Prevalence, complete genome, and metabolic potentials of a phylogenetically novel cyanobacterial symbiont in the coral-killing sponge, Terpios hoshinota.

Terpios hoshinota is an aggressive, space-competing sponge that kills various stony corals. Outbreaks of this species have led to intense damage to coral reefs in many locations. Here, the first large-scale 16S rRNA gene survey across three oceans revealed that bacteria related to the taxa Prochloron, Endozoicomonas, SAR116, Ruegeria, and unclassified Proteobacteria were prevalent in T. hoshinota. A Prochloron-related bacterium was the most dominant and prevalent cyanobacterium in T. hoshinota. The complete genome of this uncultivated cyanobacterium and pigment analysis demonstrated that it has phycobiliproteins and lacks chlorophyll b, which is inconsistent with the definition of Prochloron. Furthermore, the cyanobacterium was phylogenetically distinct from Prochloron, strongly suggesting that it should be a sister taxon to Prochloron. Therefore, we proposed this symbiotic cyanobacterium as a novel species under the new genus Candidatus Paraprochloron terpiosi. Comparative genomic analyses revealed that 'Paraprochloron' and Prochloron exhibit distinct genomic features and DNA replication machinery. We also characterized the metabolic potentials of 'Paraprochloron terpiosi' in carbon and nitrogen cycling and propose a model for interactions between it and T. hoshinota. This study builds a foundation for the study of the T. hoshinota microbiome and paves the way for better understanding of ecosystems involving this coral-killing sponge.

Reefing Viability Index for Rigs-to-Reefs (R2R) in Malaysia.

Decommissioning of the offshore platform as an artificial reef, known as Rigs-to-Reefs (R2R), has become a sustainable approach for oil companies. The platform was reused to serve the underwater ecosystem as an artificial reef for a new marine ecosystem which helps to tackle food security issue. This paper presents the findings of the formulation of the reefing viability index to recognize an offshore region that can be used for R2R projects within the South China Sea. The combined effects of spatial data, numerical modelling, and geographic system (GIS) are proposed to study the relationship of spawning ground coral reefs, diversity, and planula larvae in the process of colonization to establish a map of the reef potential environment. Coral connectivity and spawning behaviour were studied to determine the possible source of coral seedling released during the spawning season, twice a year. A geographic reef viability index was established consisting of seven parameters which are coral larval density, pelagic larval length, sea currents, temperature, chlorophyll-a, depth, and substrate availability. The ocean hydrodynamic model was designed to resemble the pattern of larval scattering. By using the simulations and rankings, there were 95 (21%) sites which could probably be used for in situ reefing, whereas 358 (79%) sites were likely ideal for ex situ reefing. Validation of the viability index was carried out using media footage assessment of remotely operated vehicle (ROV).

Stereocontrolled Self-Assembly and Self-Sorting of Luminescent Europium Tetrahedral Cages.

Coordination-directed self-assembly has become a well-established technique for the construction of functional supramolecular structures. In contrast to the most often exploited transition metals, trivalent lanthanides Ln(III) have been less utilized in the design of polynuclear self-assembled structures despite the wealth of stimulating applications of these elements. In particular, stereochemical control in the assembly of lanthanide chiral cage compounds is not easy to achieve in view of the usually large lability of the Ln(III) ions. We report here the first examples of stereoselective self-assembly of chiral luminescent europium coordination tetrahedral cages and their intriguing self-sorting behavior. Two pairs of R and S ligands are designed on the basis of the pyridine-2,6-dicarboxamide coordination unit, bis(tridentate) L1 and tris(tridentate) L2. Corresponding chiral Eu4(L1)6 and Eu4(L2)4 topological tetrahedral cages are independently assembled via edge- and face-capping design strategies, respectively. The chirality of the ligand is transferred during the self-assembly process to give either Δ or Λ metal stereochemistry. The self-assembled cages are characterized by NMR, high-resolution ESI-TOF-MS, and in one case by X-ray crystallography. Strict control of stereoselectivity is confirmed by CD spectroscopy and NMR enantiomeric differentiation experiments. Narcissistic self-sorting is observed in the self-assembly process when two differently shaped ligands L1 and L2 are mixed. More impressively, distinct self-sorting behavior between Eu4(L1)6 and Eu4(L2)4 coordination cages is observed for the first time when racemic mixtures of ligands are used. We envisage that chiral luminescent lanthanide tetrahedral cages could be used in chiroptical probes\sensors and enantioselective catalysis.

Influence of central metalloligand geometry on electronic communication between metals: syntheses, crystal structures, MMCT properties of isomeric cyanido-bridged Fe2Ru complexes, and TDDFT calculations.

To investigate how the central metalloligand geometry influences distant or vicinal metal-to-metal charge-transfer (MMCT) properties of polynuclear complexes, cis- and trans-isomeric heterotrimetallic complexes, and their one- and two-electron oxidation products, cis/trans-[Cp(dppe)Fe(II)NCRu(II)(phen)2CN-Fe(II)(dppe)Cp][PF6]2 (cis/trans-1[PF6]2), cis/trans-[Cp(dppe)Fe(II)NCRu(II)(phen)2CNFe(III)-(dppe)Cp][PF6]3 (cis/trans-1[PF6]3) and cis/trans-[Cp(dppe)Fe(III)NCRu(II)(phen)2CN-Fe(III)(dppe)Cp][PF6]4 (cis/trans-1[PF6]4) have been synthesized and characterized. Electrochemical measurements show the presence of electronic interactions between the two external Fe(II) atoms of the cis- and trans-isomeric complexes cis/trans-1[PF6]2. The electronic properties of all these complexes were studied and compared by spectroscopic techniques and TDDFT//DFT calculations. As expected, both mixed valence complexes cis/trans-1[PF6]3 exhibited different strong absorption signals in the NIR region, which should mainly be attributed to a transition from an MO that is delocalized over the Ru(II)-CN-Fe(II) subunit to a Fe(III) d orbital with some contributions from the co-ligands. Moreover, the NIR transition energy in trans-1[PF6]3 is lower than that in cis-1[PF6]3, which is related to the symmetry of their molecular orbitals on the basis of the molecular orbital analysis. Also, the electronic spectra of the two-electron oxidized complexes show that trans-1[PF6]4 possesses lower vicinal Ru(II) → Fe(III) MMCT transition energy than cis-1[PF6]4. Moreover, the assignment of MMCT transition of the oxidized products and the differences of the electronic properties between the cis and trans complexes can be well rationalized using TDDFT//DFT calculations.

From antiferromagnetic to ferromagnetic interaction in cyanido-bridged Fe(III)-Ru(II)-Fe(III) complexes by change of the central diamagnetic cyanido-metal geometry.

Cis- and trans-isomeric heterotrinuclear-metallic complexes and their two-electron-oxidation products, cis-/trans-[Cp(dppe)Fe(µ-CN)Ru(bpy)2(µ-CN)Fe(dppe)Cp][PF6]2 (cis-/trans-1[PF6]2) and cis-/trans-[Cp(dppe)Fe(µ-CN)Ru(bpy)2(µ-CN)Fe(dppe)Cp][PF6]4 (cis-/trans-1[PF6]4), have been synthesized and structurally characterized. To the best of our knowledge, the complexes are the first example of a cis-/trans-isomer with multistates. Although separated by the diamagnetic cyanido-metal bridge, the two distant paramagnetic metal centers in both the oxidized complexes exhibit quite strong magnetic couplings. As a unique example, cis-1[PF6]4 is antiferromagnetic, and trans-1[PF6]4 is ferromagnetic. Density functional theory (DFT) calculations suggest that the spin-delocalization mechanism should be responsible for the magnetic interactions between the two distant paramagnetic Fe(III) centers across the diamagnetic cyanido-metal in both cis- and trans-1(4+). Most importantly, the DFT calculations revealed that the type (antiferromagnetic or ferromagnetic) and strength (J) of the magnetic interactions in such compounds can be controlled by the variation (cis or trans) of the diamagnetic central metal configurations.

Population genetics and demography of the coral-killing cyanobacteriosponge, Terpios hoshinota, in the Indo-West Pacific.

The first occurrence of the cyanobacteriosponge Terpios hoshinota was reported from coral reefs in Guam in 1973, but was only formally described in 1993. Since then, the invasive behavior of this encrusting, coral-killing sponge has been observed in many coral reefs in the West Pacific. From 2015, its occurrence has expanded westward to the Indian Ocean. Although many studies have investigated the morphology, ecology, and symbiotic cyanobacteria of this sponge, little is known of its population genetics and demography. In this study, a mitochondrial cytochrome oxidase I (COI) fragment and nuclear ribosomal internal transcribed spacer 2 (ITS2) were sequenced to reveal the genetic variation of T. hoshinota collected from 11 marine ecoregions throughout the Indo-West Pacific. Both of the statistical parsimony networks based on the COI and nuclear ITS2 were dominated by a common haplotype. Pairwise F ST and Isolation-by-distance by Mantel test of ITS2 showed moderate gene flow existed among most populations in the marine ecoregions of West Pacific, Coral Triangle, and Eastern Indian Ocean, but with a restricted gene flow between these regions and Maldives in the Central Indian Ocean. Demographic analyses of most T. hoshinota populations were consistent with the mutation-drift equilibrium, except for the Sulawesi Sea and Maldives, which showed bottlenecks following recent expansion. Our results suggest that while long-range dispersal might explain the capability of T. hoshinota to spread in the IWP, stable population demography might account for the long-term persistence of T. hoshinota outbreaks on local reefs.

A cyanide-bridged trinuclear Fe(II)-Ru(II)-Fe(II) complex with three stable states: synthesis, crystal structures, electronic couplings and magnetic properties.

Treatment of trans-(Ph-tpy)Ru(PPh(3))(CN)(2) (Ph-tpy = 4'-phenyl-2,2':6',2''-terpyridine, PPh(3) = triphenylphosphine) with 2 equiv of Cp(dppe)Fe(NCCH(3))Br (dppe = bis(diphenylphosphino)ethane) in the presence of NH(4)PF(6) produced a trinuclear cyanide-bridged complex, trans-[Cp(dppe)Fe(CN)(Ph-tpy)Ru(PPh(3))(CN)Fe(dppe)Cp][PF(6)](2) (1[PF(6)](2)). Its one-electron oxidation product (1[PF(6)](3)) and two-electron-oxidation product (1[PF(6)](4)) were obtained by oxidation with (Cp)(2)FePF(6) and AgPF(6), respectively. Firstly, the crystal structures of the cyanide-bridged complexes with three stable states were fully characterized. The reversible electrochemistry measurement of 1(2)(+) shows the presence of a long range intervalence interaction between the external iron centres. Both 1(3)(+) and 1(4)(+) were considered to be Class II mixed valence complexes according to the classification of Robin and Day. Magnetic analysis indicated the presence of a moderately strong antiferromagnetic coupling between the two remote Fe(III) ions across the Fe-NC-Ru-CN-Fe array in 1(4)(+). This proves that the Ru(II)-dicyano complex is a bridging ligand that can transmit electro- and magneto-communication.

Effect of colistin exposure and growth phase on the surface properties of live Acinetobacter baumannii cells examined by atomic force microscopy.

The diminishing antimicrobial development pipeline has forced the revival of colistin as a last line of defence against infections caused by multidrug-resistant Gram-negative 'superbugs' such as Acinetobacter baumannii. The complete loss of lipopolysaccharide (LPS) mediates colistin resistance in some A. baumannii strains. Atomic force microscopy was used to examine the surface properties of colistin-susceptible and -resistant A. baumannii strains at mid-logarithmic and stationary growth phases in liquid and in response to colistin treatment. The contribution of LPS to surface properties was investigated using A. baumannii strains constructed with and without the lpxA gene. Bacterial spring constant measurements revealed that colistin-susceptible cells were significantly stiffer than colistin-resistant cells at both growth phases (P<0.01), whilst colistin treatment at high concentrations (32 mg/L) resulted in more rigid surfaces for both phenotypes. Multiple, large adhesive peaks frequently noted in force curves captured on colistin-susceptible cells were not evident for colistin-resistant cells. Adhesion events were markedly reduced following colistin exposure. The cell membranes of strains of both phenotypes remained intact following colistin treatment, although fine topographical details were illustrated. These studies, conducted for the first time on live A. baumannii cells in liquid, have contributed to our understanding of the action of colistin in this problematic pathogen.

Activity of colistin against heteroresistant Acinetobacter baumannii and emergence of resistance in an in vitro pharmacokinetic/pharmacodynamic model.

Three clinically relevant intermittent regimens, and a continuous infusion, of colistin were simulated in an in vitro pharmacokinetic/pharmacodynamic model against two colistin-heteroresistant strains of Acinetobacter baumannii. Extensive initial killing was followed by regrowth as early as 6 h later; bacterial density in the 24- to 72-h period was within 1 log(10) CFU/ml of growth control. Population analysis profiles revealed extensive emergence of resistant subpopulations regardless of the colistin regimen.