A catalytic cycle for oxidation of tert-butyl methyl ether by a double C−H activation-group transfer process

A square-planar, iridium(I) carbene complex is shown to effect atom and group transfer from nitrous oxide and organic azides, releasing the corresponding formate or formimidate and an iridium(I)−dinitrogen adduct. The dinitrogen complex performs C−H activation upon photolysis or thermolysis, regenerating the carbene from tert-butyl methyl ether with loss of H_2. Taken together, these reactions represent a net catalytic cycle for C−H functionalization by double C−H activation to generate metal−carbon multiple bonds. Additionally, the unusual group transfer from diazo reagents underscores the unique nature of the reactivity observed for nucleophilic-at-metal carbene complexes

Synthesis and Reactivity of Iridium(III) Dihydrido Aminocarbenes

Iridium complexes supported by the PNP amidophosphine scaffold (PNP = [N(2-PiPr2-4-Me-C6H3)2]−) perform the selective double C−H activation of methyl amines to produce iridium(III) dihydrido aminocarbenes. The reactivity of these complexes is presented and contrasted with that observed for the previously reported iridium(I) alkoxycarbenes

Complexes of iron and cobalt with new tripodal amido-polyphosphine hybrid ligands

Divalent complexes of iron and cobalt with new, monoanionic tripodal amido-polyphosphine ligands have been thoroughly characterized, and XRD analysis reveals geometries that are distinct for this class of ligand

Factors Dictating Carbene Formation at (PNP)Ir

The mechanistic subtleties involved with the interaction of an amido/bis(phosphine)-supported (PNP)Ir fragment with a series of linear and cyclic ethers have been investigated using density functional theory. Our analysis has revealed the factors dictating reaction direction toward either an iridium-supported carbene or a vinyl ether adduct. The (PNP)Ir structure will allow carbene formation only from accessible carbons α to the ethereal oxygen, such that d electron back-donation from the metal to the carbene ligand is possible. Should these conditions be unavailable, the main competing pathway to form vinyl ether can occur, but only if the (PNP)Ir framework does not sterically interfere with the reacting ether. In situations where steric hindrance prevents unimpeded access to both pathways, the reaction may progress to the initial C−H activation but no further. Our mechanistic analysis is density functional independent and whenever possible confirmed experimentally by trapping intermediate species experimentally. We have also highlighted an interesting systematic error present in the DFT analysis of reactions where steric environment alters considerably within a reaction

Difference in Knowledge of MRSA Regarding Sophomore and Senior Baccalaureate Nursing Students

Abstract Background The risk of infection by antibiotic resistant organisms is a common problem in hospital settings. Methicillin-resistant Staphylococcus Aureus (MRSA) is the most common type of resistant bacteria that can have serious consequences or even lead to death. Nurses\u27 knowledge of how to prevent and treat this problem is essential for patient safety. The purpose of this study is to determine the differences in level of knowledge of MRSA in sophomore and senior level baccalaureate nursing students. Methods This descriptive, comparative study will examine differences in knowledge of MRSA between sophomore and senior baccalaureate nursing students and determine if relationships exist between the knowledge scores and participant. Findings The mean MRSA knowledge scores were the same between both groups at 43% correct. The demographic variables showed a weak positive correlation with the MRSA knowledge scores. The only variable that has statistical significance is whether or not the student is employed, whether it is in a healthcare setting or not. Conclusions This study has revealed that the amount of MRSA knowledge does not increase as the student progresses through the nursing program. Regardless of the increased quantity of clinical hours, experience, and education provided, the knowledge level remains the same throughout the program. Adding increased education regarding MRSA may prove beneficial to the quality of nurses that the school produces

Probing the C-H Activation of Linear and Cyclic Ethers at (PNP)Ir

Interaction of the amido/bis(phosphine)-supported (PNP)Ir fragment with a series of linear and cyclic ethers is shown to afford, depending on substrate, products of α,α-dehydrogenation (carbenes), α,β-dehydrogenation (vinyl ethers), or decarbonylation. While carbenes are exclusively obtained from tert-amyl methyl ether, sec-butyl methyl ether (SBME), n-butyl methyl ether (NBME), and tetrahydrofuran (THF), vinyl ethers or their adducts are observed upon reaction with diethyl ether and 1,4-dioxane. Decarbonylation occurs upon interaction of (PNP)Ir with benzyl methyl ether, and a mechanism is proposed for this unusual transformation, which occurs via a series of C−H, C−O, and C−C bond cleavage events. The intermediates characterized for several of these reactions as well as the α,α-dehydrogenation of tert-butyl methyl ether (MTBE) are used to outline a reaction pathway for the generation of PNP-supported iridium(I) carbene complexes, and it is shown that the long-lived, observable intermediates are substrate-dependent and differ for the related cases of MTBE and THF. Taken together, these findings highlight the variety of pathways utilized by the electron-rich, unsaturated (PNP)Ir fragment to stabilize itself by transferring electron density to ethereal substrates through oxidative addition and/or the formation of π-acidic ligands

Regulation of plasmid-encoded isoprene metabolism in Rhodococcus, a representative of an important link in the global isoprene cycle

Emissions of biogenic volatile organic compounds (VOCs) form an important part of the global carbon cycle, comprising a significant proportion of net ecosystem productivity. They impact atmospheric chemistry and contribute directly and indirectly to greenhouse gases. Isoprene, emitted largely from plants, comprises one third of total VOCs, yet in contrast to methane, which is released in similar quantities, we know little of its biodegradation. Here, we report the genome of an isoprene degrading isolate, Rhodococcus sp. AD45, and, using mutagenesis shows that a plasmid-encoded soluble di-iron centre isoprene monooxygenase (IsoMO) is essential for isoprene metabolism. Using RNA sequencing (RNAseq) to analyse cells exposed to isoprene or epoxyisoprene in a substrate-switch time-course experiment, we show that transcripts from 22 contiguous genes, including those encoding IsoMO, were highly upregulated, becoming among the most abundant in the cell and comprising over 25% of the entire transcriptome. Analysis of gene transcription in the wild type and an IsoMO-disrupted mutant strain showed that epoxyisoprene, or a subsequent product of isoprene metabolism, rather than isoprene itself, was the inducing molecule. We provide a foundation of molecular data for future research on the environmental biological consumption of this important, climate-active compound

Pearling: stroke segmentation with crusted pearl strings

We introduce a novel segmentation technique, called Pearling, for the semi-automatic extraction of idealized models of networks of strokes (variable width curves) in images. These networks may for example represent roads in an aerial photograph, vessels in a medical scan, or strokes in a drawing. The operator seeds the process by selecting representative areas of good (stroke interior) and bad colors. Then, the operator may either provide a rough trace through a particular path in the stroke graph or simply pick a starting point (seed) on a stroke and a direction of growth. Pearling computes in realtime the centerlines of the strokes, the bifurcations, and the thickness function along each stroke, hence producing a purified medial axis transform of a desired portion of the stroke graph. No prior segmentation or thresholding is required. Simple gestures may be used to trim or extend the selection or to add branches. The realtime performance and reliability of Pearling results from a novel disk-sampling approach, which traces the strokes by optimizing the positions and radii of a discrete series of disks (pearls) along the stroke. A continuous model is defined through subdivision. By design, the idealized pearl string model is slightly wider than necessary to ensure that it contains the stroke boundary. A narrower core model that fits inside the stroke is computed simultaneously. The difference between the pearl string and its core contains the boundary of the stroke and may be used to capture, compress, visualize, or analyze the raw image data along the stroke boundary