Rigid biimidazole ancillary ligands as an avenue to bright deep blue cationic iridium(III) complexes

EZ-C acknowledges the University of St Andrews for financial support. Date of Acceptance: 03/06/2014Herein we report the synthesis and optoelectronic characterisation of three deep blue-emitting cationic iridium complexes, of the form [Ir(dFppy)2(N^N)]PF6, bearing biimidazole-type N^N ancillary ligands (dFppyH = 2-(2,4-difluorophenyl)pyridine). Complex 1 contains the parent biimidazole, biim, while 2 contains a dimethylated analog, dMebiim, and 3 contains an ortho-xylyl-tethered biimidzole, o-xylbiim. We explore a strategy of tethering the biimidazole in order to rigidify the complex and increase the photoluminescent quantum yield, culminating in deep blue (λmax: 457 nm in MeOH at 298 K) ligand-centered emission with a very high photoluminescent quantum yield of 68% and microsecond emission lifetime. Density functional theory calculations elucidate the origin of such disparate excited state kinetics across this series, especially in light of virtually identical optoelectronic properties observed for these compounds.PostprintPeer reviewe

Using Community-Owned Resource Persons to Provide Early Diagnosis and Treatment and Estimate Malaria Burden at Community Level in North-Eastern Tanzania.

Although early diagnosis and prompt treatment is an important strategy for control of malaria, using fever to initiate presumptive treatment with expensive artemisinin combination therapy is a major challenge; particularly in areas with declining burden of malaria. This study was conducted using community-owned resource persons (CORPs) to provide early diagnosis and treatment of malaria, and collect data for estimation of malaria burden in four villages of Korogwe district, north-eastern Tanzania.In 2006, individuals with history of fever within 24 hours or fever (axillary temperature ≥37.5°C) at presentation were presumptively treated using sulphadoxine/pyrimethamine. Between 2007 and 2010, individuals aged five years and above, with positive rapid diagnostic tests (RDTs) were treated with artemether/lumefantrine (AL) while under-fives were treated irrespective of RDT results. Reduction in anti-malarial consumption was determined by comparing the number of cases that would have been presumptively treated and those that were actually treated based on RDTs results. Trends of malaria incidence and slide positivity rates were compared between lowlands and highlands. Of 15,729 cases attended, slide positivity rate was 20.4% and declined by >72.0% from 2008, reaching <10.0% from 2009 onwards; and the slide positivity rates were similar in lowlands and highlands from 2009 onwards. Cases with fever at presentation declined slightly, but remained at >40.0% in under-fives and >20.0% among individuals aged five years and above. With use of RDTs, cases treated with AL decreased from <58.0% in 2007 to <11.0% in 2010 and the numbers of adult courses saved were 3,284 and 1,591 in lowlands and highlands respectively. Malaria incidence declined consistently from 2008 onwards; and the highest incidence of malaria shifted from children aged <10 years to individuals aged 10-19 years from 2009. With basic training, supervision and RDTs, CORPs successfully provided early diagnosis and treatment and reduced consumption of anti-malarials. Progressively declining malaria incidence and slide positivity rates suggest that all fever cases should be tested with RDTs before treatment. Data collected by CORPs was used to plan phase 1b MSP3 malaria vaccine trial and will be used for monitoring and evaluation of different health interventions. The current situation indicates that there is a remarkable changing pattern of malaria and these areas might be moving from control to pre-elimination levels

Clinical presentation and precipitating factors of diabetic ketoacidosis among patients admitted to intensive care unit at a tertiary hospital in Mwanza, Tanzania

Background: Diabetic ketoacidosis (DKA), one of the common emergencies in patient with diabetes mellitus is associated with considerable morbidity and mortality.  This study aimed to determine clinical presentation and precipitating factors of DKA among patients admitted at Bugando Medical Centre (BMC) in north-western Tanzania.Methods: This study involved a retrospective review of hospital records of DKA patients admitted to intensive care unit at BMC during 2012. Data on demographics, precipitating factors, clinical presentation, duration of hospital admission and mortality were extracted and analysed.Results: Total records of 1,906 hospitalized patients in 2012 were reviewed. Of this, 29 (1.5%) had DKA. Of the 29 DKA patients, 18(62.1%) and 11 (37.9%) were males and females, respectively. Among them 21(72.4%) were known diabetics and 8(27.6%) were newly diagnosed to be diabetics. Twelve patients (41.1%) presented with polyuria, polydipsia and general body malaise. Eleven (37.9%) patients presented with loss of consciousness while 6(20.7%), 4(13.8%), 3(10.3%) and 1(3.4%) presented with vomiting, abdominal pain, Kussmaul’s breathing and coma, respectively. Nausea, weight loss and polyphagia each were presented by 2(6.9%) patients. The precipitating factors were infection 15 (51.7%), first presentation of diabetes mellitus 6 (20.7%), missed insulin injection 6 (20.7%) and co-morbid conditions 6 (20.7%). Four (13.8%), 1 (3.45%) and 1(3.45%) had stroke, chronic renal failure and hypertension, respectively. Among the DKA patients, 22 (75.9%) improved and were discharged, and 7 (24.1%) died.Conclusion: DKA occurred in about 1.5% of the patients admitted to ICU and it was a major cause of morbidity and mortality. The main precipitating factor was infection. Since the precipitating factors are preventable, health care providers should put emphasis in educating diabetic patients at the diabetes clinic to reduce morbidity and mortality in these patients

Decomposition of Optically Active Diazo Compounds

In 1921, Levene and Mikeska, and in 1922, Noyes and Chiles prepared optically active esters in which the only possible asymmetric carbon was that doubly bound to diazo nitrogen. Due to this double bond being semipolar the nitrogen loses an electron to the carbon. The asymmetry of the carbon atom would result from the localization of this electron much the same as the localization of the ordinary bond is considered to cause asymmetry

Las mujeres en Nueva Guinea.

En Nueva Guinea, las mujeres se han insertado cada vez más en el proceso productivo de fiorma directa, sin que los hombres se hayan sentido obligados a participar en las tareas domésticas y en la crianza de los hijos

Identifying and Defining the Structures That Guide the Implementation of Participant Direction Programs and Support Program Participants: A Document Analysis

This is the author's accepted manuscript. The published version is available at http://dx.doi.org/10.1177/1044207313514112Participant direction (PD) programs offer the individual with a disability or his or her surrogate decision maker varying degrees of choice and control over the individual’s supports and services. We conducted a document analysis using grounded theory methods to identify the design elements of participant direction programs in long-term care. We analyzed 53 documents across multiple disabilities and funding sources. We identified and defined two major components of participant direction programs: policy and aid and assistance. The component of policy was represented by three structures that guide implementation of participant direction programs: (a) option to participant-direct, (b) participation stipulations, and (c) provider qualifications. The component of aid and assistance was represented by 11 structures that support program participants: (a) financial management services, (b) employer of record, (c) emergency back-up, (d) worker registry, (e) advice/counseling, (f) managerial assistance, (g) information dissemination products, (h) service quality monitoring, (i) service coordination, (j) participant training, and (k) provider training. Each structure was represented by one or more continua depicting the range of choice and control participants may have over the structure. The findings of this study have implications for improving the standardization of research on participant direction programs and the development of long-term care policy

Identifying and defining the activities of participant direction programs: A document analysis

This is the author's accepted manuscript. The published version is available at http://dx.doi.org/10.1177/1044207313502538We analyzed the design of various U.S. programs of participant direction offering participants (individual with a disability or his or her surrogate decision-maker) some level of choice and control over the individual’s long-term care supports and services. We used grounded theory methods to conduct a document analysis of 53 documents published from 2004 through 2008 representing multiple disabilities and program funding sources. In our analysis, we identified three major components (planning, budgeting, and employing) over which participants had the opportunity to exercise choice and control and the activities associated with each. Activities were represented by one or more continua illustrating the range of participant choice and control over the indicator. The component of planning consisted of the activity of care plan development. The budgeting component included the activities of (a) development, (b) individualization, and (c) authority. The employing component included the activities of (a) identifying/selecting providers, (b) hiring/employing providers, (c) scheduling providers, (d) training providers, (e) managing/directing/supervising providers, (f) disciplining/dismissing providers, (g) keeping records, (h) managing payroll, (i) locating emergency back-up, and (j) monitoring service quality. The findings of this study have implications for improving policy, practice, and research in the field of long-term care

Satisfactory safety and immunogenicity of MSP3 malaria vaccine candidate in Tanzanian children aged 12-24 months.

BACKGROUND: Development and deployment of an effective malaria vaccine would complement existing malaria control measures. A blood stage malaria vaccine candidate, Merozoite Surface Protein-3 (MSP3), produced as a long synthetic peptide, has been shown to be safe in non-immune and semi-immune adults. A phase Ib dose-escalating study was conducted to assess the vaccine's safety and immunogenicity in children aged 12 to 24 months in Korogwe, Tanzania (ClinicalTrials.gov number: NCT00469651). METHODS: This was a double-blind, randomized, controlled, dose escalation phase Ib trial, in which children were given one of two different doses of the MSP3 antigen (15 microg or 30 microg) or a control vaccine (Engerix B). Children were randomly allocated either to the MSP3 candidate malaria vaccine or the control vaccine administered at a schedule of 0, 1, and 2 months. Immunization with lower and higher doses was staggered for safety reasons starting with the lower dose. The primary endpoint was safety and reactogenicity within 28 days post-vaccination. Blood samples were obtained at different time points to measure immunological responses. Results are presented up to 84 days post-vaccination. RESULTS: A total of 45 children were enrolled, 15 in each of the two MSP3 dose groups and 15 in the Engerix B group. There were no important differences in reactogenicity between the two MSP3 groups and Engerix B. Grade 3 adverse events were infrequent; only five were detected throughout the study, all of which were transient and resolved without sequelae. No serious adverse event reported was considered to be related to MSP3 vaccine. Both MSP3 dose regimens elicited strong cytophilic IgG responses (subclasses IgG1 and IgG3), the isotypes involved in the monocyte-dependant mechanism of Plasmodium falciparum parasite-killing. The titers reached are similar to those from African adults having reached a state of premunition. Furthermore, vaccination induced seroconversion in all vaccinees. CONCLUSION: The MSP3 malaria vaccine candidate was safe, well tolerated and immunogenic in children aged 12-24 months living in a malaria endemic community. Given the vaccine's safety and its induction of cytophilic IgG responses, its efficacy against P. falciparum infection and disease needs to be evaluated in Phase 2 studies

Deslocamentos no espaço: representações da paisagem na pintura do século XXI no Brasil

No século XXI, o conceito de paisagem e sua representação na pintura continuam se transformando, inclusive em produções brasileiras. Nelas, há um diálogo com a vivência na paisagem brasileira, seus biomas e processos urbanísticos desorganizados. A partir de experiências e deslocamento nesses espaços, os artistas produzem imagens abordando questões mostrando os impasses culturais do país. O objetivo desse artigo é investigar a relação entre a experiência de deslocamento no espaço  com a representação da paisagem na produção de pintura do século XXI no Brasil, tratando dos processos artísticos envolvidos nessas produções. Para isso, serão observadas obras de artistas que tenham o deslocamento no espaço como parte do processo de produção de pintura como: Miguel Penha, David Almeida, Luiz Zerbini e Marina Rheingantz. Este artigo faz o uso de uma metodologia de pesquisa bibliográfica e de análise de imagens, fundamentada em processos artísticos, culturais, históricos e tecnológicos