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Mixed metal oxyhalides are an exciting class of photocatalysts, capable of the sustainable generation of fuels and remediation of pollutants with solar energy. Bismuth oxyhalides of the types Bi4MO8X (M = Nb and Ta; X = Cl and Br) and Bi2AO4X (A = most lanthanides; X = Cl, Br, and I) have an electronic structure that imparts photostability, as their valence band maxima (VBM) are composed of O 2p orbitals rather than X np orbitals that typify many other bismuth oxyhalides. Here, flux-based synthesis of intergrowth Bi4NbO8Cl–Bi2GdO4Cl is reported, testing the hypothesis that both intergrowth stoichiometry and M identity serve as levers toward tunable optoelectronic properties. X-ray scattering and atomically resolved electron microscopy verify intergrowth formation. Facile manipulation of the Bi4NbO8Cl-to-Bi2GdO4Cl ratio is achieved with the specific ratio influencing both the crystal and electronic structures of the intergrowths. This compositional flexibility and crystal structure engineering can be leveraged for photocatalytic applications, with comparisons to the previously reported Bi4TaO8Cl–Bi2GdO4Cl intergrowth revealing how subtle structural and compositional features can impact photocatalytic materials.more » « lessFree, publicly-accessible full text available May 6, 2025
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In this work, the local structures of durable, high-activity Bi 4 TaO 8 Cl–Bi 2 GdO 4 Cl intergrowth photocatalysts that were prepared in a molten flux are determined by pair distribution function analysis of X-ray total scattering data and correlated to their photocatalytic performance. This system gives understanding to how the local structure of photocatalysts can be manipulated controllably through incorporation of rigid and flexible layers via intergrowth formation to achieve high activity. This analysis revealed that the local symmetry and distortion of the [TaO 6 ] octahedra introduced through intergrowth formation and dictated by intergrowth stoichiometry correlate with their photocatalytic activity. That is, the greater the Ta–O–Ta bond angles, the higher the photocatalytic activity of a given intergrowth for the oxygen evolution reaction. Moreover, greater tilting of the [TaO 6 ] octahedra is associated with a larger band gap. This analysis was coupled with a structure mining approach to model the intergrowth structure by building supercells for refinement of the X-ray diffraction data. This analysis found that Ta- and Gd-domains are separated within the intergrowths, with large Gd-domains separated by small Ta-domains at high Gd% and the opposite for high Ta%. Taken together with Williamson–Hall analysis, our results highlight that the local structure of layered materials can be modulated through strain engineering enabled by the selection of rigid and flexible intergrowth layers, providing a new design pathway to high performance photocatalysts.more » « less
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Since 2010, the trypanorhynch tapeworm family Rhinoptericolidae Carvajal & Campbell, 1975 has housed just two distinctive, monotypic genera ( Rhinoptericola Carvajal & Campbell, 1975 and Nataliella Palm, 2010). However, global collections of tapeworms from sharks and rays over the last more than three decades brought to light the need for major revision of the family by suggesting a much greater species-level diversity for the nominal genus Rhinoptericola . Through synonymy and the description of new species, the number of species in the genus is increased from one to eight. A phylogenetic analysis of the D1–D3 gene region of 28S rRNA (28S), including seven of the now nine species of rhinoptericolids, and a broad sampling of the other Trypanobatoida is the first to recover a monophyletic Rhinoptericolidae. In addition to systematic revision, this study allowed for the first evaluation of the degree of intraspecific vs interspecific variation in 28S for adult trypanorhynchs across the various hosts and geographic localities from which they have been reported, suggesting a relatively consistent boundary for Rhinoptericola . It is further suggested that detailed scanning electron microscopy (SEM) images of both the basal and metabasal armatures greatly aid in the interpretation of hook arrangement and shape. A schematic to streamline determination of the tentacular surface presented in scanning electron micrographs and line drawings of trypanorhynchs is presented for species with both two and four bothria. In combination, these methodological refinements can now be used as a model to resolve issues of classification and non-monophyly within both major lineages of the Trypanorhyncha. As a result of the taxonomic work, Rhinoptericola megacantha Carvajal & Campbell, 1975 (previously only known from the American cownose ray from the Chesapeake Bay and the Ticon cownose ray from the Gulf of Mexico, Venezuela, and Brazil) is now known from an additional species of cownose ray and a species of stingray, and is revealed to have a transatlantic distribution. Data from SEM suggest a simpler interpretation of hook arrangement in the metabasal armature for Rhinoptercola and—in combination with 28S sequence data—support Shirleyrhynchus Beveridge & Campbell, 1988 (a former rhinoptericolid) as its junior synonym. The three species formerly assigned to Shirleyrhynchus are thus transferred to Rhinoptericola . Data from light microscopy on whole-mounted specimens and histological sections, SEM, and 28S showed the eutetrarhynchid Prochristianella jensenae Schaeffner & Beveridge, 2012b to be morphologically consistent with species of Rhinoptericola and it is thus transferred to the genus. The type series of P. jensenae was determined to be mixed, representing two distinct species which are here redescribed and described as new, respectively. Two additional novel species of Rhinoptericola are described from cownose rays from off Mozambique and the Gulf of California.more » « less
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Abstract Characterization of material structure with X-ray or neutron scattering using e.g. Pair Distribution Function (PDF) analysis most often rely on refining a structure model against an experimental dataset. However, identifying a suitable model is often a bottleneck. Recently, automated approaches have made it possible to test thousands of models for each dataset, but these methods are computationally expensive and analysing the output, i.e. extracting structural information from the resulting fits in a meaningful way, is challenging. Our
M achineL earning basedMot ifEx tractor (ML-MotEx) trains an ML algorithm on thousands of fits, and uses SHAP (SHapley Additive exPlanation) values to identify which model features are important for the fit quality. We use the method for 4 different chemical systems, including disordered nanomaterials and clusters. ML-MotEx opens for a type of modelling where each feature in a model is assigned an importance value for the fit quality based on explainable ML. -
The Rhoptrobothriidae are one of the more enigmatic families of cestodes of elasmobranchs. Opinions on the taxonomic status of the family’s three original genera (i.e., Myzophyllobothrium, Rhoptrobothrium, and Myzocephalus) have varied over the 115 years since they were erected. Some authors have considered all three valid, others have considered Rhoptrobothrium to be a synonym of Myzopyllobothrium or a genus inquirendum, yet others have considered Myzocephalus to be a synonym of the phyllobothriid genus Thysanocephalum. All three genera were established for specimens collected from eagle rays off Sri Lanka. The erection of Mixophyllobothrium for two specimens from a cowtail stingray off India three decades ago added additional confusion to the situation, with some authors considering it valid and others a synonym of Myzocephalus. These disagreements stem largely from differences in interpretation of the complex morphology of the scolex of members of these genera. Furthermore, with the exception of Rhoptrobothrium comprising four species, each genus is monotypic. All but Rhoptrobothrium has not been considered in detail for nearly a century, largely because of a lack of available material. The taxonomic status of these genera is assessed here based on light and scanning electron microscopy, and molecular data generated from new material collected from eagle rays off Indonesian and Malaysian Borneo, Japan, Sri Lanka, and Viet Nam. Morphological work indicates that the genera differ largely only in the degree of folding of the four remi that extend from the cephalic peduncle. A molecular phylogeny based on sequence data for the D1–D3 region of the 28S rRNA gene, which include new data for eight specimens of four species, indicates that Myzophyllobothrium, Myzocephalus, and Rhoptrobothrium are not mutually monophyletic. The latter two genera and Mixophyllobothrium are considered synonyms of Myzophyllobothrium and five species are transferred to that genus. Myzophyllobothrium okamuri n. comb. is considered a species inquirendum. Myzophyllobothrium nagasawai n. sp. is described from Aetobatus narutobiei off Japan. Myzophyllobothrium narinari n. comb. is re-described based on newly collected cestodes from the type host and locality (i.e., Aetobatus ocellatus off Sri Lanka). Despite consisting of only a single genus, the family status of the group is retained in recognition of the unusual configuration of the scolex, which bears four biloculate bothridia and four remi extending from the cephalic peduncle. The ordinal placement of the family remains uncertain, but affinities with the Phyllobothriidea, rather than “Tetraphyllidea” are considered.more » « less
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Ruiz-Rodriguez, Magdalena (Ed.)Nutritionally-based mutualisms with bacteria are known to occur in a wide array of invertebrate phyla, although less commonly in the Platyhelminthes. Here we report what appears to be a novel example of this type of association in two geographically disparate and phylogenetically distant species of tapeworms of eagle rays—the lecanicephalidean Elicilacunosus dharmadii off the island of Borneo and the tetraphyllidean Caulobothrium multispelaeum off Senegal. Scanning and transmission electron microscopy revealed that the grooves and apertures on the outer surfaces of both tapeworms open into expansive cavities housing concentrations of bacteria. This led us to reject the original hypothesis that these structures, and their associated mucopolysaccharides, aid in attachment to the host mucosa. The cavities were found to be specialized in-foldings of the tapeworm body that were lined with particularly elongate filitriches. Given tapeworms lack a gut and employ filitriches to assist in nutrient absorption, enhanced nutrient uptake likely occurs in the cavities. Each tapeworm species appeared to host different bacterial monocultures; those in E . dharmadii were coccoid-like in form, while those in C . multispelaeum were bacillus-like. The presence of bacteria in a specialized structure of this nature suggests the structure is a symbiotic organ. Tapeworms are fully capable of obtaining their own nutrients, and thus the bacteria likely serve merely to supplement their diet. Given the bacteria were also extracellular, this structure is more consistent with a mycetome than a trophosome. To our knowledge, this is not only the first evidence of an external symbiotic organ of any type in a nutritionally-based mutualism, but also the first description of a mycetome in a group of invertebrates that lacks a digestive system. The factors that might account for the independent evolution of this unique association in these unrelated tapeworms are unclear—especially given that none of their closest relatives exhibit any evidence of the phenomenon.more » « less
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null (Ed.)Two new species of the cestode genus Caulobothrium, collected from the duckbill eagle ray, Aetomylaeus bovinus, off Senegal, are described. Although postulated as sister taxa in an earlier molecular phylogenetic analysis, Caulobothrium multispelaeum n. sp. and Caulobothrium katzi n. sp., respectively, are among the smallest and largest members of the genus. The smaller species is unique among its congeners in possessing unusual medial longitudinal grooves along the dorsal and ventral surfaces of its strobila that develop into a tandem series of elliptical apertures on the posterior proglottids. The inner surfaces of these apertures stained positively with McManus’ periodic acid Schiff in a manner similar to that seen in members of the distantly related lecanicephalidean genus Elicilacunosus. The larger species differs from its congeners in size, number of proglottids, and arrangement of bothridial loculi. Both new species were found to possess a small apical sucker on the anterior margin of each of their bothridia. Scanning electron microscopy (SEM) and frontal sections of a bothridium of Caulobothrium tetrascaphium suggests that this species also bears an apical sucker. Examination of the hologenophore of the species provisionally referred to as Caulobothrium n. sp. 5 in the earlier molecular analysis indicates it is conspecific with the recently described Caulobothrium pedunculatum, which was also determined to possess bothridial apical suckers. This leads us to suspect that this feature may be found to occur in all members of the genus. SEM of specimens of Caulobothrium for the first time indicates their bothridial surfaces are covered with filitriches of various sizes but lack spinitriches; spinitriches were seen only on the cephalic peduncle of C. katzi n. sp. The geographic distribution and host associations of Caulobothrium are expanded to include data now available for all species. The diagnosis of the genus is revised to include all of this information.more » « less