Structural- and Spectroscopic-Reactivity Relationships of Nonheme Oxoiron(IV) Complexes

University of Minnesota Ph.D. dissertation. May 2019. Major: Chemistry. Advisor: Lawrence Que. 1 computer file (PDF); xxii, 247 pages.Non-heme oxoiron(IV) motifs have been identified as key intermediates that activate strong C—H bonds. Unlike the enzymatic intermediates however, most oxoiron(IV) complexes in synthetic chemistry have a triplet ground spin state and thus differ in their functional and electronic properties from the S = 2 units characterized in the enzymes. One striking exception is the complex [FeIV(O)(TQA)(L)]2+, where TQA = tris(2-quinolylmethyl)amine, which has Mössbauer parameters that closely resemble those of TauD-J, an enzymatic intermediate that has been relatively well-characterized. This oxoiron(IV) complex contains quinoline donors, and its thermal instability precludes its structural characterization (half-life = 15 minutes at 233 K). In this dissertation, several oxoiron(IV) complexes supported by pentadentate and tetradentate ligands are characterized, and examined for their reactivity and spectroscopic features. Crystallographic characterization of a few of these molecules is also reported. The structurally characterized oxoiron(IV) complexes along with some previously reported oxoiron(IV) complexes are used to set up structure-reactivity and spectroscopic-reactivity relationships, and show linear correlations with increasing isomer shifts, λmax values as well as metal-ligand distances. In addition, this thesis also uses 1H-NMR spectroscopy as an effective tool to identify solution-state structure as well the spin state of oxoiron(IV) complexes. We also characterize the first example of a spin crossover oxoiron(IV) complex, examples of which are only seen in iron(II) and iron(III) complexes

Epidemiology and clinical outcomes of hospitalized Hispanic patients with IBD: results of a large national cohort study.

INTRODUCTION: Inflammatory bowel disease (IBD) has historically been seen as predominantly affecting non-Hispanic Whites (NHW). Hispanics are the largest minority group in the USA, yet they remain grossly underrepresented in studies of IBD. With this study, we aimed to better understand the epidemiology of hospitalized Hispanic patients with IBD in the US. METHODS: This was a retrospective cohort study utilizing the National Inpatient Sample, the largest publicly available all-payer inpatient care database in the United States. We compared demographics, hospitalization characteristics, clinical outcomes, and year-to-year trends from 2016 to 2020 in Hispanic and NHW with a primary diagnosis of inflammatory bowel disease, Crohns disease, or ulcerative colitis. RESULTS: NHWs hospitalized with a primary diagnosis of IBD had significantly higher rates of hospitalization than Hispanics (122.67 vs 71.12, P < 0.01). While hospitalized Hispanics with IBD are more likely to be in the lowest quartile for household income (31.6% vs 19.3%, P < 0.01), have a younger median age (37.0 vs 45.0, P < 0.01), and be uninsured (4.3% vs 8.8%, P < 0.01) compared to NHW. Length of admission was similar, yet NHWs had higher rates of mortality (0.3% vs 0.2%, P = 0.01), while total charges for hospitalizations were significantly higher for Hispanic patients (P < 0.01). DISCUSSION: To our knowledge, this is one of the largest US-based studies of Hispanics with IBD. Our findings suggest that among hospitalized IBD patients, Hispanics are more likely to be younger, uninsured, have a lower household income, and are less likely to undergo surgery while having higher hospital charges

Organizational Resilience: A Dynamic Capability of Complex Systems

In recent years, the concept of organizational resilience has largely attracted the interest of academicians and practitioners alike. A fair number of researches have been conducted on developing the concept of organizational resilience. However, there seems to be a lack of consensus over its conceptualization mainly because the concept itself is prodigious and is used in a variety of disciplines. Furthermore, research within the domain of organizational resilience has been outcome oriented; however, questions addressing the drivers of resilience are yet to be answered. On the other hand, research within the domain of dynamic capabilities view have long been criticized as tautological, resistant to operationalization, and lacking the unification of thought. However, there exists a sufficient degree of conceptual similitude between the two concepts, mainly due to their epistemological similarities grounded within the theoretical assumptions of chaotic systems, environmental dynamism, and systems thinking. Incorporating both perspectives in parallel for understanding the theoretical connections can lead to clarifications at an ontological level. Therefore, this paper attempts to propose a holistic model of organizational resilience by incorporating a lens metaphor of dynamic capabilities view. This paper is divided into four sections. The first section of this paper lays down the multidisciplinary discourses within the realm of organizational resilience. The second section highlights the management discourse about the conceptualization of organizational resilience. The third section of this paper uses a lens metaphor of dynamic capabilities view in an attempt to add depth to the concept of organizational resilience. The fourth and the final section attempts to propose the drivers of organizational resilience from a strategic viewpoint

Novel VPS13B Mutations in Three Large Pakistani Cohen Syndrome Families Suggests a Baloch Variant with Autistic-Like Features.

BackgroundCohen Syndrome (COH1) is a rare autosomal recessive disorder, principally identified by ocular, neural and muscular deficits. We identified three large consanguineous Pakistani families with intellectual disability and in some cases with autistic traits.MethodsClinical assessments were performed in order to allow comparison of clinical features with other VPS13B mutations. Homozygosity mapping followed by whole exome sequencing and Sanger sequencing strategies were used to identify disease-related mutations.ResultsWe identified two novel homozygous deletion mutations in VPS13B, firstly a 1 bp deletion, NM_017890.4:c.6879delT; p.Phe2293Leufs*24, and secondly a deletion of exons 37-40, which co-segregate with affected status. In addition to COH1-related traits, autistic features were reported in a number of family members, contrasting with the "friendly" demeanour often associated with COH1. The c.6879delT mutation is present in two families from different regions of the country, but both from the Baloch sub-ethnic group, and with a shared haplotype, indicating a founder effect among the Baloch population.ConclusionWe suspect that the c.6879delT mutation may be a common cause of COH1 and similar phenotypes among the Baloch population. Additionally, most of the individuals with the c.6879delT mutation in these two families also present with autistic like traits, and suggests that this variant may lead to a distinct autistic-like COH1 subgroup

Spectrum of Breast Diseases in a Breast Clinic of a Tertiary Care Hospital

Background: To determine the pattern and clinical presentation of breast diseases in different age groups presenting to a breast clinic. Methods: It was a retrospective descriptive study which included all patients presenting to a breast clinic for three years. Age at presentation, symptoms, clinical features, investigations, operative findings and specimen reports were recorded and submitted for analysis. . Results: A total of 3568 patients were included. Mastalgia was the commonest findings (39.42%) followed by fibroadenoma(15.83%) and carcinoma of breast (12.61%). Pain in the breast was the commonest presenting symptom (40.38%). Lump in the breast was found in 22.84%, while pain and lump were present in 27.27% of patients. Among carcinoma breast, intra ductal carcinoma was the commonest (57.55%) followed by malignant phyllodes tumour (17.77%). Conclusion: Most common breast diseases presenting in our setting are mastalgia, fibroadenoma and breast carcinoma. Dedicated breast clinic in our public sector hospitals is need of time. It will help to create awareness about breast diseases among general public and will be a source to collect data about disease burden so that future policies can be streamline

A Shift From Logistic Software to Service Model: A Case Study of New Service-Driven-Software for Management of Emergency Supplies During Disasters and Emergency Conditions by WHO

World Health Organization (WHO) states access to medicine as a priority area for universal health coverage, wherein a well-functioning medicine supply chain is indispensable. Optimization of supply chains to cut losses related to overstocking, expiration, and inefficiencies protect the investments and strengthen health systems to better deliver the health services. This article shares the experience of developing a service-driven-software for pharmaceutical supplies during emergency conditions and disasters, and the advantages gained. In 2005, Logistic Support System (LSS), the updated version of SUMA (Supply Management), was introduced by WHO during the earthquake in Pakistan which had offered valuable but limited services to many countries. Moving from ad hoc to a more organized approach, the medical donations and stockpiles of essential medicinal supplies were inventoried on LSS database for managing the dispatch of medical supplies to the disaster-hit area in a shortest possible time. Post disaster rescue and rehabilitation work further instigated the need for development of a new software, Pharmaceutical Information Management System (PIMS), that was effective in the emergency as well as routine inventory operations. It was used for efficient and improved access of medicines and faster decision making. The new systems proved vital to anticipate over/under stocking through proactive alerts and prompting. The updated information on epidemiological and drug utilization needs were crucial for the effective quantification and ordering throughout the supply chain. Implementation of PIMS demanded appreciable customization including conversion of system from stand-alone to online system with consolidation of information on stocks from all locations. Provision of multi-user option allowed facilitation according to the user authorization, and was equipped with improved-speed, efficiency, and security. PIMS was successfully replicated by the pioneer team of pharmacist from Pakistan in other countries

Emotional burden and psychological distress in caregivers of patients with obsessive compulsive disorder

Objective: To explore the prevalence and association of emotional burden with anxiety, depression, and stress among caregivers of patients with Obsessive-Compulsive Disorder (OCD) in Southern Punjab, Pakistan. Methods: This descriptive cross-sectional study was conducted from May to December 2022 at Nishtar Medical University and hospital, Multan, Districts Head Quarters Hospital Khanewal and D.G Khan Teaching Hospital in Southern Punjab. A total of 220 caregivers (males: 89; females: 131) aged 18–60 years were recruited using a convenient sampling method. Sociodemographic data and caregiver burden were assessed using Zarit Burden Interview and Depression Anxiety Stress Scale. Data were analyzed using SPSS-21.  Results: Most caregivers (74.5%) belonged to nuclear families, and 68.2% resided in urban areas. Caregiver burden was significant, with 74.5% experiencing severe levels and 21.4% reporting moderate levels. Anxiety was the most severe distress, with 76.8% experiencing severe to extremely severe levels, followed by moderate depression (57.7%) and stress, predominantly mild (48.2%) to moderate (44.5%). Caregiver burden correlated positively with anxiety (r = 0.380, p < 0.01) and depression (r = 0.340, p < 0.05) but not with stress (r = 0.048). Female caregivers reported slightly lower anxiety and depression scores compared to males. Mothers were the most common caregivers (57.7%), and 56.8% had cared for the patient for over 5 years, highlighting long-term caregiving challenges. Conclusion: Caregivers of OCD patients in Southern Punjab, especially females, face significant emotional and psychological burdens. Severe anxiety, depression, and stress are common, emphasizing the need for targeted interventions to support their mental health

International Trade of Pharmaceutical and Health Industries Along the “Belt and Road” Countries

In recent years, the medical and health industry has become a new engine for global economic development. As a cluster of industries, the level of world's medical and health industry varies. Standards, as a comprehensive reflection and strategic resource of the competitiveness of enterprises, industries, regions, and even countries, have become an important experience and basic consensus for economic development at home and abroad. This article conducts research on the current status of standardization in the pharmaceutical and health industry both domestically and internationally. This study mainly analyzes the bilateral trade volume and industrial structure of pharmaceutical products between China and countries along the “Belt and Road” (BR), and empirically analyzes the influencing factors of pharmaceutical products trade between China and countries along the "Belt and Road" according to the trade situation. Using the explicit comparison index, the trade complementarity index, and the trade intensity index, select fifteen countries that are representative of the trade of pharmaceutical products in China and the regions along "the Belt and Road." Then, divide pharmaceutical products into traditional Chinese medicine and western medicine. Finally, analyze the problems and challenges that are associated with pharmaceutical products in China and sample countries. Through comparative analysis of organizational structure, standard system, and standard formulation and revision, combined with the practical experience of standardization in BR countries' pharmaceutical and health industry trade, measures and suggestions are proposed on how to accelerate the role of adjustment in pharmaceutical and health industry trade

Interlinkages Between Financial Markets and Minerals(1990–2023): Implications for Global Energy Transitions and Environmental Sustainability

This paper examines the nexus between financial markets (FM), mineral resources, and global energy transitions (ET) between1990 and 2023 in the 20 leading countries exporting mineral resources, focusing on their impact on environmental sustainabil-ity. Cross-sectional ARDL, augmented mean group (AMG), and common correlated effects mean group (CCEMG) estimatorsare used for cross-sectional analysis of developed and developing countries. The findings suggest that mineral markets (MM)play a pivotal role in guaranteeing sustainable energy shifts, and FM negatively impacts the situation in the short and long term.Renewable energy consumption (REC), external investment, and digital governance (DGI) are developed countries' primarystrategies for achieving COP-26 sustainability objectives. The findings indicate that the Digital Governance Index (DGI) andFDI have varied impacts on energy transition in the economies. Developed countries enjoy the opportunities of improved andmodernised digital systems and green FDI. In contrast, developing countries must strengthen e-governance and encourage sus-tainable investments to support SDGs 7, 9, and 1