Second row transition metal sulfides for the hydrotreatment of coal-derived naphtha I. Catalyst preparation, characterization and comparison of rate of simultaneous removal of total sulfur, nitrogen and oxygen

Naphtha derived from an Illinois No. 6 coal contains appreciable quantities of sulfur-, nitrogen- and oxygen-containing compounds. The hydrotreatment of this naphtha has been evaluated over unsupported transition metal sulfide catalysts of the second row in the Periodic Table. The catalysts were prepared by a room temperature precipitation reaction. Surface areas, crystalline phase and particle size distributions were determined by Brunauer-Emmet-Teller (BET), X-ray diffraction (XRD) and transmission electron microscopy (TEM), respectively. A comparison of average particle sizes calculated from these three techniques has enabled the understanding of the morphology of the transition metal sulfides. The catalysts exhibit a so-called volcano plot for the HDS of dibenzothiophene. Similar so-called volcano plots are also exhibited for the simultaneous hydrodesulfurization (HDS), hydrodenitrogenation (HDN) and the hydrodeoxygenation (HDO) of the coal-derived naphtha containing a mixture of heteroatoms. The order of reactivity of the transition metal catalysts is the same for all three of the processes. Ruthenium sulfide (RuS₂) is the most active catalyst for HDS, HDN and HDO of the coal-derived naphtha.     

Synthesis and spectral,thermal, and photocrosslinking studies of poly(benzylidene phosphoramide ester)s

A new class of poly(benzylidene phosphoramide ester)s containing a photoreactive benzylidene chromophore in the main chain were synthesized from bis(4-hydroxy-3-methoxy benzylidene) acetone with various substituted N-aryl phosphoramidic dichlorides by an interfacial polycondensation technique. The synthesized polymers were characterized by inherent viscosity, IR, and ¹H-, ¹³C-, and ³¹P-NMR spectroscopy. The molecular weights of these polymers were determined by gel permeation chromatography. These polymers were studied for their thermal stability and photochemical properties. Thermal properties were evaluated by thermogravimetric analysis and differential scanning calorimetry. It was found that halogen-containing polymers show a higher thermal stability than that of nonhalogenated polymers. The photocrosslinking property of these polymers was studied by ultraviolet spectroscopy. The photoreactive benzylidene chromophore in the main chain dimerizes via 2π + 2π cycloaddition reaction to form a cyclobutane derivative and leads to crosslinking. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 2151–2157, 1997     

Evolution of magnetic and bone mineral phases in heat-treated bioactive glass containing zinc and iron oxides

Melt-quenched 15(ZnO,Fe₂O₃) 50SiO₂·20(CaO,P₂O₅) 15Na₂O bioactive glass was heat treated at temperatures (T_A) ranging from 550°C to 850°C for different time periods (t_A=1, 2 and 3 hours) to understand its devitrification characteristics. Crystallization of calcium sodium phosphate, zinc ferrite, magnetite, and hematite phases depended on heat treatment conditions. Decrease in saturation magnetizations (M_s) with increase in t_A of glass heat treated at T_A≥750°C is attributed to the formation of hematite which is a weak magnetic material. Magnetic properties as functions of T_A and t_A are interpreted on the basis of clustering of Fe ions, super-exchange interaction between Fe²⁺ and Fe³⁺ ions and formation of ferrimagnetic and weakly magnetic iron oxide phases with different heat treatment conditions. Electron paramagnetic resonance parameters reveal the variations in site distortions and randomness in Fe ion environment in the matrix upon heat treatment. In vitro mineralization ability of the glass-ceramics was evaluated by immersion in simulated body fluid (SBF) and monitoring both the pH variation of SBF and formation of hydroxyapatite surface layer as a function of immersion time. These studies help in assessing these glass-ceramics for hyperthermia treatment and in optimizing the processing conditions for this application.     

Potential of <Emphasis Type="Italic">Jatropha curcas</Emphasis> as a Biofuel,Animal Feed and Health Products

Jatropha curcas is a multipurpose plant with numerous attributes. It can potentially become one of the world’s key energy crops. Its seed weighs 0.53–0.86 g and the seed kernel contains 22–27% protein and 57–63% lipid indicating good nutritional value. The seeds can produce crude vegetable oil that can be transformed into high quality biodiesel. Several methods for oil extraction have been developed. In all processes, about 75% of the weight of the seed remains as a press cake containing mainly carbohydrates, protein and residual oil and is a potential source of livestock feed. The highly toxic nature of whole as well as dehulled seed meal due to the presence of high levels of shells, toxic phorbol esters and other antinutrients prevents its use in animal diet. The genetic variation among accessions from different regions of the world and rich diversity among Mexican genotypes in terms of phorbol ester content and distinct molecular profiles indicates the potential for improvement of germplasm of Jatropha through breeding programs. The extracts of Jatropha display potent cytotoxic, antitumor, anti-inflammatory and antimicrobial activities. The possibilities on the exploitation potential of this plant through various applications have been explored.     

Microstructural, tribological and electrochemical corrosion studies on reactive DC magnetron sputtered zirconium nitride films with Zr interlayer on steel

Thin films of Zirconium Nitride (ZrN) were deposited by DC magnetron sputtering. The structure of the films was examined by X-ray diffraction and the crystallographic parameters were refined by Rietveld analysis. The columnar micro-structure was observed via cross-sectional SEM analysis. Defect induced, first order spectra were observed from Laser Raman studies. XPS showed the presence of Zr (N,O) ZrO₂ phases on the surface of the film. The pitting corrosion was substantially reduced by the employment of Zr film as an interlayer. Corrosion tests revealed that ZrN films with a Zr interlayer exhibited clear passivation characteristics with considerably better corrosion resistance than the film without an interlayer.     

Stereochemical modeling of disulfide bridges. Criteria for introduction into proteins by site-directed mutagenesis

A computer modeling procedure for assessing the stereochemicalsuitability of pairs of residues in proteins as potential sitesfor introduction of cystine disulfide crosslinks has been developed.Residue pairs with C – C distances of 6.5 Å andC^beta;–C^ß distances of 4.5 Å are chosenfor geometrical fixation of S atoms using the program MODIP.The stereochemistry of the modeled disulfides is evaluated usinglimits for the structural parameters of the various torsionangles and S–S bond length in the disulfide bridge. Theability of the procedure to correctly model disulfides has beenchecked with examples of cystine peptides of known crystal structuresand 103 disulfide bridges from 25 available protein crystalstructures determined at 2 Å resolution. An analysis ofresults on three proteins with engineered disulfides, T4 lysozyme,dihydrofolate reductase and subtilisin, is presented. Two positionsfor the introduction of ‘stereochemically optimal’disulfides are identified in subtilisin.     

Liver-Specific Pyruvate Dehydrogenase Complex Deficiency Upregulates Lipogenesis in Adipose Tissue and Improves Peripheral Insulin Sensitivity

The pyruvate dehydrogenase complex (PDC) plays a critical role in lipid synthesis and glucose homeostasis in the fed and fasting states. The central role of the liver in the maintenance of glucose homeostasis has been established by studying changes in key enzymes (including PDC) and the carbon-flux via several pathways under different metabolic states. In the present study we have developed a murine model of liver-specific PDC deficiency using Cre-loxP technology to investigate its consequences on lipid and carbohydrate metabolism. There was no incorporation of glucose-carbon into fatty acids by liver in vitro from liver-specific Pdha1 knockout (L-PDHKO) male mice due to absence of hepatic PDC activity. Interestingly, there was a compensatory increase in lipogenic capacity in epididymal adipose tissue from L-PDHKO mice. Both fat and lean body mass were significantly reduced in L-PDHKO mice, which might be explained by an increase in total energy expenditure compared with wild-type littermate mice. Furthermore, both liver and peripheral insulin sensitivities measured during a hyperinsulinemic-euglycemic clamp were improved in L-PDHKO mice. The findings presented here demonstrate (i) the indispensable role of PDC for lipogenesis from glucose in liver and (ii) specific adaptations in lipid and glucose metabolism in the liver and adipose tissue to compensate for loss of PDC activity in liver only.