Exploring Pd adsorption, diffusion, permeation, and nucleation on bilayer SiO₂/Ru as a function of hydroxylation and precursor environment: From UHV to catalyst preparation

The hydroxylation-dependent permeability of bilayer SiO2 supported on Ru(0001) was investigated by XPS and TDS studies in a temperature range of 100K to 600K. For this, the thermal behavior of Pd evaporated at 100K, which results in surface and sub-surface (Ru-supported) binding arrangements, was examined relative to the extent of pre-hydroxylation. Samples containing only defect-mediated hydroxyls showed no effect on Pd diffusion through the film at low temperature. If, instead, the concentration of strongly bound hydroxyl groups and associated weakly bound water molecules was enriched by an electron-assisted hydroxylation procedure, the probability for Pd diffusion through the film is decreased via a pore-blocking mechanism. Above room temperature, all samples showed similar behavior, reflective of particle nucleation above the film and eventual agglomeration with any metal atoms initially binding beneath the film. When depositing Pd onto the same SiO2/Ru model support via adsorption of [Pd(NH3)4]C2 from alkaline (pH12) precursor solution, we observe notably different adsorption and nucleation mechanisms. The resultant Pd adsorption complexes follow established decomposition pathways to produce model catalyst systems compatible with those created exclusively within UHV despite lacking the ability to penetrate the film due to the increased size of the initial Pd precursor groups

Electron stimulated hydroxylation of a metal supported silicate film

Water adsorption on a double-layer silicate film was studied by using infrared reflection–absorption spectroscopy, thermal desorption spectroscopy and scanning tunneling microscopy. Under vacuum conditions, small amounts of silanols (Si–OH) could only be formed upon deposition of an ice-like (amorphous solid water, ASW) film and subsequent heating to room temperature. Silanol coverage is considerably enhanced by low-energy electron irradiation of an ASW pre-covered silicate film. The degree of hydroxylation can be tuned by the irradiation parameters (beam energy, exposure) and the ASW film thickness. The results are consistent with a generally accepted picture that hydroxylation occurs through hydrolysis of siloxane (Si–O–Si) bonds in the silica network. Calculations using density functional theory show that this may happen on Si–O–Si bonds, which are either parallel (i.e., in the topmost silicate layer) or vertical to the film surface (i.e., connecting two silicate layers). In the latter case, the mechanism may additionally involve the reaction with a metal support underneath. The observed vibrational spectra are dominated by terminal silanol groups (ν(OD) band at 2763 cm−1) formed by hydrolysis of vertical Si–O–Si linkages. Film dehydroxylation fully occurs only upon heating to very high temperatures (∼1200 K) and is accompanied by substantial film restructuring, and even film dewetting upon cycling hydroxylation/dehydroxylation treatment

Contribution of soft-bodied meiofaunal taxa to Italian marine biodiversity

Meiofauna includes an astonishing diversity of organisms, whose census is far from being complete. Most classic ecological studies have focused on hard-bodied Ecdysozoan taxa (notably Copepoda and Nematoda), whose cuticle allows determination at species-level after fixation, rather than soft-bodied, Spiralian taxa, which most often lose any diagnostic feature in fixed samples. Yet, metabarcoding studies have recently revealed a species-richness of softbodied taxa comparable, and in cases superior, to that of Copepoda and Nematoda together. However, given objective difficulties inherent to their study, which necessarily has to be performed on living individuals, and their limited utilisation for ecological and applicative research, taxonomic expertise on soft-bodied organisms has declined over the years, and diversity of these phyla in most areas of the world is presently completely unknown. Here we present an expert-based survey of current knowledge on the composition and distribution of soft-bodied meiofaunal taxa in Italy, with special references to the predominantly or exclusively meiobenthic phyla Gastrotricha, Gnathostomulida, Platyhelminthes, Rotifera, Xenacoelomorpha, and macrofaunal taxa with conspicuous meiofaunal representatives (Annelida, Mollusca and Nemertea). A total of 638 described species have been reported from Italian coasts; furthermore, the existence of a large number of undescribed species is mentioned. Knowledge of Annelida, Gastrotricha, and Rotifera appears particularly detailed, placing Italy among the best-known country worldwide. In contrast, knowledge of Platyhelminthes and Xenacoelomorpha appears patchy, and limited to few areas. Sampling effort has been uneven, with most species recorded from the Tyrrhenian Sea, while large sections of the Adriatic and Ionian seas have been poorly explored. Results highlight the role that Marine Biological Stations, notably the Zoological Station “Anton Dohrn” in Naples, have had in promoting the study of soft-bodied taxa in Ital

Thin silica films on Ru(0001): monolayer, bilayer and three-dimensional networks of [SiO₄] tetrahedra

The atomic structure of thin silica films grown over a Ru(0001) substrate was studied by X-ray photoelectron spectroscopy, infrared reflection absorption spectroscopy, low energy electron diffraction, helium ion scattering spectroscopy, CO temperature programmed desorption, and scanning tunneling microscopy in combination with density functional theory calculations. The films were prepared by Si vapor deposition and subsequent oxidation at high temperatures. The silica film first grows as a monolayer of corner-sharing [SiO4] tetrahedra strongly bonded to the Ru(0001) surface through the Si–O–Ru linkages. At increasing amounts of Si, the film forms a bilayer of corner-sharing [SiO4] tetrahedra which is weakly bonded to Ru(0001). The bilayer film can be grown in either the crystalline or vitreous state, or both coexisting. Further increasing the film thickness leads to the formation of vitreous silica exhibiting a three-dimensional network of [SiO4]. The principal structure of the films can be monitored by infrared spectroscopy, as each structure shows a characteristic vibrational band, i.e., [similar]1135 cm-1 for a monolayer film, [similar]1300 cm⁻-1 for the bilayer structures, and [similar]1250 cm⁻-1 for the bulk-like vitreous silica

Microanatomy of the trophosome region of Paracatenula cf. polyhymnia (Catenulida, Platyhelminthes) and its intracellular symbionts

Marine catenulid platyhelminths of the genus Paracatenula lack mouth, pharynx and gut. They live in a symbiosis with intracellular bacteria which are restricted to the body region posterior to the brain. The symbiont-housing cells (bacteriocytes) collectively form the trophosome tissue, which functionally replaces the digestive tract. It constitutes the largest part of the body and is the most important synapomorphy of this group. While some other features of the Paracatenula anatomy have already been analyzed, an in-depth analysis of the trophosome region was missing. Here, we identify and characterize the composition of the trophosome and its surrounding tissue by analyzing series of ultra-thin cross-sections of the species Paracatenula cf. polyhymnia. For the first time, a protonephridium is detected in a Paracatenula species, but it is morphologically reduced and most likely not functional. Cells containing needle-like inclusions in the reference species Paracatenula polyhymnia Sterrer and Rieger, 1974 were thought to be sperm, and the inclusions interpreted as the sperm nucleus. Our analysis of similar cells and their inclusions by EDX and Raman microspectroscopy documents an inorganic spicule consisting of a unique magnesium–phosphate compound. Furthermore, we identify the neoblast stem cells located underneath the epidermis. Except for the modifications due to the symbiotic lifestyle and the enigmatic spicule cells, the organization of Paracatenula cf. polyhymnia conforms to that of the Catenulida in all studied aspects. Therefore, this species represents an excellent model system for further studies of host adaptation to an obligate symbiotic lifestyle

Bacterial Symbiosis Maintenance in the Asexually Reproducing and Regenerating Flatworm Paracatenula galateia

Bacteriocytes set the stage for some of the most intimate interactions between animal and bacterial cells. In all bacteriocyte possessing systems studied so far, de novo formation of bacteriocytes occurs only once in the host development, at the time of symbiosis establishment. Here, we present the free-living symbiotic flatworm Paracatenula galateia and its intracellular, sulfur-oxidizing bacteria as a system with previously undescribed strategies of bacteriocyte formation and bacterial symbiont transmission. Using thymidine analogue S-phase labeling and immunohistochemistry, we show that all somatic cells in adult worms – including bacteriocytes – originate exclusively from aposymbiotic stem cells (neoblasts). The continued bacteriocyte formation from aposymbiotic stem cells in adult animals represents a previously undescribed strategy of symbiosis maintenance and makes P. galateia a unique system to study bacteriocyte differentiation and development. We also provide morphological and immunohistochemical evidence that P. galateia reproduces by asexual fragmentation and regeneration (paratomy) and, thereby, vertically transmits numerous symbiont-containing bacteriocytes to its asexual progeny. Our data support the earlier reported hypothesis that the symbiont population is subjected to reduced bottleneck effects. This would justify both the codiversification between Paracatenula hosts and their Candidatus Riegeria symbionts, and the slow evolutionary rates observed for several symbiont genes

The Magnitude of Global Marine Species Diversity

Background: The question of how many marine species exist is important because it provides a metric for how much we do and do not know about life in the oceans. We have compiled the first register of the marine species of the world and used this baseline to estimate how many more species, partitioned among all major eukaryotic groups, may be discovered. Results: There are ∼226,000 eukaryotic marine species described. More species were described in the past decade (∼20,000) than in any previous one. The number of authors describing new species has been increasing at a faster rate than the number of new species described in the past six decades. We report that there are ∼170,000 synonyms, that 58,000–72,000 species are collected but not yet described, and that 482,000–741,000 more species have yet to be sampled. Molecular methods may add tens of thousands of cryptic species. Thus, there may be 0.7–1.0 million marine species. Past rates of description of new species indicate there may be 0.5 ± 0.2 million marine species. On average 37% (median 31%) of species in over 100 recent field studies around the world might be new to science. Conclusions: Currently, between one-third and two-thirds of marine species may be undescribed, and previous estimates of there being well over one million marine species appear highly unlikely. More species than ever before are being described annually by an increasing number of authors. If the current trend continues, most species will be discovered this century

Patterns of Diversity in Soft-Bodied Meiofauna: Dispersal Ability and Body Size Matter

Background: Biogeographical and macroecological principles are derived from patterns of distribution in large organisms, whereas microscopic ones have often been considered uninteresting, because of their supposed wide distribution. Here, after reporting the results of an intensive faunistic survey of marine microscopic animals (meiofauna) in Northern Sardinia, we test for the effect of body size, dispersal ability, and habitat features on the patterns of distribution of several groups.Methodology/Principal Findings: As a dataset we use the results of a workshop held at La Maddalena (Sardinia, Italy) in September 2010, aimed at studying selected taxa of soft-bodied meiofauna (Acoela, Annelida, Gastrotricha, Nemertodermatida, Platyhelminthes and Rotifera), in conjunction with data on the same taxa obtained during a previous workshop hosted at Tjärnö (Western Sweden) in September 2007. Using linear mixed effects models and model averaging while accounting for sampling bias and potential pseudoreplication, we found evidence that: (1) meiofaunal groups with more restricted distribution are the ones with low dispersal potential; (2) meiofaunal groups with higher probability of finding new species for science are the ones with low dispersal potential; (3) the proportion of the global species pool of each meiofaunal group present in each area at the regional scale is negatively related to body size, and positively related to their occurrence in the endobenthic habitat.Conclusion/Significance: Our macroecological analysis of meiofauna, in the framework of the ubiquity hypothesis for microscopic organisms, indicates that not only body size but mostly dispersal ability and also occurrence in the endobenthic habitat are important correlates of diversity for these understudied animals, with different importance at different spatial scales. Furthermore, since the Western Mediterranean is one of the best-studied areas in the world, the large number of undescribed species (37%) highlights that the census of marine meiofauna is still very far from being complete