title: Chemoecological investigations of predator-prey relationships in New Zealand nudibranchs for the discovery of new natural products

authors: Gris, Lauren

abstract: This study describes chemical ecology investigations of predator-prey relationships in New Zealand nudibranchs for the discovery of new natural products. Three predator-prey relationships were established, and twenty secondary metabolites were isolated and characterised from various New Zealand marine organisms, including five new compounds.
Predator-prey relationships were established for three nudibranch species, Polycera hedgpethi, Ceratosoma amoenum and Goniobranchus aureomarginatus by means of field studies and laboratory-based feeding-choice experiments. Results indicated that P. hedgpethi prefers the bryozoan Bugula neritina, while C. amoenum and G. aureomarginatus prefer feeding on the marine sponges Dysidea teawnui and Dictyodendrilla cf. dendyi, respectively. For two of the predator-prey relationships, common metabolites were found in both predator and prey. As such, Dysidea teawanui and C. amoenum both contain a sterol peroxide, while G. aureomarginatus and D. cf. dendyi both contain dictyodendrins C (209) and F (212). 
P. hedgpethi and B. neritina specimens were also chemically investigated but common metabolites were not found. Additionally, three nudibranch species, Dendrodoris krusensternii, Dendrodoris nigra and Aphelodoris luctuosa, were chemically investigated and yielded a range of secondary metabolites previously reported from marine invertebrates. A polymeric 3-alkyl pyridinium salt (146) was found in high concentration within A. luctuosa and its eggs. Moreover, an endemic bryozoan, Amathia gracei, was chemically investigated and yielded a known brominated alkaloid.
Investigation of G. aureomarginatus samples by LC-MS screening, to determine metabolite distribution and any ecological role of the compounds isolated, indicated that dictyodendrins C (209) and F (212) were present in the digestive glands, while a norditerpene, gracilin was only present in the mantle. Quantitative NMR spectroscopy indicated that the polymeric 3-alkyl pyridinium salt (146) was present in higher concentration in the mantle of Aphelodoris luctuosa, consistent with a defensive purpose and with its presence in high concentration within the egg masses of A. luctuosa. Morphological analysis revealed oxea spicules within the digestive gland of Aphelodoris luctuosa, suggesting that it is possibly feeding on haplosclerid sponges. 
An additional seven known polyaromatic alkaloids and five new sulphated denigrins alkaloids, denigrins H-L (262-266) were isolated and characterised from the sponge D. cf. dendyi by means of NMR spectroscopy and HR-ESI-MS guided isolation. The new and known metabolites isolated in this research were assessed in a general cytotoxicity assay against HeLa cells. Results indicated that the compounds were not particularly active (IC50 > 57 µM).

text: Chemoecological investigations of predator-prey relationships in New Zealand nudibranchs for the discovery of new natural products This study describes chemical ecology investigations of predator-prey relationships in New Zealand nudibranchs for the discovery of new natural products. Three predator-prey relationships were established, and twenty secondary metabolites were isolated and characterised from various New Zealand marine organisms, including five new compounds.
Predator-prey relationships were established for three nudibranch species, Polycera hedgpethi, Ceratosoma amoenum and Goniobranchus aureomarginatus by means of field studies and laboratory-based feeding-choice experiments. Results indicated that P. hedgpethi prefers the bryozoan Bugula neritina, while C. amoenum and G. aureomarginatus prefer feeding on the marine sponges Dysidea teawnui and Dictyodendrilla cf. dendyi, respectively. For two of the predator-prey relationships, common metabolites were found in both predator and prey. As such, Dysidea teawanui and C. amoenum both contain a sterol peroxide, while G. aureomarginatus and D. cf. dendyi both contain dictyodendrins C (209) and F (212). 
P. hedgpethi and B. neritina specimens were also chemically investigated but common metabolites were not found. Additionally, three nudibranch species, Dendrodoris krusensternii, Dendrodoris nigra and Aphelodoris luctuosa, were chemically investigated and yielded a range of secondary metabolites previously reported from marine invertebrates. A polymeric 3-alkyl pyridinium salt (146) was found in high concentration within A. luctuosa and its eggs. Moreover, an endemic bryozoan, Amathia gracei, was chemically investigated and yielded a known brominated alkaloid.
Investigation of G. aureomarginatus samples by LC-MS screening, to determine metabolite distribution and any ecological role of the compounds isolated, indicated that dictyodendrins C (209) and F (212) were present in the digestive glands, while a norditerpene, gracilin was only present in the mantle. Quantitative NMR spectroscopy indicated that the polymeric 3-alkyl pyridinium salt (146) was present in higher concentration in the mantle of Aphelodoris luctuosa, consistent with a defensive purpose and with its presence in high concentration within the egg masses of A. luctuosa. Morphological analysis revealed oxea spicules within the digestive gland of Aphelodoris luctuosa, suggesting that it is possibly feeding on haplosclerid sponges. 
An additional seven known polyaromatic alkaloids and five new sulphated denigrins alkaloids, denigrins H-L (262-266) were isolated and characterised from the sponge D. cf. dendyi by means of NMR spectroscopy and HR-ESI-MS guided isolation. The new and known metabolites isolated in this research were assessed in a general cytotoxicity assay against HeLa cells. Results indicated that the compounds were not particularly active (IC50 > 57 µM).

year: 2025

title: Extended kinship among urban Samoan migrants: Towards an explanation of its persistence in urban New Zealand

authors: Macpherson, C.

abstract: This thesis examines the structure and composition of extended kin groups among Western Samoan migrants in New Zealand, and comments on their role and significance in migrant social organisation.

Certain factors which could explain the continued significance of these groupings are identified and examined. The factors identified suggest that individuals continue to accept the rights and obligations associated with membership of an extended kin group partly because they believe that it is in their interests to do so and partly because they have little option.

The material is placed within the context of the current debate on the relationship between economic organisation and associated kinship structures. The thesis concludes that Western Samoan migrants have retained an extended kin group which closely resembles the modified extended family reported in the family literature, and that under certain conditions extended kin groups may emerge, or persist, in urban industrial societies.

text: Extended kinship among urban Samoan migrants: Towards an explanation of its persistence in urban New Zealand This thesis examines the structure and composition of extended kin groups among Western Samoan migrants in New Zealand, and comments on their role and significance in migrant social organisation.

Certain factors which could explain the continued significance of these groupings are identified and examined. The factors identified suggest that individuals continue to accept the rights and obligations associated with membership of an extended kin group partly because they believe that it is in their interests to do so and partly because they have little option.

The material is placed within the context of the current debate on the relationship between economic organisation and associated kinship structures. The thesis concludes that Western Samoan migrants have retained an extended kin group which closely resembles the modified extended family reported in the family literature, and that under certain conditions extended kin groups may emerge, or persist, in urban industrial societies.

year: 1975

title: Quantification of Nitro-toxins in Karaka (Corynocarpus laevigatus) Drupes

authors: MacAskill, Jessica Jane

abstract: The karaka (Corynocarpus laevigatus) is a tree native to New Zealand (NZ), found throughout the North and South Islands. Traditionally, many parts of the karaka were used by Māori, however the parts of the karaka of most interest are the berry and nut as they were valuable food sources, in particular the nut. Karaka was known to be a toxin-bearing food, however implementation of a traditional baking and soaking process meant that the nuts were left in states fit for consumption, more often than not. The nuts also had the benefit of being able to be stored for future use when other food sources were short in supply. Karaka was readily consumed up until the 1950s, after this consumption rates decreased rapidly, after the toxic effects were associated with the incorrect preparation of the nuts.

Studies on karaka have revealed that the toxicity of the nuts primarily arises from various nitropropanoyl glucopyranoses (NPGs), twelve of which have been detected in karaka. The quantity of these NPGs has been infrequently studied and it is often only one of the NPGs-karakin which is quantified, although it is believed the toxicity in nuts arises collectively from all of the NPGs. As a result, there is the need to be able to quantify the NPGs in karaka and look at potential toxin removal techniques. If toxin removal can be accomplished, there is the potential for karaka to be a marketable ‘traditional’ or ‘Kiwi’ food item. Additionally, the toxins removed as a by-product may prove to have their own potential commercial applications, for example as insecticides or repellents. 

Since all the NPGs are assumed to be toxic, a method was developed to quantify the total toxicity in the nuts. The method involves the release of NPA via acid hydrolysis of the nitropropanoyl ester groups of the NPGs. The NPA is then able to be measured and subsequently quantified using HPLC. The method incorporates a correction factor (CF) that was determined to give the original NPA content at a time of zero (NPA0), accounting for the unavoidable loss of NPA that arises from the hydrolysis method.

The average quantity of NPA in karaka nuts was found to range from 50.25 to 138.62 g kg-1 (dry weight) which is equivalent to 5.0 to 13.9%. These are much higher percentages than any previously reported because the method used in this study measured total NPA. Earlier methods measured a limited range of NPGs (often a single NPG) unhydrolysed and could have missed NPA arising from other compounds that contribute to total toxicity. Additionally, the concentrations of NPA in karaka nuts were influenced by a number of factors including intra and inter tree variation, storage conditions and ripeness. Although quantification was focused on determining NPA content in nuts, a test conducted also showed NPA to be present in increasingly lower levels in the berry flesh, shell and pellicle respectively. 

Nuts were subjected to various potential industrial processing techniques, treatment times and conditions, in order to determine their efficacy for toxin removal. Treatments included boiling, microwave cooking, soxhlet extraction, oven roasting, autoclaving and cold-water treatments. The efficiency of each treatment varied considerably, with both heat and water proving to be beneficial in toxin removal. However, treatments involving water were found to be more effective than heat treatments alone. Out of all treatment types, times and conditions tested, none were found to leave nuts with a NPA concentration lower than the estimated safe level of daily consumption for a 70 kg adult (< 1.75 mg). Additionally, only some of the treatments resulted in nuts being left in visually appealing states. At present, toxin removal by a single process in order to render karaka nuts safe to consume appears to be an impractical activity. However, if treatment protocols were combined and modified, there is the potential for the development of an effective detoxification process. Furthermore, tests on the treatment solutions revealed that NPA can be obtained in solution as a by-product of nut treatment; with cold-water proving to be more effective than treatments that also used heat. Obtaining NPA as a by-product of toxin removal in nuts appears to be a feasible option for a natural source of NPA.

text: Quantification of Nitro-toxins in Karaka (Corynocarpus laevigatus) Drupes The karaka (Corynocarpus laevigatus) is a tree native to New Zealand (NZ), found throughout the North and South Islands. Traditionally, many parts of the karaka were used by Māori, however the parts of the karaka of most interest are the berry and nut as they were valuable food sources, in particular the nut. Karaka was known to be a toxin-bearing food, however implementation of a traditional baking and soaking process meant that the nuts were left in states fit for consumption, more often than not. The nuts also had the benefit of being able to be stored for future use when other food sources were short in supply. Karaka was readily consumed up until the 1950s, after this consumption rates decreased rapidly, after the toxic effects were associated with the incorrect preparation of the nuts.

Studies on karaka have revealed that the toxicity of the nuts primarily arises from various nitropropanoyl glucopyranoses (NPGs), twelve of which have been detected in karaka. The quantity of these NPGs has been infrequently studied and it is often only one of the NPGs-karakin which is quantified, although it is believed the toxicity in nuts arises collectively from all of the NPGs. As a result, there is the need to be able to quantify the NPGs in karaka and look at potential toxin removal techniques. If toxin removal can be accomplished, there is the potential for karaka to be a marketable ‘traditional’ or ‘Kiwi’ food item. Additionally, the toxins removed as a by-product may prove to have their own potential commercial applications, for example as insecticides or repellents. 

Since all the NPGs are assumed to be toxic, a method was developed to quantify the total toxicity in the nuts. The method involves the release of NPA via acid hydrolysis of the nitropropanoyl ester groups of the NPGs. The NPA is then able to be measured and subsequently quantified using HPLC. The method incorporates a correction factor (CF) that was determined to give the original NPA content at a time of zero (NPA0), accounting for the unavoidable loss of NPA that arises from the hydrolysis method.

The average quantity of NPA in karaka nuts was found to range from 50.25 to 138.62 g kg-1 (dry weight) which is equivalent to 5.0 to 13.9%. These are much higher percentages than any previously reported because the method used in this study measured total NPA. Earlier methods measured a limited range of NPGs (often a single NPG) unhydrolysed and could have missed NPA arising from other compounds that contribute to total toxicity. Additionally, the concentrations of NPA in karaka nuts were influenced by a number of factors including intra and inter tree variation, storage conditions and ripeness. Although quantification was focused on determining NPA content in nuts, a test conducted also showed NPA to be present in increasingly lower levels in the berry flesh, shell and pellicle respectively. 

Nuts were subjected to various potential industrial processing techniques, treatment times and conditions, in order to determine their efficacy for toxin removal. Treatments included boiling, microwave cooking, soxhlet extraction, oven roasting, autoclaving and cold-water treatments. The efficiency of each treatment varied considerably, with both heat and water proving to be beneficial in toxin removal. However, treatments involving water were found to be more effective than heat treatments alone. Out of all treatment types, times and conditions tested, none were found to leave nuts with a NPA concentration lower than the estimated safe level of daily consumption for a 70 kg adult (< 1.75 mg). Additionally, only some of the treatments resulted in nuts being left in visually appealing states. At present, toxin removal by a single process in order to render karaka nuts safe to consume appears to be an impractical activity. However, if treatment protocols were combined and modified, there is the potential for the development of an effective detoxification process. Furthermore, tests on the treatment solutions revealed that NPA can be obtained in solution as a by-product of nut treatment; with cold-water proving to be more effective than treatments that also used heat. Obtaining NPA as a by-product of toxin removal in nuts appears to be a feasible option for a natural source of NPA.

year: 2013