Synthesis and Spectroscopic Characterization of High-Spin Mononuclear Iron(II) \u3cem\u3ep\u3c/em\u3e-Semiquinonate Complexes

Two mononuclear iron(II) p-semiquinonate (pSQ) complexes have been generated via one-electron reduction of precursor complexes containing a substituted 1,4-naphthoquinone ligand. Detailed spectroscopic and computational analysis confirmed the presence of a coordinated pSQ radical ferromagnetically coupled to the high-spin FeII center. The complexes are intended to model electronic interactions between (semi)quinone and iron cofactors in biology

Structural, Spectroscopic, and Electrochemical Properties of Nonheme Fe(II)-Hydroquinonate Complexes: Synthetic Models of Hydroquinone Dioxygenases

Using the tris(3,5-diphenylpyrazol-1-yl)borate (Ph2Tp) supporting ligand, a series of mono- and dinuclear ferrous complexes containing hydroquinonate (HQate) ligands have been prepared and structurally characterized with X-ray crystallography. The monoiron(II) complexes serve as faithful mimics of the substrate-bound form of hydroquinone dioxygenases (HQDOs) – a family of nonheme Fe enzymes that catalyze the oxidative cleavage of 1,4-dihydroxybenzene units. Reflecting the variety of HQDO substrates, the synthetic complexes feature both mono- and bidentate HQate ligands. The bidentate HQates cleanly provide five-coordinate, high-spin Fe(II) complexes with the general formula [Fe(Ph2Tp)(HLX)] (1X), where HLX is a HQate(1-) ligand substituted at the 2-position with a benzimidazolyl (1A), acetyl (1B and 1C), or methoxy (1D) group. In contrast, the monodentate ligand 2,6-dimethylhydroquinone (H2LF) exhibited a greater tendency to bridge between two Fe(II) centers, resulting in formation of [Fe2(Ph2Tp)2(μ-LF)(MeCN)]·[2F(MeCN)]. However, addition of one equivalent of “free” pyrazole (Ph2pz) ligand provided the mononuclear complex, [Fe(Ph2Tp)(HLF)(Ph2pz)]·[1F(Ph2pz)], which is stabilized by an intramolecular hydrogen bond between the HLF and Ph2pz donors. Complex 1F(Ph2pz) represents the first crystallographically-characterized example of a monoiron complex bound to an untethered HQate ligand. The geometric and electronic structures of the Fe/HQate complexes were further probed with spectroscopic (UV-vis absorption, 1H NMR) and electrochemical methods. Cyclic voltammograms of complexes in the 1X series revealed an Fe-based oxidation between 0 and −300 mV (vs. Fc+/0), in addition to irreversible oxidation(s) of the HQate ligand at higher potentials. The one-electron oxidized species (1Xoxox) were examined with UV-vis absorption and electron paramagnetic resonance (EPR) spectroscopies

Genome sequences of 12 bacterial isolates obtained from the urine of pregnant women

The presence of bacteria in urine can pose significant risks during pregnancy. However, there are few reference genome strains for many common urinary bacteria. We isolated 12 urinary strains of Streptococcus, Staphylococcus, Citrobacter, Gardnerella, and Lactobacillus. These strains and their genomes are now available to the research community

Genome sequences of 14 Firmicutes strains isolated from the human vagina

Research on vaginal infections is currently limited by a lack of available fully sequenced bacterial reference strains. Here, we present strains (now available through BEI Resources) and genome sequences for a set of 14 vaginal isolates from the phylum Firmicutes. These genome sequences provide a valuable resource for future research in understanding the role of Gram-positive bacteria in vaginal health and disease

Genome sequences of 11 human vaginal Actinobacteria strains

The composition of the vaginal microbiota is an important health determinant. Several members of the phylum Actinobacteria have been implicated in bacterial vaginosis, a condition associated with many negative health outcomes. Here, we present 11 strains of vaginal Actinobacteria (now available through BEI Resources) along with draft genome sequences

Genome sequences of nine gram-negative vaginal bacterial isolates

The vagina is home to a wide variety of bacteria that have great potential to impact human health. Here, we announce reference strains (now available through BEI Resources) and draft genome sequences for 9 Gram-negative vaginal isolates from the taxa Citrobacter, Klebsiella, Fusobacterium, Proteus, and Prevotella

Microscopic Analysis and Quality Assessment of Induced Sputum From Children With Pneumonia in the PERCH Study.

Background. It is standard practice for laboratories to assess the cellular quality of expectorated sputum specimens to check that they originated from the lower respiratory tract. The presence of low numbers of squamous epithelial cells (SECs) and high numbers of polymorphonuclear (PMN) cells are regarded as indicative of a lower respiratory tract specimen. However, these quality ratings have never been evaluated for induced sputum specimens from children with suspected pneumonia. Methods. We evaluated induced sputum Gram stain smears and cultures from hospitalized children aged 1–59 months enrolled in a large study of community-acquired pneumonia. We hypothesized that a specimen representative of the lower respiratory tract will contain smaller quantities of oropharyngeal flora and be more likely to have a predominance of potential pathogens compared to a specimen containing mainly saliva. The prevalence of potential pathogens cultured from induced sputum specimens and quantity of oropharyngeal flora were compared for different quantities of SECs and PMNs. Results. Of 3772 induced sputum specimens, 2608 (69%) had \u3c10 SECs per low-power field (LPF) and 2350 (62%) had \u3e25 PMNs per LPF, measures traditionally associated with specimens from the lower respiratory tract in adults. Using isolation of low quantities of oropharyngeal flora and higher prevalence of potential pathogens as markers of higher quality, \u3c10 SECs per LPF (but not \u3e25 PMNs per LPF) was the microscopic variable most associated with high quality of induced sputum. Conclusions. Quantity of SECs may be a useful quality measure of induced sputum from young children with pneumonia

New Cryogenian, Neoproterozoic, and middle Paleozoic U–Pb zircon ages from the Caledonia terrane, southern New Brunswick, Canada: better constrained but more complex volcanic stratigraphy

New U–Pb zircon ages from volcanic, plutonic, and sedimentary units in the Avalonian Caledonia terrane of southern New Brunswick provide better timing constraints in this geologically complex area. Previous ca. 620 Ma ages from the Broad River Group are now corroborated by additional dates from felsic tuff in the Gordon Falls Formation and rhyolite in the former Fairfield (now East Branch Black River) Formation of 620 ± 5 Ma and 622 ± 1.9 Ma, respectively. Combined with ages ranging from ca. 625 Ma to 615 Ma from crosscutting plutons, the data suggest that the minimum age of the Broad River Group is about 615 Ma. A quartzfeldspar porphyry dyke in mafic volcanic rocks of the previously undated Long Beach Formation yielded an igneous crystallization age of 685 ± 10 Ma, the oldest unit yet dated in the Caledonia terrane but similar in age to porphyry in the Stirling belt in the Avalonian Mira terrane of Nova Scotia. The age of the Coldbrook Group was constrained previously by U–Pb (zircon) ages of volcanic rocks between 560 and 550 Ma as well as by similar ages from comagmatic plutons. Five additional samples from both volcanic and plutonic units lie in the same range of 560–550 Ma, including errors, demonstrating that the Coldbrook Group and related plutons formed in less than 10 million years. Such a large volume of mainly felsic magma erupted and emplaced in a short time span suggests a “supereruption/supervolcano” environment such as the late Cenozoic southwestern USA but not yet recognized at ca. 560–550 Ma elsewhere in Avalonia. Two units yielded Paleozoic ages: felsite of the Bloomsbury Mountain Formation with a zircon population at 427 ± 9 Ma, indicating a Silurian maximum emplacement age, and dacite of the Grassy Lake Formation with several zircon grains at 382.8 ± 8.3 Ma, indicating a maximum age of middle Devonian, the first rocks of this age to be identified in the Caledonia terrane

The uses and gratifications of using Facebook music listening applications

Despite rapid adoption of social media as a means of music listening, little is known about users’ motivations. This study applies the uses and gratifications approach to users’ motivations for using music listening applications on Facebook. Participants completed an online survey, and 153 out of 576 respondents indicated that they used a Facebook music listening application. A principal axis factor analysis identified three different motivations for this usage, namely entertainment, communication, and habitual diversion gratifications. The entertainment and communication gratifications replicate those found in prior uses and gratifications research concerning other social networking features, illustrating the strong similarity between uses of music and social media. However, the habitual diversion gratification may serve to distinguish listening applications from other features. Identifying and explaining these factors is relevant to social media users, musicians and application designers, as they explain what motivates a means of music listening that is gaining prominence

The Diagnostic Utility of Induced Sputum Microscopy and Culture in Childhood Pneumonia.

Background. Sputum microscopy and culture are commonly used for diagnosing the cause of pneumonia in adults but are rarely performed in children due to difficulties in obtaining specimens. Induced sputum is occasionally used to investigate lower respiratory infections in children but has not been widely used in pneumonia etiology studies. Methods. We evaluated the diagnostic utility of induced sputum microscopy and culture in patients enrolled in the Pneumonia Etiology Research for Child Health (PERCH) study, a large study of community-acquired pneumonia in children aged 1–59 months. Comparisons were made between induced sputum samples from hospitalized children with radiographically confirmed pneumonia and children categorized as nonpneumonia (due to the absence of prespecified clinical and laboratory signs and absence of infiltrate on chest radiograph). Results. One induced sputum sample was available for analysis from 3772 (89.1%) of 4232 suspected pneumonia cases enrolled in PERCH. Of these, sputum from 2608 (69.1%) met the quality criterion of \u3c10 squamous epithelial cells per low-power field, and 1162 (44.6%) had radiographic pneumonia. Induced sputum microscopy and culture results were not associated with radiographic pneumonia, regardless of prior antibiotic use, stratification by specific bacteria, or interpretative criteria used. Conclusions. The findings of this study do not support the culture of induced sputum specimens as a diagnostic tool for pneumonia in young children as part of routine clinical practice