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Evaluation of Southwark Council’s Integrated Healthy Lifestyle Service for exercise referral
Get PDFPurpose
In Southwark (London), 68.9% of residents are physically inactive. Southwark Council’s Integrated Healthy Lifestyle Service (IHLS) offers a single point of access for residents to health services (e.g exercise referral). Referrals are managed by the Healthy Lifestyle Hub (HLH), a telephone-based triage service aiming to enhance referral efficiency and follow-up, supporting behaviour change. One of the local services the HLH refers onto is Exercise on Referral (EoR). The aim of this evaluation is to understand how Southwark Council’s HLH influences referral to and engagement in EoR.
Methods
We conducted a mixed-methods evaluation, informed by public and stakeholder consultation. Work package (WP)1 involved secondary analysis of referral, attendance, and health data from HLH and EoR; WP2 involved an online survey of HLH users, exploring reasons for non-initiation of referrals (descriptive/inferential statistics were performed as data allowed for WP1/2); WP3 involved semi-structured interviews and focus groups with service users, staff, and non-initiators to explore service experiences (codebook thematic analysis).
Results
The data shared from WP1 highlighted inconsistencies in data linkage and a high degree of missing follow-up data, making it challenging to determine any objective changes in behaviour or health. Survey data (WP2) was available for 163 people, with seven individuals providing information on why they were referred to EoR but did not intend on initiating the service (e.g. inappropriate day/time). WP3 findings found that service users experienced benefits including weight loss and improved mental health. However, they felt the duration was insufficient for behaviour change. Service users stated a lack of affordable post-programme options. Key service recommendations included improving data collection and linkage, extending post-programme support, improving communication with service users, and clarifying referral.
Conclusions
Implementation of these recommendations will improve programme accessibility & engagement, behaviour change and health outcomes, and importantly the ability to accurately evidence change
Socio-ecological dynamics of woodlands, forests and fire in southeast Angola
Get PDFAngola, a country that endured a 13-year war for independence followed by a 27-year civil war, remains one of the most understudied countries in Africa. This study develops in southeast Angola, in the watershed of the Okavango Delta and the Zambezi River, an area that has been deemed one of the largest areas of undisturbed miombo in Africa. The highlands of southeast Angola, one of the country’s most isolated and still heavily land-mined regions, contains well-preserved vegetation with scattered human populations that depend on natural resources. Because of its ecological richness and low population density, the region has been targeted for conservation interventions but the potential impact on livelihoods has not been investigated. Using a socio-ecological systems framework, this research investigates how human practices, knowledge systems, and historical events interact with ecological patterns and processes such as vegetation types, structure, floristics, and fire regimes, in a setting where human-environment relationships are primarily governed by customary practices rather than state governance. To achieve this, I begin this thesis by presenting an overview of the wooded ecosystems-livelihoods context, including savanna and miombo ecology, conservation approaches and ethical considerations during this study (Chapter 1). I then present three chapters with the main questions and results from my research. For these, I executed three main tasks, each linked to one chapter. First, I mapped vegetation types according to local classifications (Chapter 2), then I typified the vegetation bridging local classifications and Western scientific floristic approaches (Chapter 3) and lastly, I studied the effects of the war on fire dynamics in the area (Chapter 4). I end this thesis with the contributions that emerge overall across the chapters.
In Chapter 2, I address the challenges of solely using remote sensing for classifying vegetation, highlighting the potential oversimplification of complex landscapes when following this approach. This chapter incorporates participatory mapping in five rural villages to recognise local knowledge to classify woody ecosystems. My findings suggest that incorporating place-based knowledge can offer a deeper understanding of the landscape. The results reveal differences between local classifications and remote sensing ones, emphasizing the need for inclusive conservation approaches that align with local ecological knowledge. I argue that landscapes are complex socio-ecological systems and that their understanding can benefit from ground-based approaches that consider not only the physical features but also the social and cultural values of the land.
Chapter 3 focuses on woodland ecology, and challenges existing classifications of southeast Angola as a homogeneous miombo woodland. Through quantitative ecological surveys (establishment of 26 plots) and learnings from local knowledge, the study identifies five structurally and floristically distinct woodland formations, including a unique dry forest dominated by Cryptosepalum exfoliatum pseudotaxus. The latter differs greatly from miombo woodlands, as circumscribed in the literature. These findings call for a re-evaluation of current maps of Angolan vegetation, prompting the need for updated maps of African evergreen dry forests that are currently identified only in western Zambia. I argue that an accurate identification of the diverse vegetation formations in Angola is fundamental for their proper management, given that fire is widely used in miombo ecosystems but is likely not appropriate in evergreen forests.
Chapter 4 explores the impact of the Angolan civil war on fire and forest dynamics in southeast Angola, since local peoples indicate a decrease in fire events due to war, evident in satellite-derived time series. This chapter employs remote sensing, historical data, and interviews to reconstruct war-time (1985-2002) and post-war (2003-2018) fire dynamics, revealing the role of social dynamics in shaping fire regimes. The study challenges the idea that ecological and climatic factors are the main determinants of fire regimes, and highlights the intricate relationship between fire, war, and socio-ecological systems, showing that war can restrict the use of fire and change the fire dynamics of an entire ecosystem. It also advocates for interdisciplinary approaches to understand the complex socio-ecological dynamics of war.
Overall, this thesis highlights the importance of recognising local knowledge, challenging existing landscape classifications, and considering historical and socio-cultural contexts in understanding and managing vegetation and associated ecosystems in the highlands of southeast Angola. The findings emphasize the need for inclusive and multi-disciplinary approaches to vegetation classification, conservation and landscape management. Lastly, this study calls for ethical and reflective research practices that centre local voices and challenge dominant conservation narratives that often overlook lived experiences and place-based knowledge
Genetic selection of cattle for reduced bovine tuberculosis transmission
Get PDFBovine tuberculosis (bTB) is a major cattle disease with significant economic
impact on production in multiple countries. In the United Kingdom, bTB remains
a critical challenge, especially in high incidence areas despite control
programmes being in place. These programmes consist of regular skin testing
and culling of test positive cattle, movement restrictions, wildlife control, and
other biosecurity measures. Nevertheless, successful eradication of the
disease has yet to be achieved. Previous studies have suggested that breeding
cattle for enhanced bTB resistance can complement existing eradication
efforts. However, breeding for increased resistance alone may not be sufficient
to help achieve the national target to eradicate bTB in the next decade.
Therefore, genetic selection for low bTB infectivity, in addition to high bTB
resistance, has been proposed as a possible solution to accelerate this
process. However, the genetics of bTB infectivity need to be investigated in
order to demonstrate the feasibility of including infectivity into national breeding
programmes.
The overall aim of this thesis is to investigate statistical evidence of genetic
variation underlying bTB infectivity of cattle in Great Britain (GB) and assess
the feasibility and implications of considering infectivity as an additional
breeding goal.
The primary objective of this thesis is to define a bTB infectivity phenotype,
which is crucial for understanding how infection spreads among cattle.
Additionally, the thesis aims to examine various factors affecting bTB infectivity,
including environmental, management, and host genetic influences that might
contribute to variation in disease transmission. Another key objective is to
estimate genetic parameters related to bTB infectivity. Using these estimates,
the thesis derives and assesses estimated breeding values (EBVs) for bTB
infectivity. Finally, the thesis investigates the effect of selecting for reduced bTB
infectivity.
Chapter 1 presents a literature review on bTB, its transmission and
pathogenesis, diagnosis and current control strategies. Furthermore, the thesis
aim, objectives and outline are presented.
Chapter 2 explores bTB data from Great Britain on both phenotypic and genetic
levels and introduces the concept of the "index case approach" to define novel
bTB infectivity phenotypes. Index case here refers to the first single positively
tested animal in a herd that signals the start of a bTB breakdown. bTB infectivity
is then defined as the number of secondary cases (NSC) attributed to the index
case. Linear mixed models and generalized linear mixed models (GLMMs) are
used to explore the effect of multiple factors and derive estimates of the genetic
variance of bTB infectivity. The results produce the first estimates of genetic
variation and heritability in the bTB infectivity. However, more advanced
statistical models need to be explored to improve model fit and provide deeper
insights into bTB infectivity and transmission dynamics.
In Chapter 3, Markov Chain Monte Carlo (MCMC) techniques are applied to fit
GLMMs that can account for potential overdispersion and zero inflation issues
in the data. Four different GLMMs (specifically Poisson, Zero-Inflated Poisson
(ZIP), Hurdle Poisson, and Geometric models) are employed to detect and
estimate genetic variation in infectivity. Factors affecting bTB infectivity from
Chapter 2 are included in these models. The results show that genetic variation
in bTB infectivity exists and is estimable. Furthermore, sire estimated breeding
values (EBVs) are derived for bTB infectivity. Based on the estimated posterior
mean genetic variances obtained, sire selection leading to a reduction in
infectivity by one genetic standard deviation would result in a 32 - 44%
decrease in the expected NSC per index case.
Chapter 4 focuses on the implications of incorporating bTB infectivity into
breeding programmes. The potential reduction in the number of secondary
cases is calculated from hypothetical genetic gains achieved from selection
based on sire EBVs from Chapter 3. Results show that, in order to achieve 10%
reduction in number of secondary cases using the infectivity phenotype
introduced in this thesis, strong genetic progress would be required. This may
involve high selection intensity, accurate EBV evaluations, and consistent use
of genetically superior animals for breeding. Furthermore, correlations of sire
EBVs for bTB infectivity with bTB resistance and other economically important
traits are examined, using the infectivity EBVs estimated in Chapter 3 and
existing EBV estimates for the other traits. Results show no antagonistic
correlations with the other traits, suggesting no potential adverse effects from
selecting for reduced infectivity.
In conclusion, this thesis proposes and examines a proxy infectivity phenotype
for bTB. Exploration of the GB data reveals that there is underlying genetic
variation in bTB infectivity, suggesting that the trait can be improved with
genetic selection. Our results also suggest that implementing selection to
decrease bTB infectivity is feasible and effective, and does not have any
expected negative effect on other traits that are considered in the current
breeding programme. Further studies are recommended to refine the infectivity
phenotype for more accurate genetic evaluation and effective genetic selection
for low bTB transmission
Decoding generativity: unraveling the enigma of heritable patterns and psychometric phenomena in diverse contexts
Get PDFErikson's concept of generativity—the concern for nurturing future generations, contributing positively to society, and leaving a legacy—forms the basis of human civilisation and evolution. As a critical psychological trait, generativity has profound implications for mental health and well-being. This thesis explores the multifaceted nature of generativity, examining its structure, theoretical integrity, heritability, cultural manifestations, and validity through a series of comprehensive studies conducted in both Western and Eastern contexts.
The thesis begins with a comprehensive literature review on the concept of generativity. Then, the first theme investigates the structure and heritability of the Loyola Generativity Scale (LGS) within a Western context. Through structural modelling, three correlated factors were identified: 1) establishing and aiding the next generation, 2) maintaining the world, and 3) symbolic immortality through a positive legacy. To ensure the reliability and validity of these findings, this structure was then replicated in a UK sample. Following this replication, genetic and environmental influences on these factors were examined using twin modelling, revealing significant heritability for all three factors and a general factor, with substantial unique environmental effects.
Building on the established three-factor structure for generativity, Chapter 3 aims to replicate this structure of the Loyola Generativity Scale (LGS) in an Eastern cultural context and investigates the relationship between generativity and mental health outcomes, including stress, depression, anxiety, and life satisfaction among Chinese university students. The Chinese sample demonstrated a two-factor structure along with a general factor (Study 1), diverging from the three-factor model observed in Western contexts. This divergence is attributed to Chinese culture's emphasis on integrated, harmonised, and communal values. This prompted further investigation into the nature of these factors, testing their construct validity and predictive validity. Study 2 confirmed the replicability and test-retest reliability of the two-factor model. Additionally, the distinctiveness of positively and negatively phrased items and the general factor from social desirability within the Chinese cultural context was validated, confirming their discriminant validity. Study 3 examined the relationship between generativity and negative emotional states, alongside life satisfaction. The Generativity Engagement factor (positively phrased items) was positively associated with life satisfaction, indicating that active generative engagement may enhance well-being. The Social Disconnection factor (negatively phrased items) strongly predicted negative emotional states, including anxiety, stress, and depression a year later, suggesting that feelings of social exclusion and being unneeded can severely impact mental health.
The final theme, addressed in Chapter 4, extends the findings of Chapter 3 by examining self-esteem—a critical component of overall psychological well-being that reflects an individual's subjective evaluation of their own worth, in a UK sample (the same data as in Chapter 2, Study 2). By exploring self-esteem in the context of generativity, particularly through nuanced generativity dimensions, we gain deeper insights into how generativity shapes self- perception. Initially, confirmatory analysis was conducted on the structure of generativity, revealing that both the bifactor model from Chapter 3 and the correlated three-factor model from Chapter 2 fit the data well. Each model demonstrated strengths: the bifactor model provided a generalised yet comprehensive overview, cross-cultural applicability, and dimensional clarity, while the three-factor model offered a detailed breakdown of nuanced dimensions, aligning with the conceptual richness of generativity. A cross-cultural comparison revealed specific cultural differences in the expression and perception of generativity. Linear regression was used to examine the relationship between self-esteem and the dimensions of generativity using both models. Significant relationships were found between self-esteem and the "contributing to the next generation" and "maintaining society" factors in the correlated three-factor model, as well as with the Social Disconnection factor and the general factor in the bifactor model. These findings can be interpreted through Sociometer Theory and Self-Determination Theory. Generativity provides individuals with a sense of competence and relatedness, which fulfils intrinsic needs and enhances self-worth, aligning with Self-Determination Theory, while perceived social exclusion negatively impacts self-esteem. Contrary to Terror Management Theory, the anticipated positive effect of legacy-building on self-esteem was not observed.
Overall, this thesis comprehensively examines the phenotypic structure and genetic architecture of generativity, along with its significant role in the nuanced interplay with mental health, well-being, and self-esteem. This research also underscores the importance of considering cultural variations in the expression of generativity.
Throughout this thesis, the first-person plural pronoun "we" is used to reflect the research team, including the author, supervisors, and collaborators
Mechanisms of language processing in monolinguals and bilinguals: prediction and production
Get PDFFor both monolinguals and bilinguals, language comprehension is not merely a bottom-up passive process of waiting for words, but also involves actively generating top-down predictions about what is likely to occur. For example, if a speaker says It is raining outside, so you should take an …, the listener may predict that the next word is likely umbrella. For bilinguals, this prediction process is made more complicated because they can conduct language processing in two languages. That is, they can activate both their first language (L1) and second language (L2) in parallel during comprehension and production. However, it remains unclear whether this cross-language activation, especially during bilingual production, occurs in one-language contexts (where only the target language is used). In addition, while substantial evidence shows that L1 speakers can predict many aspects of upcoming words and that L2 speakers do so less effectively, the cognitive mechanisms underlying prediction—such as whether it requires cognitive resources or whether bilinguals co-activate L1 during L2 prediction—remain poorly understood. Therefore, this thesis investigated the mechanisms of language processing in monolinguals and bilinguals, focusing on prediction and production. It first examined whether prediction is constrained by cognitive resources by having L1 Mandarin Chinese speakers listen to Mandarin Chinese sentences with varying speech rates and levels of contextual predictability (highly predictive, moderately predictive, or unpredictive of a final word). We measured how quickly participants judged whether a given letter was contained in that final word (Experiment 1), named a picture corresponding to that final word (Experiment 2), and named that final word (Experiment 3). We found that participants responded more slowly at a faster speech rate, with greater effects in more than less predictable sentence contexts. These results suggested that a faster speech rate slows down prediction speed due to increased cognitive load, and that the detrimental effect of cognitive load is greater in more predictable contexts, where the prediction mechanism can be engaged to a larger extent. Overall, these results support the idea that prediction is cognitively demanding. Experiments 4 and 5 used a picture-word interference paradigm to investigate whether bilinguals activate their L1 during L2 production within a pure L2 context. We asked highly proficient Mandarin Chinese-English bilinguals (Experiment 4) and English native speakers who spoke no Mandarin (Experiment 5) to name pictures (e.g., hat, “mao zi” in Mandarin) in English while ignoring English auditory distractors that were phonologically related to the Mandarin translations of the picture names (mouth, phono-translation distractors). We found that both groups showed inhibition for semantically related distractors and facilitation for phonologically related distractors. Most importantly, Mandarin-English bilinguals were quicker to name pictures when just preceded by phono-translation distractors compared to unrelated distractors, but English native speakers were not. These findings suggest that information associated with words from the non-target language is activated even when that language is irrelevant to the task, but do not compete for selection. Experiments 6 and 7 directly tested whether bilinguals pre-activate L1 translations of predictable words during L2 comprehension and whether this depends on language contexts, using the visual-world paradigm. Specifically, Mandarin-English bilinguals listened to L2 English sentences containing a highly predictable word (e.g., You should take an umbrella with you, because there will be heavy rain at three o'clock this afternoon) while viewing a display containing a critical object and three distractors. We found that participants predictively fixated more on a competitor object whose Mandarin Chinese name was a homophone (e.g., feather [Mandarin: yu3]) of the Mandarin Chinese translation of the predictable word (e.g., rain [Mandarin: yu3]) than an unrelated object (e.g., comb [Mandarin: shu1]) when both languages were used (Experiment 7) but not when just English was used (Experiment 6). Our findings suggest that bilinguals predict across languages when both languages are contextually relevant but not otherwise
“I never thought it was my heart”: illness and health-seeking experiences of Saudi women with symptoms suggestive of acute coronary syndrome
Get PDFBACKGROUND:
Coronary heart disease (CHD) is recognised as the leading cause of mortality
and morbidity, affecting a considerable portion of men and women worldwide. CHD manifest
clinically as Acute Coronary Syndrome (ACS), a spectrum of conditions that include STelevation
MI, non-ST-elevation MI, and Angina Pectoris. Not recognising and responding to
ACS symptoms promptly can significantly contribute to delays in diagnosis and treatment,
which can exacerbate the potential for poor prognosis and the risk of mortality. While efforts
in mitigating timely response within the healthcare system have been observed, delays in
health-seeking persist, especially in women. This issue is understudied in the context of Saudi
Arabia, where CHD is on the rise.
AIM:
This PhD research aimed to explore the experiences of Saudi women with symptoms
suggestive of ACS and their subsequent health-seeking behaviours in response to the perceived
symptoms.
METHODS:
Qualitative research design with in-depth, semi-structured interviews was carried
out to explore women’s illness and health-seeking experiences within the context of Saudi
Arabia. A total of twenty Saudi women hospitalised at King Abdulaziz University Hospital
(KAUH) for an ACS event took part in this study. Data were gathered from September 2021 to
March 2022 through individual interviews conducted in-person (n=17), online (n=2), and over
the phone (n=1). The interviews took place 1-6 months after the women’s hospital discharge,
during follow-up visits at the hospital’s cardiology outpatient clinic. All interviews were audiorecorded
and transcribed verbatim. The textual data were then analysed using reflexive
thematic analysis guided by Braun and Clarke (2022).
FINDINGS:
Three key themes were constructed from the extensive accounts of the study
participants: 1) Recognising the subtle change in health and interpreting symptoms, 2)
Responses to perceived symptoms, and 3) Arriving at the final destination. The analysis
indicates that, for the women interviewed, navigating illness in the circumstances of ACS
cannot be separated from the contextual world where the acute event takes place. My research
provides a nuanced understanding of how Saudi women navigate symptoms, assess biomedical
and familial risks, manage their health issues, seek lay consultation, and ultimately attend the
hospital in response to an acute cardiac event. The women’s experiences were understood by
considering key theoretical elements of Chrisman’s (1977) health-seeking process combined
with a gender lens.
CONCLUSION:
My study contributes to the knowledge that Saudi women’s experiences in
navigating their way to the hospital were complex and multifaceted. Alongside the severity of
symptoms and worsening health conditions, gender roles and their accompanying social and
familial responsibilities, as well as family dynamics, were essential in determining how the
women engaged in health-seeking behaviours and decided to attend the hospital. By
understanding the broader sociocultural conditions of Saudi women, this study provides
valuable insights into women’s health-seeking trajectory, which may be different for women
in other contexts. This nuanced understanding can inform healthcare providers working in
community and hospital settings to be mindful of the importance of delivering socially
sensitive, context-based healthcare to address women’s specific needs in Saudi Arabia and
other similar cultural settings
Male homosexuality in Ming dynasty China
Get PDFThis thesis examines the phenomenon of male homosexuality in the context of heteronormativity and patriarchy in the Wanli period of Ming Dynasty China. It investigates three representative practices of male homosexuality: the qixiongdi marriage, the rusheng’s homoeroticism, and the menzi and xiaochang as male sex workers for men. The interaction between male homosexuality and the social context is measured through a three-stage model—trouble, tolerance, and reconstruction—inspired by Western gender theories.
This thesis argues that the above phenomena of male homosexuality in the Wanli period dynamically interacted with the heteronormativity and patriarchy of the time. Through both the institutionalisation of emerging knowledge and norms and individual acts that cause performative subversion, all three cases effectively troubled the dominant social structures related to gender and sexuality. Simultaneously, however, each also exhibited varying degrees of compromise with—and integration into—the disciplinary norms imposed by the dominant social order. The case of qixiongdi as a regional practice of male homosexual marriage was featured by recognition from local communities and acquiescence from the official government, which implied the social tolerance of this practice. However, the practice of qixiongdi adopted the heterosexual and patriarchal paradigm by assigning a fixed feminised role and an unequal internal power relationship, which explains the social tolerance of this phenomenon. The case of the rusheng’s homoeroticism was a trend in the group of Confucian disciples which was featured by the conceptualisation of qing as an ideological basis and an egalitarian internal power relationship. This practice compromised less with the heterosexual and patriarchal norms, thereby rendering the phenomenon more subversive to the latter.
However, the rusheng were inclined to veil their homoeroticism from the public in several aspects. The case of menzi and xiaochang encompassed multiple regions and social classes and was distinct for its openness to the public. This phenomenon has formed distinctive customs and to some degree acknowledged by formal institutions. In sum, during the Wanli period, the phenomena of male homosexuality troubled existing patriarchal and heteronormative structures, sometimes prompting the dominant order to adopt a more tolerant stance. However, this tolerance did not translate into a successful challenge against the dominant social structures. Instead, patriarchal and heteronormative norms largely retained their influence, particularly regarding marriage practices, even among those who engaged in homosexual activities.
Moreover, the cross-cultural applicability of the three-stage model is critically reviewed in each case. This thesis finds that, with the gradual increase of power of the homosexual community, its tension with dominant social structures was much weaker than the prediction of the three-stage model. Homosexual practices during the Wanli period often coexisted alongside heteronormativity and patriarchy without necessarily prompting conflict or requiring explicit tolerance. This coexistence reflects the distinctive capacity of Confucian ideology, as a symbolic universe, to legitimise patriarchal and heterosexual authority within a relatively flexible and integrative framework, rather than a rigidly exclusionary structure
Environmental risks in financial markets
Get PDFClimate change and biodiversity loss represent aggregate risks to global financial markets. This thesis investigates how expected or realized changes in these environmental risks affect asset prices, and the mechanisms through which these effects manifest, such as firm-level exposures, behavioral responses, regulatory restrictions, or market expectations.
I begin by examining whether the sovereign credit market incorporates expectations of coastal flooding and sea level rise (SLR). The results indicate that medium- and long-term credit default swap spreads increase for sovereigns with a substantial portion of their population vulnerable to ex-ante coastal flooding in response to news around climate summits. Predictability tests suggest that the market asynchronously incorporates changing vulnerabilities of regions into its risk assessment with such news, consistent with theories of inattention to information. A real-options model is used to consider debt financing trade-offs associated with sovereign inaction or investment into adaptation.
The second chapter shows that firms exposed to abnormal temperature variability underperform relative to their peers. A long-short strategy exploiting cross-sectional and spatial variation in this metric yields a market-adjusted alpha of 4.9\% annually. The effect operates through lower firm revenue and profitability, with heterogeneous impacts across industries. Temperature variability propagates through behavioral updating and attention channels, reducing both consumer spending and worker productivity. Firms more exposed to this variability display higher idiosyncratic return volatility and greater dispersion in analyst forecasts, reflecting heightened uncertainty in pricing damages from extreme temperatures and their fluctuations.
The final chapter examines whether biodiversity loss is internalized through market pricing or government intervention. Empirical results indicate that emissions from toxic facilities increase lead concentrations and decrease animal populations within a 12-kilometer radius. The US equity market ignores this biodiversity loss, as firms emitting pollutants near biodiverse regions attract no additional risk premium and face economically small penalties from regulatory action. A moral hazard issue likely drives these observations: firms located near ecologically sensitive areas underreport their environmental impacts both in financial disclosures and to regulatory oversight bodies.
The thesis contributes to several emerging topics in the climate and biodiversity finance literature. It develops novel methodologies for measuring climate-induced temperature changes and biodiversity loss through chemical contamination. The research explores the extent to which market participants incorporate climate projections into asset prices, how they revise their beliefs when exposed to climate shocks, and how insiders strategically disclose environmental information. Throughout the thesis, solutions are presented for market participants to optimize investment in adaptation capital, construct climate-resilient portfolios, and enhance disclosure of material environmental risks
Gedo, Jubbaland and the Translocal Marehan
No full textProcesses of state fragmentation have become more evident in Somalia in recent years, reflecting both national and sub-national factors as well as their intersection with regional and global dynamics. Gedo region – and its dominant Marehan clan constituency – provides one such example, with its ongoing and ambiguous incorporation into the Federal Member State of Jubbaland.
The report highlights the importance of understanding territoriality – the relationship between identity and territory – in processes of state fragmentation
Development of artificial fluorinases
No full textThe sustainable and selective synthesis of chiral fluorinated organic compounds is essential in chemistry, as these compounds exhibit improved chemical properties, such as enhanced bioavailability in drugs. Over the years, multiple methods have been developed for the synthesis of fluorinated compounds. Despite these advancements, the selective incorporation of fluorine remains challenging and often requires several synthesis steps. A promising alternative is enzymatic fluorination, which offers a site-selective, chiral, and sustainable approach to producing fluorine-containing organic compounds. However, enzymatic fluorination is rare, and only one natural enzyme is known to catalyse the formation of a C–F bond.
In this context, this PhD project aimed to broaden the scope of biocatalysis for organofluorine synthesis and to develop novel biosynthetic catalysts for fluorination reactions in aqueous environments. Two design strategies for the development of artificial fluorinases were explored:
Chapter 2 describes the design of artificial copper and palladium enzymes for transition-metal-catalysed electrophilic fluorination reactions. The approach involves utilising the metal centre as a catalytic site and the protein scaffold as a
chiral secondary coordination sphere. For this purpose, the human sterol carrier protein (SCP-2L) was modified to incorporate various nitrogen-based ligands
through cysteine bioconjugation methods or genetic code expansion (GCE). These modifications enabled the binding of copper and palladium complexes, and the resulting artificial metalloproteins were investigated for the potential fluorination of β-ketoesters and electron-deficient arenes. Both reactions were carried out with
the fluorination reagent Selectfluor, and the results highlight the importance for careful selection of reactions for screening artificial metalloenzymes (ArMs), as either high background reactions using β-ketoesters outcompete the coppercatalysed reaction, or the instability of higher oxidation states such as Pd(IV) in an
aqueous environment disrupts the catalytic cycle and prevents fluorination.
Chapter 3 explores the design of fluoride anion binding sites in proteins, aiming to overcome the high desolvation energy of fluoride anions in aqueous environments and enhance their reactivity for new C–F bond formation. The catalyst design was
inspired by the active site of the only known natural C–F bond-forming enzyme and by urea catalysts, which led to the development of novel non-canonical amino acids
(ncAAs) with urea groups. These ncAAs were incorporated into short peptides and their binding ability as well as their catalytic ability for nucleophilic fluorination of β-chloroamines in various solvents, including aqueous environments, was tested.
The results show that both the ncAAs and the urea peptides are catalytically active with varying selectivity between fluorination and hydrolysis. The ncAAs predominantly utilise fluoride anions even in the presence of water, whereas the peptides only yielded hydrolysis.
Ultimately, this work highlights the challenges of catalysing fluorination reactions in water and demonstrates the successful design and synthesis of several new artificial catalysts. Some of these catalysts exhibited effective fluorination in organic solvents and showed tolerance towards water
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