A modern scleractinian coral with a two-component calcite-aragonite skeleton.

One of the most conserved traits in the evolution of biomineralizing organisms is the taxon-specific selection of skeletal minerals. All modern scleractinian corals are thought to produce skeletons exclusively of the calcium-carbonate polymorph aragonite. Despite strong fluctuations in ocean chemistry (notably the Mg/Ca ratio), this feature is believed to be conserved throughout the coral fossil record, spanning more than 240 million years. Only one example, the Cretaceous scleractinian coral Coelosmilia (ca. 70 to 65 Ma), is thought to have produced a calcitic skeleton. Here, we report that the modern asymbiotic scleractinian coral Paraconotrochus antarcticus living in the Southern Ocean forms a two-component carbonate skeleton, with an inner structure made of high-Mg calcite and an outer structure composed of aragonite. P. antarcticus and Cretaceous Coelosmilia skeletons share a unique microstructure indicating a close phylogenetic relationship, consistent with the early divergence of P. antarcticus within the Vacatina (i.e., Robusta) clade, estimated to have occurred in the Mesozoic (ca. 116 Mya). Scleractinian corals thus join the group of marine organisms capable of forming bimineralic structures, which requires a highly controlled biomineralization mechanism; this capability dates back at least 100 My. Due to its relatively prolonged isolation, the Southern Ocean stands out as a repository for extant marine organisms with ancient traits.

A Devonian crinoid with a diamond microlattice.

Owing to their remarkable physical properties, cellular structures, such as triply periodic minimal surfaces (TPMS), have multidisciplinary and multifunctional applications. Although these structures are observed in nature, examples of TPMS with large length scales in living organisms are exceedingly rare. Recently, microstructure reminiscent of the diamond-type TPMS was documented in the skeleton of the modern knobby starfish Protoreaster nodosus. Here we report a similar microlattice in a 385 Myr old crinoid Haplocrinites, which pushes back the origins of this highly ordered microstructure in echinoderms into the Devonian. Despite the low Mg2+/Ca2+ ratio of the 'calcite' Devonian sea, the skeleton of these crinoids has high-Mg content, which indicates strong biological control over biomineralogy. We suggest that such an optimization of trabecular arrangement additionally enriched in magnesium, which enhances the mechanical properties, might have evolved in these crinoids in response to increased predation pressure during the Middle Palaeozoic Marine Revolution. This discovery illustrates the remarkable ability of echinoderms, through the process of evolutionary optimization, to form a lightweight, stiff and damage-tolerant skeleton, which serves as an inspiration for biomimetic materials.

Effect of Gel Exposition on Calcium and Carbonate Ions Determines the Stm-l Effect on the Crystal Morphology of Calcium Carbonate.

Biomineralization of fish otoliths is regulated by macromolecules, such as proteins, whose presence is crucial for the functionality and properties of these mineralized structures. Special regulatory effects are exerted by intrinsically disordered proteins, such as the polyanionic Starmaker-like protein from medaka, a homolog of zebrafish Starmaker. In this study, we employed a set of bioinspired mineralization experiments with a single diffusion system to investigate the effect of the Starmaker-like protein on calcium carbonate biominerals with regards to the prior exposition of the protein to calcium or carbonate ions. Interestingly, the bioinspired minerals grown in the presence of the Starmaker-like protein in calcium- or carbonate-type experiments differ significantly in terms of morphology and protein distribution within the crystals. Our deeper analysis shows that the Starmaker-like protein action is a result of the environmental conditions to which it is exposed. These findings may be of special interest in the areas of biomineralization process pathways and biomaterial sciences.

Phylogeography of recent Plesiastrea (Scleractinia: Plesiastreidae) based on an integrated taxonomic approach.

Scleractinian corals are a diverse group of ecologically important yet highly threatened marine invertebrates, which can be challenging to identify to the species level. An influx of molecular studies has transformed scleractinian systematics, highlighting that cryptic species may be more common than previously understood. In this study, we test the hypothesis that Plesiastrea versipora (Lamarck, 1816), a species currently considered to occur throughout the Indo-Pacific in tropical, sub-tropical and temperate waters, is a single species. Molecular and morphological analyses were conducted on 80 samples collected from 31 sites spanning the majority of the species putative range and twelve mitogenomes were assembled to identify informative regions for phylogenetic reconstruction. Congruent genetic data across three gene regions supports the existence of two monophyletic clades aligning with distinct tropical and temperate provenances. Multivariate macromorphological analyses based on 13 corallite characters provided additional support for the phylogeographic split, with the number of septa and corallite density varying across this biogeographic divide. Furthermore, micromorphological and microstructural analyses identified that the temperate representatives typically develop sub-cerioid corallites with sparse or absent coenosteal features and smooth septal faces. In contrast, tropical representatives typically develop plocoid corallites separated by a porous dissepimental coenosteum and have granulated septal faces. These data suggest that at least two species exist within the genus PlesiastreaMilne Edwards & Haime, 1848. Based on examination of type material, we retain the name Plesiastrea versipora (Lamarck, 1816) for the temperate representatives of the genus and resurrect the name Plesiastrea peroniMilne Edwards & Haime, 1857 for the tropical members. This study highlights how broadly distributed hard coral taxa still need careful re-examination through an integrated systematics approach to better understand their phylogeographic patterns. Furthermore, it demonstrates the utility of integrating micro-, macro-morphological and genetic datasets, and the importance of type specimens when dealing with taxonomic revisions of scleractinian taxa.

How corals made rocks through the ages.

Hard, or stony, corals make rocks that can, on geological time scales, lead to the formation of massive reefs in shallow tropical and subtropical seas. In both historical and contemporary oceans, reef-building corals retain information about the marine environment in their skeletons, which is an organic-inorganic composite material. The elemental and isotopic composition of their skeletons is frequently used to reconstruct the environmental history of Earth's oceans over time, including temperature, pH, and salinity. Interpretation of this information requires knowledge of how the organisms formed their skeletons. The basic mechanism of formation of calcium carbonate skeleton in stony corals has been studied for decades. While some researchers consider coral skeletons as mainly passive recorders of ocean conditions, it has become increasingly clear that biological processes play key roles in the biomineralization mechanism. Understanding the role of the animal in living stony coral biomineralization and how it evolved has profound implications for interpreting environmental signatures in fossil corals to understand past ocean conditions. Here we review historical hypotheses and discuss the present understanding of how corals evolved and how their skeletons changed over geological time. We specifically explain how biological processes, particularly those occurring at the subcellular level, critically control the formation of calcium carbonate structures. We examine the different models that address the current debate including the tissue-skeleton interface, skeletal organic matrix, and biomineralization pathways. Finally, we consider how understanding the biological control of coral biomineralization is critical to informing future models of coral vulnerability to inevitable global change, particularly increasing ocean acidification.

Lattice Shrinkage by Incorporation of Recombinant Starmaker-Like Protein within Bioinspired Calcium Carbonate Crystals.

The biological mediation of mineral formation (biomineralization) is realized through diverse organic macromolecules that guide this process in a spatial and temporal manner. Although the role of these molecules in biomineralization is being gradually revealed, the molecular basis of their regulatory function is still poorly understood. In this study, the incorporation and distribution of the model intrinsically disordered starmaker-like (Stm-l) protein, which is active in fish otoliths biomineralization, within calcium carbonate crystals, is revealed. Stm-l promotes crystal nucleation and anisotropic tailoring of crystal morphology. Intracrystalline incorporation of Stm-l protein unexpectedly results in shrinkage (and not expansion, as commonly described in biomineral and bioinspired crystals) of the crystal lattice volume, which is described herein, for the first time, for bioinspired mineralization. A ring pattern was observed in crystals grown for 48 h; this was composed of a protein-enriched region flanked by protein-depleted regions. It can be explained as a result of the Ostwald-like ripening process and intrinsic properties of Stm-l, and bears some analogy to the daily growth layers of the otolith.

Uncovering hidden coral diversity: a new cryptic lobophylliid scleractinian from the Indian Ocean.

Extant biodiversity can easily be underestimated owing to the presence of cryptic taxa, even among commonly observed species. Scleractinian corals are challenging to identify because of their ecophenotypic variation and morphological plasticity. In addition, molecular analyses have revealed the occurrence of cryptic speciation. Here, we describe a new cryptic lobophylliid genus and species Paraechinophyllia variabilis gen. nov., sp. nov., which is morphologically similar to Echinophyllia aspera and E. orpheensis. The new taxon occurs in Mayotte Island, Madagascar, the Gulf of Aden and the Red Sea. Six molecular markers (COI, 12S, ATP6-NAD4, NAD3-NAD5, histone H3 and ITS) and 46 morphological characters at three different levels (macromorphology, micromorphology and microstructure) were examined. The resulting molecular phylogenetic reconstruction showed that Paraechinophyllia gen. nov. represents a distinct group within the Lobophylliidae that diverged from the lineage leading to Echinophyllia and Oxypora in the Early Miocene, approximately 21.5 Ma. The morphological phylogenetic reconstruction clustered Paraechinophyllia gen. nov., Echinophyllia and Oxypora together in a single clade. A sole morphological character, calice relief, discriminated Paraechinophyllia gen. nov. from the latter two genera, suggesting that limited morphological variation has occurred over a long period. These results highlight the importance of cryptic taxa in reef corals, with implications for population genetics, ecological studies and conservation.

Correction to: Sea urchin growth dynamics at microstructural length scale revealed by Mn-labeling and cathodoluminescence imaging.

[This corrects the article DOI: 10.1186/s12983-017-0227-8.].

Sea urchin growth dynamics at microstructural length scale revealed by Mn-labeling and cathodoluminescence imaging.

BACKGROUND: Fluorochrome staining is among the most widely used techniques to study growth dynamics of echinoderms. However, it fails to detect fine-scale increments because produced marks are commonly diffusely distributed within the skeleton. In this paper we investigated the potential of trace element (manganese) labeling and subsequent cathodoluminescence (CL) imaging in fine-scale growth studies of echinoderms. RESULTS: Three species of sea urchins (Paracentrotus lividus, Echinometra sp. and Prionocidaris baculosa) were incubated for different periods of time in seawater enriched in different Mn2+ concentrations (1 mg/L; 3 mg/L; 61.6 mg/L). Labeling with low Mn2+ concentrations (at 1 mg/L and 3 mg/L) had no effect on behavior, growth and survival of sea urchins in contrast to the high Mn2+ dosage (at 61.6 mg/L) that resulted in lack of skeleton growth. Under CL, manganese produced clearly visible luminescent growth fronts in these specimens (observed in sectioned skeletal parts), which allowed for a determination of the average extension rates and provided direct insights into the morphogenesis of different types of ossicles. The three species tend to follow the same patterns of growth. Spine growth starts with the formation of microspines which are simultaneously becoming reinforced by addition of thickening layers. Spine septa develop via deposition of porous stereom that is rapidly (within less than 2 days) filled by secondary calcite. Development of the inner cortex in cidaroids begins with the formation of microspines which grow at ~3.5 µm/day. Later on, deposition of the outer polycrystalline cortex with spinules and protuberances proceeds at ~12 µm/day. The growth of tooth can be rapid (up to ~1.8 mm/day) and starts with the formation of primary plates (pp) in plumula. Later on, during the further growth of pp in aboral and lateral directions, secondary extensions develop inside (in chronological order: lamellae, needles, secondary plate, prisms and carinar processes), which are increasingly being solidified towards the incisal end. Interradial growth in the ambital interambulacral test plates exceeds meridional growth and inner thickening. CONCLUSIONS: Mn2+ labeling coupled with CL imaging is a promising, low-cost and easily applicable method to study growth dynamics of echinoderms at the micro-length scale. The method allowed us to evaluate and refine models of echinoid skeleton morphogenesis.

Merging scleractinian genera: the overwhelming genetic similarity between solitary Desmophyllum and colonial Lophelia.

BACKGROUND: In recent years, several types of molecular markers and new microscale skeletal characters have shown potential as powerful tools for phylogenetic reconstructions and higher-level taxonomy of scleractinian corals. Nonetheless, discrimination of closely related taxa is still highly controversial in scleractinian coral research. Here we used newly sequenced complete mitochondrial genomes and 30 microsatellites to define the genetic divergence between two closely related azooxanthellate taxa of the family Caryophylliidae: solitary Desmophyllum dianthus and colonial Lophelia pertusa. RESULTS: In the mitochondrial control region, an astonishing 99.8 % of nucleotides between L. pertusa and D. dianthus were identical. Variability of the mitochondrial genomes of the two species is represented by only 12 non-synonymous out of 19 total nucleotide substitutions. Microsatellite sequence (37 loci) analysis of L. pertusa and D. dianthus showed genetic similarity is about 97 %. Our results also indicated that L. pertusa and D. dianthus show high skeletal plasticity in corallum shape and similarity in skeletal ontogeny, micromorphological (septal and wall granulations) and microstructural characters (arrangement of rapid accretion deposits, thickening deposits). CONCLUSIONS: Molecularly and morphologically, the solitary Desmophyllum and the dendroid Lophelia appear to be significantly more similar to each other than other unambiguous coral genera analysed to date. This consequently leads to ascribe both taxa under the generic name Desmophyllum (priority by date of publication). Findings of this study demonstrate that coloniality may not be a robust taxonomic character in scleractinian corals.

Calcium carbonate polymorph selection in fish otoliths: A key role of phosphorylation of Starmaker-like protein.

Fish otoliths are calcium carbonate biominerals found in the inner ear commonly used for tracking fish biochronologies and as a model system for biomineralization. The process of fish otolith formation is biologically controlled by numerous biomacromolecules which not only affect crystal size, shape, mechanical properties, but also selection of calcium carbonate polymorph (e.g., aragonite, vaterite). The proteinaceous control over calcium carbonate polymorph selection occurs in many other species (e.g., corals, mollusks, echinoderms) but the exact mechanism of protein interactions with calcium and carbonate ions - constituents of CaCO3 - are not fully elucidated. Herein, we focus on a native Starmaker-like protein isolated from vaterite asteriscus otoliths from Cyprinus carpio. The proteomic studies show the presence of the phosphorylated protein in vaterite otoliths. In a series of in vitro mineralization experiments with Starmaker-like, we show that native phosphorylation is a crucial determinant for the selection of a crystal's polymorphic form. This is the first report showing that the switch in calcium carbonate phase depends on the phosphorylation pattern of a single isolated protein. STATEMENT OF SIGNIFICANCE: Calcium carbonate has numerous applications in industry and medicine. However, we still do not understand the mechanism of biologically driven polymorph selection which results in specific biomineral properties. Previous work on calcium carbonate biominerals showed that either several macromolecular factors or high magnesium concentration (non-physiological) are required for proper polymorph selection (e.g., in mollusk shells, corals and otoliths). In this work, we showed for the first time that protein phosphorylation is a crucial factor for controlling the calcium carbonate crystal phase. This is important because a single protein from the otolith organic matrix could switch between polymorphs depending on the phosphorylation level. It seems that protein post-translational modifications (native, not artificial) are more important for biomolecular control of crystal growth than previously considered.

Post-mortem recrystallization of biogenic amorphous calcium carbonate guided by the inherited macromolecular framework.

In contrast to abiotically formed carbonates, biogenetic carbonates have been observed to be nanocomposite, organo-mineral structures, the basic build-blocks of which are particles of quasi-uniform size (10-100 nm) organized into complex higher-order hierarchical structures, typically with highly controlled crystal-axis alignments. Some of these characteristics serve as criteria for inferring a biological origin and the state of preservation of fossil carbonate materials, and to determine whether the biomineralization process was biologically induced or controlled. Here we show that a calcium storage structure formed by the American lobster, a gastrolith initially consisting of amorphous calcium carbonate (ACC) and amorphous calcium phosphate (ACP), post-mortem can crystallize into (thus secondary) calcite with structural properties strongly influenced by the inherited organic matrix. This secondary calcite meets many structural criteria for biominerals (thus called the biomorphic calcite), but differs in trace element distributions (e.g., P and Mg). Such observations refine the capability to determine whether a fossil carbonates can be attributed to biogenic processes, with implications for the record of life on Earth and other terrestrial planets.

Fossil biocalcite remains open to isotopic exchange with seawater for tens of millions of years.

Fossilized remains of marine calcifiers constitute the physical basis for reconstructions of both deep ocean and sea-surface temperatures going back millions of years, but paleoclimate records derived from their isotope and trace-element chemistry can be biased by diagenesis. Experiments simulating diagenesis in the presence of an 18O-rich seawater analogue were conducted with modern and 14 Myr old foraminifera (Ammonia sp.) tests to investigate their relative susceptibility to oxygen isotope exchange. The fossilized tests were of exceptional preservation and similar to modern tests in terms of structure and crystalline organization, but had experienced partial loss of embedded organic structures, thus a priori offering fewer preferential pathways for porewaters to penetrate the tests. NanoSIMS imaging revealed that oxygen isotope exchange was pervasive in fossil tests, with isotopic exchange occurring at approximately half the rate of modern tests. The results unequivocally show that fossil biocalcites are metastable and remain more susceptible to isotope exchange than abiotic calcites millions of years after sedimentation and burial.

Magnetic-nanoparticle-decorated polypyrrole microvessels: toward encapsulation of mRNA cap analogues.

Many phosphorylated nucleoside derivatives have therapeutic potential, but their application is limited by problems with membrane permeability and with intracellular delivery. Here, we prepared polypyrrole microvessel structures modified with superparamagnetic nanoparticles for use as potential carriers of nucleotides. The microvessels were prepared via the photochemical polymerization of the monomer onto the surface of aqueous ferrofluidic droplets. A complementary physicochemical analysis revealed that a fraction of the nanoparticles was embedded in the microvessel walls, while the other nanoparticles were in the core of the vessel. SQUID (superconducting quantum interference device) measurements indicated that the incorporated nanoparticles retained their superparamagnetic properties; thus, the resulting nanoparticle-modified microvessels can be directed by an external magnetic field. As a result of these features, these microvessels may be useful as drug carriers in biomedical applications. To demonstrate the encapsulation of drug molecules, two labeled mRNA cap analogues, nucleotide-derived potential anticancer agents, were used. It was shown that the cap analogues are located in the aqueous core of the microvessels and can be released to the external solution by spontaneous permeation through the polymer walls. Mass spectrometry analysis confirmed that the cap analogues were preserved during encapsulation, storage, and release. This finding provides a foundation for the future development of anticancer therapies and for the delivery of nucleotide-based therapeutics.

Otolin-1, an otolith- and otoconia-related protein, controls calcium carbonate bioinspired mineralization.

BACKGROUND: Otoliths and otoconia are calcium carbonate biomineral structures that form in the inner ear of fish and humans, respectively. The formation of these structures is tightly linked to the formation of an organic matrix framework with otolin-1, a short collagen-like protein from the C1q family as one of its major constituents. METHODS: In this study, we examined the activity of recombinant otolin-1 originating from Danio rerio and Homo sapiens on calcium carbonate bioinspired mineralization with slow-diffusion method and performed crystals characterization with scanning electron microscopy, two-photon excited fluorescence microscopy, confocal laser scanning microscopy and micro-Raman spectroscopy. RESULTS: We show that both proteins are embedded in the core of CaCO3 crystals that form through the slow-diffusion mineralization method. Both of them influence the morphology but do not change the polymorphic mineral phase. D.rerio otolin-1 also closely adheres to the crystal surface. GENERAL SIGNIFICANCE: The results suggest, that otolin-1 is not a passive scaffold, but is directly involved in regulating the morphology of the resulting calcium carbonate biocrystals.

Earthworm granules: A model of non-classical biogenic calcium carbonate phase transformations.

Different non-classical crystallization mechanisms have been invoked to explain structural and compositional properties of biocrystals. The identification of precursor amorphous nanoparticle aggregation as an onset process in the formation of numerous biominerals (crystallization via particle attachment) constituted a most important breakthrough for understanding biologically mediated mineralization. A comprehensive understanding about how the attached amorphous particles transform into more stable, crystalline grains has yet to be elucidated. Here, we document structural, biogeochemical, and crystallographic aspects of the formation as well as the further phase transformations of the amorphous calcium carbonate particles formed by cultured specimens of earthworm Lumbricus terrestris. In-situ observations evidence the formation of proto-vaterite after dehydration of earthworm-produced ACC, which is subsequently followed by proto-vaterite transformation into calcite through nanoparticle attachment within the organic framework. In culture medium spiked with trace amounts of Mn2+, the cauliflower-like proto-vaterite structures become longer-lived than in the absence of Mn2+. We propose that the formation of calcite crystals takes place through a non-classical recrystallization path that involves migration of proto-vaterite nanoparticles to the crystallization site, and then, their transformation into calcite via a dissolution-recrystallization reaction. The latter is complemented by ion-by-ion crystal growth and associated with impurity release. These observations are integrated into a new model of the biocrystallization of earthworm-produced carbonate granules which highlights the sensibility of this process to environmental chemical changes, its potential impact on the bioavailability of contaminants as well as the threat that chemical pollution poses to the normal development of its early stages. STATEMENT OF SIGNIFICANCE: Understanding the mechanisms of nucleation, stabilization and aggregation of amorphous calcium carbonate (ACC) and factors controlling its further transformation into crystalline phases is fundamental for elucidation of biogenic mineralization. Some species of earthworms are natural workbench to understand the biogenic ACC, stabilization and the transformation mechanisms, because they create millimeter-sized calcareous granules from amorphous calcium carbonate, which crystallize to a more stable mineral phase (mostly calcite). This study undergoes into the mechanisms of ACC stabilization by the incorporation of trace elements, as manganese, and the ulterior precipitation of calcareous granules by a coupled process of amorphous particle attachment and ion-by-ion growth. The study points to sensibility of this process to environmental chemical changes.

First paleoproteome study of fossil fish otoliths and the pristine preservation of the biomineral crystal host.

Otoliths are calcium carbonate components of the stato-acoustical organ responsible for hearing and maintenance of the body balance in teleost fish. During their formation, control over, e.g., morphology and carbonate polymorph is influenced by complex insoluble collagen-like protein and soluble non-collagenous protein assemblages; many of these proteins are incorporated into their aragonite crystal structure. However, in the fossil record these proteins are considered lost through diagenetic processes, hampering studies of past biomineralization mechanisms. Here we report the presence of 11 fish-specific proteins (and several isoforms) in Miocene (ca. 14.8-14.6 Ma) phycid hake otoliths. These fossil otoliths were preserved in water-impermeable clays and exhibit microscopic and crystallographic features indistinguishable from modern representatives, consistent with an exceptionally pristine state of preservation. Indeed, these fossil otoliths retain ca. 10% of the proteins sequenced from modern counterparts, including proteins specific to inner ear development, such as otolin-1-like proteins involved in the arrangement of the otoliths into the sensory epithelium and otogelin/otogelin-like proteins that are located in the acellular membranes of the inner ear in modern fish. The specificity of these proteins excludes the possibility of external contamination. Identification of a fraction of identical proteins in modern and fossil phycid hake otoliths implies a highly conserved inner ear biomineralization process through time.

Rapid grain boundary diffusion in foraminifera tests biases paleotemperature records.

The oxygen isotopic compositions of fossil foraminifera tests constitute a continuous proxy record of deep-ocean and sea-surface temperatures spanning the last 120 million years. Here, by incubating foraminifera tests in 18O-enriched artificial seawater analogues, we demonstrate that the oxygen isotopic composition of optically translucent, i.e., glassy, fossil foraminifera calcite tests can be measurably altered at low temperatures through rapid oxygen grain-boundary diffusion without any visible ultrastructural changes. Oxygen grain boundary diffusion occurs sufficiently fast in foraminifera tests that, under normal upper oceanic sediment conditions, their grain boundaries will be in oxygen isotopic equilibrium with the surrounding pore fluids on a time scale of <100 years, resulting in a notable but correctable bias of the paleotemperature record. When applied to paleotemperatures from 38,400 foraminifera tests used in paleoclimate reconstructions, grain boundary diffusion can be shown to bias prior paleotemperature estimates by as much as +0.86 to -0.46 °C. The process is general and grain boundary diffusion corrections can be applied to other polycrystalline biocarbonates composed of small nanocrystallites (<100 nm), such as those produced by corals, brachiopods, belemnites, and molluscs, the fossils of which are all highly susceptible to the effects of grain boundary diffusion.

Differences in carbonate chemistry up-regulation of long-lived reef-building corals.

With climate projections questioning the future survival of stony corals and their dominance as tropical reef builders, it is critical to understand the adaptive capacity of corals to ongoing climate change. Biological mediation of the carbonate chemistry of the coral calcifying fluid is a fundamental component for assessing the response of corals to global threats. The Tara Pacific expedition (2016-2018) provided an opportunity to investigate calcification patterns in extant corals throughout the Pacific Ocean. Cores from colonies of the massive Porites and Diploastrea genera were collected from different environments to assess calcification parameters of long-lived reef-building corals. At the basin scale of the Pacific Ocean, we show that both genera systematically up-regulate their calcifying fluid pH and dissolved inorganic carbon to achieve efficient skeletal precipitation. However, while Porites corals increase the aragonite saturation state of the calcifying fluid (Ωcf) at higher temperatures to enhance their calcification capacity, Diploastrea show a steady homeostatic Ωcf across the Pacific temperature gradient. Thus, the extent to which Diploastrea responds to ocean warming and/or acidification is unclear, and it deserves further attention whether this is beneficial or detrimental to future survival of this coral genus.

Photopolymerized polypyrrole microvessels.

We report on the preparation of water-filled polymer microvessels through the photopolymerization of pyrrole in a water/chloroform emulsion. The resulting structures were characterized by complementary spectroscopic and microscopic techniques, including Raman spectroscopy, XPS, SEM, and TEM. The encapsulation of fluorescent, magnetic, and ionic species within the microvessels has been demonstrated. Confocal microscopy and fluorescence anisotropy measurements revealed that the encapsulated chromophore (Rhodamine 6G) resides within voids in the capsules; however, strong interaction of the dye with polypyrrole results in a measurable decrease in its rotational dynamics. Microvessels loaded with ferrofluid exhibit magnetic properties, and their structures can be directed with an external magnetic field. TEM measurements allowed imaging of individual nanoparticles entrapped within the vessels. The application of Cu(2+)-loaded microvessels as a transducer layer in all-solid-state ion-selective electrodes was also demonstrated.