Studies on natural and anthropogenic radionuclides in sediment and biota of Mumbai Harbour Bay

Mumbai Harbour Bay (MHB) is a recipient of low level treated effluents from BARC, Trombay and its also a recipient of domestic and industrial wastes from the city of Mumbai and adjoining areas. Sediment samples were collected from various locations of MHB to determine the concentrations of naturally occurring radionuclides like ²²⁶Ra, ²²⁸Ra and ⁴⁰K which varied between 4.0 and 26.0, 5.5 and 19.9, 249.6 and 557.6 Bq kg _(dry) ^?1 respectively and are comparable to the worldwide average concentration. The mean value ratio of ²²⁸Ra/²²⁶Ra in sediment was found to be 1.4, indicating a relatively higher mobility of ²³⁸U compared to ²³²Th. The concentration of anthropogenic radionuclide ¹³⁷Cs in sediment and biota ranged between 3.6 and 54.5 Bq kg _(dry) ^?1 , <0.08 and 0.5 Bq kg _(wet) ^?1 respectively. The ingestion dose to ‘General Public’ due to ¹³⁷Cs intake is 0.02 μSv years^?1 which is negligible compared to the internationally accepted limit of 1,000 μSv years^?1 to ‘members of public’.     

13C-13C rotational resonance width distance measurements in uniformly 13C-labeled peptides

The rotational resonance width (R2W) experiment is a constant-time version of the rotational resonance (R2) experiment, in which the magnetization exchange is measured as a function of sample spinning frequency rather than the mixing time. The significant advantage of this experiment over conventional R2 is that both the dipolar coupling and the relaxation parameters can be independently and unambiguously extracted from the magnetization exchange profile. In this paper, we combine R2W with two-dimensional 13C-13C chemical shift correlation spectroscopy and demonstrate the utility of this technique for the site-specific measurement of multiple 13C-13C distances in uniformly labeled solids. The dipolar truncation effects, usually associated with distance measurements in uniformly labeled solids, are considerably attenuated in R2W experiments. Thus, R2W experiments are applicable to uniformly labeled biological systems. To validate this statement, multiple 13C-13C distances (in the range of 3-6 A) were determined in N-acetyl-[U-13C,15N]l-Val-l-Leu with an average precision of +/-0.5 A. Furthermore, the distance constraints extracted using a two-spin model agree well with the X-ray crystallographic data.     

Directed evolution and substrate specificity profile of homing endonuclease I-SceI

The laboratory evolution of enzymes with tailor-made DNA cleavage specificities would represent new tools for manipulating genomes and may enhance our understanding of sequence-specific DNA recognition by nucleases. Below we describe the development and successful application of an efficient in vivo positive and negative selection system that applies evolutionary pressure either to favor the cleavage of a desired target sequence or to disfavor the cleavage of nontarget sequences. We also applied a previously described in vitro selection method to reveal the comprehensive substrate specificity profile of the wild-type I-SceI homing endonuclease. Together these tools were used to successfully evolve mutant I-SceI homing endonucleases with altered DNA cleavage specificities. The most highly evolved enzyme cleaves the target mutant DNA sequence with a selectivity that is comparable to wild-type I-SceI's preference for its cognate substrate.     

Isobutylene‐rich macromonomers: Dynamics and yields of peroxide‐initiated crosslinking

New isobutylene‐rich elastomers bearing multiple pendant styrenic, acrylic, maleimidic, vinylic, and allylic functional groups have been prepared and examined in the context of peroxide‐initiated crosslinking. Halide displacement from brominated poly(isobutylene‐co‐isoprene) (BIIR) by the requisite carboxylate nucleophiles in homogeneous toluene solutions provide the desired esters in quantitative yield without complications from dehydrohalogenation or premature crosslinking. Heating the resulting macromonomers with dicumyl peroxide to 160 °C under solvent‐free conditions gives thermoset derivatives, with reaction rates and yields depending markedly on functional group structure. In general, high cure extents can only be achieved using highly reactive pendant functional groups, owing to the competitive balance between crosslinking through C?C oligomerization, and degradation through β‐scission of backbone macroradical intermediates. Independent control of crosslinking rates and cure extents is gained through the use of nitroxyl radical traps bearing acrylate functionality. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 123–132     

Propane σ‐Complexes on PdO(101): Spectroscopic Evidence of the Selective Coordination and Activation of Primary CH Bonds

Achieving selective C? H bond cleavage is critical for developing catalytic processes that transform small alkanes to value‐added products. The present study clarifies the molecular‐level origin for an exceptionally strong preference for propane to dissociate on the crystalline PdO(101) surface via primary C? H bond cleavage. Using reflection absorption infrared spectroscopy (RAIRS) and density functional theory (DFT) calculations, we show that adsorbed propane σ‐complexes preferentially adopt geometries on PdO(101) in which only primary C? H bonds datively interact with the surface Pd atoms at low propane coverages and are thus activated under typical catalytic reaction conditions. We show that a propane molecule achieves maximum stability on PdO(101) by adopting a bidentate geometry in which a H? Pd dative bond forms at each CH₃ group. These results demonstrate that structural registry between the molecule and surface can strongly influence the selectivity of a metal oxide surface in activating alkane C? H bonds.     

Optimization of process for the production of bio-oil from eucalyptus wood

The pyrolysis of eucalyptus wood was carried out in a batch reactor to optimize the yield of bio-oil.Effect of various parameters like feed(particle) size,temperature,presence of catalyst and heating rate on the yield of bio-oil was investigated.The optimum conditions for high yield of bio-oil are for the particle size 2 mm~5 mm(average l/d=12.84/2.03 mm) at 450 ℃ in high heating rate.The reaction kinetics and the quality of bio-oil produced are independent of the presence of different catalysts like mordenite,kaoline clay,fly ash and silica alumina.The physical properties like odour,colour,PH,viscosity,heating value were determined.The FT-IR analysis of bio-oil indicates the presence of different functional groups such as monomeric alcohol,phenol,ketones,aldehydes,carboxylic acid,amines,and nitro compounds.The composition of the bio-oil at different conditions was analyzed using GC-MS and found that the components are temperature dependent but independent of catalysts used.     

Synthesis of block copolymer segments containing different ratios of ethylene and 5-norbornen-2-yl acetate

Block copolymerization of ethylene with 5-norbornen-2-yl acetate (1) by the nickel catalyst system [N-(2,6-diisopropylphenyl)-2-(2,6-diisopropylphenylimino)propanamide]Ni(eta1-CH2Ph)(PMe3) (2) and Ni(COD)2 (bis(1,4-cyclooctadiene)nickel) (3) produces a variety of block copolymer structures that demonstrate microphase separation. Typical block copolymerizations were carried out in an autoclave charged with a solution of the catalyst mixture and 1 (0.15 M) in toluene. The autoclave was sealed and exposed to PC2H4 = 50 psi for a period of time (T1). A pressure jump to PC2H4 = 1100 psi was then applied and the reaction allowed to proceed for another predetermined interval (T2). Independent experiments were performed to isolate and examine the molecular weight and comonomer composition of the first block. Narrow molecular weight distributions and the increase of polymer molecular weight with increases in T1 or T2 are consistent with a product in which an initial block is formed at low ethylene pressures and quantitatively converted to a block copolymer by the jump to high pressure. Transmission electron microscopy confirms that the materials are microphase separated.     

Aggregation of a peptide antibiotic alamethicin at the air-water interface and its influence on the viscoelasticity of phospholipid monolayers

The aggregation properties of an antibiotic membrane-active peptide alamethicin at the air-water interface have been studied using interfacial rheology and fluorescence microscopy techniques. Fluorescence microscopy of alamethicin monolayers revealed a coexistence of liquid expanded (LE) and solid phases at the surface concentrations studied. Interfacial oscillatory shear measurements on alamethicin monolayers indicate that its viscoelastic properties are determined by the area fraction of the solid domains. The role of zwitterionic phospholipids dioleoylphosphatidyl choline (DOPC) and dioleoylphosphatidyl ethanolamine (DOPE) on the peptide aggregation behavior was also investigated. Fluorescence microscopy of alamethicin/phospholipid monolayers revealed an intermediate phase (I) in addition to the solid and LE phase. In mixed monolayers of phospholipid (L)/alamethicin (P), with increase in L/P, the monolayer transforms from a viscoelastic to a viscous fluid with the increase in area fraction of the intermediate phase. Further, a homogeneous mixing of alamethicin/lipid molecules is observed at L/P > 4. Our studies also confirm that the viscoelasticity of alamethicin/phospholipid monolayers is closely related to the alamethicin/phospholipid interactions at the air-water interface.     

Thermochemical pretreatment of water hyacinth for improved biomethanation

Water hyacinth was subjected to various thermochemical pretreatments and used as a substrate in anaerobic digestion for biomethanation. Results indicate that the pretreatment increased the solubility of biomass and improved gas production. Best results were obtained when water hyacinth was treated at pH 11.00 and temperature 121‡C. Severe treatment conditions showed a negative effect, especially on methanogenic bacteria caused by toxic compounds produced during treatment.