Recycling resources: silica of diatom frustules as a source for spicule building in Antarctic siliceous demosponges

Dissolved silicon (DSi) is biologically processed to produce siliceous skeletons by a variety of organisms including radiolarians, silicoflagellates, choanoflagellates, plants, diatoms and some animals. In the photic ocean, diatoms are dominant consumers over competing other silicifiers. In Antarctica, where DSi is not particularly limiting, diatoms and sponges coexist in high abundances. Interestingly, diatom ingestion by sponges is a regular feeding strategy there. Although it was known that the diatom organic nutrients are readily metabolized by the sponges, what happened to the inorganic diatom silica skeleton remained unexplored. Here, we have conducted a multi-analytical approach to investigate the processing of diatom silica and whether it is reconverted into sponge silica. We have documented widespread diatom consumption by several demosponges, identifying storage vesicles for the diatom-derived silica by electron microscopy and microanalysis. Diatom-consuming sponges showed upregulation of silicatein and silicase genes, which in addition to the δ 30Si values of their silica, supports that the sponges are converting the ingested diatom silica into sponge silica without much further Si fractionation. Our multidisciplinary approach suggests that the reutilization of diatom silica by sponges is a common feature among Antarctic sponges, which should be further investigated in other latitudes and in other silicifiers.

Molecular Imprinting of Bisphenol A on Silica Skeleton and Gold Pinhole Surfaces in 2D Colloidal Inverse Opal through Thermal Graft Copolymerization

This study successfully fabricated BPA-imprinted poly(4-vinylpyridine-co-ethylene glycol dimethacrylate) (poly(4-VP-co-EGDMA)) quartz crystal microbalance (MIP-QCM) sensors on a silica skeleton surface and gold pinholes of silica inverse opal through surface-initiated atom transfer radical polymerization (SI-ATRP). The sensing features of the two MIP films on the structured silica surface and nano-scale local gold surface were investigated by measuring the resonant frequency change (∆f) in QCM sensors. The ∆f values for the p-MIP (MIP on gold pinholes) and s-MIP films (MIP on silica skeleton surface) were obtained with the ∆f value of −199 ± 4.9 Hz and −376 ± 19.1 Hz, respectively, whereas for p-/s-NIP films, the ∆f values were observed to be −115 ± 19.2 Hz and −174 ± 5.8 Hz by the influence of non-specific adsorption on the surface of the films. Additionally, the imprinting factor (IF) appeared to be 1.72 for p-MIP film and 2.15 for s-MIP film, and the limits of quantitation (LOQ) and detection (LOD) were 54.924 and 18.125 nM (p-MIP film) and 38.419 and 12.678 nM (s-MIP film), respectively. Using the Freundlich isotherm model, the binding affinity of the BPA-imprinted films was evaluated. This was measured in an aqueous solution of BPA whose concentration ranged between 45 and 225 nM. It was found that the p-MIP film (m = 0.39) was relatively more heterogeneous than the s-MIP film (m = 0.33), both of which were obtained from the slope of the linear regressions. Finally, the selectivity of the MIP-QCM sensors for BPA detection was determined by measuring the effect of other analogous chemicals, such as bisphenol F (BPF), bisphenol AP (BPAP), and bisphenol B (BPB), in aqueous solutions. The selectivity coefficients (k*) of the two MIP films had ~1.9 for the p-MIP and ~2.3 for the s-MIP films, respectively. The results reveal that, with respect to signal amplification of the QCM sensors, the s-MIP film has better sensing features and faster detection responses than the p-MIP film.

FERROELECTRIC NANOCOMPOSITES WITH GOVERNED INTERFACE ON BASE OF MAGNETIC POROUS GLASSES

Two-phase (nonporous) magnetic alkali borosilicate glasses have been produced by induction melting. Their macroscopic properties and crystal structure have been studied and it is shown that in the silica skeleton there are the agglomerates of Fe3O4. These agglomerates are formed by monodomain nanoparticles of magnetite and demonstrate the superparamagnetic properties. After special thermal treatment (liquation process) and chemical etching the nanoporous matrices with random dendrite pore structure and magnetic properties have been produced. The channels (porous space) were filled by ferroelectric materials KH2PO4 (KDP), KH2PO4+(NH4)H2PO4 (KDP-ADP or KADP), and NaNO2 and the effect of applied magnetic fields on phase transitions in these nanocomposite have been studied. It has also been established that a restricted geometry changed essentially the phase diagram of KADP.

Intermolecular interactions in AST zeolites through 14N NMR and DFT calculations

The structure of the silica AST zeolites (octadecasil) synthesized in fluoride medium using tetramethylammonium (TMA) as the organic structure-directing agent has been reinvestigated using 14N NMR quadrupolar parameters and DFT calculations. The value of the experimental 14N quadrupolar coupling constant (CQ = 27 kHz) is larger than expected for a TMA cation possessing a high degree of motion. The analysis of a DFT-optimized octadecasil cluster along with the comparison between measured and calculated 14N NMR parameters demonstrate the presence of weak C—H...O hydrogen bonds between the TMA in the [46612] cages and the silica skeleton. These intermolecular interactions can be related to the presence of Si...F tetrel bonds within the [46] cages. These new results provide additional information with regard to the formation mechanisms and structure of the octadecasil zeolites.

Taxonomic Significance of Glume Morphology and Leaf Epidermal Characteristics in some Taxa of Tribe Aveneae (Poaceae)

The numerical classification of tribe Aveneae (Poaceae) is discussed regarding the glume morphology and silica skeleton morphologies. The present study dealt with 18 species belonging to 10 genera of the tribe to cover as many groups as possible within Aveneae. The total of 31 structural characters and 71 character states were scored comparatively. The resulted data matrix was analyzed under a combination of Euclidean distance measure and Ward’s clustering method included in the program package PC-ORD version 5. The resulted dendrogram separated the tribe into five basic sub-ordinate groups created from three major groups A, B and C. The taxonomic significance of these results was discussed. The results showed congruence between the clustering and PCA method, in suggesting three major groups and 5 sub-ordinate groups.

Ghosts in absentia

One of the books that changed my perception of the world is The Open Sea, Part 1, by the marine biologist Sir Alister Hardy. He had set out to write one book about the sea, but found that there was so much to say about the world of the plankton that it took up a whole book (he then had to write another book about everything else). It’s now more than half a century old, and yet this hidden world remains marvellously evoked by his words, and by the antique black and white photographs and line drawings. Coming to this as a palaeontologist, it was eye-opening. I was aware that in the strata, one normally only finds the remains of those forms of life that had some hard parts to fossilize. Bones, teeth, shells—and in the case of the acritarchs, chitinozoa and graptolites, their tough organic casings and homes. I knew that there had been other soft-bodied things out there of course, but alas these don’t register often enough on the radar of the geologically programmed. So the sheer variety and exuberance of this world, revealed in those pages, took me by surprise. The remains of some of this life, within the pebble, lie somewhere within the amorphous black carbon that gives this object its dark colour, and in some of the subtle chemical signals of the rock itself. Parts of the hidden Silurian sea are beginning to be decoded from this unpromising material, and the stories emerging—fragmentary, ambiguous, tantalizing— sometimes have surprising uses. Tow a fine-mesh net behind a ship for a few minutes, as Hardy did as a working scientist, and then examine its contents with a microscope, and a small fraction of this world is revealed—enough to reveal its almost boundless diversity. There are microscopic plants, the base of the food chain: the diatoms, for instance, single-celled algae with a silica skeleton that looks like a tiny ornate hatbox; the coccolithophores, even smaller algae with a bizarre calcium carbonate skeleton made of overlapping shield-like discs, and the dinoflagellates, too.

Micromechanical properties of biological silica in skeletons of deep-sea sponges

The silica skeleton of the deep-sea sponge Euplectella aspergillum was recently shown to be structured over at least six levels of hierarchy with a clear mechanical functionality. In particular, the skeleton is built of laminated spicules that consist of alternating layers of silica and organic material. In the present work, we investigated the micromechanical properties of the composite material in spicules of Euplectella aspergillum and the giant anchor spicule of Monorhaphis chuni. Organic layers were visualized by backscattered electron imaging in the environmental scanning electron microscope. Raman spectroscopic imaging showed that the organic layers are protein-rich and that there is an OH-enrichment in silica near the central organic filament of the spicule. Small-angle x-ray scattering revealed the presence of nanospheres with a diameter of only 2.8 nm as the basic units of silica. Nanoindentation showed a considerably reduced stiffness of the spicule silica compared to technical quartz glass with different degrees of hydration. Moreover, stiffness and hardness were shown to oscillate as a result of the laminate structure of the spicules. In summary, biogenic silica from deep-sea sponges has reduced stiffness but an architecture providing substantial toughening over that of technical glass, both by structuring at the nanometer and at the micrometer level.