Effects of drought on the production of electrophysiologically active biogenic volatiles important for cereal pest management

Thesis submitted to the Faculty of Science, University of the Witwatersrand, in partial fulfillment of the requirements for the degree PhD Science Johannesburg, September 2014Drought has the potential to reset trophic interactions within natural and managed ecosystems. I tested how drought stress in maize and companion plants that are used in cereal agroecosystems of Kenya affect oviposition preference, larval feeding, and development of the spotted stemborer, Chilo partellus Swinhoe (Lepidoptera: Crambidae). Five host species were tested (all Poaceae): maize (Zea mays L.), Napier grass (Pennisetum purpureum Schumach), signal grass [Brachiaria brizantha (A. Rich) Stapf], Brachiaria cv ‘Mulato’, and molasses grass [Melinis minutiflora (Beauv.)]. Under periods of water deficit, maize was oviposited on as much as under control unstressed maize in both choice and no-choice experiments. Similarly, larval leaf damage was not significantly different in drought-stressed and unstressed maize. However in Napier and signal grasses, oviposition occurred less on drought-stressed than on unstressed corresponding individuals of the same species. Oviposition acceptance and foliar damage remained low in both drought-stressed and unstressed molasses grass and Mulato. Larval survival and development remained high in drought-stressed maize, but not in Napier, signal, and molasses grass and Mulato, where survival and development were low in both drought-stressed and unstressed plants. Drought stress resulted in increased total plant volatile emission in Napier and signal grasses. This significant change in total volatile emission of the plants upon stress was not present in molasses grass, Mulato II, Silverleaf and Greenleaf Desmodium despite variable changes in the quantities and qualities of particular constituent compounds among all the plant species during water deficit. In wind tunnel bioassays, volatile organic compounds (VOCs) from irrigated Napier and signal grasses were more attractive to C. partellus than the treatment plants. However, volatiles from molasses grass, Mulato II, Silverleaf and Greenleaf Desmodium were never preferred by the gravid moths in both irrigated and drought stressed v conditions. These changes in chemical constituents of the plant VOCs also elicited behavioural responses in parasitoids. Drought-stressed Napier grass attracted gravid Cotesia sesamiae parasitoids. Other companion plant species such as molasses grass and Mulato which constitutively emit these terpenes remained attractive to the parasitoids even under periods of drought. I attribute this differential preference of the moths to the constitutive and/or induced emission of key terpenoid compounds in plants that were tested. The induction of terpenoid compounds was coupled with a reduction in the amount of green leaf volatiles such as (Z)-3-hexenyl acetate in Napier and signal grasses. Taken together, the results suggest that control of stemborer pests using stimulo-deterrent diversion tactics remains possible under periods of environmental change

Spectroscopic and photophysicochemical behaviour of novel cadmium phthalocyanine derivatives tetra-substituted at the alpha and beta positions

The syntheses of three cadmium phthalocyanine derivatives tetrakis{1,(4)-(4-benzyloxy)phenoxyphthalocyaninato} (5a), tetrakis{1,(4)-(2-pyridyloxy)phthalocyaninato} (5b) and tetrakis{2,(3)-(4-benzyloxy)phenoxyphthalocyaninato} (6a) are reported here for the first time. Spectroscopic and photophysical properties have also been determined and the results are discussed here paying particular attention to the influence of various organic solvents in relation to the position and type of substitution. Singlet oxygen quantum yields (ΦΔ) and photodegradation quantum yields (ΦPd) have also been discussed. The triplet quantum yields have been determined and ranged from ΦT = 0.36 to 0.85, where the peripherally (β) substituted derivatives generally give higher values than those substituted at the non-peripheral (α) positions. The triplet lifetimes ranged from τT = 5 to 40 μs. In all cases (except toluene, due to the lack of data), the highest singlet oxygen quantum yields obtained were for the pyridyloxy-substituted derivatives 5b (ΦΔ = 0.60 in DMF) and 6b (ΦΔ = 0.74 in DMSO)

Achieving Optimal Performance and Quality in LAN and WLAN for Mission-Critical Applications

© 2024 The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. This is the accepted manuscript version of a conference paper which has been published in final form at https://doi.org/10.1007/978-981-99-6974-6_17Voice Over Internet Protocol (VoIP) properties are vital for its reliability in mission-critical applications. This research aims to find network topology, call signalling and voice codecs property combinations that meet reliability targets of VoIP communication in a Small Office Home Office (SOHO) environment where network resources may be limited but reliable and secured operation is essential. Local Area Network (LAN) and Wireless LAN (WLAN) scenarios are evaluated using Quality of Service (QoS) and Mean Opinion Score (MOS) measurements to find which property combinations satisfy predefined classes; best quality and best performance. The research extended Roslin et al. [1] on LAN VoIP to WLANs, and validated Khiat et al. [2] s and Guy [3]’s work that argued SIP was effective in optimal set up. This research found that VoIP combinations offer some desirable characteristics, but at the cost of other properties required, leading to categorisation being based on the interpretation of the results, concluding that though, not ideal for mission-critical applications, combinations function well in replicating real-world scenarios. The analysis also established VoIP's scalability for application-based configurations, impact of VoIP’s modularity and ease of configuration in achieving user expectations. Further property testing can solidify VoIP’s capabilities to function for mission-critical environments

Photophysiochemical studies of d¹⁰ metallophthalocyanines and their interaction with nanoparticles

The syntheses, extensive spectroscopic characterization, photophysical and photochemical studies have been conducted for a variation of d10 metallophthaloycanines (MPcs). Comparisons have been made taking into consideration the nfluence of the central metal ion, solvent properties, substituent type and position. Coordination to heavy central metals i.e. Hg gives enhanced triplet state properties. Low symmetry metallophthalocyanine complexes were similarly haracterized and the influence of nteractions with nanoparticles on their photophysical and photochemical properties determined. The MPcs have been linked and adsorbed or mixed with nanoparticles i.e. hemically functionalized single-walled carbon nanotubes SWCNT) and mercaptocarboxylic acid capped CdTe quantum dots (QDs) and changes in the spectra accounted for with respect to the proposed conjugate structures. Distinct differences ccur for linked and adsorbed or mixed conjugates in the bsorption, infrared (IR) and Raman spectra and for thermal ravimetric decay profiles, suggesting successful formation f covalent bonds (linked) and point to structurally ifferent materials. SWCNT quench MPc fluorescence by a photoinduced electron transfer mediated process to give low fluorescence quantum yields. The QDs were used as energy transfer donors and facilitate energy transfer, through Förster resonance energy transfer (FRET) from the QDs to the MPcs. Improved FRET efficiencies were found for linked MPc-QD conjugates relative to the mixed species. Photophysicochemical properties of MPcs were, in general, improved as a result of interactions with nanoparticles

Ecological chemistry of pest control in push-pull intercropping systems: What we know, and where to go?

Push-pull technology (PPT) employs mixed cropping for sustainable intensification: an intercrop repels or suppresses pests of the focal crop (push), while a trap crop attracts pests out of the field (pull), where they may be targeted for control. Underlying chemical-ecological mechanisms have been demonstrated in controlled settings, primarily for some of the best-established cereal PPT systems developed in east Africa. Yet, many questions remain regarding mechanisms, and strategies to adapt PPT for different crops and locations. We conducted a systematic review of scientific literature on PPT and related practices for biological control of pests of food and fodder. Of 3335 results, we identified 45 reporting on chemistry of trap- or intercropping systems for pest control, of which 30 focused on cereals or African pests. Seven of these reported primary chemical data: measurements from glasshouse and laboratory studies (5), or of field-collected samples (2). From these 30, we provide a database of compounds, discussing degrees of evidence for their mediation of push-pull. We depict hypothesized spatial distributions of selected compounds in PPT fields from physical properties and emission/exudation rates, and design of the east African cereal PPT system, and discuss influences on activity in field settings likely to affect success

Ecological Chemistry of Pest Control in Push-Pull Intercropping Systems: What We Know, and Where to Go?

Push-pull technology (PPT) employs mixed cropping for sustainable intensification: an intercrop repels or suppresses pests of the focal crop (push), while a trap crop attracts pests out of the field (pull), where they may be targeted for control. Underlying chemical-ecological mechanisms have been demonstrated in controlled settings, primarily for some of the best-established cereal PPT systems developed in east Africa. Yet, many questions remain regarding mechanisms, and strategies to adapt PPT for different crops and locations. We conducted a systematic review of scientific literature on PPT and related practices for biological control of pests of food and fodder. Of 3335 results, we identified 45 reporting on chemistry of trap- or intercropping systems for pest control, of which 30 focused on cereals or African pests. Seven of these reported primary chemical data: measurements from glasshouse and laboratory studies (5), or of field-collected samples (2). From these 30, we provide a database of compounds, discussing degrees of evidence for their mediation of push-pull. We depict hypothesized spatial distributions of selected compounds in PPT fields from physical properties and emission/exudation rates, and design of the east African cereal PPT system, and discuss influences on activity in field settings likely to affect success

Syntheses and photophysics of new phthalocyanine derivatives of zinc, cadmium and mercury

The syntheses of novel tetra{2,(3)-pyridyloxyphthalocyaninato} complexes of zinc, cadmium and mercury (TPyZnPc, TPyCdPc and TPyHgPc) are presented. Their spectral and photophysical properties (as well as those of their unsubstituted counterparts: ZnPc, CdPc and HgPc) are investigated. TPyZnPc and TPyCdPc are aggregated in non-coordinating solvents such as chloroform, while TPyHgPc is demetallated, as evident from their respective absorption spectra. The trends in fluorescence (ΦF), triplet (ΦT) and singlet oxygen (ΦΔ) quantum yields are explained in terms of relative strengths of spin–orbit coupling induced by the respective central metal ions in the complexes. The effect of the pyridyloxy substituents is a decrease in ΦF and an increase in ΦT values. The complexes are less fluorescent in DMSO but possess higher ΦT, triplet lifetimes (τT) and ΦΔ therein

Global Climate Change as a Driver of Bottom-Up and Top-Down Factors in Agricultural Landscapes and the Fate of Host-Parasitoid Interactions

The global climate is rapidly changing and the evidence is increasingly manifesting across various biological systems. For arthropods, several studies have demonstrated how changing climates affect their distribution through phenological and physiological responses, largely focusing on various organismal fitness parameters. However, the net-effect of the changing climate among ecological communities may be mediated by the feedback pathways among interacting trophic groups under environmental change. For agroecosystems, the maintenance of the integrity of trophic interactions even under climate variability is a high priority. This is even more important in this era where there is advocacy for sustainable agriculture, with higher emphasis on environmentally benign methods. For this reason, pest management in food production systems using biological control (especially use of parasitoid antagonists) has come to the forefront. In this review, we give an overview of the diversity of physiological responses among host insect and parasitoid populations and how this may influence their interactions. We highlight how climate change may modify bottom-up and top-down factors among agroecosystems with a particular focus on plant-insect host-parasitoid tritrophic interactions. We also outline how habitat management may influence arthropod population dynamics and how it can be manipulated to improve on-farm climate resilience and parasitoid conservation. We wrap-up by highlighting how the application of knowledge of conservation biodiversity, designing of multifunctional resilient landscapes, and evolutionary physiology of arthropods under thermal stress may be used to improve the fitness of mass-reared parasitoids (in or ex situ) for the improvement in efficacy of parasitoids ecosystem services under thermally stressful environment

Photophysical behaviour of asymmetrically substituted metal free, Mg and Zn phthalocyanines in the presence of folic acid

This work reports on the synthesis, characterisation and photophysical properties of new asymmetric metal free, magnesium and zinc phthalocyanines containing a mono carboxylic acid group for possible linking to biological molecules via an amide bond. Successful synthesis of the phthalocyanines was achieved through the statistical condensation method. The phthalocyanines were mixed with folic acid and their photophysical properties were examined. The triplet quantum yield values for all the complexes in DMSO were between 0.49 and 0.74 and in the presence of folic acid they were between 0.37 and 0.63. The lifetimes were generally good ranging from 70 to 290 μs in the absence or presence of folic acid