Effect of Pt on interdiffusion and mechanical properties of the γ and γ′ phases in the Ni–Pt–Al system

The effect of Pt on the growth kinetics of the γ′-[Ni(Pt)]₃Al ordered intermetallic phase and the γ-Ni(Pt, Al) solid solution diffusion rates of the species, hardness and elastic modulus was examined by employing the diffusion couple experimental technique. Experiments were conducted by using the β-Ni(Pt)Al phase and Ni(Pt) alloy couples, each of which had a fixed amount of Pt (5, 10 and 15 at. %) in both the end members so that the Pt content is more or less constant throughout the interdiffusion zone. The results suggest that the growth kinetics of both phases and the average effective interdiffusion coefficients of Ni and Al increase with the increase in Pt content. Nanoindentation studies across the compositional gradients show that the mechanical properties of the intermetallic phase in the superalloy are relatively insensitive to the presence of Pt but are more sensitive to the Ni/Al ratio. In contrast, the marked variation in the hardness of the γ phase were noted, increasing markedly with Al concentration in a given couple and also increasing with increasing Pt content. Possible causes for the observed variations are discussed.     

Self-stabilized passive, harmonically mode-locked stretched-pulse erbium fiber ring laser

We have studied a passive, harmonically mode-locked stretched-pulse erbium fiber ring laser with net positive dispersion that is self-stabilized by gain depletion and electrostriction. Periodic pulses with supermode suppression of >75 dB and picosecond jitter are achieved. The pulses are compressible to 125 fs by external chirp compensation. The repetition rate is 220 MHz, and the average power is as high as 80 mW.     

Crystal structure of sulfamerazine

The structure of sulfamerazine, C₁₁H₁₂N₄O₂S, a very important sulfonamide drug, has been solved by direct methods with X-ray diffraction data collected using CuK radiation. The crystals are orthorhombic, witha=9.145(1),b=11.704(1),c=22.884(2) Å and space groupPbca. The structure was refined with 2082 observed independent reflections, measured on a CAD-4 diffractometer, to a finalR value of 0.078. The molecule has similar conformational features to those observed in other sulfonamide drugs.     

Large-area broadband saturable Bragg reflectors by use of oxidized AlAs

Broadband saturable Bragg reflectors (SBRs) are designed and fabricated by monolithic integration of semiconductor saturable absorbers with broadband Bragg mirrors. The wet oxidation of AlAs creates low-index AlxOy layers for broadband, high-index-contrast AlGaAs/AlxOy or InGaAlP/AlxOy mirrors. SBR mirror designs indicate greater than 99% reflectivity over bandwidths of 294, 466, and 563 nm for center wavelengths of 800, 1300, and 1550 nm, respectively. Highly strained and unstrained absorbers are stably integrated with the oxidized mirrors. Large-scale lateral oxidation techniques permit the fabrication of SBRs with diameters of 500 microm. Large-area, broadband SBRs are used to self-start and mode lock a variety of laser systems at wavelengths from 800 to 1550 nm.     

Compressibility effects on steady streaming from a noncompact rigid sphere

The problem of steady streaming around a rigid isolated sphere in a plane standing acoustic field is considered. Existing results in the literature have been generalized to allow for noncompactness of the sphere, and the influence of fluid compressibility on the streaming behavior has been included. It is found that in the high-frequency limit of interest for which the streaming is strongest, the effective steady slip velocity at the edge of the inner boundary layer region that is responsible for driving the steady streaming in the bulk of the fluid in the outer region, has a complex variation over the surface of the sphere that depends on (i) the sphere position (with respect to the node/antinode of the acoustic field), (ii) the extent of sphere compactness, and (iii) on a well-defined function (representing compressibility effects) of the fluid Prandtl number and its ratio of specific heats. Not surprisingly, the contribution from this function is negligible when the host fluid is a liquid. The steady streaming behavior around the sphere is demonstrated with the help of flow streamlines for various cases in the diffusive limit of weak outer flow for low streaming Reynolds numbers.     

Heterogeneous catalysis by new bead‐shaped polymer‐supported multisite phase transfer catalysts

Three different new insoluble bead‐shaped polymer‐supported multisite phase transfer catalysts containing two, four and six active sites have been prepared and characterized by FTIR, TGA, [chloride ion] and SEM analyses. The presence of number of active sites in each catalyst and their corresponding catalytic ability were studied by determining pseudo‐first order rate constants for C‐alkylation of phenylacetonitrile (PAN) and four different substituted PAN as the substrate using a low concentration of NaOH (25% w/w) at 50 °C. The observed rate constants were compared with rate constants of same reactions catalyzed by single‐site catalyst under identical reaction conditions. From comparative study, the efficiency of catalysts were found to be in the order six‐site>four‐site>two‐site>single‐site thus confirming number of active sites in each catalyst. Further, the detailed kinetic profile of C‐alkylation of PAN has been investigated using the superior six‐site catalyst by varying stirring speed, [substrate], [catalyst], [NaOH], and temperature. Based on the observed kinetic and activation parameters, an interfacial mechanism was proposed. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 771–785, 2009     

The effect of external forces on the initial dissociation of RDX (1,3,5‐trinitro‐1,3,5‐triazine): A mechanochemical study

Experimental and theoretical studies have proposed different initiation reactions for the decomposition of hexahydro‐1,3,5‐trinitro‐1,3,5‐triazine (RDX). Three primary reactions are considered to start RDX decomposition: homolytic N? N bond fission, HONO elimination, and concerted fission of C? N bonds. The focus of this article is to study the effect of external forces on the energy barrier and reaction energies of all three mechanisms. We used the Nudged Elastic Band method along with ab initio Density Functional Theory within the framework of a generalized force‐modified potential energy surface (G‐FMPES) to calculate the minimum energy paths at different compressive (corresponding to pressure between approximately 6 and 294 MPa) and expansive force values (between 10 and 264 pN). For all three reactions, the application of an expansive force increases the exothermicity and lowers the energy barriers to different extents, while a compressive force decreases the exothermicity and raises the energy barrier to different extents.     

Preactivation‐Based,One‐Pot Combinatorial Synthesis of Heparin‐like Hexasaccharides for the Analysis of Heparin–Protein Interactions

Heparin (HP) and heparan sulfate (HS) play important roles in many biological events. Increasing evidence has shown that the biological functions of HP and HS can be critically dependent upon their precise structures, including the position of the iduronic acids and sulfation patterns. However, unraveling the HP code has been extremely challenging due to the enormous structural variations. To overcome this hurdle, we investigated the possibility of assembling a library of HP/HS oligosaccharides using a preactivation‐based, one‐pot glycosylation method. A major challenge in HP/HS oligosaccharide synthesis is stereoselectivity in the formation of the cis‐1,4‐linkages between glucosamine and the uronic acid. Through screening, suitable protective groups were identified on the matching glycosyl donor and acceptor, leading to stereospecific formation of both the cis‐1,4‐ and trans‐1,4‐linkages present in HP. The protective group chemistry designed was also very flexible. From two advanced thioglycosyl disaccharide intermediates, all of the required disaccharide modules for library preparation could be generated in a divergent manner, which greatly simplified building‐block preparation. Furthermore, the reactivity‐independent nature of the preactivation‐based, one‐pot approach enabled us to mix the building blocks. This allowed rapid assembly of twelve HP/HS hexasaccharides with systematically varied and precisely controlled backbone structures in a combinatorial fashion. The speed and the high yields achieved in glycoassembly without the need to use a large excess of building blocks highlighted the advantages of our approach, which can be of general use to facilitate the study of HP/HS biology. As a proof of principle, this panel of hexasaccharides was used to probe the effect of backbone sequence on binding with the fibroblast growth factor‐2 (FGF‐2). A trisaccharide sequence of 2‐O‐sulfated iduronic acid flanked by N‐sulfated glucosamines was identified to be the minimum binding motif and N‐sulfation was found to be critical. This provides useful information for further development of more potent compounds towards FGF‐2 binding, which can have potential applications in wound healing and anticancer therapy.     

Regioselective addition reactions at C-2 of 3,4-dihydropyrimidinones. Synthesis and evaluation of multifunctionalized tetrahydropyrimidines

Multifunctionalized tetrahydropyrimidines derivatives have been synthesized from Biginelli 3,4-dihydropyrimidin-2-(1H)-thiones (DHPMs) efficiently. The transformation includes desulfurization of DHPMs with Raney-Ni and subsequent regioselective C-2 functionalization using a variety of C-nucleophiles with simultaneous activation with ethyl chloroformate. Functionalized pyrimidine derivatives containing bulky substituents at C-2 of the pyrimidine ring are cytostatic.     

Conformational control in a bipyridine linked π-conjugated oligomer: cation mediated helix unfolding and refolding

A chiral π-conjugated oligomer having alternate bipyridine and carbazole moieties connected through acetylinic bonds undergoes helical folding in chloroform-acetonitrile (40/60, v/v) as evident by fluorescence and circular dichroism changes. In the presence of transition metal cations such as Zn(2+) defolding of the helical conformation occurs. Upon decomplexation of the cation with EDTA, the helical conformation is regained.