Thermal and plasma enhanced atomic layer deposition of ultrathin TiO2 on silicon from amide and alkoxide precursors: growth chemistry and photoelectrochemical performance

Due to its low cost and suitable band gap, silicon has been studied as a photoanode material for some time. However, as a result of poor stability during the oxygen evolution reaction (OER), Si still remains unsuitable for any extended use. Ultra-thin titanium dioxide (TiO2) films have been used as protective coatings and are shown to enhance Si photoanode lifetime with added solar to hydrogen performance improvements through distancing the oxidation reaction away from the Si photoanode surface and improved charge transport through the anode. This study details the nucleation, growth chemistry, and performance of TiO2 thin films prepared via thermal and plasma enhanced atomic layer deposition (ALD) using both titanium isopropoxide and tetrakis(dimethylamido)titanium as the precursor material. The effect of post ALD treatments of plasma and air annealing was also studied. Films were investigated using photoelectrochemical cell testing to evaluate photoelectrochemical performance, and in-vacuum cycle-by-cycle x-ray photoelectron spectroscopy was used as the primary characterisation technique to study nucleation mechanisms and film properties contributing to improvements in cell performance. TiO2 grown by plasma enhanced ALD results in cleaner films with reduced carbon incorporation. However, despite increased carbon incorporation, thermally grown films showed improved photocurrent as a result of oxygen vacancies in these films. Post deposition annealing in a H2 ambient is shown to further improve photocurrent in all cases, while annealing in atmosphere leads to uniform film chemistry and enhanced photocurrent stability in all cases

An exploratory study of international opportunity identification among family firms

This research examines how family firms identify international opportunities. Family firms are characterised by long-term orientation, being risk averse, and benefiting from familiness capital, resources and capabilities related to family involvement and interactions. Built upon opportunity identification theory and in two perspectives of accidental discovery and purposeful search, we explore the role of social and business networks, and prior knowledge in a first and subsequent international opportunity identification by family firms. In addition, we attempt to understand the role of family characteristics in the process of opportunity identification. Multiple case studies were carried out with seven family businesses from emerging economies, namely, India, Turkey and Taiwan. The findings of this research illustrate that because of being risk averse and long-term oriented, family firms are more likely to identify the first international opportunity through accidental discovery and subsequent international opportunities through purposeful search. The findings of this research show that, as risk-averse firms, family firms are not proactive in initiating international opportunity identification but rather learn about opportunities through accidental discovery. After the first experience of internationalisation, family firms engage in a more purposeful search to identify avenues that will aid their longevity through internationalisation. In the identification of firms' first international opportunities, it is mainly social networks that play a crucial role, especially those that contain international industry and market-specific knowledge. There is also a positive relationship between a family entrepreneur's prior knowledge and international opportunity identification and this relationship is moderated by the prior knowledge of their network. Familiness capital of these organisations can also play a role in long-term international opportunity identification

Tephrochronology

Tephrochronology is the use of primary, characterized tephras or cryptotephras as chronostratigraphic marker beds to connect and synchronize geological, paleoenvironmental, or archaeological sequences or events, or soils/paleosols, and, uniquely, to transfer relative or numerical ages or dates to them using stratigraphic and age information together with mineralogical and geochemical compositional data, especially from individual glass-shard analyses, obtained for the tephra/cryptotephra deposits. To function as an age-equivalent correlation and chronostratigraphic dating tool, tephrochronology may be undertaken in three steps: (i) mapping and describing tephras and determining their stratigraphic relationships, (ii) characterizing tephras or cryptotephras in the laboratory, and (iii) dating them using a wide range of geochronological methods. Tephrochronology is also an important tool in volcanology, informing studies on volcanic petrology, volcano eruption histories and hazards, and volcano-climate forcing. Although limitations and challenges remain, multidisciplinary applications of tephrochronology continue to grow markedly

Tephrochronology and its application: A review

Tephrochronology (from tephra, Gk ‘ashes’) is a unique stratigraphic method for linking, dating, and synchronizing geological, palaeoenvironmental, or archaeological sequences or events. As well as utilising the Law of Superposition, tephrochronology in practise requires tephra deposits to be characterized (or ‘fingerprinted’) using physical properties evident in the field together with those obtained from laboratory analyses. Such analyses include mineralogical examination (petrography) or geochemical analysis of glass shards or crystals using an electron microprobe or other analytical tools including laser-ablation-based mass spectrometry or the ion microprobe. The palaeoenvironmental or archaeological context in which a tephra occurs may also be useful for correlational purposes. Tephrochronology provides greatest utility when a numerical age obtained for a tephra or cryptotephra is transferrable from one site to another using stratigraphy and by comparing and matching inherent compositional features of the deposits with a high degree of likelihood. Used this way, tephrochronology is an age-equivalent dating method that provides an exceptionally precise volcanic-event stratigraphy. Such age transfers are valid because the primary tephra deposits from an eruption essentially have the same short-lived age everywhere they occur, forming isochrons very soon after the eruption (normally within a year). As well as providing isochrons for palaeoenvironmental and archaeological reconstructions, tephras through their geochemical analysis allow insight into volcanic and magmatic processes, and provide a comprehensive record of explosive volcanism and recurrence rates in the Quaternary (or earlier) that can be used to establish time-space relationships of relevance to volcanic hazard analysis. The basis and application of tephrochronology as a central stratigraphic and geochronological tool for Quaternary studies are presented and discussed in this review. Topics covered include principles of tephrochronology, defining isochrons, tephra nomenclature, mapping and correlating tephras from proximal to distal locations at metre- through to sub-millimetre-scale, cryptotephras, mineralogical and geochemical fingerprinting methods, numerical and statistical correlation techniques, and developments and applications in dating including the use of flexible depositional age-modelling techniques based on Bayesian statistics. Along with reference to wide-ranging examples and the identification of important recent advances in tephrochronology, such as the development of new geoanalytical approaches that enable individual small glass shards to be analysed near-routinely for major, trace, and rare-earth elements, potential problems such as miscorrelation, erroneous-age transfer, and tephra reworking and taphonomy (especially relating to cryptotephras) are also examined. Some of the challenges for future tephrochronological studies include refining geochemical analytical methods further, improving understanding of cryptotephra distribution and preservation patterns, improving age modelling including via new or enhanced radiometric or incremental techniques and Bayesian-derived models, evaluating and quantifying uncertainty in tephrochronology to a greater degree than at present, constructing comprehensive regional databases, and integrating tephrochronology with spatially referenced environmental and archaeometric data into 3-D reconstructions using GIS and geostatistics

Performance-based vs socially supportive culture:a cross-national study of descriptive norms and entrepreneurship

This paper is a cross-national study testing a framework relating cultural descriptive norms to entrepreneurship in a sample of 40 nations. Based on data from the Global Leadership and Organizational Behavior Effectiveness project, we identify two higher-order dimensions of culture – socially supportive culture (SSC) and performance-based culture (PBC) – and relate them to entrepreneurship rates and associated supply-side and demand-side variables available from the Global Entrepreneurship Monitor. Findings provide strong support for a social capital/SSC and supply-side variable explanation of entrepreneurship rate. PBC predicts demand-side variables, such as opportunity existence and the quality of formal institutions to support entrepreneurship

The Role of Purported Mucoprotectants in Dealing with Irritable Bowel Syndrome, Functional Diarrhea, and Other Chronic Diarrheal Disorders in Adults

Chronic diarrhea is a frequent presenting symptom, both in primary care medicine and in specialized gastroenterology units. It is estimated that more than 5% of the global population suffers from chronic diarrhea. and that about 40% of these subjects are older than 60 years. The clinician is frequently faced with the need to decide which is the best therapeutic approach for these patients. While the origin of chronic diarrhea is diverse, impairment of intestinal barrier function, dysbiosis. and mucosal micro-inflammation are being increasingly recognized as underlying phenomena characterizing a variety of chronic diarrheal diseases. In addition to current pharmacological therapies, there is growing interest in alternative products such as mucoprotectants, which form a mucoadhesive film over the epithelium to reduce and protect against the development of altered intestinal permeability, dysbiosis, and mucosal micro-inflammation. This manuscript focuses on chronic diarrhea in adults, and we will review recent evidence on the ability of these natural compounds to improve symptoms associated with chronic diarrhea and to exert protective effects for the intestinal barrier

Heterozygous Variants in KMT2E Cause a Spectrum of Neurodevelopmental Disorders and Epilepsy.

We delineate a KMT2E-related neurodevelopmental disorder on the basis of 38 individuals in 36 families. This study includes 31 distinct heterozygous variants in KMT2E (28 ascertained from Matchmaker Exchange and three previously reported), and four individuals with chromosome 7q22.2-22.23 microdeletions encompassing KMT2E (one previously reported). Almost all variants occurred de novo, and most were truncating. Most affected individuals with protein-truncating variants presented with mild intellectual disability. One-quarter of individuals met criteria for autism. Additional common features include macrocephaly, hypotonia, functional gastrointestinal abnormalities, and a subtle facial gestalt. Epilepsy was present in about one-fifth of individuals with truncating variants and was responsive to treatment with anti-epileptic medications in almost all. More than 70% of the individuals were male, and expressivity was variable by sex; epilepsy was more common in females and autism more common in males. The four individuals with microdeletions encompassing KMT2E generally presented similarly to those with truncating variants, but the degree of developmental delay was greater. The group of four individuals with missense variants in KMT2E presented with the most severe developmental delays. Epilepsy was present in all individuals with missense variants, often manifesting as treatment-resistant infantile epileptic encephalopathy. Microcephaly was also common in this group. Haploinsufficiency versus gain-of-function or dominant-negative effects specific to these missense variants in KMT2E might explain this divergence in phenotype, but requires independent validation. Disruptive variants in KMT2E are an under-recognized cause of neurodevelopmental abnormalities

Using an Intersectional Approach to Explore the Lived Mental Health Experiences of Traveller Men Affected by Suicide in Ireland

Rates of suicide are seven times higher among Traveller men, an Indigenous ethnic minority group in Ireland, compared with non-Traveller men. Several factors are implicated, including racism, social exclusion, discrimination, inadequate accommodation, unemployment, and lower educational attainment. Systemic and cultural barriers inhibit Traveller men from seeking support. This study addresses a gap in the literature by exploring the lived mental health experiences of Traveller men affected by suicide. Semi-structured interviews ( n = 13; aged 19–50) were conducted with Traveller men affected by suicide. Interviews were recorded and transcribed verbatim. Thematic content analysis was used to analyze the data, which yielded three broad themes. Theme 1, “key determinants of Traveller men’s mental health,” describes the impact on Traveller men of issues relating to accommodation/homelessness, education, and unemployment, as well as frequent exposure to prejudice, discrimination, and racism. Theme 2, “contemporary Traveller masculinities,” considers how Traveller masculinities were shaped by a patrilineal tradition and by historical/ongoing tensions related to their ethnicity. Theme 3, “navigating support seeking and coping with distress,” encapsulates both resistant and proactive approaches used by participants to manage their mental health. The intersection of structural inequalities, internalized racism, Traveller masculinities, and strong historical associations between stigma and mental health/suicide within the Traveller community lies at the heart of the heavy burden of suicide carried by Traveller men. Findings provide a deeper understanding of the sources of distress and pathways to resilience/recovery among Traveller men affected by suicide and can inform the development of more gender- and culturally appropriate suicide prevention interventions