31 research outputs found

    Fragmentation pathways of [Re₂(μ-OR)₃(CO)₆]– (R = H, Me) and ligand exchange reactions with oxygen donor ligands, investigated by electrospray mass spectrometry

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    The rhenium hydroxy and methoxy carbonyl complexes [Re₂(μOR)₃(CO)₆]⁻ (R = H or Me) have been studied by negative-ion electrospray mass spectrometry (ESMS). The complexes undergo facile exchange reactions with protic compounds, including alcohols and phenols. With dimethyl malonate, ester hydrolysis occurs giving carboxylate-containing complexes, and with H₂O₂ or ButOOH, oxidation to ReO₄⁻occurs. The feasibility and extent of these reactions can conveniently, rapidly, and unambiguously be determined by electrospray mass spectrometry, and is dependent on the acidity and steric bulk of the protic compound. The results also suggest that the complexes can be used as versatile starting materials for the synthesis of a wide range of analogous [Re₂(μ-OR)₃(CO)₆]⁻ complexes by simple reaction with an excess of the appropriate alcohol. By varying the applied cone voltage the fragmentation pathways have been investigated; the hydroxy complex undergoes dehydration followed by CO loss, whereas for the methoxy complex -hydride elimination (and CO loss) is observed, with confirmation provided by deuterium labelling studies. Under ESMS conditions, the neutral complexes [Re₂(μ-OR)₂(μ-dppf )(CO)₆] [R = H or Me; dppf = 1,1 -bis(diphenylphosphino)ferrocene] undergo substantial solvolysis and hydrolysis to give mainly mononuclear species; simple parent ions (e.g. [M + H]⁺) are not formed in appreciable abundance, probably due to the lack of an efficient ionisation pathway

    Staphylococcus aureus Bacteremia in Children of Rural Areas of The Gambia, 2008–2015

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    Staphylococcus aureus bacteremia is a substantial cause of childhood disease and death, but few studies have described its epidemiology in developing countries. Using a population-based surveillance system for pneumonia, sepsis, and meningitis, we estimated S. aureus bacteremia incidence and the case-fatality ratio in children <5 years of age in 2 regions in the eastern part of The Gambia during 2008–2015. Among 33,060 children with suspected pneumonia, sepsis, or meningitis, we performed blood culture for 27,851; of 1,130 patients with bacteremia, 198 (17.5%) were positive for S. aureus. S. aureus bacteremia incidence was 78 (95% CI 67–91) cases/100,000 person-years in children <5 years of age and 2,080 (95% CI 1,621–2,627) cases/100,000 person-years in neonates. Incidence did not change after introduction of the pneumococcal conjugate vaccine. The case-fatality ratio was 14.1% (95% CI 9.6%–19.8%). Interventions are needed to reduce the S. aureus bacteremia burden in The Gambia, particularly among neonates

    Expression profiles of genes involved in TLRs and NLRs signaling pathways of water buffaloes infected with Fasciola gigantica

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    Infection of ruminants and humans with Fasciola gigantica is attracting increasing attention due to its economic impact and public health significance. However, little is known of innate immune responses during F. gigantica infection. Here, we investigated the expression profiles of genes involved in Toll-like receptors (TLRs) and NOD-like receptors (NLRs) signaling pathways in buffaloes infected with 500 F. gigantica metacercariae. Serum, liver and peripheral blood mononuclear cell (PBMC) samples were collected from infected and control buffaloes at 3, 10, 28, and 70 days post infection (dpi). Then, the levels of 12 cytokines in serum samples were evaluated by ELISA. Also, the levels of expression of 42 genes, related to TLRs and NLRs signaling, in liver and PBMCs were determined using custom RT2 Profiler PCR Arrays. At 3 dpi, modest activation of TLR4 and TLR8 and the adaptor protein (TICAM1) was detected. At 10 dpi, NF-κB1 and Interferon Regulatory Factor signaling pathways were upregulated along with activation of TLR1, TLR2, TLR6, TLR10, TRAF6, IRF3, TBK1, CASP1, CD80, and IFNA1 in the liver, and inflammatory response with activated TLR4, TLR9, TICAM1, NF- κB1, NLRP3, CD86, IL-1B, IL-6, and IL-8 in PBMCs. At 28 dpi, there was increase in the levels of cytokines along with induction of NLRP1 and NLRP3 inflammasomes-dependent immune responses in the liver and PBMCs. At 70 dpi, F. gigantica activated TLRs and NLRs, and their downstream interacting molecules. The activation of TLR7/9 signaling (perhaps due to increased B-cell maturation and activation) and upregulation of NLRP3 gene were also detected. These findings indicate that F. gigantica alters the expression of TLRs and NLRs genes to evade host immune defenses. Elucidation of the roles of the downstream effectors interacting with these genes may aid in the development of new interventions to control disease caused by F. gigantica infection

    Epidemiology, microbiology and mortality associated with community-acquired bacteremia in northeast Thailand: a multicenter surveillance study

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    BACKGROUND: National statistics in developing countries are likely to underestimate deaths due to bacterial infections. Here, we calculated mortality associated with community-acquired bacteremia (CAB) in a developing country using routinely available databases. METHODS/PRINCIPAL FINDINGS: Information was obtained from the microbiology and hospital database of 10 provincial hospitals in northeast Thailand, and compared with the national death registry from the Ministry of Interior, Thailand for the period between 2004 and 2010. CAB was defined in patients who had pathogenic organisms isolated from blood taken within 2 days of hospital admission without a prior inpatient episode in the preceding 30 days. A total of 15,251 CAB patients identified, of which 5,722 (37.5%) died within 30 days of admission. The incidence rate of CAB between 2004 and 2010 increased from 16.7 to 38.1 per 100,000 people per year, and the mortality rate associated with CAB increased from 6.9 to 13.7 per 100,000 people per year. In 2010, the mortality rate associated with CAB was lower than that from respiratory tract infection, but higher than HIV disease or tuberculosis. The most common causes of CAB were Escherichia coli (23.1%), Burkholderia pseudomallei (19.3%), and Staphylococcus aureus (8.2%). There was an increase in the proportion of Extended-Spectrum Beta-Lactamases (ESBL) producing E. coli and Klebsiella pneumoniae over time. CONCLUSIONS: This study has demonstrated that national statistics on causes of death in developing countries could be improved by integrating information from readily available databases. CAB is neglected as an important cause of death, and specific prevention and intervention is urgently required to reduce its incidence and mortality
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