Novel Oxidation of Pyridoxal in Ternary Metal Complexes. An X-Ray Study of the Products

Attempts to prepare ternary metal complexes of pyridoxylidene-amino acid Schiff bases culminated in the oxidation of pyridoxal to pyridoxic acid or to its lactone and their complex formation, as evidenced from an X-ray study.

Photooxidative and pyrolytic degradation of methyl methacrylate-alkyl acrylate copolymers

Different compositions of poly(methyl methacrylate-co-methyl acrylate) (PMMAMA), poly(methyl methacrylate-co-ethyl acrylate) (PMMAEA) and poly(methyl methacrylate-co-butyl acrylate) (PMMABA) copolymers were synthesized and characterized. The photocatalytic oxidative degradation of all these copolymers were studied in presence of two different catalysts namely Degussa P-25 and combustion synthesized titania using azobis-iso-butyronitrile and benzoyl peroxide as oxidizers. Gel permeation hromatography (GPC) was used to determine the molecular weight distribution of the samples as a function of time. The GPC chromatogram indicated that the photocatalytic oxidative degradation of all these copolymers proceeds by both random and chain end scission.Continuous distribution kinetics was used to develop a model for photocatalytic oxidative degradation considering both random and specific end scission. The degradation rate coefficients were determined by fitting the experimental data with the model. The degradation rate coefficients of the copolymers decreased with increase in the percentage of alkyl acrylate in the copolymer. This indicates that the photocatalytic oxidative stability of the copolymers increased with increasing percentage of alkyl acrylate. From the degradation rate coefficients, it was observed that the photocatalytic oxidative stability follows the order PMMABA > PMMAEA > PMMAMA. The thermal degradation of the copolymers was studied by using thermogravimetric analysis (TGA). The normalized weight loss and differential fractional weight loss profiles indicated that the thermal stability of the copolymer increases with an increase in the percentage of alkyl acrylate and the thermal stability of poly(methyl methacrylate-co-alkyl acrylate)s follows the order PMMAMA > PMMAEA > PMMABA. The observed contrast in the order of photostability and thermal stability of the copolymers was attributed to different mechanisms involved for the scission of polymer chain and formation of different products in both the processes.

HPLC analysis of plant sterol oxidation products

Increased interest in the cholesterol-lowering effect of plant sterols has led to development of plant sterol-enriched foods. When products are enriched, the safety of the added components must be evaluated. In the case of plant sterols, oxidation is the reaction of main concern. In vitro studies have indicated that cholesterol oxides may have harmful effects. Due their structural similarity, plant sterol oxidation products may have similar health implications. This study concentrated on developing high-performance liquid chromatography (HPLC) methods that enable the investigation of formation of both primary and secondary oxidation products and thus can be used for oxidation mechanism studies of plant sterols. The applicability of the methods for following the oxidation reactions of plant sterols was evaluated by using oxidized stigmasterol and sterol mixture as model samples. An HPLC method with ultraviolet and fluorescence detection (HPLC-UV-FL) was developed. It allowed the specific detection of hydroperoxides with FL detection after post-column reagent addition. The formation of primary and secondary oxidation products and amount of unoxidized sterol could be followed by using UV detection. With the HPLC-UV-FL method, separation between oxides was essential and oxides of only one plant sterol could be quantified in one run. Quantification with UV can lead to inaccuracy of the results since the number of double bonds had effect on the UV absorbance. In the case of liquid chromatography-mass spectrometry (LC-MS), separation of oxides with different functionalities was important because some oxides of the same sterol have similar molecular weight and moreover epimers have similar fragmentation behaviour. On the other hand, coelution of different plant sterol oxides with the same functional group was acceptable since they differ in molecular weights. Results revealed that all studied plant sterols and cholesterol seem to have similar fragmentation behaviour, with only relative ion abundances being slightly different. The major advantage of MS detection coupled with LC separation is the capability to analyse totally or partly coeluting analytes if these have different molecular weights. The HPLC-UV-FL and LC-MS methods were demonstrated to be suitable for studying the photo-oxidation and thermo-oxidation reactions of plant sterols. The HPLC-UV-FL method was able to show different formation rates of hydroperoxides during photo-oxidation. The method also confirmed that plant sterols have similar photo-oxidation behaviour to cholesterol. When thermo-oxidation of plant sterols was investigated by HPLC-UV-FL and LC-MS, the results revealed that the formation and decomposition of individual hydroperoxides and secondary oxidation products could be studied. The methods used revealed that all of the plant sterols had similar thermo-oxidation behaviour when compared with each other, and the predominant reactions and oxidation rates were temperature dependent. Overall, these findings showed that with these LC methods the oxidation mechanisms of plant sterols can be examined in detail, including the formation and degradation of individual hydroperoxides and secondary oxidation products, with less sample pretreatment and without derivatization.

X-Ray Spectroscopic Studies of the Surface Species in Co-Mo-Al2O3 Hydrodesulphurization Catalysts

Octahedrally coordinated CoII and MoIV species are present on the surfaces of sulfided Co-Mo-Al2O3 catalysts used for hydrodesulfurization. They were characterized by XPE, EXAFS and XANES data. An excess of sulfur in the surface species can be explained in terms of the presence of S[stack 22 ] ions. Disulfide bridges could play a role in the hydrodesulfurization.

Unusual products of oxidation with Cr(VI) of methyl 5-methyl-7-methoxy-8-isopropyl-3,4-2-naphthoate

Abstract is not available.

Prospects for the classical biological control of Calotropis procera (Apocynaceae) using co-evolved insects

Calotropis procera (Apocynaceae), a native of tropical Africa, the Middle East and the Indian subcontinent, is a serious environmental and rangeland weed of Australia and Brazil. It is also a weed in Hawaii in USA, the Caribbean Islands, the Seychelles, Mexico, Thailand, Vietnam and many Pacific Islands. In the native range C. procera has many natural enemies, thus classical biological control could be the most cost-effective option for its long-term management. Based on field surveys in India and a literature search, some 65 species of insects and five species of mites have been documented on C. procera and another congeneric-invador C. gigantea in the native range. All the leaf-feeding and stem-boring agents recorded on Calotropis spp. have wide host range. Three pre-dispersal seed predators,the Aak weevil Paramecops farinosus and the Aak fruit fly Dacuspersicus in the Indian subcontinent, and the Sodom apple fruit fly Dacus longistylus in the Middle East have been identified as prospective biological control agents based on their field host range. In Australia and Brazil, where C. procera has the potential to spread across vast areas, pre-dispersal seed predators would help to limit the spread of the weed. While the fruits of C. procera vary in size and shape across its range, those from India are similar to the ones in Australia and Brazil. Hence, seed-feeding insects from India are more likely to be suitable due to adaptation to fruit size and morphology. Future survey efforts for potential biological control agents should focus on North Africa.

Structural Veneer Based Composite Products from Hardwood Thinning - Part II: Testing of Hollow Utility Poles

Australian utility pole network is aging and reaching its end of life, with 70% of the 5 million poles currently in-service nationally installed within the 20 years following the end of World War II. The estimated investment required for the replacement or remedial maintenance of the aging 3.5 millions poles is as high as 1.75 billion dollars. Additionally, an estimated 21,700 high-durability new poles are required each year, representing further investment of 13.5 million dollars per year. Yet, agreements which progressively phase out logging of native forests around Australia have been signed, giving the industry about 25 years to make the transition from Crown native forests to plantations and private forests. As utility poles were traditionally cut from native forest hardwood species, finding solutions to source new poles currently presents a challenge. This paper presents tests on Veneer Based Composite hardwood hollow utility poles manufactured from Gympie messmate (Eucalyptus cloeziana) plantation thinning. Small diameter poles of nominal 115 mm internal diameter and 15 mm wall-thickness were manufactured in two half-poles butt jointed together, using 9 veneers per halfpole. The poles were tested in bending and shear, and experimental test results are presented. The mechanical performance of the hollow poles is discussed and compared to hardwood poles cut from mature trees and of similar size. Future research and different options for improving the current concept are proposed in order to provide a more reliable and cost effective technical solution to the current shortage of utility poles. © RILEM 2014.

Biology and Management of Psocids Infesting Stored Products

Previously regarded as minor nuisance pests, psocids belonging to the genus Liposcelis now pose a major problem for the effective protection of stored products worldwide. Here we examine the apparent biological and operational reasons behind this phenomenon and why conventional pest management seems to be failing. We investigate what is known about the biology, behavior, and population dynamics of major pest species to ascertain their strengths, and perhaps find weaknesses, as a basis for a rational pest management strategy. We outline the contribution of molecular techniques to clarifying species identification and understanding genetic diversity. We discuss progress in sampling and trapping and our comprehension of spatial distribution of these pests as a foundation for developing management strategies. The effectiveness of various chemical treatments and the availability and potential of nonchemical control methods are critically examined. Finally, we identify research gaps and suggest future directions for research.

Structural Veneer Based Composite Products from Hardwood Thinning - Part I: Background and Manufacturing

In Australia, plantation forests have increased in area by around 50% in the last 10 years. While this expansion has seen a modest 8% increase for softwoods, hardwood plantations have dramatically increased by over 150%. Hardwood plantations grown for high quality sawn timber are slow to mature, with a crop rotation time potentially reaching 35 years. With this long lead-time, each year the risk from fire, pests and adverse weather events dramatically increases, while not translating into substantially higher financial returns to the grower. To justify continued expansion of Australia's current hardwood plantation estate, it is becoming necessary to develop higher value end-uses for both pulpwood and smaller 'sawlog' resources. The use of the low commercial value stems currently culled during thinning appears to be a necessary option to improve the industry profitability and win new markets. This paper provides background information on Australian forests and plantations and gives an overview of potential uses of Australian hardwood plantation thinning logs, as their mechanical properties. More specifically, this paper reports on the development of structural Veneer Based Composite (VBC) products from hardwood plantation thinning logs, taking advantage of a recent technology developed to optimise the processing of this resource. The process used to manufacture a range of hollow-form veneer laminated structural products is presented and the mechanical characteristics of these products are investigated in the companion paper. The market applications and future opportunities for the proposed products are also discussed, as potential benefits to the timber industry. © RILEM 2014.

Parents as co-researchers at home: Using an observational method to document young children’s use of technology

This paper discusses the use of observational video recordings to document young children’s use of technology in their homes. Although observational research practices have been used for decades, often with video-based techniques, the participant group in this study (i.e., very young children) and the setting (i.e., private homes), provide a rich space for exploring the benefits and limitations of qualitative observation. The data gathered in this study point to a number of key decisions and issues that researchers must face in designing observational research, particularly where non-researchers (in this case, parents) act as surrogates for the researcher at the data collection stage. The involvement of parents and children as research videographers in the home resulted in very rich and detailed data about children’s use of technology in their daily lives. However, limitations noted in the dataset (e.g., image quality) provide important guidance for researchers developing projects using similar methods in future. The paper provides recommendations for future observational designs in similar settings and/or with similar participant groups.

Creating the reasonable adventurer: The co-evolution of student and learning environment

Purpose: This paper seeks to address the issue of how are graduate skills developed. The focus is not on which skills, but rather what type of learning environments is required within Higher Education to support the development of skills valued and demanded by SMEs within Australia. Approach: This paper takes a step back to consider the underlying issue of how an individual student's habits of thought are altered. In doing so, the past works of Morgan, Dewey, Whitehead, and Tyler are synthesized with the modern work of Baxter Magolda, Heath, and Biggs. Findings: It is argued that that without the development of a student-centred learning environment, most graduates will not develop the types of skills demanded by SMEs in a meaningfully way. That the failure to treat knowledge and skills as equal drivers of curriculum design will result in an imbalance that relegates skill development to a secondary learning outcome. Practical Implications: By removing the distraction of what skills should be developed, a clearer focus is possible regarding how educators should assist students to develop a broad array of generic graduate skills. From this perspective, skills can be viewed as an essential element of the educational process, rather than a new element that must be squeezed in between content. Value of Paper: This paper extends recent discussion of skills development through the use of an evolutionary perspective. Viewed as a process of creating social change, education becomes increasingly connected to a world that lays beyond institutional boundaries, thus promoting the notion of developing graduates for the world that awaits them.