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The pH behavior in the μm to cm thick diffusion boundary layer (DBL) surrounding many aquatic species is dependent on light-controlled metabolic activities. This DBL microenvironment exhibits different pH behavior to bulk seawater, which can reduce the exposure of calcifying species to ocean acidification conditions. A low-cost time-domain dual-lifetime referencing (t-DLR) interrogation system and an optical fiber fluorescent pH sensor were developed for pH measurements in the DBL interface. The pH sensor utilized dual-layer sol-gel coatings of pH-sensitive iminocoumarin and pH-insensitive Ru(dpp)3-PAN. The sensor has a dynamic range of 7.41 (±0.20) to 9.42 ± 0.23 pH units (95% CI, T = 20 °C, S = 35), a response time (t90) of 29 to 100 s, and minimal salinity dependency. The pH sensor has a precision of approximately 0.02 pHT units, which meets the Global Ocean Acidification Observing Network (GOA-ON) “weather” measurement quality guideline. The suitability of the t-DLR optical fiber pH sensor was demonstrated through real-time measurements in the DBL of green seaweed Ulva sp. This research highlights the practicability of optical fiber pH sensors by demonstrating real-time pH measurements of metabolic-induced pH changes.

Combining powder X-ray and neutron diffraction, the first crystallographic characterization of diacetylene (IUPAC designation 1,3-butadiyne) is presented and supplemented by Raman spectroscopy and periodic-DFT calculations. The structure is described in the space group Pnma , with a  = 9.348 (2), b  = 5.9890 (6), c  = 5.6746 (11) Å and V  = 317.69 (6) Å 3 at 5 K, with four molecules in the unit cell resulting in a density of 1.0466 g cm −3 . The diacetylene molecules are arranged in a layered structure dominated by C—H...π interactions, which leads to anisotropic thermal expansion behaviour. No structural phase transitions were observed across the 5–220 K temperature range at ambient pressure. The structural similarity with acetylene identifies it as a potential cocrystal component of particular importance for Titan's surface chemistry in view of the upcoming NASA Dragonfly mission.

The crystal structure and thermal expansion behaviour of di­acet­y­lene were determined via diffraction methods and supplemented by spectroscopic techniques. The similarities to the structure of acetylene and implications for Titan in situ exploration are discussed. Combining powder X-ray and neutron diffraction, the first crystallographic characterization of di­acet­y­lene (IUPAC designation 1,3-butadiyne) is presented and supplemented by Raman spectroscopy and periodic-DFT calculations. The structure is described in the space group Pnma, with a = 9.348 (2), b = 5.9890 (6), c = 5.6746 (11) Å and V = 317.69 (6) Å3 at 5 K, with four molecules in the unit cell resulting in a density of 1.0466 g cm−3. The di­acet­y­lene molecules are arranged in a layered structure dominated by C—H⋯π interactions, which leads to anisotropic thermal expansion behaviour. No structural phase transitions were observed across the 5–220 K tem­per­a­ture range at ambient pressure. The structural similarity with acetylene identifies it as a potential cocrystal component of particular importance for Titan’s surface chemistry in view of the upcoming NASA Dragonfly mission.

Currently, feed enzyme supplementation into commercial broiler diets is a routine practice due to hydrolysis of antinutrients, such as non-starch polysaccharides (NSP) and phytate (IP6); ultimately leading to optimized broiler production. As a result, the market has grown rapidly, and a multitude of feed enzymes are commercially available. Complete removal of antinutrients has not been achieved and research has primarily focused on the use of singular enzyme inclusion. Due to biochemical differences among enzyme characteristics, there may be potential for synergistic action to remove antinutrients and further maximize broiler performance. Therefore, the overall objective of this dissertation was to investigate enzyme strategies to determine optimal inclusion for broilers. Chapter 2 investigated the interactive effects of phytase dose (PD; 250 to 1500 FTU/kg) and carbohydrase enzyme (CE) of xylanase (XAN), β-mannanase (MAN), or their combination (XM). These data demonstrated an interaction between CE and PD for d 0-14 FCR, but this significance was lost during the remainder of the study. Overall benefits for performance and processing were demonstrated with feeding a PD of 1500 FTU/kg and XAN. Chapter 3 took a preliminary approach (0-14 d) to investigate the potential synergy among 3 phytase enzymes of varying biochemical properties when fed alone or in combination with low PD (120 or 240 FTU/kg). These data demonstrated potential synergy with the supplementation of 2 phytases combined at a higher PD (240 FTU/kg), as identified from ileal IP (inositol phosphate) lower ester concentration and tibia ash. Chapter 4 built upon the previous chapter, choosing 2 phytases (A or B) and addressing previous limitations by including a broader/more practical range of phytase activity (250 or 1500 FTU/kg); providing 3 diets varying in calcium (Ca) and non-phytate phosphorus (nPP); and using an entire grow-out. Feeding diets lowest in Ca and nPP along with 1500 FTU/kg of A, B, or A+B resulted in improved broiler performance. Additionally, the use of A+B at 250 FTU/kg within diets of medium Ca and nPP levels demonstrated synergism through improved broiler performance and tibia ash. Overall, data suggest that the strategic utilization of enzyme combinations may provide additional benefits towards broiler production.

The total removal of antibiotic growth promoters (AGP) from poultry feed is underway in the United States. Feed additive strategies will be utilized to maintain the efficient growth, health, and economic value found with current commercial broiler production. Experiment 1 investigated the effects of feeding an encapsulated butyric acid and zinc product (EBAZ) at 3 inclusions on d 0- 49 Ross x Ross 708 male and female broiler performance, blood chemistry, and cecal short-chain fatty acid content. These data suggest that EBAZ can be safely included at 0.5 g/kg and at 2.5 g/kg into diets for Ross x Ross 708 male and female broilers. The objective of the second experiment was to examine the efficacy of 2 commercially available carbohydrases in commercial diets on d 0-57 male broiler performance and processing. The resulting data demonstrates that the inclusion of xylanase (CE2) improved broiler performance thus, increased potential gross profits.

This paper makes a case for digital mental health and provides insights into how digital technologies can enhance (but not replace) existing mental health services. We describe digital mental health by presenting a suite of digital technologies (from digital interventions to the application of artificial intelligence). We discuss the benefits of digital mental health, for example, a digital intervention can be an accessible stepping-stone to receiving support. The paper does, however, present less-discussed benefits with new concepts such as ‘poly-digital’, where many different apps/features (e.g. a sleep app, mood logging app and a mindfulness app, etc.) can each address different factors of wellbeing, perhaps resulting in an aggregation of marginal gains. Another benefit is that digital mental health offers the ability to collect high-resolution real-world client data and provide client monitoring outside of therapy sessions. These data can be collected using digital phenotyping and ecological momentary assessment techniques (i.e. repeated mood or scale measures via an app). This allows digital mental health tools and real-world data to inform therapists and enrich face-to-face sessions. This can be referred to as blended care/adjunctive therapy where service users can engage in ‘channel switching’ between digital and non-digital (face-to-face) interventions providing a more integrated service. This digital integration can be referred to as a kind of ‘digital glue’ that helps join up the in-person sessions with the real world. The paper presents the challenges, for example, the majority of mental health apps are maybe of inadequate quality and there is a lack of user retention. There are also ethical challenges, for example, with the perceived ‘over-promotion’ of screen-time and the perceived reduction in care when replacing humans with ‘computers’, and the trap of ‘technological solutionism’ whereby technology can be naively presumed to solve all problems. Finally, we argue for the need to take an evidence-based, systems thinking and co-production approach in the form of stakeholder-centred design when developing digital mental health services based on technologies. The main contribution of this paper is the integration of ideas from many different disciplines as well as the framework for blended care using ‘channel switching’ to showcase how digital data and technology can enrich physical services. Another contribution is the emergence of ‘poly-digital’ and a discussion on the challenges of digital mental health, specifically ‘digital ethics’.

In recent years, advances in technology have led to an influx of mental health apps, in particular the development of mental health and well-being chatbots, which have already shown promise in terms of their efficacy, availability, and accessibility. The ChatPal chatbot was developed to promote positive mental well-being among citizens living in rural areas. ChatPal is a multilingual chatbot, available in English, Scottish Gaelic, Swedish, and Finnish, containing psychoeducational content and exercises such as mindfulness and breathing, mood logging, gratitude, and thought diaries. The primary objective of this study is to evaluate a multilingual mental health and well-being chatbot (ChatPal) to establish if it has an effect on mental well-being. Secondary objectives include investigating the characteristics of individuals that showed improvements in well-being along with those with worsening well-being and applying thematic analysis to user feedback. A pre-post intervention study was conducted where participants were recruited to use the intervention (ChatPal) for a 12-week period. Recruitment took place across 5 regions: Northern Ireland, Scotland, the Republic of Ireland, Sweden, and Finland. Outcome measures included the Short Warwick-Edinburgh Mental Well-Being Scale, the World Health Organization-Five Well-Being Index, and the Satisfaction with Life Scale, which were evaluated at baseline, midpoint, and end point. Written feedback was collected from participants and subjected to qualitative analysis to identify themes. A total of 348 people were recruited to the study (n=254, 73% female; n=94, 27% male) aged between 18 and 73 (mean 30) years. The well-being scores of participants improved from baseline to midpoint and from baseline to end point; however, improvement in scores was not statistically significant on the Short Warwick-Edinburgh Mental Well-Being Scale (P=.42), the World Health Organization-Five Well-Being Index (P=.52), or the Satisfaction With Life Scale (P=.81). Individuals that had improved well-being scores (n=16) interacted more with the chatbot and were significantly younger compared to those whose well-being declined over the study (P=.03). Three themes were identified from user feedback, including \"positive experiences,\" \"mixed or neutral experiences,\" and \"negative experiences.\" Positive experiences included enjoying exercises provided by the chatbot, while most of the mixed, neutral, or negative experiences mentioned liking the chatbot overall, but there were some barriers, such as technical or performance errors, that needed to be overcome. Marginal improvements in mental well-being were seen in those who used ChatPal, albeit nonsignificant. We propose that the chatbot could be used along with other service offerings to complement different digital or face-to-face services, although further research should be carried out to confirm the effectiveness of this approach. Nonetheless, this paper highlights the need for blended service offerings in mental health care.

Conversational user interfaces, or chatbots, are becoming more popular in the realm of digital health and well-being. While many studies focus on measuring the cause or effect of a digital intervention on people's health and well-being (outcomes), there is a need to understand how users really engage and use a digital intervention in the real world. In this study, we examine the user logs of a mental well-being chatbot called ChatPal, which is based on the concept of positive psychology. The aim of this research is to analyze the log data from the chatbot to provide insight into usage patterns, the different types of users using clustering, and associations between the usage of the app's features. Log data from ChatPal was analyzed to explore usage. A number of user characteristics including user tenure, unique days, mood logs recorded, conversations accessed, and total number of interactions were used with k-means clustering to identify user archetypes. Association rule mining was used to explore links between conversations. ChatPal log data revealed 579 individuals older than 18 years used the app with most users being female (n=387, 67%). User interactions peaked around breakfast, lunchtime, and early evening. Clustering revealed 3 groups including \"abandoning users\" (n=473), \"sporadic users\" (n=93), and \"frequent transient users\" (n=13). Each cluster had distinct usage characteristics, and the features were significantly different (P<.001) across each group. While all conversations within the chatbot were accessed at least once by users, the \"treat yourself like a friend\" conversation was the most popular, which was accessed by 29% (n=168) of users. However, only 11.7% (n=68) of users repeated this exercise more than once. Analysis of transitions between conversations revealed strong links between \"treat yourself like a friend,\" \"soothing touch,\" and \"thoughts diary\" among others. Association rule mining confirmed these 3 conversations as having the strongest linkages and suggested other associations between the co-use of chatbot features. This study has provided insight into the types of people using the ChatPal chatbot, patterns of use, and associations between the usage of the app's features, which can be used to further develop the app by considering the features most accessed by users.

A proposal to require drug companies to pass discounts directly to Medicare patients at the point of sale would fundamentally change the role of medication rebates in Part D — and with it, drug pricing in general. How might it affect the program and its beneficiaries?

Low-fat hypocaloric diets reduce insulin resistance and prevent type 2 diabetes in those at risk. Low-carbohydrate, high-fat diets are advocated as an alternative, but reciprocal increases in dietary fat may have detrimental effects on insulin resistance and offset the benefits of weight reduction. We investigated a low-fat (20% fat, 60% carbohydrate) versus a low-carbohydrate (60% fat, 20% carbohydrate) weight reduction diet in 24 overweight/obese subjects ([mean +/- SD] BMI 33.6 +/- 3.7 kg/m(2), aged 39 +/- 10 years) in an 8-week randomized controlled trial. All food was weighed and distributed, and intake was calculated to produce a 500 kcal/day energy deficit. Insulin action was assessed by the euglycemic clamp and insulin secretion by meal tolerance test. Body composition, adipokine levels, and vascular compliance by pulse-wave analysis were also measured. Significant weight loss occurred in both groups (P < 0.01), with no difference between groups (P = 0.40). Peripheral glucose uptake increased, but there was no difference between groups (P = 0.28), and suppression of endogenous glucose production was also similar between groups. Meal tolerance-related insulin secretion decreased with weight loss with no difference between groups (P = 0.71). The change in overall systemic arterial stiffness was, however, significantly different between diets (P = 0.04); this reflected a significant decrease in augmentation index following the low-fat diet, compared with a nonsignificant increase within the low-carbohydrate group. This study demonstrates comparable effects on insulin resistance of low-fat and low-carbohydrate diets independent of macronutrient content. The difference in augmentation index may imply a negative effect of low-carbohydrate diets on vascular risk.