at the indented region. Microindentation studies were carried out for different atomic fraction of the quaternary InGaAsP/InP compound semiconductor alloys. The microhardness values of InGaAsP/InP epilayers were found to be in the range of 5.08 and 5.73 GPa. These results show that the hardness value of the quaternary alloy drastically increases as the composition of As was increased by 0.01 atomic fraction and when the phosphorous concentration decreases from 0.4 to 0.38. The reason may be that the increase in As concentration hardens the lattice when phosphorous concentration was less and hardness decreases when phosphorous was increased.     

Critical phenomena in FINEMET alloy

The Fe_73.5Cu₁Nb₃Si_13.5B₉ FINEMET alloy has been prepared by the rapid solidification technique. The critical behaviour of this alloy in the amorphous as well as in its nanocrystalline states has been studied near their respective Curie temperatures. From the values of the critical exponents one can conclude that the alloy behaves like a 3D Heisenberg ferromagnet in the amorphous and nanocrystalline states. But there exists a slight increase in the value of β for the alloy annealed at 823 K (the nanocrystalline state) as observed in most of the amorphous alloys.     

Precise lattice parameter measurements in CsCl-Br solid solutions between room temperature and 90°K by powder x-ray diffraction

Solid solutions of CsCl-Br in five different concentrations were prepared in sealed quartz tubes by heating the mixture to 1123°K for 6–8 hr and quenching to room temperature. X-ray diffractograms were taken at eight different temperatures between room temperature and 90°K for these solid solutions using the YPC50NM powder diffractometer and a continuous flow cryostat. The observed lattice parameters for each sample at each temperature obtained from the powder diffractograms were then extrapolated to give the true lattice parameters using the least square method with Nelson-Riley extrapolation scheme. The values of the true lattice parameters at each concentration and at each temperature were tabulated and the results discussed. It is shown that the lattice parameters vs temperature for some concentrations exhibit an anomalous behaviour. Contribution No. 691     

A total synthesis of spiruchostatin A

We achieved the total synthesis of the histone deacetylase inhibitor spiruchostatin A, as the prelude to the preparation of a combinatorial library of its analogues. Two key reactions were an asymmetric acetate aldol reaction using a Zr-enolate and macrolactonization using the Shiina method.     

Globin chain separation by SDS polyacrylamide gel electrophoresis. Simple screening method for elongated hemoglobin chains

A simple method for the separation of hemoglobin chains from hemolysate or globin, by sodium dodecyl sulfate polyacrylamide gel electrophoresis, is described. The alpha, beta, and gamma chains can be clearly separated from each other. The alpha chain has the highest mobility, the beta chain has a slower mobility than the gamma chain, while the delta chain has about the same mobility as the beta chain. Hemoglobins with elongated chains can easily be detected by this method. Tak-beta, elongated by 11 residues, moves much more slowly than betaA but is much faster than alpha Constant Spring which is elongated by 31 residues. Screening of several individuals with slow-moving hemoglobins using this method led to the finding of a case with Hb Tak-beta thalassemia and other carriers of Hb Tak.     

Rupture of thin stagnant films on a solid surface due to random thermal and mechanical perturbations

A generalized formalism for the rupture of a nondraining thin film on a solid support due to imposed random thermal and mechanical perturbations, modeled as a Gaussian white noise, is presented. The evolution of amplitude of perturbation is described by a stochastic differential equation. The average film rupture time is the average time for the amplitude of perturbation to equal to the film thickness and is calculated by employing a first passage time analysis for different amplitudes of imposed perturbations, wavenumbers, film thickness, van der Waals and electrostatic interactions and surface tensions. The results indicate the existence of an optimum wavenumber at which the rupture time is minimum. A critical film thickness is identified based on the sign of the disjoining pressure gradient, below which the film is unstable in that the rupture time is very small. The calculated values of rupture time as well as the optimum wavenumber in the present analysis agree well with the results of linear stability analysis for immobile as well as completely mobile gas-liquid film interfaces. For stable films, the rupture time is found to increase dramatically with film thickness near the critical film thickness. As expected, the average rupture time was found to be higher for smaller amplitudes of imposed perturbations, larger surface potentials, larger surface tensions and smaller Hamaker constants.     

Regioselective synthesis of 3-alkylindoles mediated by zinc triflate

Zinc triflate was found to be an effective reagent for the C3-alkylation of indoles by alkyl halides in the presence of Hünig's base and tetrabutylammonium iodide. This new method for indole alkylation proceeds by a S(N)1-like pathway, and is general for allylic, benzylic, and tertiary halides.     

Total Synthesis of (+)-okaramine J featuring an exceptionally facile N-reverse-prenyl to C-prenyl aza-Claisen rearrangement

[reaction: see text] The convergent total synthesis of (+)-okaramine J was achieved in a longest linear sequence of 12 steps from l-tryptophan tert-butyl ester. A key reaction was the acid-catalyzed room-temperature aza-Claisen rearrangement of a N-reverse-prenylated hexahydro[2,3-b]pyrroloindole to a C-prenylated derivative.     

Synthesis, structure and catalytic properties of [Cp*Cr(C6F5)(Bn)(THF)] toward ethylene in the presence of AlEt3

Treatment of [Cp*CrCl(C₆F₅)]₂ with BnMgCl (Bn = benzyl) in Et₂O/THF affords [Cp*Cr(C₆F₅)(Bn)(THF)] (1) which has been isolated in 72% yield. This compound whose magnetic moment is equal to of 4.037 μ_B has been characterized by NMR and single crystal X-ray analysis. Compound 1 alone does not polymerize ethylene when dissolved in toluene. However, addition of excess AlEt₃ to a solution of 1 in toluene leads to a catalytically active system which readily oligomerizes ethylene under standard conditions. Oligomerization experiments carried out with [1] = 10⁻³ M and [AlEt₃] = 9 × 10⁻² M for 15 min lead to the production of ethylene oligomers with an activity of 280 kg mol Cr⁻¹ h⁻¹. The experimental molecular weight distribution observed at intermediate times during the reaction is satisfactorily accounted for by the Poisson distribution formula, which is indicative of a living polymerization system. These observations are in agreement with a catalytic cycle in which the growing alkyl chain is transferred from chromium to aluminum via a bimetallic complex in which the chromium and aluminum centers are bridged by an alkyl group and the growing polymer chain.     

In vitro and in vivo investigations on the photodynamic activity of core-modified expanded porphyrin--ammonium salt of 5,10,15,20-tetrakis-(meso-p-sulfonato phenyl)-25,27,29-trithia sapphyrin

The core modification of expanded porphyrins has been proved to have better photochemical properties, which are favorable for photodynamic therapy (PDT) applications. In this context, this study was aimed to investigate the in vitro and in vivo photodynamic activity of one such core-modified expanded porphyrin, namely, ammonium salt of 5,10,15,20-tetrakis-(meso-p-sulfonato phenyl)-25,27,29-trithia sapphyrin. For the in vitro studies, human erythrocytes were used as a membrane semimodel system to investigate the partitioning ability and drug-uptake characteristics. The partition studies on the membrane semimodel system revealed that maximum partitioning occurs at 12 microgm/mL concentration, and from the drug-uptake studies it is observed that maximum amount of the sensitizer is bound to the erythrocyte membranes during a 45 min incubation period. Photohemolysis studies at different concentrations of the sensitizer and exposure time showed maximum damage at 5 microgm/mL and 30 min exposure time. In vivo studies were performed on 7,12-dimethylbenz(a)nthracene-induced superficial squamous cell carcinoma on mouse skin. The sensitizer at a concentration of 2.5% in 2.0% dimethyl sulfoxide was applied topically on the tumor spot. After 1 h incubation the tumor spot was exposed to laser irradiation from Nd-YAG laser at its second harmonic wavelength of 532 nm. The photodynamic efficacy was estimated by tumor volume measurements at regular intervals after the treatment. One month after PDT exposure a 3.9-fold decrease in the tumor volume was observed with respect to the tumor volume before treatment. The treatment efficacy was further confirmed by histological and fluorescence spectroscopic evaluations of the tissue biopsy sample from the treated area. The results of our study suggest that the ammonium salt of 5,10,15,20-tetrakis-(meso-p-sulfonato phenyl)-25,27,29-trithia sapphyrin may find possible applications in the new modality of cancer treatment.