title: Quantifying cooperative intermolecular interactions for improved carbon dioxide capture materials

authors: Lane, Joseph R.

subjects: adsorption

abstract: We have optimized the geometry and calculated interaction energies for over 100 different complexes of CO₂ with various combinations of electron accepting (Lewis acid) and electron donating (Lewis base) molecules. We have used the recently developed explicitly correlated coupled cluster singles doubles and perturbative triples [CCSD(T)-F12] methods and the associated VXZ-F12 (where X = D,T,Q) basis sets. We observe only modest changes in the geometric parameters of CO₂ upon complexation, which suggests that the geometry of CO₂  adsorbed in a nanoporous material should be similar to that of CO₂  in gas phase. When CO₂  forms a complex with two Lewis acids via the two electron rich terminal oxygen atoms, the interaction energy is less than twice what would be expected for the same complex involving a single Lewis acid. We consider a series of complexes that exhibit simultaneous CO₂-Lewis acid and CO₂-Lewis base intermolecular interactions, with total interaction energies spanning 14.1–105.9 kJ mol⁻¹. For these cooperative complexes, we find that the total interaction energy is greater than the sum of the interaction energies of the constituent complexes. Furthermore, the intermolecular distances of the cooperative complexes are contracted as compared to the constituent complexes. We suggest that metal-organic-framework or similar nanoporous materials could be designed with adsorption sites specifically tailored for CO₂ to allow cooperative intermolecular interactions, facilitating enhanced CO₂ adsorption.

text: Quantifying cooperative intermolecular interactions for improved carbon dioxide capture materials We have optimized the geometry and calculated interaction energies for over 100 different complexes of CO₂ with various combinations of electron accepting (Lewis acid) and electron donating (Lewis base) molecules. We have used the recently developed explicitly correlated coupled cluster singles doubles and perturbative triples [CCSD(T)-F12] methods and the associated VXZ-F12 (where X = D,T,Q) basis sets. We observe only modest changes in the geometric parameters of CO₂ upon complexation, which suggests that the geometry of CO₂  adsorbed in a nanoporous material should be similar to that of CO₂  in gas phase. When CO₂  forms a complex with two Lewis acids via the two electron rich terminal oxygen atoms, the interaction energy is less than twice what would be expected for the same complex involving a single Lewis acid. We consider a series of complexes that exhibit simultaneous CO₂-Lewis acid and CO₂-Lewis base intermolecular interactions, with total interaction energies spanning 14.1–105.9 kJ mol⁻¹. For these cooperative complexes, we find that the total interaction energy is greater than the sum of the interaction energies of the constituent complexes. Furthermore, the intermolecular distances of the cooperative complexes are contracted as compared to the constituent complexes. We suggest that metal-organic-framework or similar nanoporous materials could be designed with adsorption sites specifically tailored for CO₂ to allow cooperative intermolecular interactions, facilitating enhanced CO₂ adsorption.

year: 2011

title: Reproductive investment and strategies of Gobiomorphus cotidianus

authors: Pepper, Kate Louise

subjects: Gobiomorphus cotidianus

abstract: The New Zealand common bully (Gobiomorphus cotidianus) is a member of the family Eleotridae which comprises around 35 genera and some 150 species worldwide. G. cotidianus are abundant throughout New Zealand and thrive in streams, large rivers and lakes, with broad tolerances for temperature, pH, flow and lake trophic status. It is known that male bullies clean and guard a nest site and attract one or possibly more females to spawn within the nest which is then guarded until the eggs hatch. However, due to intraspecific competition, some males miss out. Male alternative reproductive tactics (MARTs) are commonly used to achieve a successful reproductive outcome when the usual reproductive strategy becomes energetically inefficient for the individual. MART’s are common within the closely related family Gobiidae but have not yet been observed in the Eleotridae.
Differential investments in gonadal mass versus parental care are known in many animals from fish to humans. Greater parental investment typically correlates with smaller gonad size. I investigated the relative investment made by male common bully in gonads versus seminal vesicles on the assumption that if non-guarding (parasitic) males occur, they would invest significantly less effort in seminal vesicles (SVs) compared with “bourgeois” (nest guarding) males. I examined these traits monthly to determine possible seasonal changes in reproductive strategies. We found that male investment in SVs does vary significantly between individuals and that the greatest investment in this structure in males coincides with the peak summer breeding season. A small proportion of males (usually larger individuals) invest heavily in SVs but it is currently unknown whether these, and only these, defend nest sites and whether the remainder rely on MART strategies for reproductive success. Seminal vesicle size was positively correlated with fish size whereas testis size declined with increasing size of males.
Sampling of common bully from Lake Karapiro began in December 2013 and finished in January 2015 providing fourteen months of data to
predominantly investigate male reproductive investment using calculations of gonadosomatic index (GSI) and seminal vesicle somatic index (SVSI).
I found that although investment in both gonads and seminal vesicles increase in preparation for the breeding season, the increase in SVSI is considerably greater than the comparatively slight increase in GSI. I also examined female GSI and found that it followed similar trends to that of the SVSI with sharp increases occurring throughout late winter and spring.
Calculations of somatic condition indices were made for both males and females throughout the 14 month sampling period. This identified similar condition trends for both sexes with peaks throughout summer suggesting a slight increase in somatic condition post-breeding season. Male condition was slightly higher and more varied during this summer period.
A behavioural experiment was carried out to investigate male nest preference and guarding behaviour. Obvious nest guarding was displayed in 14 of the 40 nest arenas and 11 of the guarded nests were large pots compared with only 3 guarded small pots. GSI and SVSI data from the males within the experiment suggest an increased investment in seminal vesicles by males displaying nest guarding behaviour. However, the sample size for both of these elements was too small to provide statistically significant results.

text: Reproductive investment and strategies of Gobiomorphus cotidianus The New Zealand common bully (Gobiomorphus cotidianus) is a member of the family Eleotridae which comprises around 35 genera and some 150 species worldwide. G. cotidianus are abundant throughout New Zealand and thrive in streams, large rivers and lakes, with broad tolerances for temperature, pH, flow and lake trophic status. It is known that male bullies clean and guard a nest site and attract one or possibly more females to spawn within the nest which is then guarded until the eggs hatch. However, due to intraspecific competition, some males miss out. Male alternative reproductive tactics (MARTs) are commonly used to achieve a successful reproductive outcome when the usual reproductive strategy becomes energetically inefficient for the individual. MART’s are common within the closely related family Gobiidae but have not yet been observed in the Eleotridae.
Differential investments in gonadal mass versus parental care are known in many animals from fish to humans. Greater parental investment typically correlates with smaller gonad size. I investigated the relative investment made by male common bully in gonads versus seminal vesicles on the assumption that if non-guarding (parasitic) males occur, they would invest significantly less effort in seminal vesicles (SVs) compared with “bourgeois” (nest guarding) males. I examined these traits monthly to determine possible seasonal changes in reproductive strategies. We found that male investment in SVs does vary significantly between individuals and that the greatest investment in this structure in males coincides with the peak summer breeding season. A small proportion of males (usually larger individuals) invest heavily in SVs but it is currently unknown whether these, and only these, defend nest sites and whether the remainder rely on MART strategies for reproductive success. Seminal vesicle size was positively correlated with fish size whereas testis size declined with increasing size of males.
Sampling of common bully from Lake Karapiro began in December 2013 and finished in January 2015 providing fourteen months of data to
predominantly investigate male reproductive investment using calculations of gonadosomatic index (GSI) and seminal vesicle somatic index (SVSI).
I found that although investment in both gonads and seminal vesicles increase in preparation for the breeding season, the increase in SVSI is considerably greater than the comparatively slight increase in GSI. I also examined female GSI and found that it followed similar trends to that of the SVSI with sharp increases occurring throughout late winter and spring.
Calculations of somatic condition indices were made for both males and females throughout the 14 month sampling period. This identified similar condition trends for both sexes with peaks throughout summer suggesting a slight increase in somatic condition post-breeding season. Male condition was slightly higher and more varied during this summer period.
A behavioural experiment was carried out to investigate male nest preference and guarding behaviour. Obvious nest guarding was displayed in 14 of the 40 nest arenas and 11 of the guarded nests were large pots compared with only 3 guarded small pots. GSI and SVSI data from the males within the experiment suggest an increased investment in seminal vesicles by males displaying nest guarding behaviour. However, the sample size for both of these elements was too small to provide statistically significant results.

year: 2015

title: “This is not a riot, it is a protest”: A discourse analysis of prison violence in New Zealand news media

authors: Membery, Liam

subjects: Prison Violence

abstract: This thesis examines the discourses of prison violence in the New Zealand news media. Prison violence is a pressing social issue that harms those involved and has permeating consequences for the institution. Prison riots, specifically, involve serious instances of disorder and violence that incur physical, psychological, social and economic harm. Despite prisons being private institutions, prison riots are public events that amass large social responses through news media coverage. The public often use news media to co-construct their perceptions of social phenomena, and policymakers use both public opinion and the news media to guide their decisions when shaping policy. Subsequently, the ways in which the news media discursively construct prison riots will have direct consequences for public attitudes and policy relating to prison violence, a phenomenon that exists outside of the public eye. However, there is currently no research that has examined discourses of prison violence and, further, what the consequences of these discourses may be. Therefore, using a Foucauldian approach to discourse analysis, this study examined the discourses in the news media representations of the large-scale prison violence at the Spring Hill Corrections Facility (2013) and Waikeria Prison (2020-2021). The results uncovered three discourses: the riot discourse, the gang discourse, and the protest discourse. The riot discourse was identified as dominant and constructed prison violence as an individualised issue perpetrated by inherently violent prisoners. The gang discourse worked in conjunction with the riot discourse, constructing prison violence as an individualised issue perpetrated by gang members. The protest discourse was identified as a counter-discourse and constructed the unrest at both facilities as protests against living conditions and inhumane treatment. Each discourse has consequences for public attitudes and in turn, penal policy and practice.

text: “This is not a riot, it is a protest”: A discourse analysis of prison violence in New Zealand news media This thesis examines the discourses of prison violence in the New Zealand news media. Prison violence is a pressing social issue that harms those involved and has permeating consequences for the institution. Prison riots, specifically, involve serious instances of disorder and violence that incur physical, psychological, social and economic harm. Despite prisons being private institutions, prison riots are public events that amass large social responses through news media coverage. The public often use news media to co-construct their perceptions of social phenomena, and policymakers use both public opinion and the news media to guide their decisions when shaping policy. Subsequently, the ways in which the news media discursively construct prison riots will have direct consequences for public attitudes and policy relating to prison violence, a phenomenon that exists outside of the public eye. However, there is currently no research that has examined discourses of prison violence and, further, what the consequences of these discourses may be. Therefore, using a Foucauldian approach to discourse analysis, this study examined the discourses in the news media representations of the large-scale prison violence at the Spring Hill Corrections Facility (2013) and Waikeria Prison (2020-2021). The results uncovered three discourses: the riot discourse, the gang discourse, and the protest discourse. The riot discourse was identified as dominant and constructed prison violence as an individualised issue perpetrated by inherently violent prisoners. The gang discourse worked in conjunction with the riot discourse, constructing prison violence as an individualised issue perpetrated by gang members. The protest discourse was identified as a counter-discourse and constructed the unrest at both facilities as protests against living conditions and inhumane treatment. Each discourse has consequences for public attitudes and in turn, penal policy and practice.

year: 2022