Photodynamics of Porphyric Insecticides

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Abstract
The discovery of porphyric insecticides was a direct fallout of the discovery and development of photodynamic herbicides. Tetrapyrrole-dependent photodynamic herbicides are compounds that force green plants to accumulate undesirable amounts of metabolic intermediates of the chlorophyll and heme metabolic pathways, namely, tetrapyrroles. In light, the accumulated tetrapyrroles photosensitize the formation of singlet oxygen that kills treated plants by oxidation of their cellular membranes. Demonstration of the potential for tetrapyrrole accumulation in insects was achieved by spraying T. ni larvae with δ-aminolevulinic acid (ALA) and 2,2-dipyridyl (Dpy). Treated larvae were placed overnight in darkness at 28°C in order to allow for tetrapyrrole accumulation. Extraction of treated, dark-incubated larvae with ammoniacal acetone, followed by spectrofluorometric examination of the larval extract, revealed the accumulation of massive amounts of protoporphyrin IX (Proto). A high degree of correlation was observed between Proto accumulation in darkness and larval death in the light. A few hours after exposure to light, the larvae became sluggish and flaccid due to loss of body fluids. Death was accompanied by extensive desiccation. Because control of insects by ingestion is as viable an option as control by spraying, and offers certain advantages under household conditions, studies were conducted to determine whether combinations of ALA and porphyric insecticide modulators would be effective if ingested with the food. The effect of ALA and 1,10-phenanthroline (Oph) were determined by incorporating them into the diet of T. ni larvae. After exposure to light, following 17 h of dark incubation, larvae underwent violent convulsions and vomiting and died within 20 to 40 s. Tetrapyrrole analysis of the treated larvae immediately after dark incubation revealed significant amounts of Proto and Zn-Proto accumulation. Correlation between tetrapyrrole accumulation and larval death was significant. Similar results were obtained when ALA and Dpy were administered to the larvae with the diet. The above results indicated that in addition to contact via spraying, porphyric insecticides had the potential to be very potent when ingested. For a more thorough understanding of the mode of action of porphyric insecticides, the phenomenology of tissue, cellular, and subcellular sites of tetrapyrrole accumulation in representative insect species was investigated. In T. ni larvae, on a unit protein basis, about 59% of the accumulated Proto was observed in the hemolymph, 35% in the gut, and 6% in the integument. Further understanding of the response of insect organs and tissues to porphyric insecticide treatment was obtained by investigating the response of isolated organs and tissues to incubation with ALA + Dpy or ALA + Oph in adult Blattella germanica (German cockroach), adult Anthonomus grandis (cotton boll weevil), fifth instar larvae of Heliothus zea (corn earworm), and fifth instar larvae of T. ni (cabbage looper). In T. ni, and H. zea, significant Proto accumulation was observed in incubated midgut and fat bodies. Proto accumulation occurred when tissues were incubated with Dpy, ALA + Dpy, Oph, and ALA + Oph (2). No response to treatment with ALA alone was observed. In cockroaches, more of the Proto appeared to accumulate in the male and female guts than in their abdomen. As in T. ni and H. zea, the response was elicited by each of the treatments that included Dpy or Oph. Cotton boll weevil abdomens appeared to be less responsive than the abdomens of the other three species. To determine whether Proto accumulation resulted in photodynamic damage of incubated tissues, T. ni midguts were incubated in darkness either in buffer, with ALA, or with Oph + ALA. Oxygen consumption of the tissue was monitored before and after exposure to 2-h of illumination. A 30% decrease in O2 consumption was observed in midguts treated with Oph or with ALA + Oph after 2 h in the light. The decrease in oxygen consumption observed in isolated T. ni midguts was shown to be caused by photodynamic damage to mitochondrial enzymes. Finally, structure-function photodynamic insecticidal studies led to the identification of 36 compounds belonging to 10 different chemical families that were effective (>70% mortality) against at least one insect species. Of the 36 modulators, 10 exhibited potent activity toward cockroaches.

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