Ag-ZnO catalysts for UV-photodegradation of methylene blue

High surface area Ag-ZnO catalysts have been made by flame spray pyrolysis (FSP) and characterized by X-ray diffraction (XRD), nitrogen adsorption, UV–vis spectroscopy and electron microscopy (SEM and transmission electron microscopy (TEM)) combined with energy dispersive X-ray spectroscopy (EDXS) for elemental mapping. Silver metal clusters deposited directly on ZnO nanocrystals were obtained from this process. The Ag loading (1–5 at.%) controlled the Ag cluster size from 5 to 25 nm but did not influence the ZnO crystal size. Photodegradation of 10 ppm methylene blue (MB) solution was used to evaluate the performance of these FSP-made Ag-ZnO and was compared to wet-made Ag-ZnO and reference titania photocatalysts. The rate of photodegradation was optimal for Ag loading around 3 at.%. The best photocatalytic performance was exhibited by flame-made Ag-ZnO produced at the longest high-temperature residence times having high crystallinity as determined by XRD and UV–vis.     

The comparative effect of a mixed urea,ammonium nitrate,ammonium sulphate granular formulation on the efficiency of N recovery by perennial ryegrass

The¹⁵N isotope was used to study the mode of action of individual nitrogen sources in a 30% urea:30% ammonium nitrate: 10% ammonium sulphate:30% filler (w/w) granular fertilizer for perennial ryegrass in a greenhouse pot experiment. The fertilizer consisted of two types of granules, one containing 80% urea and 20% filler and the second containing 48% ammonium nitrate (AN), 16% ammonium sulphate (AS) and 36% filler. In addition the effect of dolomite compared with silica as the filler was investigated on nitrogen recovery from the 30:30:10:30 formulation.Dolomite adversely affected the recovery of nitrate N from the system and evidence suggested that MgCO₃ was the active component. Granules containing dolomite resulted in a lower dry-matter yield than those containing silica, however the difference was not significant as nitrate contributed only 20% of the N in the formulation. AN gave the greatest DM yield and urea the lowest with AS being intermediate. The¹⁵N budget in shoots, roots and soil indicated that only 65% of the N from urea was recovered at the end of the experiment compared with 86% for AN and 91% for AS. The dry-matter yield of the 30:30:10:30 formulation using silica as the filler was intermediate between urea and AN; however, the apparent N recovery was significantly higher than expected from the sum of the individual components. The use of¹⁵N labelling indicated that using separate granules for ammonium N and urea the recovery of urea was improved by 11% in the triple N mixture when both AN and AS were present in the second granule compared to the recovery on its own. The enhanced recovery of urea appeared to be a function of AN and AS acting together as neither source in double combination with urea had any effect on urea N recovery.Urea enhanced the recovery of nitrate N by 10% but decreased the recovery of AS by 6% (in the 30:30:10:30 formulation) in comparison with the single sources on their own. The results indicate that interactions can occur between N sources even when they are physically separated by being in different granules.     

Applications of laser Raman microprobe spectroscopy to the characterization of coals and cokes

Optical microscopy is widely used in the characterization of coals and cokes. This Paper shows that the laser Raman microprobe (MOLE) which combines an optical microscope and a Raman spectrometer can provide useful additional information. Three main areas were investigated: identification of minerals in coal and coke; structural characterization of coals and cokes; and the interaction of inorganic additives and coal. Where possible, the results were compared with conventional optical microscopy measurements whereby it was shown that the optical texture and Raman spectra of cokes are not closely related. The Raman spectra of high temperature cokes were used to estimate the size of microcrystalline regions.     

Diterpene resin acids: Major active principles in tall oil against Variegated cutworm,Peridroma saucia (Lepidoptera: Noctuidae)

Tall oil, a by-product of the kraft process for pulping softwood, has been shown to have insecticidal properties. In the present study, the active principles in tall oil against the variegated cutworm,Peridroma saucia Hübner, were investigated. GC-MS analysis showed that abietic, dehydroabietic, and isopimaric acids were major resin acid components of crude tall oil and depitched tall oil. When crude tall oil samples of differing resin acid composition were incorporated into artificial diet at a concentration of 2.0% fresh weight, they suppressed larval growth by 45–60% compared to controls. This suppression was significantly (P0.05) correlated with the equivalent contents of abietic, dehydroabietic, isopimaric, and total resin acids. These results were also evident from a diet choice test, showing that the second-instar larvae obviously selected diets with low levels of resin acids when different diets were randomly arranged in a Petri dish. Bioassays with pure resin acids (abietic, dehydroabietic, and isopimaric acids) demonstrated that all individual chemicals have similar bioactivity against this insect. Comparison of the bioactivities of depitched tall oil and an equivalent mixture of pure resin acids in thePeridroma chronic growth bioassay indicated that pure resin acids and depitched tall oil share a common mode of action to this insect. This study confirms that resin acids are major active principles in tall oil against the variegated cutworm, but other chemicals likely also contribute to the bioactivity of tall oil.     

Analysis of the Insect OS-D-Like Gene Family

Insect OS-D-like proteins, also known as chemosensory (CSP) or sensory appendage proteins (SAP), are broadly expressed in various insect tissues, where they are thought to bind short to medium chain length fatty acids and their derivatives. Although their specific function remains uncertain, OS-D-like members have been isolated from sensory organs (including the sensillum lymph in some cases), and a role in olfaction similar to that of the insect odorant binding proteins (OBP) has been suggested for some. We have identified 15 new OS-D-like sequences: four from cDNA clones described herein and 11 from sequence databases. The os-d-like genes from the Anopheles gambiae, Apis mellifera, Drosophila melanogaster, and Drosophila pseudoobscura genomes typically have single, small introns with a conserved splice site. Together with all family members entered on GenBank, a total of 70 OS-D-like proteins, representing the insect orders Diptera, Dictyoptera, Hymenoptera, Lepidoptera, Orthoptera, and Phasmatodea, were analyzed. A neighbor joining distance phenogram identified several protein similarity classes that were characterized by highly conserved sequence motifs, including (A) N-terminal YTTKYDN(V/I)(N/D)(L/V)DEIL, (B) central DGKELKXX(I/L)PDAL, and (C) C-terminal KYDP. In contrast, three similarity classes were characterized by their diversion from these conserved motifs. The functional importance of conserved amino acid residues is discussed in relation to the crystal and NMR structures of MbraCSPA6.     

The role of fats and oils in cosmetics

The earliest emollients in the history of cosmetics were the naturally occurring animal fats and vegetable oils. These provided soothing and smoothing action on the skin and grooming effects on head and beard hair. For the most part, odor problems limited the interest in oils derived from fish. With the increasing sophistication of users and increasing understanding of the technology of these materials, the short-comings of natural fats and oils were overcome in several ways: (a) increased stability through use of antioxidants; (b) reduced odor through improved processing; (c) improved stability and diversification through chemical modification; (d) increased diversity through preparation of derivatives, and (e) substitution of mineral oil. Today the most important single cosmetic use of an unmodified natural fat or oil is that of castor oil as the base for lipsticks. Other unmodified oils have largely minor specialty uses, particularly in higher-priced cosmetics. These include almond oil, apricot kernel oil, sesame oil, safflower oil, wheat germ oil, avocado oil, turtle oil and mink oil. Cocoa butter is used to some extent in suntan products. Reconstituted fractionated coconut oil is widely used. Polyglycerol esters of fatty acids are increasing in importance. Hydrogenation has produced stable oils useful in cosmetics. Alkyl esters and monoglycerol esters of fatty acids offer a wider range of properties than the original oils. Improvements in the naturally occurring fats and oils have made it possible for them to compete in some characteristics, and current interest in “natural” cosmetics may turn the attention of the cosmetic chemist back to improved versions of the classical raw materials. One of five papers in the symposium “Fats and Oils in Cosmetics and Pharmaceuticals,” presented at the AOCS Meeting, Atlantic City, October 1971.     

Diastereoselective Heterogeneous Catalytic Hydrogenation of Aromatic or Heteraromatic Compounds

The diastereoselective hydrogenation catalyzed by heterogeneous metallic catalysts uses a covalently bound chiral auxiliary to induce the chirality. It remains an active synthetic methodology in the asymmetric synthesis of chiral products and may proceed with high diastereoselectivity. This review describes recent examples using this method, such as hydrogenation of C=C, C=O, and C=N bonds. The use of a chiral auxiliary group has also been successfully applied to the hydrogenation of aromatic and heteroaromatic rings. The choice of the chiral auxiliary was found to play a key role in the asymmetric hydrogenation. The results could be explained in terms of steric effect, with a preferred conformation of the adduct substrate and the addition occurring from the less bulky side. The catalytic metal, the support and the presence of additives were also found to have a significant influence.     

Effect of amino acid deletions in the O-glycosylated region of Aspergillus awamori glucoamylase

Aspergillus awamori glucoamylase (GA) contains globular catalyticand starch-binding domains (residues 1–471 and 509–616,respectively). A heavily O-glycosylated sequence comprises twoparts. The first (residues 441–471) in the crystal structurewraps around an /-barrel formed by residues 1–440. Thesecond (residues 472–508) is an extended, semi-rigid linkerbetween the two domains. To investigate the functional roleof this linker, we made internal deletions to remove residues466–512 (GA1), 485–512 (GA2) and 466–483 (GA3).GA2 and GA3 were expressed in Saccharomyces cerevisiae culturesupernatants at 60 and 20% the wild-type level, respectively,while GA1 was almost undetectable. Western blots comparing extracellularand intracellular fractions indicated that the region deletedin GA3 was critical for secretion, while the region deletedin GA2 contributed to the production of a stable enzyme structure.The activities of purified GA2 and GA3 on soluble and insolublestarch were similar to those of wild-type GA, indicating thatfor soluble starch their deletions did not affect the catalyticdomain and for insoluble starch the linker does not coordinatethe activities of the catalytic and starch-binding domains.The deletions had a significant negative effect on GA2 and GA3thermos tabilities.     

Fundamentals of bitumen coking processes analogous to granulations: A critical review

A number of coking processes use hot particles to heat liquid bitumen or petroleum residue to cause cracking reactions. These particles may be mineral or coke solids. Interactions of these particles, in fluid beds, moving beds and other types of contactors, are governed by the liquid films on the particle surfaces. This paper explores the analogy between granulation and coking, and suggests that the key relationships that will govern the behavior of wet particles in coking processes are the Stokes number of the particles, the thickness or the liquid films, and the diameter and surface roughness of the particles. The implications for distribution of liquid feed in the reactor, fouling, and defluidization or bogging are discussed. This analysis suggests experiments that can be performed under non‐reactive conditions with scaled variables in order to study phenomena that cannot be observed in situ in high‐temperature cracking processes.     

Investigation of Flow Patterns in Continuous‐flow Stirred Vessels by Laser Doppler Velocimetry

The flow structure of a continuous‐flow reactor stirred by a Rushton turbine was investigated by laser Doppler velocimetry for two different mean residence time‐mixing time ratios. Velocity measurements were obtained for two inlet locations, corresponding to the incoming liquid stream being fed co‐currently or counter‐currently to the flow discharged by the turbine. In all investigated configurations and for all operating conditions, it was found that the flow disruption caused by the incoming liquid stream was observable mainly in the first vessel quarter, which followed the feed‐tube plane. From comparison of the velocities encountered in the various planes in the continuous‐flow reactor to the velocities of the batch reactor, it was also concluded that it may be possible to intensify the usage of the turbine‐stirred vessel by decreasing the characteristic times ratio, without considerable flow by‐pass and/or short‐circuiting problems.