title: Polymetallic Silyl-Iron and -Ruthenium Compounds

authors: Masters, Neville Kingston

subjects: Inorganic Polymers

abstract: The synthesis of iron and ruthenium compounds which contain either end-capped silyl units Fe-Si-Si-Fe or the linear sequence Si-Ru-Ru-Si respectively were explored.  
   		(I)			(II) 			          (III)

End-capped iron species, e.g. I, were prepared using literature methods and two new related iron containing silyl species II and III were synthesised.  These were prepared as model compounds for comparison with polymeric analogues.

 		 
	          (IV)					  (V)

Ruthenium silyl species of the type IV that maintain metal - metal bonding have been prepared.  As an extension to this work inorganic polymeric species such as V were synthesised using the same preparation techniques.

The polymeric compounds were difficult to characterise as they were unable to be chromatographed or crystallised therefore, all data was from crude mixtures.  Spectroscopic techniques involved FT - IR, ESMS, LDI-TOF and NMR spectroscopy.  ESMS was an ineffective technique for the polymeric compounds however, LDI-TOF mass spectrometry gave broad curves with an average molecular weight ranging from 60,000 to 200,000 for different preparations.

Flexible siloxanes such as HSiMe2OSiMe2OSiMe2H gave molecular cluster derivatives with bridging ligands rather than polymers.

text: Polymetallic Silyl-Iron and -Ruthenium Compounds The synthesis of iron and ruthenium compounds which contain either end-capped silyl units Fe-Si-Si-Fe or the linear sequence Si-Ru-Ru-Si respectively were explored.  
   		(I)			(II) 			          (III)

End-capped iron species, e.g. I, were prepared using literature methods and two new related iron containing silyl species II and III were synthesised.  These were prepared as model compounds for comparison with polymeric analogues.

 		 
	          (IV)					  (V)

Ruthenium silyl species of the type IV that maintain metal - metal bonding have been prepared.  As an extension to this work inorganic polymeric species such as V were synthesised using the same preparation techniques.

The polymeric compounds were difficult to characterise as they were unable to be chromatographed or crystallised therefore, all data was from crude mixtures.  Spectroscopic techniques involved FT - IR, ESMS, LDI-TOF and NMR spectroscopy.  ESMS was an ineffective technique for the polymeric compounds however, LDI-TOF mass spectrometry gave broad curves with an average molecular weight ranging from 60,000 to 200,000 for different preparations.

Flexible siloxanes such as HSiMe2OSiMe2OSiMe2H gave molecular cluster derivatives with bridging ligands rather than polymers.

year: 2010

title: New Zealand Calanoid Copepod Invasions: Has Artificial Lake Construction Facilitated Invasions, and are our Coastal Waters Uninvaded?

authors: Banks, Christopher Mark

subjects: Invasive species

abstract: Non-indigenous species have become a global issue of increasing importance in recent years, with many causing significant environmental and economic damage. Identifying locations vulnerable to invasion allows for focus of management efforts towards prevention of invasions at those locations. In order to determine whether constructed water bodies, such as reservoirs, ornamental lakes or retired mines, are more easily invaded environments than natural water bodies, owing to decreased biotic resistance, the distributions of native and non-indigenous freshwater calanoid copepod species in the North Island were examined. Calanoid copepods in ports and other coastal environments were also examined, in order to determine whether ports are more frequently invaded owing to increased propagule supplies from visiting ships and other sources.
The distributions of the native freshwater calanoid copepod species Boeckella hamata, B. propinqua, B. delicata and B. tanea are confined in the North Island of New Zealand to specific technostratigraphic terranes when natural waters only are examined, and as such each species can be considered to have a native range. The recently colonised calanoid copepod species Boeckella minuta (6 locations), Skistodiaptomus pallidus (3 locations) and Sinodiaptomus valkanovi (2 locations) are to date confined to constructed water bodies. Boeckella symmetrica (2 locations) may be confined to constructed water bodies, but the status of one location is unclear. Boeckella triarticulata, a species common in the South Island, is known only from a single farm dam in the North Island. The native species Boeckella hamata, B. propinqua and B. delicata were found to occur in constructed waters, but only B. 
propinqua was found in constructed water bodies outside their natural ranges (9 locations). Calamoecia lucasi is found in lakes throughout most of the North Island, and is not confined to any one terrane. My results indicate that constructed water bodies are more easily invaded by non-indigenous species than natural water bodies, represents a potential pathway for future invaders to establish, and provides locations for species to spread.
In order to determine whether recently established freshwater calanoid copepod species have the potential to spread from their present habitats into other water bodies, the prosomal lengths of non-indigenous calanoid copepod species were measured and compared with those for native species. The results suggest that dietary overlap should prevent the non-indigenous species present to date from spreading into any water bodies with established Boeckella populations, although Sinodiaptomus valkanovi and Boeckella triarticulata could potentially spread to lakes containing only Calamoecia lucasi. Data on the co-occurrences of native freshwater calanoid copepod species support the theory of dietary exclusion, as Boeckella species have not been found to coexist.
In order to test whether New Zealand marine environments have been invaded by non-indigenous calanoid copepods, and whether ports have been more regularly invaded than non-port areas, calanoid copepods were sampled from various coastal locations around the North Island. With the possible exception of Sulcanus conflictus, no non-indigenous species were found, indicating that non-indigenous marine calanoid copepod species are not establishing in New Zealand despite a history of invasion elsewhere.

text: New Zealand Calanoid Copepod Invasions: Has Artificial Lake Construction Facilitated Invasions, and are our Coastal Waters Uninvaded? Non-indigenous species have become a global issue of increasing importance in recent years, with many causing significant environmental and economic damage. Identifying locations vulnerable to invasion allows for focus of management efforts towards prevention of invasions at those locations. In order to determine whether constructed water bodies, such as reservoirs, ornamental lakes or retired mines, are more easily invaded environments than natural water bodies, owing to decreased biotic resistance, the distributions of native and non-indigenous freshwater calanoid copepod species in the North Island were examined. Calanoid copepods in ports and other coastal environments were also examined, in order to determine whether ports are more frequently invaded owing to increased propagule supplies from visiting ships and other sources.
The distributions of the native freshwater calanoid copepod species Boeckella hamata, B. propinqua, B. delicata and B. tanea are confined in the North Island of New Zealand to specific technostratigraphic terranes when natural waters only are examined, and as such each species can be considered to have a native range. The recently colonised calanoid copepod species Boeckella minuta (6 locations), Skistodiaptomus pallidus (3 locations) and Sinodiaptomus valkanovi (2 locations) are to date confined to constructed water bodies. Boeckella symmetrica (2 locations) may be confined to constructed water bodies, but the status of one location is unclear. Boeckella triarticulata, a species common in the South Island, is known only from a single farm dam in the North Island. The native species Boeckella hamata, B. propinqua and B. delicata were found to occur in constructed waters, but only B. 
propinqua was found in constructed water bodies outside their natural ranges (9 locations). Calamoecia lucasi is found in lakes throughout most of the North Island, and is not confined to any one terrane. My results indicate that constructed water bodies are more easily invaded by non-indigenous species than natural water bodies, represents a potential pathway for future invaders to establish, and provides locations for species to spread.
In order to determine whether recently established freshwater calanoid copepod species have the potential to spread from their present habitats into other water bodies, the prosomal lengths of non-indigenous calanoid copepod species were measured and compared with those for native species. The results suggest that dietary overlap should prevent the non-indigenous species present to date from spreading into any water bodies with established Boeckella populations, although Sinodiaptomus valkanovi and Boeckella triarticulata could potentially spread to lakes containing only Calamoecia lucasi. Data on the co-occurrences of native freshwater calanoid copepod species support the theory of dietary exclusion, as Boeckella species have not been found to coexist.
In order to test whether New Zealand marine environments have been invaded by non-indigenous calanoid copepods, and whether ports have been more regularly invaded than non-port areas, calanoid copepods were sampled from various coastal locations around the North Island. With the possible exception of Sulcanus conflictus, no non-indigenous species were found, indicating that non-indigenous marine calanoid copepod species are not establishing in New Zealand despite a history of invasion elsewhere.

year: 2007

title: Association of Single Nucleotide Polymorphisms in Surfactant Protein A and D with Otitis Media.

authors: Barnett, Catherine Margaret Eleanor

subjects: otitis media

abstract: Otitis Media is one of the most common childhood diseases. Recurrent acute otitis media RAOM is characterized by repeated episodes of inflammation of the middle ear in conjunction with middle ear fluid, and often with an inflamed or bulging eardrum. Defective clearance by the Eustachian tube results in mucus build-up and is characteristic of otitis media with effusion (OME). Streptococcus pneumoniae, Haemophilus influenzae, Moraxella catarrhalis, respiratory syncytial virus, and rhinovirus are the most common contributors to otitis media pathogenesis. In New Zealand, OME has been implicated with conductive hearing loss in childhood and has been shown to significantly impact on speech and language development. New Zealand Māori and Polynesian children have displayed significantly higher hearing test failure rates than European-Caucasian children.

The collectins, Surfactant Protein (SP)-A and -D are encoded by three genes (SP-A1, SP-A2, and SP-D) and are host defense proteins present in the middle ear and Eustachian tube. Single nucleotide polymorphisms (SNPs) in SP-A1 and SP-A2 have been associated with increased or decreased susceptibility to otitis media, meningococcal disease, and range of respiratory diseases. Using allele-specific primers and real-time PCR with SYBR  Green I melting curve analysis, four groups of individuals were genotyped for eleven SP-A1, SP-A2, and SP-D SNPs: European-Caucasian individuals with RAOM/OME; New Zealand Māori/Polynesian individuals with RAOM/OME; individuals with meningococcal disease; and a control group. The computer program, Haploview, was employed to perform χ2 analyses and identify statistically significant associations of alleles/haplotypes with RAOM/OME or meningococcal disease.

In the European-Caucasian population, two SP-A1 alleles, one SP-A2 allele, and four haplotypes (CGAGC, 1A3, 1A9, and 1A10) were found to be associated with increased risk of RAOM/OME (P lt; 0.05). Conversely, haplotypes 6A2 and 1A2 were found to be protective against susceptibility to RAOM/OME (P lt; 0.05). In New Zealand Māori and Polynesian individuals, two SP-A1 alleles, three SP-A2 alleles, one SP-D allele, and four haplotypes (6A8, 6A10, 1A3, and 1A10) were found to be associated with increased risk of RAOM/OME (P lt; 0.05). An additional four haplotypes (6A2, 1A0, 1A2, and TA) were determined to be protective against susceptibility to RAOM/OME (P lt; 0.05). However, protective SPA1/SPA2/SPD haplotype 6A2-1A0-TA was significantly under-represented in the New Zealand Māori and Polynesian population (P lt; 0.05). A single allele and haplotype were associated with increased risk of meningococcal disease (P lt; 0.05).

The findings of this study confirm that specific genetic variants of SP-A and SP-D are associated with either increased or decreased risk of developing RAOM and/or OME. Furthermore, it was demonstrated that New Zealand Māori and Polynesian individuals appear to exhibit more haplotypes susceptible to RAOM/OME. This may provide a partial explanation for the higher RAOM/OME-related failure rates of hearing tests in New Zealand Māori and Polynesian children. However, there are numerous socio-economic and environmental factors that also contribute to otitis media pathogenesis which were not considered in this study. The effects of the SP-A1, SP-A2, and SP-D alleles and haplotypes on the bacterial/viral binding efficiencies of SP-A and SP-D need to be investigated by further research, using a large population, to confirm the association with susceptibility or resistance with RAOM/OME.

text: Association of Single Nucleotide Polymorphisms in Surfactant Protein A and D with Otitis Media. Otitis Media is one of the most common childhood diseases. Recurrent acute otitis media RAOM is characterized by repeated episodes of inflammation of the middle ear in conjunction with middle ear fluid, and often with an inflamed or bulging eardrum. Defective clearance by the Eustachian tube results in mucus build-up and is characteristic of otitis media with effusion (OME). Streptococcus pneumoniae, Haemophilus influenzae, Moraxella catarrhalis, respiratory syncytial virus, and rhinovirus are the most common contributors to otitis media pathogenesis. In New Zealand, OME has been implicated with conductive hearing loss in childhood and has been shown to significantly impact on speech and language development. New Zealand Māori and Polynesian children have displayed significantly higher hearing test failure rates than European-Caucasian children.

The collectins, Surfactant Protein (SP)-A and -D are encoded by three genes (SP-A1, SP-A2, and SP-D) and are host defense proteins present in the middle ear and Eustachian tube. Single nucleotide polymorphisms (SNPs) in SP-A1 and SP-A2 have been associated with increased or decreased susceptibility to otitis media, meningococcal disease, and range of respiratory diseases. Using allele-specific primers and real-time PCR with SYBR  Green I melting curve analysis, four groups of individuals were genotyped for eleven SP-A1, SP-A2, and SP-D SNPs: European-Caucasian individuals with RAOM/OME; New Zealand Māori/Polynesian individuals with RAOM/OME; individuals with meningococcal disease; and a control group. The computer program, Haploview, was employed to perform χ2 analyses and identify statistically significant associations of alleles/haplotypes with RAOM/OME or meningococcal disease.

In the European-Caucasian population, two SP-A1 alleles, one SP-A2 allele, and four haplotypes (CGAGC, 1A3, 1A9, and 1A10) were found to be associated with increased risk of RAOM/OME (P lt; 0.05). Conversely, haplotypes 6A2 and 1A2 were found to be protective against susceptibility to RAOM/OME (P lt; 0.05). In New Zealand Māori and Polynesian individuals, two SP-A1 alleles, three SP-A2 alleles, one SP-D allele, and four haplotypes (6A8, 6A10, 1A3, and 1A10) were found to be associated with increased risk of RAOM/OME (P lt; 0.05). An additional four haplotypes (6A2, 1A0, 1A2, and TA) were determined to be protective against susceptibility to RAOM/OME (P lt; 0.05). However, protective SPA1/SPA2/SPD haplotype 6A2-1A0-TA was significantly under-represented in the New Zealand Māori and Polynesian population (P lt; 0.05). A single allele and haplotype were associated with increased risk of meningococcal disease (P lt; 0.05).

The findings of this study confirm that specific genetic variants of SP-A and SP-D are associated with either increased or decreased risk of developing RAOM and/or OME. Furthermore, it was demonstrated that New Zealand Māori and Polynesian individuals appear to exhibit more haplotypes susceptible to RAOM/OME. This may provide a partial explanation for the higher RAOM/OME-related failure rates of hearing tests in New Zealand Māori and Polynesian children. However, there are numerous socio-economic and environmental factors that also contribute to otitis media pathogenesis which were not considered in this study. The effects of the SP-A1, SP-A2, and SP-D alleles and haplotypes on the bacterial/viral binding efficiencies of SP-A and SP-D need to be investigated by further research, using a large population, to confirm the association with susceptibility or resistance with RAOM/OME.

year: 2007