Highly Monodisperse Colloidal Magnesium Nanoparticles by Room Temperature Digestive Ripening

Nanoclusters of 25 nm sized Mg-THF have been prepared by the solvated metal atom dispersion method. Room-temperature digestive ripening of these nanoclusters in the presence of hexadecylamine (HDA) resulted in highly monodisperse colloidal Mg-HDA nanoparticles of 2.8 ± 0.2 nm. An insight into the room-temperature digestive ripening process was obtained by studying the disintegration of clusters for various Mg:HDA ratios. The Mg colloids are quite stable with respect to precipitation of particles under Ar atmosphere. Using this procedure, pure Mg(0) nanopowders were obtained in gram scale quantities. The Mg powder precipitated from the colloid was fully hydrided at 33 bar and 118 °C. Initial desorption of H2 from samples of MgH2 was achieved at a remarkably low temperature, 115 °C compared to >350 °C in bulk Mg, demonstrating the importance of the size on the desorption temperatures.

Mössbauer studies of the corrosion products of iron formed in aqueous ammonium nitrate solution

The products of corrosion reaction of electrolytic iron in 45% ammonium nitrate solution formed under various conditions of time, temperature and pH have been analysed mainly by Mössbauer spectroscopy, in combination with X-ray diffraction, infrared absorption and electron microscopy techniques. γ-Fe00H is found to be the major product of hydrolytic precipitation at pH > 5.6 while only α-FeOOH is formed at pH < 3.0. In the pH range 3.0 < pH < 5.0, α-Fe00H and ferrihydrite are both formed. However, once the nuclei of α-Fe00H are formed under low pH conditions, their growth is favoured even in the otherwise unfavourable slightly acidic medium, resulting in a hydrous α-Fe00H which has two distinct hyperfine fields at the 57Fe nucleus. Magnetite is always formed in the vicinity of the metal and its rate of formation on the surface increases with temperature. α-Fe203 is the major product of hydrolytic precipitation at temperatures >80C. The possible mechanisms for the formation of each of the corrosion products are discussed.

Studies on the purification of banana polyphenoloxidase

Studies on the extractability of polyphenoloxidase (PPO) from the pulp of five banana cultivars revealed a varietal difference in the nature of binding of the PPO in the cell, with the enzyme being entirely in the soluble fraction in one and partly associated with the cell wall in others, necessitating use of a detergent to release it from the latter. Partial purification by acetone precipitation and chromatography using a DEAE-cellulose column yielded two major fractions DE-I and DE-II with purifications of 4- and 16·3-fold and activity recoveries of 38·2 and 43·3% respectively. Further gel filtration of the two fractions on a Sephadex G-100 column improved the purifications to 44- and 50-fold respectively with full activity recovery. Polyacrylamide gel electrophoretic studies showed the two fractions to be composed of isoenzymes differing in pattern. The purified enzyme showed maximum absorption at 275 nm.

A mechanism for the west-north-west movement of monsoon depressions

The monsoon depressions intensify over the Bay of Bengal, move in a west-north-west (WNW) direction and dissipate over the Indian continent. No convincing physical explanation for their observed movement has so far been arrived at, but here, I suggest why the maximum precipitation occurs in the western sector of the depression and propose a feedback mechanism for the WNW movement of the depressions. We assume that a heat source is created over the Bay of Bengal due to organization of cumulus convection by the initial instability. In a linear sense, heating at this latitude (20° N), produces an atmospheric response mainly in the form of a stationary Rossby–gravity wave to the west of the heat source. The low-level vorticity (hence the frictional convergence) and the vertical velocity associated with the steady-state response is such that the maximum moisture convergence (and precipitation) is expected to occur in the WNW sector at a later time. Thus, the heat source moves to the WNW sector at a later time and the feedback continues resulting in the WNW movement of the depressions.

Low cycle fatigue behaviour of a low interstitial Ni-base superalloy

The low cycle fatigue behaviour of precipitation strengthened nickel-base superalloy 720Li containing a low concentration of interstitial carbon and boron was studied at 25, 400 and 650 degrees C. Cyclic stress response at all temperatures was stable under fully reversed constant total strain amplitude (Delta epsilon/2) when Delta epsilon/2 <= 0.6%. At Delta epsilon/2 > 0.6%, cyclic hardening was followed by softening, until fracture at 25 and 650 degrees C. At 400 degrees C, however, cyclic stress plateaued after initial hardening. Dislocation-dislocation interactions and precipitate shearing were the micromechanisms responsible for the cyclic hardening and softening, respectively. The number of reversals to failure vs. plastic strain amplitude plot exhibits a bilinear Coffin-Manson relation. Transmission electron microscopy substructures revealed that planar slip was the major deformation mode under the conditions examined. However, differences in its distribution were observed to be the cause for the bilinearity in fatigue lives. The presence of fine deformation twins at low Delta epsilon/2 at 650 degrees C suggests the role of twinning in homogenization of cyclic deformation.

Choice of the End Functional Groups in Tri(p-phenylenevinylene) Derivatives Controls Its Physical Gelation Abilities

New supramolecular organogels based on all-trans-tri(p-phenylenevinylene) (TPV) systems possessing different terminal groups, e.g., oxime, hydrazone, phenylhydrazone, and semicarbazone have been synthesized. The self-assembly properties of the compounds that gelate in specific organic solvents and the aggregation motifs of these molecules in the organogels were investigated using UV−vis, fluorescence, FT-IR, and 1H NMR spectroscopy, electron microscopy, differential scanning calorimetry (DSC), and rheology. The temperature variable UV−vis and fluorescence spectroscopy in different solvents clearly show the aggregation pattern of the self-assemblies promoted by hydrogen bonding, aromatic π-stacking, and van der Waals interactions among the individual TPV units. Gelation could be controlled by variation in the number of hydrogen-bonding donors and acceptors in the terminal functional groups of this class of gelators. Also wherever gelation is observed, the individual fibers in gels change to other types of networks in their aggregates depending on the number of hydrogen-bonding sites in the terminal functions. Comparison of the thermal stability of the gels obtained from DSC data of different gelators demonstrates higher phase transition temperature and enthalpy for the hydrazone-based gelator. Rheological studies indicate that the presence of more hydrogen-bonding donors in the periphery of the gelator molecules makes the gel more viscoelastic solidlike. However, in the presence of more numbers of hydrogen-bonding donor/acceptors at the periphery of TPVs such as with semicarbazone a precipitation as opposed to gelation was observed. Clearly, the choice of the end functional groups and the number of hydrogen-bonding groups in the TPV backbone holds the key and modulates the effective length of the chromophore, resulting in interesting optical properties.

Texture dependent stress corrosion failure of commercial titanium sheets in bromine-methanol solution

The stress corrosion cracking (SCC) characteristics of agr-titanium sheets in a bromine-methanol solution have been studied in the annealed and cold-rolled conditions using longitudinal and transverse specimens. The times to failure for annealed longitudinal specimens were longer than those for similarly tested transverse specimens. The cold-rolled specimens developed resistance to SCC, but failed by cleavage when notched, unlike the intergranular separation in annealed titanium. The apparent activation energy was found to be texture dependent and was in the range 30 to 51 kJ mol–1 for annealed titanium, and 15kJ mol–1 for cold-rolled titanium. The dependence of SCC behaviour on the texture is related to the changes in the crack initiation times. These are caused by changes in the passivation and repassivation characteristics of the particular thickness plane. The thickness planes are identified with the help of X-ray pole figures obtained on annealed and cold-rolled material. On the basis of the activation energy and the electrochemical measurements, the mechanism of SCC in annealed titanium is identified to be the one involving stress-aided anodic dissolution. On the other hand, the results on the cold-rolled titanium are in support of the hydrogen embrittlement mechanism consisting of hydride precipitation. The cleavage planes identified from the texture data match with the reported habit planes for hydride formation.

Fluid dynamics of the monsoon

The monsoonal regions of the world are characterized by a seasonal reversal in the direction of winds associated with the excursion of the equatorial trough (or the ITCZ) in response to the variation in the latitude of maximum insolation. This monsoonal circulation is a planetary scale phenomenon. However, the associated precipitation is critically dependent on the organization of the cumulus clouds (typically a few kilometers in horizontal extent) over the scale of synoptic vortices (typically a few hundred kilometers in horizontal extent). Thus modelling of the seasonal transitions and intraseasonal fluctuations requires an understanding of the fluid mechanics of these three scales of organizations and their interactions. The present paper is an attempt to outline the current state of understanding of these phenomena.

Enzymatic cleavage of carotenoids

1. 1.|Carotene 15,15′-dioxygenase (EC 1.13.11.21) has been isolated from the intestine of guinea pig and rabbit and purified 38- and 30-fold, respectively, but subjecting the intestinal homogenate to protamine sulfate treatment, (NH4)2SO4 fractionation and acetone precipitation. 2. 2.|The guinea pig enzyme showed a pH optimum at 8.5, an optimum substrate concentration of 200 nmoles of β,β-carotene per 25 ml of reaction mixture, an apparent Km with β,β-carotene as substrate of 9.5 · 10−6 M and a V 3.3 nmoles of retinal formation/mg protein per h. The reaction was linear upto 3 h and the reaction rate increased linearly with increase in enzyme protein concentration. The enzyme was activated by GSH and Fe2+ and inhibited by sodium dodecylsulfate, sulfhydryl binding and iron chelating agents. 3. 3.|The reaction catalysed by guinea pig enzyme was strictly stoichiometric. 4. 4.|Rabbit enzyme showed a close similarity with guinea pig enzyme with respect to time course, optimum substrate concentration, activation by Fe2+ and GSH, inhibition by sodium dodecylsulfate, iron chelating and sulfhydryl binding agents. However, it showed a slightly lower pH optimum (pH 7.8). 5. 5.|The enzyme from guinea pig and rabbit showed remarkable similarity with respect to cleavage of carotenoids. The enzyme from both the species was more specific for β,β-carotene but could also cleave a number of other carotenoids at the 15,15′-double bond. 6. 6.|10′-Apo-β-carotenal and 10′-apo-β-carotenol were readily cleaved compared with other apo-β-carotenals and apo-β-carotenols tested. 7. 7.|It has been conclusively shown for the first time that mono-ring substituted carotenoids are also cleaved at the 15,15′-double bond.

Enzymatic cleavage of carotenoids

1. 1.|Carotene 15,15′-dioxygenase (EC 1.13.11.21) has been isolated from the intestine of guinea pig and rabbit and purified 38- and 30-fold, respectively, but subjecting the intestinal homogenate to protamine sulfate treatment, (NH4)2SO4 fractionation and acetone precipitation. 2. 2.|The guinea pig enzyme showed a pH optimum at 8.5, an optimum substrate concentration of 200 nmoles of β,β-carotene per 25 ml of reaction mixture, an apparent Km with β,β-carotene as substrate of 9.5 · 10−6 M and a V 3.3 nmoles of retinal formation/mg protein per h. The reaction was linear upto 3 h and the reaction rate increased linearly with increase in enzyme protein concentration. The enzyme was activated by GSH and Fe2+ and inhibited by sodium dodecylsulfate, sulfhydryl binding and iron chelating agents. 3. 3.|The reaction catalysed by guinea pig enzyme was strictly stoichiometric. 4. 4.|Rabbit enzyme showed a close similarity with guinea pig enzyme with respect to time course, optimum substrate concentration, activation by Fe2+ and GSH, inhibition by sodium dodecylsulfate, iron chelating and sulfhydryl binding agents. However, it showed a slightly lower pH optimum (pH 7.8). 5. 5.|The enzyme from guinea pig and rabbit showed remarkable similarity with respect to cleavage of carotenoids. The enzyme from both the species was more specific for β,β-carotene but could also cleave a number of other carotenoids at the 15,15′-double bond. 6. 6.|10′-Apo-β-carotenal and 10′-apo-β-carotenol were readily cleaved compared with other apo-β-carotenals and apo-β-carotenols tested. 7. 7.|It has been conclusively shown for the first time that mono-ring substituted carotenoids are also cleaved at the 15,15′-double bond.

Purification and kinetic mechanism of 5,10-metliyienetetrahydrofolate reductase from sheep liver

5,10-Methylenetetrahydrofolate reductase (EC 1.1.1.68) was purified from the cytosolic fraction of sheep liver by (NH4)2 SO4 fractionation, acid precipitation, DEAE-Sephacel chromatography and Blue Sepharose affinity chromatography. The homogeneity of the enzyme was established by sodium dodecyl sulphate-polyacrylamide gel electrophoresis, ultracentrifugation and Ouchterlony immunodiffusion test. The enzyme was a dimer of molecular weight 1,66,000 ± 5,000 with a subunit molecular weight of 87,000 ±5,000. The enzyme showed hyperbolic saturation pattern with 5-methyltetrahydrofolate.K 0.5 values for 5-methyltetrahydrofolate menadione and NADPH were determined to be 132 ΜM, 2.45 ΜM and 16 ΜM. The parallel set of lines in the Lineweaver-Burk plot, when either NADPH or menadione was varied at different fixed concentrations of the other substrate; non-competitive inhibition, when NADPH was varied at different fixed concentrations of NADP; competitive inhibition, when menadione was varied at different fixed concentrations of NADP and the absence of inhibition by NADP at saturating concentration of menadione, clearly established that the kinetic mechanism of the reaction catalyzed by this enzyme was ping-pong.

Mechanistic Aspects of Shape Selection and Symmetry Breaking during Nanostructure Growth by Wet Chemical Methods

The control of shapes of nanocrystals is crucial for using them as building blocks for various applications. In this paper, we present a critical overview of the issues involved in shape-controlled synthesis of nanostructures. In particular, we focus on the mechanisms by which anisotropic structures of high-symmetry materials (fcc crystals, for instance) could be realized. Such structures require a symmetry-breaking mechanism to be operative that typically leads to selection of one of the facets/directions for growth over all the other symmetry-equivalent crystallographic facets. We show how this selection could arise for the growth of one-dimensional structures leading to ultrafine metal nanowires and for the case of two-dimensional nanostructures where the layer-by-layer growth takes place at low driving forces leading to plate-shaped structures. We illustrate morphology diagrams to predict the formation of two-dimensional structures during wet chemical synthesis. We show the generality of the method by extending it to predict the growth of plate-shaped inorganics produced by a precipitation reaction. Finally, we present the growth of crystals under high driving forces that can lead to the formation of porous structures with large surface areas.

Variability of Indian summer monsoon rainfall in daily data from gauge and satellite

It has long been thought that tropical rainfall retrievals from satellites have large errors. Here we show, using a new daily 1 degree gridded rainfall data set based on about 1800 gauges from the India Meteorology Department (IMD), that modern satellite estimates are reasonably close to observed rainfall over the Indian monsoon region. Daily satellite rainfalls from the Global Precipitation Climatology Project (GPCP 1DD) and the Tropical Rainfall Measuring Mission (TRMM) Multisatellite Precipitation Analysis (TMPA) are available since 1998. The high summer monsoon (June-September) rain over the Western Ghats and Himalayan foothills is captured in TMPA data. Away from hilly regions, the seasonal mean and intraseasonal variability of rainfall (averaged over regions of a few hundred kilometers linear dimension) from both satellite products are about 15% of observations. Satellite data generally underestimate both the mean and variability of rain, but the phase of intraseasonal variations is accurate. On synoptic timescales, TMPA gives reasonable depiction of the pattern and intensity of torrential rain from individual monsoon low-pressure systems and depressions. A pronounced biennial oscillation of seasonal total central India rain is seen in all three data sets, with GPCP 1DD being closest to IMD observations. The new satellite data are a promising resource for the study of tropical rainfall variability.

Immunological studies on nucleic-acids and their components .5. Antibodies specific to a deoxyribodinucleotide sequence

Antibodies were raised in rabbits against the bovine serum albumin conjugate of dpApT. Analysis by double diffusion in agar gel and quantitative precipitation test showed the presence of antibodies specific to the hapten in the antisera. Quantitative data on the specificity of the antibodies were obtained by studying the inhibition of the binding of 3H-dpApT to the anti-sera by various nonradioactive mono- and oligonucleotides, using a nitrocellulose membrane binding assay. The antibodies were found to be highly specific for the dinucleotide sequence dpApT. The antibodies were able to bind to synthetic oligonucleotides containing the sequence dpApT and to denatured calf thymus DNA.

Thiol-Disulfide Interchange Mediated Reversible Dendritic Megamer Formation and Dissociation

We report the formation of dynamic, reversible cross-linked dendritic megamers and their dissociation to monomeric dendrimers, through a thiol-disulfide interchange reaction. For this study, poly(alkyl aryl ether) dendrimers up to three-generations presenting thiol functionalities, were prepared. The series from zero to three generations of dendrimers were installed with 3, 6, 12, and 24 thiol functionalities at their peripheries. Upon synthesis, cross-linking of the dendrimer was accomplished through disulfide bond formation. The cross-linking of dendrimers was monitored through optical density changes at 420 nm. Dense cross-linking led to visible precipitation of dendritic megamers and the morphologies of the megamers were characterized by transmission electron microscopy. The disulfide cross-links between megamer monomers could be dissociated readily upon reduction of disulfide bond by dithiothreitol reagent. Preliminary studies show that dendritic megamers encapsulate C-60 and the efficiency of encapsulation increased with increasing generation of dendritic megamer.