The production of oxygenated polycrystalline graphene by one-step ethanol-chemical vapor deposition

Large-area mono- and bilayer graphene films were synthesized on Cu foil (∼1 in.²) in about 1 min by a simple ethanol-chemical vapor deposition (CVD) technique. Raman spectroscopy and high resolution transmission electron microscopy revealed the synthesized graphene films to have polycrystalline structures with 2–5 nm individual crystallite size which is a function of temperature up to 1000 °C. X-ray photoelectron spectroscopy investigations showed about 3 at.% carboxylic (COOH) functional groups were formed during growth. The field-effect transistor devices fabricated using polycrystalline graphene as conducting channel (L_c = 10 μm; W_c = 50 μm) demonstrated a p-type semiconducting behavior with high drive current and Dirac point at ∼35 V. This simple one-step method of growing large area polycrystalline graphene films with semiconductor properties and easily functionalizable groups should assist in the realization of potential of polycrystalline graphene for nanoelectronics, sensors and energy storage devices.     

Formation of Hydroperoxy-, Keto- and Hydroxy-Dienes in FAME from Oils: Influence of Temperature and Addition of α-Tocopherol

The influence of temperature (40, 60 and 80 °C) and addition of α-tocopherol (0, 500 mg/kg) on the formation and distribution of the main oxidation products of linoleic acid, i.e. hydroperoxy-, keto- and hydroxy-dienes, were studied in samples of fatty acid methyl esters (FAME) derived from high-linoleic (HL) and high-oleic (HO) sunflower oils. In the range of temperatures studied, the formation of hydroperoxydienes showed monomolecular and bimolecular rate constants that ranged from 0.01 to 1 mmol^1/2kg^−1/2h⁻¹ and from 0.02 to 0.9 h⁻¹, respectively. The overall activation energies involved were similar for both samples and for the monomolecular and bimolecular periods (63–68 kJ/mol). The relative oxidation of methyl linoleate, which depended on the fatty acid composition of the FAME sample, was unaffected by temperature. At the three temperatures assayed, hydroperoxydienes constituted approximately 90 and 50% of total hydroperoxides in the HL and HO samples, respectively. Formation of keto- and hydroxy-dienes was influenced by temperature in a similar way to hydroperoxydienes and, consequently, changes in the distribution of compounds were not observed. The addition of α-tocopherol not only decreased the overall oxidation rate, but also affected the distribution of compounds. The content of hydroperoxydienes relative to that of total hydroperoxides was not affected by the presence of the antioxidant in the HL sample, whereas a significant increase (75%) was found in the HO sample compared with the control (50%). The addition of α-tocopherol in both samples also resulted in a slight increase of keto- and hydroxy-dienes in relation to hydroperoxydienes.     

Supercritical Fluid Extraction of Eucalyptus globulus Bark-A Promising Approach for Triterpenoid Production

Eucalyptus bark contains significant amounts of triterpenoids with demonstrated bioactivity, namely triterpenic acids and their acetyl derivatives (ursolic, betulinic, oleanolic, betulonic, 3-acetylursolic, and 3-acetyloleanolic acids). In this work, the supercritical fluid extraction (SFE) of Eucalyptus globulus deciduous bark was carried out with pure and modified carbon dioxide to recover this fraction, and the results were compared with those obtained by Soxhlet extraction with dichloromethane. The effects of pressure (100-200 bar), co-solvent (ethanol) content (0, 5 and 8% wt), and multistep operation were studied in order to evaluate the applicability of SFE for their selective and efficient production. The individual extraction curves of the main families of compounds were measured, and the extracts analyzed by GC-MS. Results pointed out the influence of pressure and the important role played by the co-solvent. Ethanol can be used with advantage, since its effect is more important than increasing pressure by several tens of bar. At 160 bar and 40 °C, the introduction of 8% (wt) of ethanol greatly improves the yield of triterpenoids more than threefold.     

Dispersing Behavior of Hydroxyapatite Powders Produced by Wet-Chemical Synthesis

Three hydroxyapatite powders with different surface properties were produced by wet-chemical synthesis and characterized. The electrokinetic properties of powders dispersed in water were investigated by electroacoustic spectroscopy measurements. The different surface reactivity (pH_iep and ζ potential versus pH curves) was related to the interplay of dissolution and adsorption of Ca²⁺ ions. With a view toward the preparation of porous bodies by sponge impregnation, the behavior of powder suspensions was studied. Four deflocculants were tested, and the optimum dispersing conditions for each powder were found. Anionic polyelectrolytes resulted in the best effective dispersing agent, with different optimum amounts added to the suspensions.     

Viscoelastic properties of poly(vinyl alcohol) hydrogels and ferrogels obtained through freezing-thawing cycles

We report the preparation of poly(vinyl alcohol) (PVA) hydrogels obtained through freezing-thawing cycles. The viscoelastic properties of these gels using parallel-plate shear mode were evaluated as a function of temperature, time, degree of swelling, concentration and the number of freezing-thawing cycles. The storage modulus was analyzed on the basis of a theoretical model based on the scaling approach. These results provide additional evidence for a non-crystalline nature of the structure of PVA cryogels.Furthermore, PVA ferrogels have been prepared from PVA aqueous solutions and a ferrofluid through freezing-thawing cycles. The viscoelastic properties of these materials have been evaluated. It is shown that the variation of the storage modulus with ferrofluid concentration cannot be fitted using classical theories what has been attributed to the small dimensions of the particles in the ferrogels and to the magnetic interactions between particles.     

The Extended Community-Level Effects of Genetic Variation in Foliar Wax Chemistry in the Forest Tree <Emphasis Type="Italic">Eucalyptus globulus</Emphasis>

Genetic variation in foundation trees can influence dependent communities, but little is known about the mechanisms driving these extended genetic effects. We studied the potential chemical drivers of genetic variation in the dependent foliar community of the focal tree Eucalyptus globulus. We focus on the role of cuticular waxes and compare the effects to that of the terpenes, a well-studied group of secondary compounds known to be bioactive in eucalypts. The canopy community was quantified based on the abundance of thirty-nine distinctive arthropod and fungal symptoms on foliar samples collected from canopies of 246 progeny from 13 E. globulus sub-races grown in a common garden trial. Cuticular waxes and foliar terpenes were quantified using gas chromatography - mass spectrometry (GC-MC). A total of 4 of the 13 quantified waxes and 7 of the 16 quantified terpenes were significantly associated with the dependent foliar community. Variation in waxes explained 22.9% of the community variation among sub-races, which was equivalent to that explained by terpenes. In combination, waxes and terpenes explained 35% of the genetic variation among sub-races. Only a small proportion of wax and terpene compounds showing statistically significant differences among sub-races were implicated in community level effects. The few significant waxes have previously shown evidence of divergent selection in E. globulus, which signals that adaptive variation in phenotypic traits may have extended effects. While highlighting the role of the understudied cuticular waxes, this study demonstrates the complexity of factors likely to lead to community genetic effects in foundation trees.     

Phytal: A Candidate Sex Pheromone Component of the Moroccan Locust Dociostaurus maroccanus

Outbreaks of locusts cause enormous economic losses to agriculture in many countries. To develop environmentally friendly strategies for their control, much research has been focused on the factors that influence locust biology, particularly infochemical‐mediated interactions. We present herein the identification and synthesis of both Z and E isomers of phytal (3,7,11,15‐tetramethylhexadec‐2‐enal, 1 ), which are involved in chemical communication and behaviour of the Moroccan locust, Dociostaurus maroccanus, a serious agricultural pest. The compound was identified by comparison of its chromatographic and spectrometric features and microchemical reactions with those of a synthetic sample. The natural compound was shown to have the R,R configuration by chiral HPLC analysis, and its structure is unique as an insect pheromone component. Both isomers of phytal are produced by sexually mature adult males and elicit electroantennographic responses in antennae of both sexes. In two‐choice olfactometer bioassays, males and females significantly preferred the stream enriched with racemic phytal to the control. In contrast, hydrogenated phytal was behaviourally inert. Both isomers of phytal are specific to D. maroccanus as they are absent in the closely related, habitat‐sharing species Dociostaurus jagoi and Calliptamus wattenwylianus. Legs and wings are the main release sites of the compound: approximately 90 % of that emitted by living individuals. In biosynthetic studies, phytal appears to proceed from oxidation of phytol ( 2 ) after injection of deuterated phytol into the abdomen of the insect or after administration in the diet. Our results demonstrate that phytal is a candidate sex pheromone component of the Moroccan locust; it is produced by mature males, and might be eavesdropped upon by conspecific males.