Computational chemistry of organometallic and inorganic species

This thesis presents computational investigations of problems related to redox processes and structural rearrangement in inorganic systems. Density functional theory has been used to gain insight into the origin and nature of such reactions. The work presented concerns two main topics: hydrogenase-like systems containing an Fe2 core and carbonphosphorus cluster compounds. In chapters II and III, we describe the impact of reduction, an important phenomenon in the H2 production catalytic cycle, on a hydrogenase-like model. In collaboration with Talarmin and co-workers who have conducted careful electrochemical studies, we have used DFT to identify structures of species observed in cyclic voltammetry. We have also studied the binding of a proton to similar systems and, through the calculation of chemical shifts and coupling constants, confirmed the structures of iron hydrides observed by 1H NMR spectroscopy. In chapter V we focus on carbon-phosphorus systems that can exist in 2 or more isomeric forms. We address first the case of a system of formula C6H4P3 which has the right valence configuration to exist either as a planar structure or as a 3-dimensional cluster (nido according to Wade’s rules). We then examine whether it is possible to control the preferred conformation by the addition of substituents on the phenyl ring. Finally, we look at the rearrangement of a planar diphosphene into a cage isomer and try to understand the mechanism and in particular the role of the protonation in the conversion from planar to 3-dimensional structure

Ageing in rural China: migration and care circulation

This article applies the concept of care circulation (Baldassar and Merla, Transnational families, migration and the circulation of care: understanding mobility and absence in family life, 2013) to the processes involved in the care of old people in rural China,an area which has hitherto been predominantly located in a quantitatively based intergenerational transfer framework. Drawing upon a qualitative study of rural families in the context of rural to urban migration, this article examines the multidirectional and asymmetrical exchanges of caregiving and care-receiving and seeks to provide a more nuanced understanding of the impact of migration upon ageing and familial care in rural China. First, going beyond a unidirectional flow or two-way transfer, this article reveals that care circulates between different family members, in different locations, to differing degrees, over the life course. This circulation framework enables an examination of intra-generational dynamics as well as intergenerational relations. Second, this article draws attention to the mediating factors that impact upon the ways in which adult children care for the older generation. It reveals how the employment status of migrating adult children, the temporal dimension of migration and family life cycle of migrating children as well as family relations between the older generation and adult child generation are critical factors. These factors also contribute to the quality of care provided. Finally, while confirming existing scholarship that gender is an important dimension in structuring old age support in rural China, this article calls for a more differentiated approach among generations of women and between regions, revealing the ways in which local migration history interacts with intergenerational dynamics to determine the cohort of women that endure the greatest burden of care

The Structure and Origin of Switchbacks: Parker Solar Probe Observations

Switchbacks are rapid magnetic field reversals that last from seconds to hours. Current Parker Solar Probe (PSP) observations pose many open questions in regards to the nature of switchbacks. For example, are they stable as they propagate through the inner heliosphere, and how are they formed? In this work, we aim to investigate the structure and origin of switchbacks. In order to study the stability of switchbacks, we suppose the small scale current sheets therein may work to braid and stabilize the switchbacks. Thus, we use the partial variance of increments method to identify the small scale current sheets, and then compare their distributions in switchbacks. With more than one thousand switchbacks identified with PSP observations in seven encounters, we find many more current sheets inside than outside switchbacks, indicating that these micro-structures should work to stabilize the S-shape structures of switchbacks. Additionally, with the helium measurements, we study the variations of helium abundance ratios and alpha-proton differential speeds to trace switchbacks to their origins. We find both helium-rich and helium-poor populations in switchbacks, implying the switchbacks could originate from both closed and open magnetic field regions in the Sun. Moreover, we observe that the alpha-proton differential speeds also show complex variations as compared to the local Alfv\'en speed. The joint distributions of both parameters show that low helium abundance together with low differential speed is the dominant state in switchbacks. The presence of small scale current sheets in switchbacks along with the helium features are in line with the hypothesis that switchbacks could originate from the Sun via interchange reconnection process. However, other formation mechanisms are not excluded

Meeting the home-care needs of disabled older persons living in the community: does integrated services delivery make a difference?

<p>Abstract</p> <p>Background</p> <p>The PRISMA Model is an innovative coordination-type integrated-service-delivery (ISD) network designed to manage and better match resources to the complex and evolving needs of elders. The goal of this study was to examine the impact of this ISD network on unmet needs among disabled older persons living in the community.</p> <p>Methods</p> <p>Using data from the PRISMA study, we compared unmet needs of elders living in the community in areas with or without an ISD network. Disabilities and unmet needs were assessed with the Functional Autonomy Measurement System (SMAF). We used growth-curve analysis to examine changes in unmet needs over time and the variables associated with initial status and change. Sociodemographic characteristics, level of disability, self-perceived health status, cognitive functioning, level of empowerment, and the hours of care received were investigated as covariates. Lastly, we report the prevalence of needs and unmet needs for 29 activities in both areas at the end of the study.</p> <p>Results</p> <p>On average, participants were 83 years old; 62% were women. They had a moderate level of disability and mild cognitive problems. On average, they received 2.07 hours/day (SD = 1.08) of disability-related care, mostly provided by family. The findings from growth-curve analysis suggest that elders living in the area where ISD was implemented and those with higher levels of disability experience better fulfillment of their needs over time. Besides the area, being a woman, living alone, having a higher level of disability, more cognitive impairments, and a lower level of empowerment were linked to initial unmet needs (r²= 0.25; p < 0.001). At the end of the study, 35% (95% CI: 31% to 40%) of elders with needs living in the ISD area had at least one unmet need, compared to 67% (95% CI: 62% to 71%) in the other area. In general, unmet needs were highest for bathing, grooming, urinary incontinence, walking outside, seeing, hearing, preparing meals, and taking medications.</p> <p>Conclusions</p> <p>In spite of more than 30 years of home-care services in the province of Quebec, disabled older adults living in the community still have unmet needs. ISD networks such as the PRISMA Model, however, appear to offer an effective response to the long-term-care needs of the elderly.</p

Anti-infectives in Drug Delivery-Overcoming the Gram-Negative Bacterial Cell Envelope.

Infectious diseases are becoming a major menace to the state of health worldwide, with difficulties in effective treatment especially of nosocomial infections caused by Gram-negative bacteria being increasingly reported. Inadequate permeation of anti-infectives into or across the Gram-negative bacterial cell envelope, due to its intrinsic barrier function as well as barrier enhancement mediated by resistance mechanisms, can be identified as one of the major reasons for insufficient therapeutic effects. Several in vitro, in silico, and in cellulo models are currently employed to increase the knowledge of anti-infective transport processes into or across the bacterial cell envelope; however, all such models exhibit drawbacks or have limitations with respect to the information they are able to provide. Thus, new approaches which allow for more comprehensive characterization of anti-infective permeation processes (and as such, would be usable as screening methods in early drug discovery and development) are desperately needed. Furthermore, delivery methods or technologies capable of enhancing anti-infective permeation into or across the bacterial cell envelope are required. In this respect, particle-based carrier systems have already been shown to provide the opportunity to overcome compound-related difficulties and allow for targeted delivery. In addition, formulations combining efflux pump inhibitors or antimicrobial peptides with anti-infectives show promise in the restoration of antibiotic activity in resistant bacterial strains. Despite considerable progress in this field however, the design of carriers to specifically enhance transport across the bacterial envelope or to target difficult-to-treat (e.g., intracellular) infections remains an urgently needed area of improvement. What follows is a summary and evaluation of the state of the art of both bacterial permeation models and advanced anti-infective formulation strategies, together with an outlook for future directions in these fields

Researching COVID to Enhance Recovery (RECOVER) Adult Study Protocol: Rationale, Objectives, and Design

IMPORTANCE: SARS-CoV-2 infection can result in ongoing, relapsing, or new symptoms or other health effects after the acute phase of infection; termed post-acute sequelae of SARS-CoV-2 infection (PASC), or long COVID. The characteristics, prevalence, trajectory and mechanisms of PASC are ill-defined. The objectives of the Researching COVID to Enhance Recovery (RECOVER) Multi-site Observational Study of PASC in Adults (RECOVER-Adult) are to: (1) characterize PASC prevalence; (2) characterize the symptoms, organ dysfunction, natural history, and distinct phenotypes of PASC; (3) identify demographic, social and clinical risk factors for PASC onset and recovery; and (4) define the biological mechanisms underlying PASC pathogenesis. METHODS: RECOVER-Adult is a combined prospective/retrospective cohort currently planned to enroll 14,880 adults aged ≥18 years. Eligible participants either must meet WHO criteria for suspected, probable, or confirmed infection; or must have evidence of no prior infection. Recruitment occurs at 86 sites in 33 U.S. states, Washington, DC and Puerto Rico, via facility- and community-based outreach. Participants complete quarterly questionnaires about symptoms, social determinants, vaccination status, and interim SARS-CoV-2 infections. In addition, participants contribute biospecimens and undergo physical and laboratory examinations at approximately 0, 90 and 180 days from infection or negative test date, and yearly thereafter. Some participants undergo additional testing based on specific criteria or random sampling. Patient representatives provide input on all study processes. The primary study outcome is onset of PASC, measured by signs and symptoms. A paradigm for identifying PASC cases will be defined and updated using supervised and unsupervised learning approaches with cross-validation. Logistic regression and proportional hazards regression will be conducted to investigate associations between risk factors, onset, and resolution of PASC symptoms. DISCUSSION: RECOVER-Adult is the first national, prospective, longitudinal cohort of PASC among US adults. Results of this study are intended to inform public health, spur clinical trials, and expand treatment options

Firms' Pattern of Trade and Access to Finance

This paper summarizes recent advances in the empirical research on firms' learning from trade participation and the role of finance in both starting to trade, surviving in export markets as well as expanding along the intensive and extensive trade margins. It highlights the increased importance of imports, which impacts at firms' perfirmance primarily through relaxed technological constraints by increasing firms' scope of inputs and by lowering their input price index. In addition, imports are shown to boost firms' innovation and introduction of new products, which facilitates firms' decisions to start exporting. Another important aspect that has been highlighted is the essential role of finance in furthering firms' survival and expansion in export markets

Control of Oxo-Group Functionalization and Reduction of the Uranyl Ion

yesUranyl complexes of a large, compartmental N8-macrocycle adopt a rigid, “Pacman” geometry that stabilizes the UV oxidation state and promotes chemistry at a single uranyl oxo-group. We present here new and straightforward routes to singly reduced and oxo-silylated uranyl Pacman complexes and propose mechanisms that account for the product formation, and the byproduct distributions that are formed using alternative reagents. Uranyl(VI) Pacman complexes in which one oxo-group is functionalized by a single metal cation are activated toward single-electron reduction. As such, the addition of a second equivalent of a Lewis acidic metal complex such as MgN″2 (N″ = N(SiMe3)2) forms a uranyl(V) complex in which both oxo-groups are Mg functionalized as a result of Mg−N bond homolysis. In contrast, reactions with the less Lewis acidic complex [Zn(N″)Cl] favor the formation of weaker U−O−Zn dative interactions, leading to reductive silylation of the uranyl oxo-group in preference to metalation. Spectroscopic, crystallographic, and computational analysis of these reactions and of oxo-metalated products isolated by other routes have allowed us to propose mechanisms that account for pathways to metalation or silylation of the exo-oxogroup