Synthesis and Application of Novel NiMoK/TS-1 for Selective Conversion of Fatty Acid Methyl Esters/Triglycerides to Olefins.

Methyl palmitate (or triglyceride) was converted into C15 olefin with remarkable selectivity using nickel-molybdenum oxides on the mesoporous titanosilicate support. The olefin has one carbon atom less than the acid portion of the ester. A new catalyst NiMoK/TS-1 was synthesized in which the effect of acidity of supports and molybdenum loading on the decarboxylation conversion along with product selectivity was investigated in methyl palmitate conversion into C15 olefin. The prepared catalysts were analyzed using ammonia-temperature-programmed desorption (NH3-TPD), thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and Brunauer-Emmett-Teller (BET) techniques. The reaction was carried out using a vapor-phase fixed-bed downflow reactor system at atmospheric pressure. The NiMoK/TS-1 catalyst at a weight hourly space velocity (WHSV) of 5.6/h was found to be selective toward C15 olefin. The catalyst was stable up to 15 h, and it can be regenerated with no considerable decrease in the activity even after fourth reuse. Beyond 653 K, the conversion of methyl palmitate increased but the selectivity for C15 products and C15 olefin was decreased.

Highly Enantioselective One-Pot Synthesis of Chiral ß-Heterosubstituted Alcohols via Ruthenium-Prolinamide-Catalyzed Asymmetric Transfer Hydrogenation.

The utility of a chiral Ru-prolinamide catalytic system has been demonstrated in one-pot synthesis of optically active ß-triazolylethanol and ß-hydroxy sulfone derivatives. The said methodology proceeds through asymmetric transfer hydrogenation of in situ formed ketones of the corresponding chiral products. Various chiral prolinamide ligands were screened, and ligand L6 with isopropyl groups substituted at the ortho position has shown excellent activity at 60 °C in aqueous medium producing up to 95% yield and 99.9% enantioselectivity.

Microbial synthesis of polyhydroxyalkanoate using seaweed-derived crude levulinic acid as co-nutrient.

Production of polyhydroxyalkanoates (PHAs) from Jatropha biodiesel residues, namely crude glycerol and oil cake hydrolysate, has been reported previously. Halomonas hydrothermalis (MTCC accession no. 5445; NCBI Genbank accession no. GU938192), a wild marine strain, was used in the bio-synthesis. The present study was initiated to vary the properties of the polymer. Seaweed-derived crude levulinic acid (SDCLA), containing formic acid, residual sugars and dissolved minerals additionally, was proposed as co-feed along with the biodiesel residues. Experiments were conducted at 100mL scale in batch process. Whereas the PHA yield was only 0.40 ± 0.01 g when only biodiesel residues were employed, it rose to 1.07 ± 0.02 g in presence of 0.35% (w/v) of SDCLA. The corresponding carbon utilisation efficiencies were 29.3% and 57.5%, respectively. 3-Hydroxy valerate incorporation in the PHA was pronounced in presence of SDCLA, with associated changes in polymer properties. The microbial synthesis fared poorly when SDCLA was substituted with pure levulinic acid. Thus, Halomonas hydrothermalis had a poor response to levulinic acid, as such, and other constituents present in SDCLA appear to have played a vital role in bacterial cell division and accumulation of PHA. Biodegradability tests in moist soil were also conducted as part of the study. Marine microalgal cultivation for biodiesel and seaweed cultivation for fuels may help generate biodiesel residues and crude levulinic acid in proximity, which would open up the possibility of large scale PHA manufacture in efficient and practical manner in the future through the methodology of the present study.

Solar photothermochemical reaction and supercritical CO2 work up for a fully green process of preparation of pure p-nitrobenzyl bromide.

It has been reported by us recently that p-nitrobenzyl bromide (PNBBr) can be synthesized from p-nitrotoluene (PNT) in high isolated yield with respect to available bromine in 2:1 Br(-)-BrO3(-) employed as brominating reagent. The reaction was conducted in ethylene dichloride (EDC) and the substrate was taken in excess to suppress dibromo impurity formation. The product was "cold crystallized" from the reaction mass and the mother liquor was recycled in the subsequent batch thereby eliminating organic discharge. The present work attempts to further advance the synthesis of this commercially important molecule employed in protection-deprotection strategies. Herein its successful synthesis employing neat substrate and solar radiation as the sole energy source to drive this photothermochemical reaction is reported. Further, 100% pure PNBBr could be isolated from the solid reaction mass in 87% yield by leaching out the excess substrate through supercritical CO2 (Sc-CO2) extraction. The reaction was therefore accomplished cleanly in all respects and with low carbon footprint.

Temperature invariance of NaCl solubility in water: inferences from salt-water cluster behavior of NaCl, KCl, and NH4Cl.

The growth and stability of salt-water clusters have been experimentally studied in aqueous solutions of NaCl, KCl, and NH(4)Cl from dilute to near-saturation conditions employing dynamic light scattering and zeta potential measurements. In order to examine cluster stability, the changes in the cluster sizes were monitored as a function of temperature. Compared to the other cases, the average size of NaCl-water clusters remained almost constant over the studied temperature range of 20-70 °C. Information obtained from the temperature-dependent solution compressibility (determined from speed of sound and density measurements), multinuclear NMR ((1)H, (17)O, (35)Cl NMR), and FTIR were utilized to explain the cluster behavior. Comparison of NMR chemical shifts of saturated salt solutions with solid-state NMR data of pure salts, and evaluation of spectral modifications in the OH stretch region of saturated salt solutions as compared to that of pure water, provided important clues on ion pair-water interactions and water structure in the clusters. The high stability and temperature independence of the cluster sizes in aqueous NaCl shed light on the temperature invariance of its solubility.

Kappaphycus alvarezii as a source of bioethanol.

The present study describes production of bio-ethanol from fresh red alga, Kappaphycus alvarezii. It was crushed to expel sap--a biofertilizer--while residual biomass was saccharified at 100 °C in 0.9 N H2SO4. The hydrolysate was repeatedly treated with additional granules to achieve desired reducing sugar concentration. The best yields for saccharification, inclusive of sugar loss in residue, were 26.2% and 30.6% (w/w) at laboratory (250 g) and bench (16 kg) scales, respectively. The hydrolysate was neutralized with lime and the filtrate was desalted by electrodialysis. Saccharomyces cerevisiae (NCIM 3523) was used for ethanol production from this non-traditional bio-resource. Fermentation at laboratory and bench scales converted ca. 80% of reducing sugar into ethanol in near quantitative selectivity. A petrol vehicle was successfully run with E10 gasoline made from the seaweed-based ethanol. Co-production of ethanol and bio-fertilizer from this seaweed may emerge as a promising alternative to land-based bio-ethanol.

Detection and quantification of some plant growth regulators in a seaweed-based foliar spray employing a mass spectrometric technique sans chromatographic separation.

The sap expelled from the fresh harvest of Kappaphycus alvarezii , a red seaweed growing in tropical waters, has been reported to be a potent foliar spray. Tandem mass spectrometry of various organic extracts of the sap confirmed the presence of the plant growth regulators (PGRs) indole 3-acetic acid, gibberellin GA(3), kinetin, and zeatin. These PGRs were quantified in fresh state and after 1 year of storage by ESI-MS without recourse to chromatographic separation. Quantification was validated against HPLC data. The results may be useful in correlating with the efficacy of the sap. The methodology was extended to two other seaweeds. The method developed is convenient and precise and may find application in other agricultural formulations containing these growth hormones.

Halonium ion-assisted deiodination of styrene-based vicinal iodohydrins followed by rearrangement through phenyl migration.

Acid activation of bromate/bromide couple at 0-10 degrees C was found to trigger the deiodination of styrene-based vicinal iodohydrins. Violet coloration of the organic layer was ascribed to formation of IBr. Deiodination was followed by phenyl migration and deprotonation leading to formation of phenyl acetone and 2-phenylpropanal in good yields from 1-iodo-2-phenylpropan-2-ol and 2-iodo-1-phenylpropan-1-ol, respectively. Phenyl acetaldehyde--which was obtained in 92% GC yield from styrene iodohydrin--was also presumably formed in analogous manner. NBS and HOCl too were effective for transformation of styrene iodohydrin into phenyl acetaldehyde.

Agars of Gelidiella acerosa of west and southeast coasts of India.

Seventeen agar samples were extracted from Gelidiella acerosa (Forsskal) Feldmann and Hamel (Rhodophyta, Gelidiales) specimens collected from nine different sites on the Indian coast-five from southeast coast and four from the west coast. The agar samples were analysed. The stability characteristics of the gels of selected agar samples were studied by rheometry under applied stress conditions, i.e. variation of the storage (G') and loss moduli (G'') were studied under varying frequency and duration (time) of the stress applied. Yield, apparent and dynamic viscosities, gelling and melting temperatures, 3,6-anhydrogalactose (3,6-AG), sulphate contents and TGA (Thermogravimetric Analysis) measurements of the products were done. It was observed that the best quality agar was produced by G. acerosa occurring in the Gulf of Mannar region in the southeast coast. The gel strengths and the viscosities of agars extracted from Gelidiella acerosa occurring in the Gulf of Mannar ranged from 500 to 700gcm(-2) and 33 to 45cP for 2001 collections and for 2002 collections the corresponding values were 450 to 845gcm(-2) and 55 to 67cP respectively. On the other hand, for the agar samples extracted from the west coast of India, the gel strength and viscosities values ranged from 225 to 400gcm(-2) and from 15 to 30cP, respectively. The agars obtained from G. acerosa collected from southeast coast have been found to be suitable for bacterial culture and molecular biology. This is the first report of superior quality of agar from the Indian agarophytes.

On the properties of agar gel containing ionic and non-ionic surfactants.

Rheological and thermal properties of agar sol and gel in presence of various cationic, anionic and non-ionic surfactants are reported. The agar used was from the red seaweed Gelidiella acerosa. The gel strength, viscosity, rigidity (G'), gelling temperature and melting temperature were observed to decrease in presence of non-ionic surfactants whereas these were enhanced in presence of ionic surfactants. TGA studies showed that 1.5% agar gels containing non-ionic surfactants lose water at a lower temperature than the control agar gel whereas gels containing ionic surfactants hold on to water more tenaciously. DSC studies, on the other hand, show that the gel to sol transition occurs at lower temperatures in presence of non-ionic surfactants and at higher temperature in presence of ionic surfactants when compared with the control gel. The non-ionic surfactants, Triton X-100 and Brij 35, enabled relatively concentrated agar extractive to be filtered readily, as a result of which water usage in the process could be reduced by 50%. The surfactant was subsequently removed through freeze-thaw operations to restore the gelling capacity of the agar. The finding that 0.3-0.4% (w/v) sodium lauryl sulfate (SLS) lowers the sol-gel transition temperature from 41 to 36 degrees C without adversely affecting gel strength is another useful outcome of the study that may enable better formulations of bacteriological agar to be prepared.

X-ray crystallographic studies on C-phycocyanins from cyanobacteria from different habitats: marine and freshwater.

C-phycocyanins from three cyanobacterial cultures of freshwater and marine habitat, Spirulina, Phormidium and Lyngbya spp., were purified to homogeneity and crystallized using the hanging-drop vapour-diffusion method. Blue-coloured crystals in different crystal forms, monoclinic and hexagonal, were obtained for the three species. The crystals took 1-12 weeks to grow to full size using polyethylene glycols of different molecular weights as precipitants. The amino-acid sequences of these proteins show high similarity to other known C-phycocyanins from related organisms; however, the C-phycocyanins reported here showed different biochemical and biophysical properties, i.e. molecular weight, stability etc. The X-ray diffraction data were collected at resolutions of 3.0 A for the monoclinic and 3.2 and 3.6 A for the hexagonal forms. The unit-cell parameters corresponding to the monoclinic space group P2(1) are a = 107.33, b = 115.64, c = 183.26 A, beta = 90.03 degrees for Spirulina sp. C-phycocyanin and are similar for crystals of Phormidium and Lyngbya spp. C-phycocyanins. Crystals belonging to the hexagonal space group P6(3), with unit-cell parameters a = b = 154.97, c = 40.35 A and a = b = 151.96, c = 39.06 A, were also obtained for the C-phycocyanins from Spirulina and Lyngbya spp., respectively. The estimated solvent content is around 50% for the monoclinic crystals of all three species assuming the presence of two hexamers per asymmetric unit. The solvent content is 66.5 and 64.1% for the hexagonal crystals of C-phycocyanin from Spirulina and Lyngbya spp. assuming the presence of one alphabeta monomer per asymmetric unit.