ABSTRACT
Protochlorophyllide (Pchlide) reduction in the late stage of chlorophyll a (Chl) biosynthesis is catalyzed by two enzymes: light-dependent Pchlide oxidoreductase (LPOR) and dark-operative Pchlide oxidoreductase (DPOR). The differential operation of LPOR and DPOR enables a stable supply of Chl in response to changes in light conditions and environmental oxygen levels. When a DPOR-deficient mutant (YFC2) of the cyanobacterium Leptolyngbya boryana is grown heterotrophically in the dark, Pchlide accumulates in the cells and is secreted into the culture medium. In this study, we demonstrated the extracellular vesicle-mediated secretion of Pchlide. Pchlide fractions were isolated from the culture medium using sucrose density gradient centrifugation. Mass spectrometry analysis revealed that the Pchlide fractions contained porin isoforms, TolC, and FG-GAP repeat-containing protein, which are localized in the outer membrane. Transmission electron microscopy revealed extracellular vesicle-like structures in the vicinity of YFC2 cells and the Pchlide fractions. These findings suggested that the Pchlide secretion is mediated by extracellular vesicles in dark-grown YFC2 cells.
ABSTRACT
Although nitrogen removal by partial nitritation and anammox is more cost-effective than conventional nitrification and denitrification, one downside is the production and accumulation of nitrous oxide (N2O). The potential exploitation of N2O-reducing bacteria, which are resident members of anammox microbial communities, for N2O mitigation would require more knowledge of their ecophysiology. This study investigated the phylogeny of resident N2O-reducing bacteria in an anammox microbial community and quantified individually the processes of N2O production and N2O consumption. An up-flow column-bed anammox reactor, fed with NH4+ and NO2- and devoid of oxygen, emitted N2O at an average conversion ratio (produced N2O: influent nitrogen) of 0.284%. Transcriptionally active and highly abundant nosZ genes in the reactor biomass belonged to the Burkholderiaceae (clade I type) and Chloroflexus genera (clade II type). Meanwhile, less abundant but actively transcribing nosZ strains were detected in the genera Rhodoferax, Azospirillum, Lautropia, and Bdellovibrio and likely act as an N2O sink. A novel 15N tracer method was adapted to individually quantify N2O production and N2O consumption rates. The estimated true N2O production rate and true N2O consumption rate were 3.98 ± 0.15 and 3.03 ± 0.18 mgN·gVSS-1·day-1, respectively. The N2O consumption rate could be increased by 51% (4.57 ± 0.51 mgN·gVSS-1·day-1) with elevated N2O concentrations but kept comparable irrespective of the presence or absence of NO2-. Collectively, the approach allowed the quantification of N2O-reducing activity and the identification of transcriptionally active N2O reducers that may constitute as an N2O sink in anammox-based processes.
Subject(s)
Bioreactors , Denitrification , Nitrification , Nitrogen , Nitrous Oxide , Oxidation-ReductionABSTRACT
The trinuclear palladium addition to monocyclic unsaturated hydrocarbons was revealed. The trinuclear adduct of [2.2]paracyclophane, cycloheptatriene (CHT), or cyclooctatetraene (COT) was obtained by treatment of the corresponding tripalladium sandwich complexes with 3 equiv. of 1,10-phenanthroline. In the trinuclear adduct of [2.2]paracyclophane or CHT, a Pd2 unit and a Pd1 unit synfacially coordinate through a (µ-η(3)-allyl):(η(3)-allyl) manner. A trinuclear adduct of COT exhibited an unusual bonding structure in which a formally tetraanionic COT coordinates to three Pd(II) centers through a synfacial η(3):η(1):η(3):η(1) coordination mode. The tetraanionic COT ligand bearing three Pd(II) moieties undergoes a unique intramolecular 1,5-C-C coupling.
ABSTRACT
Sandwich time! The mixed-metal triangular-trinuclear sandwich complexes of Pd(2)Pt and PdPt(2) were selectively synthesized. The Pd(2)Pt and PdPt(2) triangles in a cycloheptatrienyl sandwich framework were identified by (31)Pâ NMR analyses of the tris-triphenylphosphine complexes (see scheme).
ABSTRACT
The transmetallation of the palladacyclopentadiene complex Pd{C(COOMe)C(COOMe)C(COOMe)C(COOMe)}(bipy) with the dicationic Pd(II) complex [Pd(bipy)(CH(3)CN)(2)][BF(4)](2) afforded a terminally σ-palladated diene complex [Pd(2){µ-η(1):η(1)-C(COOMe)C(COOMe)C(COOMe)C(COOMe)}(bipy)(2)(CH(3)CN)(2)][BF(4)](2). It was revealed by X-ray crystallographic analysis that replacement of the acetonitrile ligands in a terminally σ-palladated diene complex with PPh(3) ligands resulted in the conformation change of the σ-palladated diene moiety from skewed s-cis to planar s-trans. Treatment of a bis-triphenylphosphine dipalladium complex [Pd(2)(PPh(3))(2)(CH(3)CN)(4)][PF(6)](2) with dimethoxyacetylene dicarboxylate (DMAD) (1 equiv.) in acetonitrile resulted in the insertion of DMAD to the Pd-Pd bond to afford [Pd(2){µ-η(1):η(1)-C(COOMe)C(COOMe)}(PPh(3))(2)(CH(3)CN)(4)][PF(6)](2). Addition of the second DMAD gave the ylide-type complex [Pd(2){µ-η(2):η(3)-C(COOMe)C(COOMe)C(COOMe)C(COOMe)(PPh(3))}(PPh(3))(2)(CH(3)CN)(3)][PF(6)](2) of which the structure was determined by X-ray crystallographic analysis.
ABSTRACT
An unusual square tetrapalladium sheet sandwich complex, [Pd(4)(mu(4)-C(9)H(9))(mu(4)-C(8)H(8))][B(Ar(f))(4)] has been isolated and structurally characterized. X-ray structure analysis showed that the square palladium sheet is flanked by the nine-membered cyclononatetraenyl and eight-membered cyclooctatetraene ligands to form a square metal sheet molecular sandwich structure. The coordinative unsaturation of the complex was revealed by phosphine titration experiments.
