title: Structural changes to Pinus radiata wood lignin during kraft pulping and bleaching

authors: More, Nicole

abstract: The aim of this thesis was to improve the quality of the information available concerning the structure of native (within wood) and residual (within pulps) lignins. A better understanding of the structure of lignin will assist the development of improved pulping and bleaching sequences. However, before this can be done, it is necessary to develop approaches to lignin isolation which provide more representative lignin samples without resorting to what are often very tedious extraction procedures. A key requirement for such isolation methods would be to isolate lignins in high yield with a structure as unmodified as possible. This would allow meaningful comparisons to be drawn with respect to structural changes occurring during the pulping and bleaching processes.

An improved method for the isolation of lignin from Pinus radiata wood was developed. The method involves a three day enzymatic hydrolysis of ball milled wood, followed by a second ball milling stage. A combination of extraction and purification steps enables isolated yields of approximately 75% of the lignin present in the wood to be obtained. The key step is the second ball milling treatment, which allows essentially all the lignin in the enzyme digest residue to be extracted. The resulting cellulolytic enzyme lignins (CEL) contain  approximately 5-8% carbohydrates and less than 2% protein.

The CEL lignins, which were soluble in common lignin solvents, were characterised chemically and spectroscopically. They were shown to be remarkably similar to milled wood lignin (MWL) in terms of the total phenolic hydroxyl content, uncondensed β-O-4 ether content, and the distribution of interunit linkages, although there was some indication that the CEL lignins had a higher molecular weight than MWL. This shows that MWL, as far as a soluble lignin is concerned, is a reasonable representation of native lignin. However, the CEL method developed in this study is superior to the MWL method in that much higher yields of lignin can be obtained, thus less effort is required to obtain the same quantities of lignin from wood by the CEL method as compared to the standard MWL method.

Unfortunately, when this CEL method (and modifications of) were applied to Pinus radiata kraft pulps no significant improvement, in terms of yield or protein contamination, were achieved compared to other reported CEL methods. However, as part of this work it was shown that an enzyme hydrolysis treatment to enrich the residual lignin content in kraft and kraft-oxygen pulps had the potential to make the analysis of in situ residual lignin by degradation studies easier. 

In order to study the structure of the residual lignin in pulps bleached with elemental chlorine free sequences residual lignins were isolated by dioxane acidolysis instead. The approach taken in this thesis was to compare residual lignin from pulps bleached to the same kappa number. Such a comparison should remove the variables associated with the different oxidising powers of each reagent and yield a more comparable residual lignin, thus a kraft-oxygen pulp was bleached to approximately kappa number 10 with cyanamide activated hydrogen peroxide (KOQPn), ozone (KOQZE), and chlorine dioxide (KODE). For comparison a hydrogen peroxide bleached pulp (KOQP) was generated using the same peroxide charge as KOQPn; and unextracted ozone and chlorine dioxide bleached pulps (KOQZ and KOD, respectively) were also studied.

The residual lignins from the bleached pulps were very similar in structure and resembled the kraft pulp residual lignin in many aspects except in having slightly elevated levels of oxidised groups. Additionally, many of the structural elements expected to be highly reactive during bleaching (for example phenolic and catechol type structures) were detected in the residual lignins. These results support the view that the removal of lignin during bleaching is controlled to a significant extent by the accessibility of the lignin and penetration of the bleaching reagents rather than just by the nature of the functional groups present in the lignin.

text: Structural changes to Pinus radiata wood lignin during kraft pulping and bleaching The aim of this thesis was to improve the quality of the information available concerning the structure of native (within wood) and residual (within pulps) lignins. A better understanding of the structure of lignin will assist the development of improved pulping and bleaching sequences. However, before this can be done, it is necessary to develop approaches to lignin isolation which provide more representative lignin samples without resorting to what are often very tedious extraction procedures. A key requirement for such isolation methods would be to isolate lignins in high yield with a structure as unmodified as possible. This would allow meaningful comparisons to be drawn with respect to structural changes occurring during the pulping and bleaching processes.

An improved method for the isolation of lignin from Pinus radiata wood was developed. The method involves a three day enzymatic hydrolysis of ball milled wood, followed by a second ball milling stage. A combination of extraction and purification steps enables isolated yields of approximately 75% of the lignin present in the wood to be obtained. The key step is the second ball milling treatment, which allows essentially all the lignin in the enzyme digest residue to be extracted. The resulting cellulolytic enzyme lignins (CEL) contain  approximately 5-8% carbohydrates and less than 2% protein.

The CEL lignins, which were soluble in common lignin solvents, were characterised chemically and spectroscopically. They were shown to be remarkably similar to milled wood lignin (MWL) in terms of the total phenolic hydroxyl content, uncondensed β-O-4 ether content, and the distribution of interunit linkages, although there was some indication that the CEL lignins had a higher molecular weight than MWL. This shows that MWL, as far as a soluble lignin is concerned, is a reasonable representation of native lignin. However, the CEL method developed in this study is superior to the MWL method in that much higher yields of lignin can be obtained, thus less effort is required to obtain the same quantities of lignin from wood by the CEL method as compared to the standard MWL method.

Unfortunately, when this CEL method (and modifications of) were applied to Pinus radiata kraft pulps no significant improvement, in terms of yield or protein contamination, were achieved compared to other reported CEL methods. However, as part of this work it was shown that an enzyme hydrolysis treatment to enrich the residual lignin content in kraft and kraft-oxygen pulps had the potential to make the analysis of in situ residual lignin by degradation studies easier. 

In order to study the structure of the residual lignin in pulps bleached with elemental chlorine free sequences residual lignins were isolated by dioxane acidolysis instead. The approach taken in this thesis was to compare residual lignin from pulps bleached to the same kappa number. Such a comparison should remove the variables associated with the different oxidising powers of each reagent and yield a more comparable residual lignin, thus a kraft-oxygen pulp was bleached to approximately kappa number 10 with cyanamide activated hydrogen peroxide (KOQPn), ozone (KOQZE), and chlorine dioxide (KODE). For comparison a hydrogen peroxide bleached pulp (KOQP) was generated using the same peroxide charge as KOQPn; and unextracted ozone and chlorine dioxide bleached pulps (KOQZ and KOD, respectively) were also studied.

The residual lignins from the bleached pulps were very similar in structure and resembled the kraft pulp residual lignin in many aspects except in having slightly elevated levels of oxidised groups. Additionally, many of the structural elements expected to be highly reactive during bleaching (for example phenolic and catechol type structures) were detected in the residual lignins. These results support the view that the removal of lignin during bleaching is controlled to a significant extent by the accessibility of the lignin and penetration of the bleaching reagents rather than just by the nature of the functional groups present in the lignin.

year: 1999

title: It only took 2 clicks and he’d lost me: Dimensions of inclusion and exclusion in ICT supported tertiary engineering education

authors: Khoo, Elaine G.L.

subjects: ICT

abstract: Current conceptualisations of the digital divide have broadened beyond the notion of ‘haves’ and ‘have nots’ to include a more multifaceted perspective in which individuals and the contexts in which they learn are explicitly considered. This paper reports on a qualitative case study of a compulsory Engineering foundations course at a tertiary institution in New Zealand. The course provides a broad introduction to engineering concepts, with particular emphasis on problem solving, the design process, and use of 3-dimensional computer-aided design (CAD) software. Findings illustrate and illuminate the multidimensional nature of information and communication technology (ICT) inclusion/ exclusion and are described within three themes – technological, conceptual, and aspirational/ professional. Implications are presented for course designers and lecturers interested in providing more inclusive learning environments.

text: It only took 2 clicks and he’d lost me: Dimensions of inclusion and exclusion in ICT supported tertiary engineering education Current conceptualisations of the digital divide have broadened beyond the notion of ‘haves’ and ‘have nots’ to include a more multifaceted perspective in which individuals and the contexts in which they learn are explicitly considered. This paper reports on a qualitative case study of a compulsory Engineering foundations course at a tertiary institution in New Zealand. The course provides a broad introduction to engineering concepts, with particular emphasis on problem solving, the design process, and use of 3-dimensional computer-aided design (CAD) software. Findings illustrate and illuminate the multidimensional nature of information and communication technology (ICT) inclusion/ exclusion and are described within three themes – technological, conceptual, and aspirational/ professional. Implications are presented for course designers and lecturers interested in providing more inclusive learning environments.

year: 2011

title: Effective implementation science processes for Māori and Indigenous health interventions

authors: Harding, Truely Janine

subjects: Implementation science

abstract: Background
This thesis considers the implications implementation science has for Indigenous communities, specifically in reducing health inequities for the Māori community of New Zealand. Implementation science has been discussed among many Western health interventions and this thesis adds to that body of literature while highlighting the impact implementation has for Indigenous communities. 
Implementation science is a growing body of literature that can identify the most effective processes for health organisations and governments to best engage with Indigenous communities facing health inequities. An important aspect of that is ensuring the Indigenous voices and perspectives are represented just as much as the academics and scholars in those fields. The purpose of this thesis is to highlight the facilitators and barriers of implementing health interventions with Māori communities in Aotearoa New Zealand. This thesis aims to contribute to the conversation about reducing health inequities Māori communities’ face in New Zealand by enhancing implementation effectiveness. Therefore, it is an effort to illuminate the importance of the inclusion of community voice and perspectives when implementing health interventions with Indigenous communities. The thesis is with publications and includes four distinct studies.
Methodology & Methods
The key methodologies used in this study were Kaupapa Māori methodology and the He Pikinga Waiora (HPW) Implementation framework. Kaupapa Māori has been used as both a form of resistance and a methodological strategy, where research is created, developed, and carried within a Māori worldview with the aim to have positive outcomes that are beneficial for Māori. The HPW framework provided a holistic approach to guide this research through its key elements of: culture-centered approach, community engagement, systems thinking, and integrated knowledge translation. It is a forward-thinking approach as it is flexible in its design, which allows the framework to be tailored to a variety of implementation situations. The framework is centred in Kaupapa Māori methodology. Each principle of Kaupapa Māori and each element of HPW provide a holistic approach to implementation science.
Given this thesis includes four publications, a range of methods were employed for data collection. The first study was a systematic review of studies that was completed using preferred reporting items for systematic reviews and meta-analysis (PRISMA) guidelines. This involved a stringent search strategy and inclusion criteria where studies included went through data extraction and methodological appraisal followed by an analysis through a qualitative synthesis of findings. Studies two and three employed semi-structured interviews that were analysed through thematic analysis. Study two included 19 participants who were either health professionals or researchers, and study three included 17 participants who were health professionals. The fourth study included an online cross-sectional survey of 200 health professionals and used statistical modelling to identify factors important for implementation effectiveness.
Results 
The first study included a systematic literature review to examine the implementation of a non-communicable disease health intervention for Indigenous communities using HPW as an evaluation tool. Twenty-one studies were included. Two thirds of these studies demonstrated high levels of community engagement and community voice/ agency, while 40% had individual-level outcomes with some systems thinking, and 33% included individual-level outcomes and limited systems thinking. Finally, almost 40% of studies included high levels of end-user engagement reflective of integrated knowledge translation, but nearly half had limited end-user engagement with the remaining neither high or low. This study found that the HPW Implementation Framework is a comprehensive model for understanding implementation effectiveness in Indigenous communities and highlighted the high levels of community engagement and community voice. It also brings to light that the long-term sustainability and translation of evidence to practice may be inhibited because of lower levels of systems thinking and integrated knowledge translation. 
The second study researched the perceptions health professionals have on co-designing health-promotion interventions with Indigenous communities in New Zealand. Co-designing health-promotion interventions with Indigenous communities presents many benefits and challenges. This study identified that the facilitators for co-designing health-promotion interventions with Māori communities were collaboration and community voice. Furthermore, the two key barriers identified were mismanaged expectations between the researcher and community and the research constraints placed by funding agencies. The findings support the development of more effective co-design health-promotion interventions within Māori communities which may address health inequities. 
The third study endeavoured to identify the facilitators and barriers in disseminating and adopting a health intervention developed by a community-academic partnership. This study explored general perceptions of the implementation process and also included a case study of an innovative intervention. The facilitators included community engagement, programme structure, programme adaptability and creators’ experience. The barriers consisted of funding access, funding constraints and organisational constraints. This study also highlights the importance of community engagement and adaptability suggesting a need for translation as well as diffusion. Additionally, this study identified nuanced aspects of funding and resources for organisations that constrain organisations in employing health interventions designed by others.
The final study identified factors that New Zealand health professionals rate as important for implementation effectiveness for health interventions with Māori communities. This study provided a unique perspective of health professionals on implementation effectiveness when working with Māori/Indigenous communities. Paired sample t-tests revealed four levels of importance for implementation effectiveness with organisational teamwork and community autonomy as most important. Only 24% of participants had prior experience with a previous health intervention with Māori communities. The two key overall factors that were associated with participants’ rating of implementation effectiveness in these previous interventions were process and community. This study identified the key areas of implementation effectiveness as community engagement and participatory process. Furthermore, the final study contributes to the body of literature that challenges traditional top-down approaches of implementation.
Conclusion
This research aimed to identify the facilitators and barriers to disseminating and implementing health interventions with Māori communities in New Zealand. A synthesis of the four studies provided four key themes for this thesis. This thesis reinforces the position that Indigenous and Māori implementation science should be focused on the process and community engagement. In doing so, community engagement ensures a cultural-centred approach that prioritises Indigenous knowledge and autonomy in the process of implementation. Furthermore, the barriers identified in this thesis recognise the challenges that remain in limited funding for translating research into implementation practice and managing expectations amongst the implementation team. This thesis has implications for New Zealand district health boards and health organisations who are wanting to increase the effectiveness of the health interventions they are implementing with Māori communities, particularly when trying to address health inequities. Overall, this study is an attempt to bridge the gap between translating research and the processes of putting it into practice.

text: Effective implementation science processes for Māori and Indigenous health interventions Background
This thesis considers the implications implementation science has for Indigenous communities, specifically in reducing health inequities for the Māori community of New Zealand. Implementation science has been discussed among many Western health interventions and this thesis adds to that body of literature while highlighting the impact implementation has for Indigenous communities. 
Implementation science is a growing body of literature that can identify the most effective processes for health organisations and governments to best engage with Indigenous communities facing health inequities. An important aspect of that is ensuring the Indigenous voices and perspectives are represented just as much as the academics and scholars in those fields. The purpose of this thesis is to highlight the facilitators and barriers of implementing health interventions with Māori communities in Aotearoa New Zealand. This thesis aims to contribute to the conversation about reducing health inequities Māori communities’ face in New Zealand by enhancing implementation effectiveness. Therefore, it is an effort to illuminate the importance of the inclusion of community voice and perspectives when implementing health interventions with Indigenous communities. The thesis is with publications and includes four distinct studies.
Methodology & Methods
The key methodologies used in this study were Kaupapa Māori methodology and the He Pikinga Waiora (HPW) Implementation framework. Kaupapa Māori has been used as both a form of resistance and a methodological strategy, where research is created, developed, and carried within a Māori worldview with the aim to have positive outcomes that are beneficial for Māori. The HPW framework provided a holistic approach to guide this research through its key elements of: culture-centered approach, community engagement, systems thinking, and integrated knowledge translation. It is a forward-thinking approach as it is flexible in its design, which allows the framework to be tailored to a variety of implementation situations. The framework is centred in Kaupapa Māori methodology. Each principle of Kaupapa Māori and each element of HPW provide a holistic approach to implementation science.
Given this thesis includes four publications, a range of methods were employed for data collection. The first study was a systematic review of studies that was completed using preferred reporting items for systematic reviews and meta-analysis (PRISMA) guidelines. This involved a stringent search strategy and inclusion criteria where studies included went through data extraction and methodological appraisal followed by an analysis through a qualitative synthesis of findings. Studies two and three employed semi-structured interviews that were analysed through thematic analysis. Study two included 19 participants who were either health professionals or researchers, and study three included 17 participants who were health professionals. The fourth study included an online cross-sectional survey of 200 health professionals and used statistical modelling to identify factors important for implementation effectiveness.
Results 
The first study included a systematic literature review to examine the implementation of a non-communicable disease health intervention for Indigenous communities using HPW as an evaluation tool. Twenty-one studies were included. Two thirds of these studies demonstrated high levels of community engagement and community voice/ agency, while 40% had individual-level outcomes with some systems thinking, and 33% included individual-level outcomes and limited systems thinking. Finally, almost 40% of studies included high levels of end-user engagement reflective of integrated knowledge translation, but nearly half had limited end-user engagement with the remaining neither high or low. This study found that the HPW Implementation Framework is a comprehensive model for understanding implementation effectiveness in Indigenous communities and highlighted the high levels of community engagement and community voice. It also brings to light that the long-term sustainability and translation of evidence to practice may be inhibited because of lower levels of systems thinking and integrated knowledge translation. 
The second study researched the perceptions health professionals have on co-designing health-promotion interventions with Indigenous communities in New Zealand. Co-designing health-promotion interventions with Indigenous communities presents many benefits and challenges. This study identified that the facilitators for co-designing health-promotion interventions with Māori communities were collaboration and community voice. Furthermore, the two key barriers identified were mismanaged expectations between the researcher and community and the research constraints placed by funding agencies. The findings support the development of more effective co-design health-promotion interventions within Māori communities which may address health inequities. 
The third study endeavoured to identify the facilitators and barriers in disseminating and adopting a health intervention developed by a community-academic partnership. This study explored general perceptions of the implementation process and also included a case study of an innovative intervention. The facilitators included community engagement, programme structure, programme adaptability and creators’ experience. The barriers consisted of funding access, funding constraints and organisational constraints. This study also highlights the importance of community engagement and adaptability suggesting a need for translation as well as diffusion. Additionally, this study identified nuanced aspects of funding and resources for organisations that constrain organisations in employing health interventions designed by others.
The final study identified factors that New Zealand health professionals rate as important for implementation effectiveness for health interventions with Māori communities. This study provided a unique perspective of health professionals on implementation effectiveness when working with Māori/Indigenous communities. Paired sample t-tests revealed four levels of importance for implementation effectiveness with organisational teamwork and community autonomy as most important. Only 24% of participants had prior experience with a previous health intervention with Māori communities. The two key overall factors that were associated with participants’ rating of implementation effectiveness in these previous interventions were process and community. This study identified the key areas of implementation effectiveness as community engagement and participatory process. Furthermore, the final study contributes to the body of literature that challenges traditional top-down approaches of implementation.
Conclusion
This research aimed to identify the facilitators and barriers to disseminating and implementing health interventions with Māori communities in New Zealand. A synthesis of the four studies provided four key themes for this thesis. This thesis reinforces the position that Indigenous and Māori implementation science should be focused on the process and community engagement. In doing so, community engagement ensures a cultural-centred approach that prioritises Indigenous knowledge and autonomy in the process of implementation. Furthermore, the barriers identified in this thesis recognise the challenges that remain in limited funding for translating research into implementation practice and managing expectations amongst the implementation team. This thesis has implications for New Zealand district health boards and health organisations who are wanting to increase the effectiveness of the health interventions they are implementing with Māori communities, particularly when trying to address health inequities. Overall, this study is an attempt to bridge the gap between translating research and the processes of putting it into practice.

year: 2021