Positional analysis of isovaleroyl triglycerides using proton magnetic resonance with Eu(fod)3 and Pr(fod)3 shift reagents: II. Cetacean triglycerides

The positional distribution of isovaleric acid in natural cetacean triglycerides has been studied using proton magnetic resonance with lanthanide shift reagents. Twenty-nine samples of melon, jaw, and blubber triglycerides from 13 genera in the Delphinidae, Phocoenidae, and Monodontidae families were examined. Isovaleric acid was found esterified only at the 1,3-positions in the monoisovaleroyl and diisovaleroyl triglycerides of these animals.     

Determination of compositional sequences in PCT/FT aromatic copolyterephthalate by 1H-NMR spectroscopy and Pr(fod)3 lanthanide shift reagent

Summary Standard 100 MHz ¹H-NMR spectrum of the PCT/FT copolyterephthalate gives little information on its microstructure and exhibits only slight splitting of the terephthalic signal which was found to be useful for evaluating distribution of compositional sequences. Application of Pr(fod)₃ provides clear splitting of this signal into lines of compositional diads with traces of compositional tetrads, while Eu(fod)₃ compresses the lines already split in the standard spectrum and yields one featureless broad terephthalic signal containing no microstructural information. The splitting induced by Pr(fod)₃ is comparable to that obtained using a superconducting spectrometer operating at 300 MHz.     

Application of europium and praseodymium shift reagents to the n.m.r. spectra of polymers

The use of Eu(fod)₃ and Pr(fod)₃ shift reagents for the investigation of the nuclear magnetic resonance spectra of polymers is reported for the following samples: poly(vinyl methyl ether), poly(vinyl ethyl ether), poly(vinyl acetate) and poly-(propylene oxide).     

NMR chemical shift reagents in structural determination of lipid derivatives: II. Methyl petroselinate and methyl oleate

Whentris(1,1,1,2,2,3,3-heptafluoro-7,7-dimethyl-4,6-octaneodionato)europium (III)—Eu(fod)₃—forms a complex with a sufficiently basic functional group in a donor molecule, the change in the magnetic environment of protons near the coordination site causes their nuclear magnetic resonance (NMR) signals to shift to different positions. Consequently Eu(fod)₃ and other compounds that similarly affect NMR signals have been designated chemical shift reagents (csr). Because of their ability to shift proton signals, csr substantially increase the amount of structural information that can be obtained from NMR spectroscopy, frequently converting complicated splitting patterns into first-order spectra. Some generally useful experimental and interpretive csr techniques are described here using methyl petroselinate and methyl oleate as examples. Csr studies of methyl petroselinate reveal that the position of the double bond is at C-6, and that there is no chain substitution or branching before C-9. Csr studies of methyl oleate reveal that the position of the double bond is at or beyond C-9, and that there is no chain substitution or branching before C-6. Some suggestions are presented for expanding the amount of structural information that can be obtained by csr studies of unsaturated lipid derivatives. Presented in part at AOCS Meeting, Atlantic City, October, 1971.     

MgO-supported cluster catalysts with Pt–Ru interactions prepared from Pt3Ru6(CO)21(μ3-H)(μ-H)3

Bimetallic MgO-supported catalysts were prepared by adsorption of Pt₃Ru₆(CO)₂₁(μ₃-H)(μ-H)₃ on porous MgO. Characterization of the supported clusters by infrared (IR) spectroscopy showed that the adsorbed species were still in the form of metal carbonyls. The supported clusters were decarbonylated by treatment in flowing helium at 300 °C, as shown by IR and extended X-ray absorption fine structure (EXAFS) data, and the resulting supported PtRu clusters were shown by EXAFS spectroscopy to have metal frames that retained Pt–Ru bonds but were slightly restructured relative to those of the precursor; the average cluster size was almost unchanged as a result of the decarbonylation. These are among the smallest reported bimetallic clusters of group-8 metals. The decarbonylated sample catalyzed ethylene hydrogenation with an activity similar to that reported previously for γ-Al₂O₃-supported clusters prepared in nearly the same way and having nearly the same structure. Both samples were also active for n-butane hydrogenolysis, with the MgO-supported catalyst being more active than the γ-Al₂O₃-supported catalyst.     

Application of lanthanide n.m.r. shift reagents for functional group studies of shale bitumen asphaltenes

Ytterbium (fod)₃ was used as a shift reagent in conjunction with solution ¹H n.m.r. studies of asphaltene isolated from Devonian shale bitumen. Upon addition of the reagent, bands attributed to protons on alkyl groups alpha to oxygen atoms were shifted and separated from that attributed to protons alpha to two aromatic systems. Similar experiments with Green River bitumen asphaltene did not show any observable shift. The presence and absence of the ether formations in shale asphaltenes can be substantiated by ¹³C n.m.r.     

The catalytic removal of CO and NO over Co-Pt(Pd, Rh)/γ-Al2O3 catalysts and their structural characterizations

A series of Co-Pt(Pd, Rh)/γ- Al₂O₃ catalysts were prepared by successive wetness impregnation. The catalytic activities for CO oxidation, NO decomposition and NO selective catalytic reduction (SCR) by C₂H₄ over the samples calcined at 500°C and reduced at 450°C were determined. The activities of the samples calcined at 750°C and reduced at 450°C for NO selective catalytic reduction (SCR) by C₂H₄ were also determined. All the samples were characterized by XRD, XPS, XANES, EXAFS, TPR, TPO and TPD techniques. The results of activity measurements show that the presence of noble metals greatly enhances the activity of Co/γ-Al₂O₃ for CO or C₂H₄ oxidation. For NO decomposition, the H₂-reduced Co-Pt(Pd, Rh)/γ- Al₂O₃ catalysts exhibit very high activities during the initial period of catalytic reaction, but with the increase of reaction time, the activities decrease obviously because of the oxidation of surface cobalt phase. For NO selective reduction by C₂H₄, the reduced samples are oxidized more quickly by the excess oxygen in reaction gas. The oxidized samples possess very low activities for NO selective reduction. The results of XRD, XPS and EXAFS indicate that all the cobalt in Co-Pt(Pd, Rh)/γ-Al₂O₃ has been reduced to zero valence during reduction by H₂ at 450°C, but in Co/γ-Al₂O₃ only a part of the cobalt has been reduced to zero valence, the rest exists as CoAl₂O₄-like spinel which is difficult to reduce. For the samples calcined at 750°C, the cobalt exists as CoAl₂O₄ which cannot be reduced by H₂ at 450°C and possesses better activities for NO selective reduction. The results of XANES spectra show that the cobalt in Co/γ- Al₂O₃ has lower coordination symmetry than that in Co-Pt(Pd, Rh)/γ-Al₂O₃. This difference mainly results from the distorting tetrahedrally- coordinated Co²⁺ ions which have lower coordination symmetry than Co⁰ in the catalysts. The coordination number for the Co-Co shell from EXAFS has shown that the cobalt phase is highly dispersed on Co-Pt(Pd, Rh)/γ- Al₂O₃ catalysts. The TPR results indicate that the addition of noble metals to Co/γ- Al₂O₃ makes the TPR peaks shift to lower temperatures, which implies the spillover of hydrogen species from noble metals to cobalt oxides. The oxygen spillover from noble metals to cobalt is also inferred from the shift of TPO peaks to lower temperatures and the increased amount of desorbed oxygen from TPD. For CO oxidation, the Co⁰ is the main active phase. For NO decomposition and selective reduction, Co⁰ is also catalytically active, but it can be oxidized into Co₃O₄ by oxygen at high reaction temperature. This revised version was published online in July 2006 with corrections to the Cover Date.     

Composition of wax esters,triglycerides and diacyl glyceryl ethers in the jaw and blubber fats of the Amazon River dolphin (Inia geoffrensis)

The lower jaw fat of the Amazon River dolphinInia geoffrensis contains 52.8% wax ester, 44.7% triglyceride and 2.5% diacyl glyceryl ether, while its dorsal blubber fat is >98% triglyceride. Examination of the intact lipids, the derived fatty acids and the derived fatty alcohols by gas chromatography reveals that the blubber triglycerides show characteristics of freshwater fish fats, but the jaw fat lipids have several distinctive features. Jaw fat wax esters, triglycerides and diacyl glyceryl ethers are all rich in C₁₀, C₁₂ and C₁₄ fatty acids and contain no polyunsaturated acids. The fatty alcohols in the wax esters are over 90% saturated. The major carbon numbers in the jaw fat triglycerides (C₃₈–C₄₆) are considerably lower than those of the blubber triglycerides (C₄₈–C₅₄). The possible adaptation of the jaw lipids for use in the underwater echolocation process of this dolphin is discussed.     

Correlating Low-temperature Hydrogenation Activity of Co/Pt(111) Bimetallic Surfaces to Supported Co/Pt/γ-Al2O3 Catalysts

The low-temperature self-hydrogenation (disproportionation) of cyclohexene was used as a probe reaction to correlate the reactivity of Co/Pt(111) bimetallic surfaces with supported Co/Pt/γ-Al₂O₃ catalysts. Temperature-programmed desorption (TPD) experiments show that cyclohexene undergoes self-hydrogenation on the ~1 ML Co/Pt(111) surface at ~219 K, which does not occur on either pure Pt(111) or a thick Co film on Pt(111). Supported catalysts with a 1:1 atomic ratio of Co:Pt were synthesized on a high surface area γ-Al₂O₃ to verify the bimetallic effect on the self-hydrogenation of cyclohexene. EXAFS experiments confirmed the presence of Co–Pt bonds in the catalyst. Using FTIR in a batch reactor configuration, the bimetallic catalyst showed a higher activity toward the self-hydrogenation of cyclohexene at room temperature than either Pt/γ-Al₂O₃ or Co/γ-Al₂O₃ catalysts. The comparison of Co/Pt(111) and Co/Pt/γ-Al₂O₃ provided an excellent example of correlating the self-hydrogenation activity of cyclohexene on bimetallic model surfaces and supported catalysts.     

New dinuclear lanthanide(III) complexes based on 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedione and 2,2′-bipyrimidine

Reaction of mononuclear Ln(fod)₃ chelates (where fod is the anion of 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedione and Ln = Nd, Eu, Tb and Lu) with potentially bridging ligand 2,2′-bipyrimidine (bpm) in 2:1 mole ratio in ethanol afforded new dinuclear lanthanide complexes of the form [Ln(fod)₃-(μ-bpm)-Ln(fod)₃]. Neodymium complex is one of the rare bipyrimidine-bridged dinuclear complexes. The absorption spectrum of the neodymium complex displays characteristic hypersensitive as well as non-hypersensitive transitions. The excitation of Eu–Eu and Tb–Tb complexes at 355 nm produces an intense red and green luminescence, respectively.     

Induced chemical shifts in the NMR spectrum of methyl petroselinate

The use of a pseudo contact shift reagent, (Eu[fod]₃), to obtain simplified NMR spectra of a typical long chain monounsaturated fatty acid methyl ester, methyl petroselinate, is described. Spectra were obtained in which individual methylene groups are identifiable from their splitting patterns. Non-equivalent splitting patterns were observed for the methine protons with varying amounts of reagent used. The effect of concentration of the shift reagent on the chemical shift is discussed. Presented in part at the Meeting of the Gulf Coast Instrumental Analysis Group, Houston, October 1971. S. Market. and Nutr. Res. Div., ARS, USDA     

Effects of feeding ethyl-dihomo-γ-linolenate on rabbit renomedullary lipid composition and prostaglandin production in vitro

Feeding the ethyl ester of dihomo-γ-linolenic acid for 25 days to rabbits resulted in increased PGE₁ (20to30-fold) and PGE₂ (1.5-fold) output by a hormone responsive, in vitro, renal papilla preparation. The relative amount of PGE₁ increased from <5% of PGE₂ in controls to 25–35% of PGE₂ in the papillae of 20∶3ω6-supplemented animals. During the study renomedullary triglycerides in the 20∶3ω6-supplemented animals increased 2.8-fold compared to animals fed an equal amount of a control fatty acid mixture, and in addition to a marked enrichment in 20∶3ω6, also contained increased proportions of 20∶4ω6 and longer chain polyenes. The increase in triglyceride content found in the renal medulla was not seen in the renal cortex or liver. There was no increase in renomedullary phospholipid content during the study, and phopholipids of treated animals contained increased proportions of 20∶3ω6 and 20∶4ω6, but not longer chain polyenes. The results indicate that enriching the prostaglandin precursor pool by feeding 20∶3ω6 can alter the type and amount of prostaglandin released by the renal papilla, at least in vitro. Also, the selective changes in amount and long chain polyene content of renomedullary triglycerides during the study suggest some special functions for this lipid class in prostaglandin precursor metabolism. *** DIRECT SUPPORT *** A00M6131 00010     

Role of cobalt on γ-Al2O3 based NO x storage catalyst

Co/Pt/Ba/γ-Al₂O₃, Co/Ba/γ-Al₂O₃, Pt/Ba/γ-Al₂O₃, Co/Pt/γ-Al₂O₃, Ba/γ-Al₂O₃, Pt/γ-Al₂O₃, and Co/γ-Al₂O₃ type catalysts were prepared by a conventional impregnation method, and their NO _x storage capacities were evaluated by colorimetric assay. Co-containing catalysts had a higher NO _x storage capacity than that of Co-free counterparts. The role of each component, especially Co, for the catalysts prepared was investigated by using in-situ FTIR. The high NO _x storage for Co-containing catalysts including Co/Ba/γ-Al₂O₃ and Co/Pt/Ba/γ-Al₂O₃ is mainly due to the formation of Co₃O₄ on the catalyst surface identified by XAFS.     

Preparation and Characterization of α-(Fe, Al)2O3 Solid Solutions by Sol–Gel Method

The aim of this paper is to synthesize α-(Fe, Al)₂O₃ solid solutions from precursors prepared by the sol–gel method. The powders were characterized by X-ray diffraction, particle size analysis and TGA-DSC. The results indicated that the precursor prepared by sol–gel method will translate into α-(Fe, Al)₂O₃ solid solutions after calcined at 1300 °C for 3 h, with the average grain size of 14 μm. And Fe₂O₃ reduced the temperature of the γ-Al₂O to α-Al₂O₃ phase transition from 1,300 to 850 °C.     

Preparation and photocatalytic properties of a novel kind of loaded photocatalyst of TiO2/SiO2/γ‐Fe2O3

A novel kind of loaded photocatalyst of TiO₂/SiO₂/γ‐Fe₂O₃ (TSF) that can photodegrade effectively organic pollutants in the dispersion system and can be recycled easily by a magnetic field is reported in this paper. The γ‐Fe₂O₃ cores in TiO₂/γ‐Fe₂O₃ are found to reduce the activity of the TiO₂ photocatalyst in the photodegradation of dyes under either UV or visible light irradiation. Addition of a SiO₂ membrane between the γ‐Fe₂O₃ core and the TiO₂ shell weakens efficiently the influence of the γ‐Fe₂O₃ cores on the TiO₂ photocatalytic activity and leads to a highly active and magnetically separable photocatalyst on TSF. Comparison of the photodegradation processes of dyes under UV and visible irradiation is also carried out. This revised version was published online in July 2006 with corrections to the Cover Date.     

The incorporation of orally administered radiolabeled dihomo γ-linolenic acid (20∶3ω6) into rat tissue lipids and its conversion to arachidonic acid

Radioactivity from orally administered radiolabeled dihomo-γ-linolenic acid (20∶3ω6) was recovered from the liver, plasma and brain lipid fractions. After administration the fatty acid was metabolized to arachidonic acid, the 22 carbon chain length fatty acid, and was also β-oxidized. However, 22 hr after administration of [1-¹⁴C]20∶3 between one-third and one-half of the recovered radioactivity was still associated with dihomo-γ-linolenic acid in the liver and plasma lipid fractions. Orally administered dihomo-γ-linolenic acid is incorporated into lipid fractions and is, therefore, available in the metabolic pool for PGE₁ synthesis.     

Kinetic studies on copolycondensation processes. VI. Influence of copolycondensation temperature on tetrad distribution of the PDT/FT aromatic copolyterephthalate by 1H-NMR spectroscopy

¹H-NMR and Eu(fod)₃ lanthanide shift reagent were used to determine tetrad distribution of comonomer units of the PDT/FT copolyterephthalate obtained from terephthaloyl chloride (intermonomer) and 3,3′-dimethylbisphenol A and phenolphtalein (comonomers). Computer simulations of the terephthalic proton signal split into the lines of compositional tetrads were performed to obtain quantitative data. To characterize the microstructure of the copolymer samples synthesized at different temperatures, the degree of randomness and the degree of alternation were calculated. It was shown that the latter can differentiate the chains which seemed to be identical concerning the diad distribution only.     

Methane conversion over nanostructured Pt/γAl2O3 catalysts in dielectric-barrier discharge

Spherical nanostructured γ-Al₂O₃ granules were prepared by combining the modified Yoldas process and oil-drop method, followed by the Pt impregnation inside mesopores of the granules by incipient wetness method. Prepared Pt/γ-Al₂O₃ catalysts were reduced by novel method using plasma, which was named plasma assisted reduction (PAR), and then used for methane conversion in dielectric-barrier discharge (DBD). The effect of Pt loading, calcination temperature on methane conversion, and selectivities and yields of products were investigated. Prepared Pt/γ-Al₂O₃ catalysts were successfully reduced by PAR. The main products of methane conversion were the light alkanes such as C₂H₆, C₃H₈ and C₄H₁₀ when the catalytic plasma reaction was carried out with Pt/γ-Al₂O₃ catalyst. Methane conversion was in the range of 38–40% depending on Pt loading and calcination temperature. The highest yield of C₂H₆ was 12.7% with 1 wt% Pt/γ-Al₂O₃ catalysts after calcinations at 500 ‡C.     

A Promising Coupled Process of Pd/γ-Al2O3–NH4VO3 Catalyzing the Hydroxylation of Benzene with Hydrogen Peroxide Produced In Situ by an Anthraquinone Redox Route

A coupled process, of which Pd/γ-Al₂O₃–NH₄VO₃ catalyzed the hydroxylation of benzene with hydrogen peroxide produced in situ by an anthraquinone (AQ) redox route, was carried out via a sealed gaseous inner-circulated device under the atmospheric pressure. By means of such process, 0.57% of benzene conversion, 100% of phenol selectivity and 26.6% of anthraquinone-utilized efficiency were achieved upon the mixed Pd/γ-Al₂O₃–NH₄VO₃ (V/Pd molar ratio for 4) in the presence of benzene/acetic acid (4v/10v). Above all, after the coupled reaction system was recycled three times, the accumulated phenol amount could achieve ca. 0.833 mmol and its average value (ca. 0.278 mmol) was slightly higher than phenol amount obtained in the first run (ca. 0.255 mmol), indicating that such coupled reaction system could be recycled efficiently. In addition, a synergistic mechanism was proposed to explain the favorable effect of V compound on the Pd/γ-Al₂O₃ catalyst.