Thermal decomposition of zirconyl oxalates I. Barium zirconyl oxalate

Conditions for the preparation of stoichiometric barium zirconyl oxalate heptahydrate (BZO) have been standardized. The thermal decomposition of BZO has been investigated employing TG, DTG and DTA techniques and chemical and gas analysis. The decomposition proceeds through four steps and is not affected much by the surrounding gas atmosphere. Both dehydration and oxalate decomposition take place in two steps. The formation of a transient intermediate containing both oxalate and carbonate groups is inferred. The decomposition of oxalate groups results in a carbonate of composition Ba2Zr2OsCO3, which decomposes between 600 and 800 ~ and yields barium zirconate. Chemical analysis, IR spectra and X-ray powder diffraction data support the identity of the intermediate as a separate entity.

Thermal decomposition of zirconyl oxalates I. Barium zirconyl oxalate

Conditions for the preparation of stoichiometric barium zirconyl oxalate heptahydrate (BZO) have been standardized. The thermal decomposition of BZO has been investigated employing TG, DTG and DTA techniques and chemical and gas analysis. The decomposition proceeds through four steps and is not affected much by the surrounding gas atmosphere. Both dehydration and oxalate decomposition take place in two steps. The formation of a transient intermediate containing both oxalate and carbonate groups is inferred. The decomposition of oxalate groups results in a carbonate of composition Ba2Zr2O5CO3, which decomposes between 600 and 800° and yields barium zirconate. Chemical analysis, IR spectra and X-ray powder diffraction data support the identity of the intermediate as a separate entity.Die Bedingungen für die Herstellung von stöchiometrischem Barium-zirconyl-oxalat Heptahydrat (BZO) wurden standardisiert. Die thermische Zersetzung von BZO wurde unter Einsatz der TG-, DTG- und DTA, sowie der chemischen und Gasanalyse untersucht. Die Zersetzung verläuft über vier Stufen und wird von der umgebenden Gasathmosphäre nicht besonders beeinflusst. Sowohl die Dehydratisierung als auch die Oxalatzersetzung erfolgt in zwei Stufen. Die Bildung einer intermediären Übergangsverbindung mit sowohl Oxalat- als auch Carbonatgruppen wirken hierbei mit. Die Zersetzung der Oxalatgruppen ergibt ein Carbonat der Zusammensetzung Ba2Zr2O5CO3, das zwischen 600 und 800° zersetzt wird und Bariumzirconat ergibt. Die Angaben der chemischen Analyse, der IR-Spekren und der Röntgen-Pulver-Diffraktion unterstützen die Identität der Intermediärverbindung als eine separate Einheit.On a standardisé les conditions de préparation de l'oxalate heptahydraté de zirconyle et de baryum (BZO) stoechiométrique. On a étudié la décomposition thermique de BZO par TG, TGD et ATD ainsi que par analyses chimiques et analyses des gaz. La décomposition a lieu en quatre étapes et n'est pas trop influencée par l'atmosphère ambiante. La déshydratation et la décomposition de l'oxalate ont lieu en deux étapes. Il se forme un composé intermédiaire de transition contenant à la fois les groupes oxalate et carbonate. La décomposition des groupes oxalate fournit un carbonate de composition Ba2Zr2O5CO3 qui se décompose entre 600 et 800° pour fournir du zirconate de baryum. L'analyse chimique, les spectres IR et la diffraction des rayons X sur poudre, apportent les preuves de l'existence d'un composé intermédiaire comme entité séparée.

Molecular modelling of saccharide-lipid interactions

Certain saccharides, including trehalose, sucrose and glucose, stabilize lipid bilayers against dehydration. It has been suggested that these saccharides replace waters of hydration as the system is dried, thereby maintaining the headgroups at their hydrated spacing. The lipid acyl chains consequently have sufficient free volume to remain in the liquid crystallines state, and the processes that disrupt membrane integrity are inhibited. Initial molecular graphic investigations of a model trehalose/DMPC system supported this idea (Chandrasekhar, I. and Gaber, B.P. (1988) J. Biomol. Stereodyn, 5, 1163–1171). We have extended these studies to glucose and sucrose. A set of AMBER potential parameters has been established that reproduce simple saccharide conformations, including the anomeric effect. Extensive energy minimizations have been conducted on all three systems. The saccharide-lipid interaction energies become less stable in the order trehalose

Bubble formation at closely spaced orifices in aqueous solutions

A filter cloth with 182 holes per 10−4 m2 has been used to generate air bubbles both in pure water and in aqueous solutions of electrolytes and non-electrolytes at various air flow rates. Potassium bromide and ammonium perchlorate were the electrolytes used, while the non-electrolytes were isopropanol, urea and glycerol. Bubble diameters and their size distribution were measured from photographs. The role of solutes in affecting bubble sizes and their distribution compared to that of pure water is discussed in the light of a hypothesis. This hypothesis assumes that if the final bubble diameter is less than the inter-orifice distance, then bubbles do not coalesce; on the other hand, if it is greater, then coalescence occurs when tf greater-or-equal, slantedti+ts, but does not occur when t

Effect of thiocarbamate, urea, and uracil herbicides on lipid metabolism in groundnut (Arachis hypogaea) leaves

The effect of thiocarbamates (S-ethyldipropylthiocarbamate and diallate), substituted ureas (monuron and diuron), and uracils (bromacil and terbacil) on lipid metabolism in groundnut (Arachis hypogaea) leaves was investigated under nonphotosynthetic conditions. The uptake of [1-14C]acetate by leaf disks was inhibited by the thiocarbamates and marginally by the substituted ureas, but not by the uracil herbicides. The uptake of [methyl-14C]choline was inhibited to a lesser extent by thiocarbamates, while the other herbicides showed a slight stimulation. The thiocarbamates almost completely inhibited uptake of [32P]orthophosphate at 1.0 mM concentration, while diuron and terbacil showed significant inhibition. [1-14C]Acetate incorporation into lipids was inhibited only by diallate. [methyl-14C]Choline incorporation into the choline phosphoglycerides was inhibited by diallate, diuron, and bromacil. The incorporation of [32P]orthophosphate into phospholipids was substantially inhibited (over 90% at 1.0 mM) by the thiocarbamates, but not by the other herbicides. [35S]Sulfate incorporation into sulfoquinovosyl diglycerides was markedly inhibited only by the thiocarbamates. Fatty acid synthesis by isolated chloroplasts was inhibited 40–85% by thiocarbamates, substituted ureas, and bromacil, but not by terbacil. The inhibitory effect of the urea derivatives was reversible, but that of thiocarbamates was irreversible. sn-Glycerol-3-phosphate acyltransferase(s) of the chloroplast and microsomal fractions were profoundly inhibited by thiocarbamates, but not by the other two groups of herbicides. Phosphatidic acid phosphatase was insensitive to all the herbicides tested.

Radical Annulation Strategy to Chiral Pupukeanones: Total Synthesis of (+)-10-ex&l(- Naphthyl)pupukean-9-onea nd (+)-lO-exo-l(- Naphthyl)-5-epipupukean-9-ones1

Intramolecular alkylation reaction of the bromoenone 12, obtained from S-carvone in three steps, furnished the bicyclo[2.2.2]octenone 13. Contrary to the anticipated radical annulation reaction, the bicyclic bromides 14 and 15, obtained from the enone 13, generated exclusively the cyclopropane product 18 via a 3-exo-trig radical cyclization on reaction with nBu3SnH and AIBN, even in the presence of a large excess of a radicophile. On the other hand, bromoenone 24, synthesized from R-carvone via S-naphthylcarvone 21, underwent radical annulation reaction in the presence of radicophiles to furnish the isotwistanes 25-28 in a regio- and stereospecific manner. Hydrogenation of the olefin 34, obtained from the diketone 27 via a regiospecific Wittig reaction, furnished the naphthyl-5-epipupukean-9-one 33, whereas stereoselective hydrogenation of the enone 36, prepared from the keto ester 25 via a Grignard reaction and dehydration sequence, generated the naphthylpupukeanone 32.

Reaction of spironaphthalenones with hydroxylamine: Part III. A novel mechanism for the formation of products and trapping of an intermediate.

A mechanism involving the intermediacy of nitrene 5, formed from the oxime of spironaphthalenone 1 by acid catalysed dehydration, has been proposed to explain the formation of pyrrolotropones/pyrrolo esters from spironaphthalenones. The initially formed nitrene rearranges to the isopyrrole 6, which either undergoes sigmatropic migration to the pyrrolotropone 2 or adds alcohol to form the pyrrolo ester depending on substitution at 1′ position. The isopyrrole intermediate 6 has been trapped as a Diels-Alder adduct 8.

Studies on the 14α-hydroxylation of progesterone in mucor piriformis

Cell-free extracts with high 14?-hydroxylase activity were prepared from induced vegetative cell cultures of Mucor piriformis by grinding in potassium phosphate buffer (0.05 M, pH 8.0) containing glucose (0.25 M), KCl (1 mM), glutathione (1.0 mM) and glycerol (10%). Although the ideal pH for preparing the cell-free extract from vegetative cells was 8.0, the pH optimum of the hydroxylase was found to be 7.6. Microsomes (2.0 mg) prepared from the crude cell-free extract hydroxylated progesterone to 14?-hydroxyprogesterone in not, vert, similar60% yields in 30 min in the presence of NADPH and O2. Microsomes prepared from the uninduced cells did not contain any 14?-hydroxylase activity. The hydroxylase activity was inhibited to a significant extent by CO and p-chloromercuribenzoate whereas moderate inhibition was noticed in the presence of SKF-525A, metyrapone and N-methylmaleimideindicating the possible involvement of the cytochromeP-450 system in the reaction. The membrane bound hydroxylase was solubilized using Triton X-100 and the solubilized fraction contained nearly 35% of the original hydroxylase activity.

Poly-ols Based Sol-Gel Synthesis of Zinc Oxide Thin Films

We demonstrate that the structural and optical properties of a sol-gel deposited zinc oxide thin film can be tuned by varying the composition of the sol, consisting of ethylene glycol and glycerol. A systematic study of the effect of the composition of sol on the mean grain size, thickness, and defect density of the zinc oxide film is presented. About 20% glycerol content in the sol is observed to improve the quality of the film, as evaluated by X-ray diffraction and photoluminescence studies. Thus, optimizing the composition of the sol for about 60 nm thick ZnO film using 20% glycerol resulted in the zinc oxide film that is about 80% transparent in visible spectrum, exhibiting electrical resistivity of about 18 Omega cm and field-effect mobility of 0.78 cm(2)/(V s). (C) 2010 The Electrochemical Society. DOI: 10.1149/1.3515894] All rights reserved.

Conformation of polymerizable diacetylenic lecithin, DC8,9PC, by 1H-NMR spectroscopy

Diacetylenic phospholipid, 1,2 bis-(tricosa-10,12-diynoyl)-sn-glycero-3-phosphocholine (DC8,9PC), forms helices and tubules in addition to liposomes. The diacetylenic moiety responsible for the transformation is probed by 2-D NMR correlated spectroscopy. Chemical shift assignments and the analysis of 2D-COSY measurements were done on the lipid in chloroform-d solution. Based on this analysis, a model for the lipid is proposed. The geometry of the headgroup, glycerol backbone and acyl chains up to three methylenes from glycerol backbone [-(CH2)(3)-] is similar to that of dipalmitoyl phosphatidylcholine. The estimated torsional angle for methylene groups adjacent to diacetylenic moieties suggested an overall tilt of the diacetylenic lipid molecule from the bilayer axis of 25-30 degrees. This tilt could be negative or positive depending on the handedness of the resultant microstructures.

Soft chemical synthesis of new layered and three-dimensional oxide hydrates, hxVxW1-xO3×yH2O, related to WO3×2 H2O and WO3. times.1/3 H2O

Two new vanadium-tungsten oxide hydrates of the formulas, H0.125V0.125W0.875O3.1.5H2O (I) and Ho.33V0.33W0.67O3.1/3H2O (II), have been synthesized by acid-leaching of LiVWO6 with aqueous HNO3/HCl. While phase I obtained by treatment of LiVWO6 with dilute HNO3/HCl possesses an orthorhombic structure (a = 7.77(3), b = 13.87(6), c = 7.44(3) angstrom) related to WO3.2H2O, phase II, prepared by refluxing LiVWO6 with concentrated HNO3, is isostructural with WO3.1/3H2O. Dehydration of II around 330-degrees-C yields a hexagonal phase (III, a = 7.25(4), c = 7.74(3) angstrom) isotypic with hexagonal WO3. Both land III exhibit redox and acid-base intercalation reactivity characteristic of layered and tunnel structures.

Synthesis and characterization of barium bis(citrato) oxozirconate(iv) tetrahydrate--A new molecular precursor for fine particle BaZrO3

Barium metazirconate (BaZrO3) fine powder has been produced by thermally decomposing a molecular precursor, barium bis(citrato)oxozirconate(IV) tetrahydrate at about 700-degrees-C. The precursor, Ba[ZrO(C6H6O7)2] . 4H2O (BZO) has been synthesized and characterized by employing a combination of spectroscopic and thermoanalytical techniques. The precursor undergoes thermal decomposition in three major stages: (i) dehydration to give an anhydrous barium zirconyl citrate, (ii) decomposition of the anhydrous citrate in a multistep process to form an ionic oxycarbonate intermediate, Ba2Zr2O5CO3, and (iii) decomposition of the oxycarbonate to produce BaZrO3 fine powder. The particle size of the resultant BaZrO3 is about 0.2 mum, and the surface area is found to be 4.0 m2 g-1.

Synthesis of Trilaurin by Developing Pisa Seeds (Actinodaphne hookeri)

The developing seeds of Actinodaphne hookeri were investigated to delineate their ability to synthesize large amounts of trilaurin. Until 88 days after flowering the embryos contained 71% neutral lipids (NL) and 29% phospholipids (PL) and both these components contained C-16:0, C-18:0, C-18:2, and C-18:3 as the major fatty acids (FA). At 102 days after flowering the seeds began to accumulate triacylglycerols (TAG) and to synthesize lauric acid (C-12:0). By 165 days after flowering, when the seeds were mature, they contained about 99% NL and 1% FL. At this stage the TAG contained exclusively C-12:0, while the PL consisted of long-chain fatty acids (LCFA) only. Leaf lipids in contrast did not contain any C-12:0. Experiments on [1-C-14]acetate incorporation into developing seed slices showed that at 88 days after flowering only 4% of the label was in TAG, 1% in diacylglycerols (DAG), and 87% in FL. One hundred two days after flowering seeds incorporated only 2% of the label into TAG, 30% into DAG, and 64% into FL. In contrast at 114 days after flowering 71% of the label was incorporated into TAG, 25% into DAG, and only 2% into FL. Analysis of labeled FA revealed that up to 102 days after flowering it was incorporated only into LCFA, whereas at 114 days after flowering it was incorporated exclusively into C-12:0. Furthermore, 67% of the label in PL at 114 days after flowering was found to be dilaurylglycerophosphate. Analysis of the label in DAG at this stage showed that it was essentially in dilaurin species. These observations indicate the induction of enzymes of Kennedy pathway for the specific synthesis of trilaurin at about 114 days after flowering, Homogenates of seeds (114 days after flowering) incubated with labeled FA in the presence of glycerol-3-phosphate and coenzymes A and ATP incorporated 84% of C-12:0 and 61% of C-14:0, but not C-16:0, C-18:2, and C-18:3, into TAG. In contrast the LCFA were incorporated preferentially into FL. It is concluded that, between 102 and 114 days after flowering, a switch occurs in A. hookeri for the synthesis of C-12:0 and trilaurin which is tissue specific. Since the seed synthesizes exclusively C-12:0 at 114 days after flowering onwards and incorporates specifically into TAG, this system appears to be ideal for identifying the enzymes responsible for medium-chain fatty acid as well as trilaurin synthesis and for exploiting them for genetic engineering. (C) 1994 Academic Press, Inc.

Methanol-to-gasoline (MTG) conversion over ZSM-5. A temperature programmed surface reaction study

The conversion of methanol to gasoline over zeolite ZSM-5 has been studied by temperature programmed surface reaction (TPSR). The technique is able to monitor the two steps in the process: the dehydration of methanol to dimethyl ether and the subsequent conversion of dimethyl ether to hydrocarbons. The activation barriers associated with each step were evaluated from the TPSR profiles and are 25.7 and 46.5 kcal/mol respectively. The methanol desorption profile shows considerable change with the amount of methanol molecules adsorbed per Bronsted site of the zeolite. The energy associated with the desorption process, (CH3OHH+-ZSM5 --> (CH3OHH+-ZSM5 + CH3OH, shows a spectrum of values depending on n.

Thermo and photoluminescence properties of Eu3+ activated hexagonal, monoclinic and cubic gadolinium oxide nanorods

Different phases of Eu3+ activated gadolinium oxide (Gd (OH)(3), GdOOH and Gd2O3) nanorods have been prepared by the hydrothermal method with and without cityl trimethyl ammonium bromide (GAB) surfactant. Cubic Gd2O3:Eu (8 mol%) red phosphor has been prepared by the dehydration of corresponding hydroxide Gd(OH)(3):Eu after calcinations at 350 and 600 degrees C for 3 h, respectively. When Eu3+ ions were introduced into Gd(OH)(3), lattice sites which replace the original Gd3+ ions, a strong red emission centered at 613 nm has been observed upon UV illumination, due to the intrinsic Eu3+ transition between D-5(0) and F-7 configurations. Thermoluminescence glow curves of Gd (OH)(3): Eu and Gd2O3:Eu phosphors have been recorded by irradiating with gamma source ((CO)-C-60) in the dose range 10-60 Gy at a heating rate of 6.7 degrees C sec(-1). Well resolved glow peaks in the range 42-45, 67-76,95-103 and 102-125 degrees C were observed. When gamma-irradiation dose increased to 40 Gy, the glow peaks were reduced and with increase in gamma-dose (50 and 60 Gy) results the shift in first two glow peak temperatures at about 20 degrees C and a new shouldered peak at 86 degrees C was observed. It is observed that there is a shift in glow peak temperatures and variation in intensity, which is mainly attributed to different phases of gadolinium oxide. The trapping parameters namely activation energy (E), order of kinetics (b) and frequency factor were calculated using peak shape and the results are discussed. (C) 2010 Elsevier B.V. All rights reserved.