Significant quantum effects in hydrogen activation

Dissociation of molecular hydrogen is an important step in a wide variety of chemical, biological, and physical processes. Due to the light mass of hydrogen, it is recognized that quantum effects are often important to its reactivity. However, understanding how quantum effects impact the reactivity of hydrogen is still in its infancy. Here, we examine this issue using a well-defined Pd/Cu(111) alloy that allows the activation of hydrogen and deuterium molecules to be examined at individual Pd atom surface sites over a wide range of temperatures. Experiments comparing the uptake of hydrogen and deuterium as a function of temperature reveal completely different behavior of the two species. The rate of hydrogen activation increases at lower sample temperature, whereas deuterium activation slows as the temperature is lowered. Density functional theory simulations in which quantum nuclear effects are accounted for reveal that tunneling through the dissociation barrier is prevalent for H2 up to ∼190 K and for D2 up to ∼140 K. Kinetic Monte Carlo simulations indicate that the effective barrier to H2 dissociation is so low that hydrogen uptake on the surface is limited merely by thermodynamics, whereas the D2 dissociation process is controlled by kinetics. These data illustrate the complexity and inherent quantum nature of this ubiquitous and seemingly simple chemical process. Examining these effects in other systems with a similar range of approaches may uncover temperature regimes where quantum effects can be harnessed, yielding greater control of bond-breaking processes at surfaces and uncovering useful chemistries such as selective bond activation or isotope separation.

Animal pigment bilirubin discovered in plants

The bile pigment bilirubin-IXα is the degradative product of heme, distributed among mammals and some other vertebrates. It can be recognized as the pigment responsible for the yellow color of jaundice and healing bruises. In this paper we present the first example of the isolation of bilirubin in plants. The compound was isolated from the brilliant orange-colored arils of Strelitzia nicolai, the white bird of paradise tree, and characterized by HPLC−ESMS, UV−visible, 1H NMR, and 13C NMR spectroscopy, as well as comparison with an authentic standard. This discovery indicates that plant cyclic tetrapyrroles may undergo degradation by a previously unknown pathway. Preliminary analyses of related plants, including S. reginae, the bird of paradise, also revealed bilirubin in the arils and flowers, indicating that the occurrence of bilirubin is not limited to a single species or tissue type.

Development of face recognition: Infancy to early childhood

Perception and recognition of faces are fundamental cognitive abilities that form a basis for our social interactions. Research has investigated face perception using a variety of methodologies across the lifespan. Habituation, novelty preference, and visual paired comparison paradigms are typically used to investigate face perception in young infants. Storybook recognition tasks and eyewitness lineup paradigms are generally used to investigate face perception in young children. These methodologies have introduced systematic differences including the use of linguistic information for children but not infants, greater memory load for children than infants, and longer exposure times to faces for infants than for older children, making comparisons across age difficult. Thus, research investigating infant and child perception of faces using common methods, measures, and stimuli is needed to better understand how face perception develops. According to predictions of the Intersensory Redundancy Hypothesis (IRH; Bahrick & Lickliter, 2000, 2002), in early development, perception of faces is enhanced in unimodal visual (i.e., silent dynamic face) rather than bimodal audiovisual (i.e., dynamic face with synchronous speech) stimulation. The current study investigated the development of face recognition across children of three ages: 5 – 6 months, 18 – 24 months, and 3.5 – 4 years, using the novelty preference paradigm and the same stimuli for all age groups. It also assessed the role of modality (unimodal visual versus bimodal audiovisual) and memory load (low versus high) on face recognition. It was hypothesized that face recognition would improve across age and would be enhanced in unimodal visual stimulation with a low memory load. Results demonstrated a developmental trend (F(2, 90) = 5.00, p = 0.009) with older children showing significantly better recognition of faces than younger children. In contrast to predictions, no differences were found as a function of modality of presentation (bimodal audiovisual versus unimodal visual) or memory load (low versus high). This study was the first to demonstrate a developmental improvement in face recognition from infancy through childhood using common methods, measures and stimuli consistent across age.

Hidden Communication Deficits in Children with Autism and Early Behavioral Interventions

Taking a behavioral systems approach to autism, early hidden communicative deficits are introduced as precursors of autistic development. This paper argues that early identification of communication (language and cognition) impairments followed by intensive behavioral interventions, as early as infancy, may have the most preventive effect on the development of autism.

Sales Promotion in Hotels:A British Perspective

In their article - Sales Promotion In Hotels: A British Perspective - by Francis Buttle, Lecturer, Department of Hotel, Restaurant, and Travel Administration, University of Massachusetts and Ini Akpabio, Property Manager, Trusthouse Forte, Britain, Buttle and Akpabio initially state: “Sales promotion in hotels is in its infancy. Other industries, particularly consumer goods manufacturing, have long recognized the contribution that sales promotion can make to the cost-effective achievement of marketing objectives. Sales promotion activities in hotels have remained largely uncharted. The authors define, identify and classify these hotel sales promotion activities to understand their function and form, and to highlight any scope for improvement.” The authors begin their discussion by attempting to define what the phrase sales promotion [SP] actually means. “The Institute of Sales Promotion regards sales promotions as “adding value, usually of a temporary nature, to a product or service in order to persuade the end user to purchase that particular brand as opposed to a competitive brand,” the authors offer. Williams, however, describes sales promotions more broadly as “short term tactical marketing tools which are used to achieve specific marketing objectives during a defined time period,” Buttle and Akpabio present with attribution. “The most significant difference between these two viewpoints is that Williams does not limit his definition to activities which are targeted at the consumer,” is their educated view. A lot of the discussion is centered on the differences in the collective marketing-promotional mix. “…it is not always easy to definitively categorize promotional activity,” Buttle and Akpabio say. “For example, in personal selling, a sales promotion such as a special bonus offer may be used to close the sale; an advertisement may be sales promotional in character in that it offers discounts.” Are promotion and marketing distinguishable as two separate entities? “…not only may there be conceptual confusion between components of the promotional mix, but there is sometimes a blurring of the boundaries between the elements of the marketing mix,” the authors suggest. “There are several reasons why SP is particularly suitable for use in hotels: seasonality, increasing competitiveness, asset characteristics, cost characteristics, increased use of channel intermediaries, new product launches, and deal proneness.” Buttle and Akpabio offer their insight on each of these segments. The authors also want you to know that SP customer applications are not the only game in town, SP trade applications are just as essential. Bonuses, enhanced commission rates, and vouchers are but a few examples of trade SP. The research for the article was compiled from several sources including, mail surveys, telephone surveys, personal interviews, trade magazines and newspapers; essentially in the U.K.

Sex offender risk assessment and management in Ireland

This research examined sex offender risk assessment and management in Ireland. It focused on the statutory agencies with primary responsibility (Garda Síochána and the Probation Service). The goal was to document the historical, contextual and current systems, in addition to identifying areas of concern/improvements. The research was a mixed-methods approach. Eight studies were conducted. This incorporated documentary reviews of four Commission to Inquire Reports, qualitative interviews/focus groups with Garda staff, Probation Service staff, statutory agencies, community stakeholders, various Non-Governmental Organisations (NGOs) and sex offenders. Quantitative questionnaires were also administered to Garda staff. In all over 70 interviews were conducted and questionnaires were forwarded to 270 Garda members. The overall findings are: •Sex offender management in Ireland has become formal only since 2001. Knowledge, skills and expertise is in its infancy and is still evolving. •Mixed reviews and questions regarding fitness for purpose of currently used risk assessments tools were noted. •The Sex Offender Act 2001 requires additional elements to ensure safe sex offender monitoring and public protection. A judicial review of the Sex Offender Act 2001 was recommended by many respondents. •Interagency working under SORAM was hugely welcomed. The sharing of information has been welcomed by managing agencies as the key benefit to improving sex offender management. •Respondents reported that in practice, sex offender management in Ireland is fragmented and unevenly implemented. The research concluded that an independent National Sex Offender Authority should be established as an oversight and regulatory body for policy, strategy and direction in sex offender management. Further areas of research were also highlighted: ongoing evaluation and audits of the joint agency process and systems in place; recidivism studies tracking the risk assessment ratings and subsequent offending; and an evaluation of the current status of sex offender housing in Ireland.

Socialization of Early Prosocial Behavior: Parents' Talk about Emotions is Associated with Sharing and Helping in Toddlers.

What role does socialization play in the origins of prosocial behavior? We examined one potential socialization mechanism, parents' discourse about others' emotions with very young children in whom prosocial behavior is still nascent. Two studies are reported, one of sharing in 18- and 24-month-olds (n = 29), and one of instrumental and empathy-based helping in 18- and 30-month-olds (n = 62). In both studies, parents read age-appropriate picture books to their children and the content and structure of their emotion-related and internal state discourse were coded. Results showed that children who helped and shared more quickly and more often, especially in tasks that required more complex emotion understanding, had parents who more often asked them to label and explain the emotions depicted in the books. Moreover, it was parents' elicitation of children's talk about emotions rather than parents' own production of emotion labels and explanations that explained children's prosocial behavior, even after controlling for age. Thus, it is the quality, not the quantity, of parents' talk about emotions with their toddlers that matters for early prosocial behavior.

IL-10-producing Regulatory B Cell Development in Human Autoimmune Disease

B cell abnormalities contribute to the development and progress of autoimmune disease. Traditionally, the role of B cells in autoimmune disease was thought to be predominantly limited to the production of autoantibodies. Nevertheless, in addition to autoantibody production, B cells have other functions potentially relevant to autoimmunity. Such functions include antigen presentation to and activation of T cells, expression of costimulatory molecules and cytokine production. Recently, the ability of B cells to negatively regulate cellular immune responses and inflammation has been described and the concept of “regulatory B cells” has emerged. A variety of cytokines produced by regulatory B cell subsets have been reported with interleukin-10 (IL-10) being the most studied. IL-10-producing regulatory B cells predominantly localize within a rare CD1dhiCD5+ B cell subset in mice and the CD24hiCD27+ B cell subset in adult humans. This specific IL-10-producing subset of regulatory B cells have been named “B10 cells” to highlight that the regulatory function of these rare B cells is primarily mediated by IL-10, and to distinguish them from other regulatory B cell subsets that regulate immune responses through different mechanisms. B10 cells have been studies in a variety of animal models with autoimmune disease and clinical settings of human autoimmunity. There are many unsolved questions related to B10 cells including their surface phenotype, their origin and development in vivo, and their role in autoimmunity.

In Chapter 3 of this dissertation, the role of the B cell receptor (BCR) in B10 cell development is highlighted. First, the BCR repertoire of mouse peritoneal cavity B10 cells is examined by single cell sequencing; peritoneal cavity B10 cells have clonally diverse germline BCRs that are predominantly unmutated. Second, mouse B10 cells are shown to have higher frequencies of λ+ BCRs compared to non-B10 cells which may indicate the involvement of BCR light chain editing early in the process of B10 cell development in vivo. Third, human peripheral blood B10 cells are examined and are also found to express higher frequencies of λ chains compared to non-b10 cells. Therefore, B10 cell BCRs are clonally diverse and enriched for unmutated germline sequences and λ light chains.

In Chapter 4 of this dissertation, B10 cells are examined in the healthy developing human across the entire age range of infancy, childhood and adolescence, and in a large cohort of children with autoimmunity. The study of B10 cells in the developing human documents a massive transient expansion during middle childhood when up to 30% of blood B cells were competent to produce IL-10. The surface phenotype of pediatric B10 cells was variable and reflective of overall B cell development. B10 cells down-regulated CD4+ T cell interferon-gamma (IFN-γ) production through IL-10-dependent pathways and IFN-γ inhibited whereas interleukin-21 (IL-21) promoted B cell IL-10 competency in vitro. Children with autoimmunity had a contracted B10 cell compartment, along with increased IFN-γ and decreased IL-21 serum levels compared to age-matched healthy controls. The decreased B10 cell frequencies and numbers in children with autoimmunity may be partially explained by the differential regulation of B10 cell development by IFN-γ and IL-21 and alterations in serum cytokine levels. The age-related changes of the B10 cell compartment during normal human development provide new insights into immune tolerance mechanisms involved in inflammation and autoimmunity.

These studies collectively demonstrate that BCR signals are the most important early determinant of B10 cell development in vivo, that human B10 cells are not a surface phenotype defined developmental B cell subset but a functionally defined regulatory B cell subset that regulates CD4+ T IFN-γ production through IL-10-dependent pathways and that human B10 cell development can be regulated by soluble factors in vivo such as the cytokine milieu. The findings of these studies provide new insights into immune tolerance mechanisms involved in human autoimmunity and the potent effects of IL-21 on human B cell IL-10 competence in vitro open new horizons in the development of autologous B10 cell-based therapies as an approach to treat human autoimmune disease in the future.

Iron status in early life and associations with developmental outcomes

Infants and young children are at particular risk of iron deficiency and its associated consequences for growth and development. The main objectives of this thesis were to quantify iron intakes, status and determinants of status in two year olds; explore determinants of neonatal iron stores; investigate associations between iron status at birth and two years with neurodevelopmental outcomes at two years and explore the influence of growth on iron status in early childhood, using data from the Cork BASELINE (Babies after SCOPE: Evaluating Longitudinal Impact using Neurological and Nutritional Endpoints) Birth Cohort Study (n=2137). Participants were followed prospectively with interviewer-led questionnaires and clinical assessments at day 2 and at 2, 6, 12 and 24 months. At two years, there was a low prevalence of iron deficiency and iron deficiency anaemia in this cohort, representing the largest study of iron status in toddlers in Europe, to date. The increased consumption of iron-fortified products and compliance with recommendations to limit unmodified cows’ milk intakes in toddlers has contributed to the observed improvements in status. Low serum ferritin concentrations at birth, which reflect neonatal iron stores, were shown to track through to two years of age; delivery by Caesarean section, being born small-for-gestational age and maternal obesity and smoking in pregnancy were all associated with significantly lower neonatal iron stores. Despite a low prevalence of iron deficiency in this cohort, both a mean corpuscular volume <74fl and ferritin concentrations <20μg/l were associated with lower neurodevelopmental outcomes at two years. An inverse association between growth in the second year of life and iron status at two years was also observed. This thesis has presented data from one of the largest, extensively-characterised cohorts of young children, to date, to explore iron and its associations with growth and development.

Allocentric spatial performance higher in early-blind and sighted adults than in retinopathy-of-prematurity adults

The question as to whether people totally blind since infancy process allocentric or ‘external’ spatial information like the sighted has caused considerable debate within the literature. Due to the extreme rarity of the population, researchers have often included individuals with Retinopathy of Prematurity (RoP – over oxygenation at birth) within the sample. However, RoP is inextricably confounded with prematurity per se. Prematurity, without visual disability, has been associated with spatial processing difficulties. In this experiment, blindfolded sighted and two groups of functionally totally blind participants heard text descriptions from a survey (allocentric) or route (egocentric) perspective. One blind group lost their sight due to retinopathy of prematurity (RoP – over oxygenation at birth) and a second group before 24 months of age. The accuracy of participants’ mental representations derived from the text descriptions were assessed via questions and maps. The RoP participants had lower scores than the sighted and early blind, who performed similarly. In other words, it was not visual impairment alone that resulted in impaired allocentric spatial performance in this task, but visual impairment together with RoP. This finding may help explain the contradictions within the existing literature on the role of vision in allocentric spatial processing.

ENVIRONMENTAL INFLUENCES AND EPIGENETIC MECHANISMS IN RISK FOR DEPRESSION

Genetic and environmental factors interact to influence vulnerability for internalizing psychopathology, including Major Depressive Disorder (MDD). The mechanisms that account for how environmental stress can alter biological systems are not yet well understood yet are critical to develop more accurate models of vulnerability and targeted interventions. Epigenetic influences, and more specifically, DNA methylation, may provide a mechanism by which stress could program gene expression, thereby altering key systems implicated in depression, such as frontal-limbic circuitry and its critical role in emotion regulation. This thesis investigated the role of environmental factors from infancy and throughout the lifespan affecting the serotonergic (5-HT) system in the vulnerability to and treatment of depression and anxiety and potential underlying DNA methylation processes. First, we investigated the contributions of additive genetic vs. environmental factors on an early trait phenotype for depression (negative emotionality) in infants and their stability over time in the first 2 years of life. We provided evidence of the substantial contributions of both genetic and shared environmental factors to this trait, as well as genetically- and environmentally- mediated stability and innovation. Second, we studied how childhood environmental stress is associated with peripheral DNA methylation of the serotonin transporter gene, SLC6A4, as well as long-term trajectories of internalizing behaviours. There was a relationship between childhood psychosocial adversity and SLC6A4 methylation in males, as well as between SLC6A4 methylation and internalizing trajectory in both sexes. Third, we investigated changes in emotion processing and epigenetic modification of the SLC6A4 gene in depressed adolescents before and after Mindfulness-Based Cognitive Therapy (MBCT). The alterations from pre- to post-treatment in connectivity between the ACC and other network regions and SLC6A4 methylation suggested that MBCT may work to optimize the connectivity of brain networks involved in cognitive control of emotion as well as also normalize the relationship between SLC6A4 methylation and activation patterns in frontal-limbic circuitry. Our results from these three studies strengthen the theory that environmental influences are critical in establishing early vulnerability factors for MDD, driving epigenetic processes, and altering brain processes as an individual undergoes treatment, or experiences relapse.

Waste Not, Want Not: Managing Perishables in Small and Medium Retail Enterprises

Purpose of this paper:
Recent literature indicates that around one third of perishable products finish as waste (Mena et al., 2014): 60% of this waste can be classified as avoidable (EC, 2010) suggesting logistics and operational inefficiencies along the supply chain. In developed countries perishable products are predominantly wasted in wholesale and retail (Gustavsson et al., 2011) due to customer demand uncertainty the errors and delays in the supply chain (Fernie and Sparks, 2014). While research on logistics of large retail supply chains is well documented, research on retail small and medium enterprises’ (SMEs) capabilities to prevent and manage waste of perishable products is in its infancy (c.f. Ellegaard, 2008) and needs further exploration. In our study, we investigate the retail logistics practice of small food retailers, the factors that contribute to perishable products waste and the barriers and opportunities of SMEs in retail logistics to preserve product quality and participate in reverse logistics flows.

Design/methodology/approach:
As research on waste of perishable products for SMEs is scattered, we focus on identifying key variables that contribute to the creation of avoidable waste. Secondly we identify patterns of waste creation at the retail level and its possibilities for value added recovery. We use explorative case studies (Eisenhardt, 1989) and compare four SMEs and one large retailer that operate in a developed market. To get insights into specificities of SMEs that affect retail logistics practice, we select two types of food retailers: specialised (e.g. greengrocers and bakers) and general (e.g. convenience store that sells perishable products as a part of the assortment)

Findings:
Our preliminary findings indicate that there is a difference between large retailers and SME retailers in factors that contribute to the waste creation, as well as opportunities for value added recovery of products. While more factors appear to affect waste creation and management at large retailers, a small number of specific factors appears to affect SMEs. Similarly, large retailers utilise a range of practices to reduce risks of product perishability and short shelf life, manage demand, and manage reverse logistics practices. Retail SMEs on the other hand have limited options to address waste creation and value added recovery. However, our findings show that specialist SMEs could successfully minimize waste and even create possibilities for value added recovery of perishable products. Data indicates that business orientation of the SME, the buyersupplier relationship, and an extent of adoption of lean principles in retail coupled with SME resources, product specific regulations and support from local authorities for waste management or partnerships with other organizations determine extent of successful preservation of a product quality and value added recovery.

Value:
Our contribution to the SCM academic literature is threefold: first, we identify major factors that contribute to the generation waste of perishable products in retail environment; second, we identify possibilities for value added recovery for perishable products and third, we present opportunities and challenges for SME retailers to manage or participate in activities of value added recovery. Our findings contribute to theory by filling a gap in the literature that considers product quality preservation and value added recovery in the context of retail logistics and SMEs.

Research limitations/implications:
Our findings are limited to insights from five case studies of retail companies that operate within a developed market. To improve on generalisability, we intend to increase the number of cases and include data obtained from the suppliers and organizations involved in reverse logistics flows (e.g. local authorities, charities, etc.).

Practical implications:
With this paper, we contribute to the improvement of retail logistics and operations in SMEs which constitute over 99% of business activities in UK (Rhodes, 2015). Our findings will help retail managers and owners to better understand the possibilities for value added recovery, investigate a range of logistics and retail strategies suitable for the specificities of SME environment and, ultimately, improve their profitability and sustainability.

Jaundice and Hyperbilirubinaemia

Chapter explains the processes by which babies become jaundiced and the physiology of tis condition; explains also the different types of neonatal jaundice

Black-White Wage Gap Among Restaurant Servers: A Replication, Extension, and Exploration of Consumer Racial Discrimination in Tipping

There is a rich history of social science research centering on racial inequalities that continue to be observed across various markets (e.g., labor, housing, and credit markets) and social milieus. Existing research on racial discrimination in consumer markets, however, is relatively scarce and that which has been done has disproportionately focused on consumers as the victims of race-based mistreatment. As such, we know relatively little about how consumers contribute to inequalities in their roles as perpetrators of racial discrimination. In response, in this paper we elaborate on a line of research that is only in its’ infancy stages of development and yet is ripe with opportunities to advance the literature on consumer racial discrimination and racial earnings inequities among tip dependent employees in the United States. Specifically, we analyze data derived from a large exit survey of restaurant consumers (n=378) in an attempt to replicate, extend, and further explore the recently documented effect of service providers’ race on restaurant consumers’ tipping decisions. Our results indicate that both White and Black restaurant customers discriminate against Black servers by tipping them less than their White coworkers. Importantly, we find no evidence that this Black tip penalty is the result of interracial differences in service skills possessed by Black and White servers. We conclude by delineating directions for future research in this neglected but salient area study.

Real-time functional magnetic resonance imaging neurofeedback in motor neurorehabilitation

Purpose of review Recent developments in functional magnetic resonance imaging (fMRI) have catalyzed a new field of translational neuroscience. Using fMRI to monitor the aspects of task-related changes in neural activation or brain connectivity, investigators can offer feedback of simple or complex neural signals/patterns back to the participant on a quasireal-time basis [real-time-fMRI-based neurofeedback (rt-fMRI-NF)]. Here, we introduce some background methodology of the new developments in this field and give a perspective on how they may be used in neurorehabilitation in the future. Recent findings The development of rt-fMRI-NF has been used to promote self-regulation of activity in several brain regions and networks. In addition, and unlike other noninvasive techniques, rt-fMRI-NF can access specific subcortical regions and in principle any region that can be monitored using fMRI including the cerebellum, brainstem and spinal cord. In Parkinson’s disease and stroke, rt-fMRI-NF has been demonstrated to alter neural activity after the self-regulation training was completed and to modify specific behaviours. Summary Future exploitation of rt-fMRI-NF could be used to induce neuroplasticity in brain networks that are involved in certain neurological conditions. However, currently, the use of rt-fMRI-NF in randomized, controlled clinical trials is in its infancy.