Attraction of sphingid moths (Lepidoptera: Sphingidae) to 10,12-hexadecadienyl aldehydes and acetates: Evidence of pheromone components

A field survey of 10,12-hexadecadienyl alcohols, acetates, and aldehydes showed attraction to a wide range of sphingid moths. Data are presented showing the attraction ofSmerinthus jamaicensis, Smerinthus cerisyi, Pachysphinx modesta, Hemaris diffinis, andProserpinus flavofasciata to these compounds. Mass spectral, EAG, and EAD data show evidence for the presence of these dienes in female extracts ofS. cerisyi, Hyles gallii, andSphinx drupiferarum. NRCC No. 25857.In this paper the chemical nomenclature is abbreviated as follows: Z and E indicate thecis andtrans configurations of the double bond, the number followingZ orE indicates the position of that double bond, the last number indicates the carbon chain length, the terminal functional groups are: Ac=acetate; :OH=alcohol; :Aid=aldehyde.     

Characterisation of properties of various halloysites relevant to their use as nanotubes and microfibre fillers

There is increasing research interest on new industrial applications for the clay mineral halloysite where greater use is made of its natural tubular morphology, nano-scale diameter and contrasting chemistry on external and internal surfaces. Halloysite nanotubes, commonly referred to as HNTs, have potential applications as microfibre fillers, carriers for the supply and controlled or sustained release of active agents for drug delivery and anticorrosion coatings, in nanoreactors or nanotemplates, and for the uptake of contaminants or pollutants. In this study, various properties were measured on 6 halloysites from different geographical and geological environments from Australia, New Zealand and the USA. From the results, inferences were drawn on their comparative suitability for new uses. The characterisation included identification of impurities by X-ray diffraction (XRD), morphology, surface area and pore volume by electron microscopy and nitrogen absorption, the determination of exchangeable cations, and measurement of zeta potential over a wide range of pH. Halloysite content in individual samples ranged from 84 to 98%. Impurities included minor quartz, cristobalite, kaolinite, gibbsite, alunite, iron oxides and anatase. Variation in halloysite morphology and the levels of impurities had the most effect on surface area and internal pore volume. Samples with low levels of impurities and regular, thin-walled tubes reported the highest pore volumes associated with the cylindrical cavity or lumen in halloysite tubes. Surface areas varied from 22 to 81 m².g^− 1 and the proportion of pore space associated with the HNT lumen ranged from 11 to 39%. When the properties of the 6 different halloysites were assessed relative to the requirements for halloysite as nanotubes for either additives or carriers, one showed exceptional characteristics for both types of application but it occurs only rarely. Another halloysite that is moderately suitable for use as an additive but not a carrier occurs in a large deposit. The other samples each showed some limitations of suitability for use as an additive and/or as a carrier.     

The production of fatty acid isopropyl esters and their use as a diesel engine fuel

Biodiesel is an alternative fuel for diesel engines that consists of the monoalkyl esters of vegetable oils or animal fats. Currently, most biodiesel consists of methyl esters, which have poor cold-flow properties. Methyl esters of soybean oil will crystallize and plug fuel filters and lines at about 0°C. However, isopropyl esters have better cold-flow properties than methyl esters. This paper describes the production of isopropyl esters and their evaluation in a diesel engine. The effects of the alcohol amount, the catalyst amount, and two different catalysts on producing quality biodiesel were studied. Both sodium isopropoxide and potassium isopropoxide were found to be suitable for use in the transesterification process. A 20∶1 alcohol/TG molar ratio and a catalyst amount equal to 1% by weight (based on the TG amount) of sodium metal was the most cost-effective way to produce biodiesel fuel. The emissions from a diesel engine running on isopropyl esters made from soybean oil and yellow grease were investigated by comparing them with No. 2 diesel fuel and methyl esters. For nitrogen oxide emission, the difference between the biodiesel produced from soybean oil and yellow grease was greater than the difference between the methyl and isopropyl esters of both feedstocks. The other emissions from using isopropyl esters were about 50% lower in hydrocarbons, 10–20% lower in carbon monoxide, and 40% lower in smoke number when compared with No. 2 diesel fuel.     

Foliar oxidative stress and insect herbivory: Primary compounds,secondary metabolites,and reactive oxygen species as components of induced resistance

Oxidative responses of plants to pathogens and other environmental stresses have received considerable recent attention. We propose that an oxidative response also occurs following attack by herbivores. Our data strongly indicate a shift in the oxidative status of soybean following herbivory by the insectHelicoverpa zea. Herbivory caused significant increases in lipid peroxidation and ·OH radical formation. The activity of several oxidative enzymes including lipoxygenases, peroxidase, diamine oxidase, ascorbate oxidase, and NADH oxidase I increased after herbivory on soybean. The enhanced production of phenolic compounds is indicated by an increase in the activity of phenylalanine ammonia lyase in wounded tissues. On the other hand, the level of soybean foliar antioxidants such as ascorbic acid, total carotenoids, nonprotein thiols, and catalase decreased significantly following herbivory. These results implicate primary compounds (e.g., ascorbic acid, proteins), secondary metabolites (e.g., phenolics), and reactive oxygen species (e.g., hydroxyl radical, hydrogen peroxide) as multiple components of induced resistance. The oxidative changes in the host plant correspond with increased oxidative damage in the midgut of insects feeding on previously wounded plants. Decreases in nonprotein thiols and reduced ascorbic acid occurred in midgut epithelial tissue from insects feeding on wounded plants compared to the insects on control plants. In contrast, midgut hydroperoxides and dehydroascorbic acid concentrations were greater in insects on wounded plants compared to their counterparts on control plants. We conclude that oxidative responses in soybean may have both positive and negative effects upon the host plant: a decrease in herbivory and an increase in oxidative damage to the plant. The salient benefit to the plant, in terms of insect resistance, is the relative balance between these opposing effects.     

The use of atomic force microscopy to measure the formation and development of chocolate bloom in pralines

Atomic force microscopy (AFM) has been used to study the surface of chocolate as well as the progress of chocolate bloom over time. Fresh chocolate was found to be relatively smooth but with deep holes. These could be pipes leading deep down into the body of the chocolate, perhaps reaching the filling. After storage for a few weeks, we observed the growth of small drops around these holes. With increasing time, these drops became larger and more structured. After further storage, a crystalline structure and bloom were revealed. These results suggest that bloom growth in pralines is a two-phase process, with drops initially forming on the surface and then bloom crystals nucleating and growing from them. Further, we deduced pipes leading down into the center of the chocolate through which the migration of filling fats can preferentially occur.     

The contribution of bisfurfurylamine to the development and properties of polyureas

Polyureas are versatile polymers with diversified properties dependent on their chemical composition. Furan diamines can be interesting monomers for such materials because of their renewable character and ready availability from furfural, but they have not been extensively studied. The synthesis of furfurylamine‐based diamine and its condensation with an aliphatic and an aromatic diisocyanate to generate polyureas are described here together with the structure and properties of the ensuing materials. The thermoplastic features of both polymers were exploited through hot pressing of their respective powders, indicating the versatile properties of these polyureas based on a renewable comonomer. © 2020 Society of Chemical Industry     

The interaction of alkaline earth cations with metal-oxygen cluster compounds and the implications for their use as heterogeneous catalysts

The magnesium, calcium, strontium and barium salts of 12-tungstophosphoric and 12-molybdophosphoric acids have been prepared. Evidence of the presence of the Keggin anion (primary structure) was obtained from infrared spectroscopic measurements but powder X-ray diffraction and differential thermal analysis measurements indicated that changes to the secondary structure had occurred. BET surface areas were small for all of the materials studied and no dependence on the cation radius was observed. A crystallographic investigation demonstrated that divalent cations were not incorporated into the lattice suggesting that materials believed to be divalent 12-heteropoly salts are mixtures of the parent acid and a divalent cation salt.     

Behavioral and neurosensory responses of the boll weevil,Anthonomus grandis Boh. (Coleoptera: Curculionidae), to fluorinated analogs of aldehyde components of its pheromone

Competitive field tests with -fluorinated analogs of compounds III and IV (III--F and IV--F, respectively) of the boll weevil,Anthonomus grandis Boh., aggregation pheromone showed these compounds, when combined with the other pheromone components [(±)-I and II], to be as attractive as grandlure [(+)-I, II, and III+IV]. Dose-response curves constructed from electroantennograms of male boll weevils to serial stimulus loads of III, IV, III--F, IV--F, and the corresponding acyl fluorinated analogs (III-acyl-F and IV-acyl-F) showed the -fiuorinated analogs to be as active as the pheromone components (threshold=0.1 g), while the acyl fluorinated analogs had a 10-100 x higher threshold (=1-10 g). Single-neuron recordings showed that IV neurons and II neurons (Dickens, 1990) responded to IV--F and III--F, respectively, while IV-acyl-F and III-acyl-F were inactive. Since a previous study showed compounds I, II, and IV to be essential for behavioral responses in the field, it seems likely that the activity of the -fluorinated analogs observed here is due to the stimulation of IV neurons by IV--F as indicated in single neuron recordings.     

Nitroxide polymer brushes as efficient and recoverable catalysts for the selective oxidation of primary alcohols to aldehydes

2,2,6,6‐Tetramethylpiperidinyloxyl (TEMPO)‐containing polymer brushes were grafted onto crosslinked polystyrene microspheres via surface‐initiated activators regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP) of 2,2,6,6‐tetramethyl‐4‐piperidyl methacrylate, followed by an oxidation process with 3‐chloroperoxybenzoic acid as oxidant. The synthesized nitroxide polymer brushes included homopolymer brushes, block copolymer brushes, and random copolymer brushes with various TEMPO contents and molecular weights. They were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, nuclear magnetic resonance spectroscopy, and gel permeation chromatography. These nitroxide brushes bearing high TEMPO contents were used as recoverable catalysts for the hypochlorite and aerobic oxidation of primary alcohols to aldehydes. The effects of polymer brush structure on the catalytic properties were studied and discussed. The results showed that these nitroxide polymer brushes had excellent catalytic properties and good recycling performances. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44365.     

The instantaneous image effect: A novel contribution to the mechanism of heterogeneous catalysis

A novel contribution to the mechanism of heterogeneous catalysis is discussed for a model H₂-on-nickel (100) system. The effect, which corresponds in a first approximation to the dispersion energy between adsorbate molecule and metal, is calculated through (1) admixture of an ionic component in the wave function of the adsorbate; (2) interaction between this ionic component and the image dipole which it creates in the polarizable metal. A single VB model, using an Anderson-type evaluation of the delocalization energy between adsorbate and metal, shows the image contribution to be 10 to 15% of the total adsorbate metal interaction energy.Presented in part at the 3rd International Symposium on the Mechanisum of Heterogeneous Catalysis Berkeley, Cal., 12–14 November, 1990.     

Effects of pheromone components and their degradation products on the response ofHeliothis spp. to traps

None of the isolated degradation products of (Z)-11-hexadecenal [(Z)-11-HDAL] affected the catches of either tobacco budworm [Heliothis virescens (F.)] or bollworm [H. zea (Boddie)] moths when dispensed with pheromone from cotton dental rolls in cone traps. Also, none of the degradation products of (Z)-9-tetradecenal [(Z)-9-TDAL] had an effect on trap catches of tobacco budworm moths. Two of the three chemicals that have previously been identified in ovipositor washes of tobacco budworms but that are absent in those of bollworms caused a reduction in capture of bollworms: (Z)-9-TDAL (1.0 g/trap) caused a 96% reduction in trap catch and (Z)-11-hexadecen-1-ol (20.0 g/trap) caused a similar reduction. Tetradencenal (40 g/trap) had no effect on trap catch.In cooperation with the Texas Agricultural Experiment Station, Texas A&M University, College Station, Texas 77843.This paper reports the results of research only. Mention of a pesticide in this paper does not constitute a recommendation for use by the USDA nor does it imply registration under FIFRA as amended. Also, mention of a commercial or proprietary product in this paper does not constitute an endorsement of this product by the USDA.     

Hot melt adhesives: An outline scheme for the separation and identification of their components

Methods are described for identifying polyamides, polyurethanes, ethylene–vinyl acetate resins, polyesters, rosins and their esters, polyisobutenes and paraffin waxes in “hot-melt” adhesives, by a combination of chemical tests and infrared spectrophotometry. Mixtures are separated quantitatively into their components by selective solvent extraction before testing.     

Studies on the concentration of oxidized components of abused fats and the application of HPLC to their separation

The efficiency of five separation techniques at removing unaltered compounds from the methyl esters of oxidized fats was compared, as were concentrations of oxidized products. A batch type distribution method using acetonitrile/hexane was the most effective in concentrating the polar products and removal of palmitate and stearate from abused fats which had been hydrogenated. The level of high molecular weight material present in samples was measured indirectly by determination of the percent elutable material via gas chromatography. A high performance liquid chromatography system developed to partially separate or “profile” the oxidized products used an octadecyl bonded phase column and a linear gradient from 50% aqueous acetonitrile to 85% aqueous acetonitrile, at a rate of 5%/min. The resultant chromatograms can be useful in assessing the quality of used fats.     

Prediction of the air permeability of fabrics for institutional use after exposure to light and weather

The effect of natural and artificial light and weather on the air permeability of blended fabrics was compared. An empirical dependence was established for calculating the air permeability of fabrics of different fibre composition; the error of the dependence is a maximum of 7.60%. The possibility of predicting the air permeability of fabrics for institutional use with consideration of the duration of exposure to light and weather was demonstrated. __________ Translated from Khimicheskie Volokna, No. 3, pp. 39–41, May–June, 2007.     

Combination of bifunctional aldehydes and poly(vinyl alcohol) as the crosslinking systems to improve paper wet strength

Two bifunctional aldehydes (i.e., glyoxal and glutaraldehyde) are used as the crosslinking agents to improve paper wet strength in the presence of fully hydrolyzed poly(vinyl alcohol) (PVA) as a co‐reactant. These bifunctional aldehydes alone improve paper wet strength but diminish its folding endurance. The use of PVA as a co‐reactant not only improves paper wet strength but also increases its dry strength and folding endurance. Glutaraldehyde is able to impart much higher levels of wet strength to the treated paper than glyoxal when a catalyst is present. The wet strength of the treated paper increases as the amount of PVA added is increased, and it also increases as the molecular weight (M_w) of the PVA increases. The data suggest that the reaction between glutaraldehyde and PVA promotes the formation of interfiber crosslinking, thus improving the wet strength without diminishing the flexibility of the treated paper. The use of a catalyst is critical to achieve high levels of durable wet strength of the treated paper. We studied the effects of different Lewis acids as the catalysts for crosslinking of pulp cellulose by glutaraldehyde and found that Zn(NO₃)₂ is the most effective one. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1673–1680, 2004     

The contribution of singlet oxygen to the photofading of triphenylmethane and related dyes

The contribution of singlet oxygen (¹Δ_gO₂) to the photofading of Crystal Violet in some solvents is examined. The rates of photofading in dichloromethane or acetone are accelerated in the presence of singlet oxygen sensitizers, e.g. Methylene Blue. The rates are retarded by adding effective singlet oxygen quenchers such as β-carotene or nickel dimethyldithiocarbamate. It seem shtat Crystal Violet is mainly photooxidized to give Michler's ketone and p-dimethylaminophenol via the reaction with singlet oxygen, which can be generated by the dye itself or by an added sensitizer. The effect of various singlet oxygen quenchers on the photostability of coloured materials derived from colour formers, such as Crystal Violet Lactone and 3-diethylamino-6-methyl-7-anilinofluoran, is examined also on silica gel.