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- Deeming, AJ, et al.
(author)
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Mechanisms of concurrent hydride migration processes in a triruthenium cluster capped by a phenylphosphinidene (PPh) ligand
- 2005
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In: European Journal of Inorganic Chemistry. - : Wiley. - 1099-0682 .- 1434-1948. ; :21, s. 4352-4360
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Journal article (peer-reviewed)abstract
- Two methods were used to synthesise [Ru-3(mu-H)(2)(mu(3)-PPh)-(CO)(7) (mu-dppm)] (3) (dppm = Ph2PCH2PPh2), the subject of this paper. Treatment of [Ru-3(CO)(10)(mu-dppm)] (1) with phenylphosphane in refluxing THF gave both [Ru-3(mu-H)(2)(mu-PHPh)-(CO)(8)(mu-dppm)] (2) and [Ru-3(mu-H)(2)(mu(3)-PPh)(CO)(7)(mu-dppm)] (3). Cluster 2 converts to 3 in refluxing THF. Alternatively the phenylphosphinidene cluster [Ru-3(mu-H)(2)(mu(3)-PPh)(CO)(9)] (4), prepared by the reported method of treating [Ru-3(CO)(12)] with phenylphosphane, reacts with dppm to produce cluster 3. The single-crystal X-ray structures of 2 and 3 are reported. Hydride mobility in [Ru-3(mu-H)(2)(mu(3)-PPh)(CO)(7)(mu-dppm)] (3) was analysed by variable-temperature H-1 and P-31(H-1) NMR methods. The variations in the spectra with temperature could not be interpreted by a single process, several of which were explored and which gave inadequately matching computed and experimental spectra. However, the spectra were successfully analysed by two concurrent processes, both involving the migration of hydride ligands between Ru-Ru edges. The faster process leads to the exchange of the nonequivalent phosphorus nuclei but not hydride exchange, whereas the hydrides are also exchanged in the slower process. Both processes require hydride ligand migration from one Ru-Ru edge to a vacant one. The hydride ligand bridging the same pair of ruthenium atoms as the dppm ligand is the slower to migrate.
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- Denning, DW, et al.
(author)
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Chronic pulmonary aspergillosis: rationale and clinical guidelines for diagnosis and management
- 2016
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In: The European respiratory journal. - : European Respiratory Society (ERS). - 1399-3003 .- 0903-1936. ; 47:1, s. 45-68
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Journal article (peer-reviewed)abstract
- Chronic pulmonary aspergillosis (CPA) is an uncommon and problematic pulmonary disease, complicating many other respiratory disorders, thought to affect ∼240 000 people in Europe. The most common form of CPA is chronic cavitary pulmonary aspergillosis (CCPA), which untreated may progress to chronic fibrosing pulmonary aspergillosis. Less common manifestations include:Aspergillusnodule and single aspergilloma. All these entities are found in non-immunocompromised patients with prior or current lung disease. Subacute invasive pulmonary aspergillosis (formerly called chronic necrotising pulmonary aspergillosis) is a more rapidly progressive infection (<3 months) usually found in moderately immunocompromised patients, which should be managed as invasive aspergillosis. Few clinical guidelines have been previously proposed for either diagnosis or management of CPA. A group of experts convened to develop clinical, radiological and microbiological guidelines. The diagnosis of CPA requires a combination of characteristics: one or more cavities with or without a fungal ball present or nodules on thoracic imaging, direct evidence ofAspergillusinfection (microscopy or culture from biopsy) or an immunological response toAspergillusspp. and exclusion of alternative diagnoses, all present for at least 3 months.Aspergillusantibody (precipitins) is elevated in over 90% of patients. Surgical excision of simple aspergilloma is recommended, if technically possible, and preferablyviavideo-assisted thoracic surgery technique. Long-term oral antifungal therapy is recommended for CCPA to improve overall health status and respiratory symptoms, arrest haemoptysis and prevent progression. Careful monitoring of azole serum concentrations, drug interactions and possible toxicities is recommended. Haemoptysis may be controlled with tranexamic acid and bronchial artery embolisation, rarely surgical resection, and may be a sign of therapeutic failure and/or antifungal resistance. Patients with singleAspergillusnodules only need antifungal therapy if not fully resected, but if multiple they may benefit from antifungal treatment, and require careful follow-up.
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