A Solid State NMR Investigation of Recent Marine Siliceous Sponge Spicules

Masse, Sylvie; Pisera, Andrzej; Laurent, Guillaume; Coradin, Thibaud

doi:10.3390/min6010021

Cited by 6 publications

(5 citation statements)

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“…In the 31 P MAS NMR spectra, similar modifications as previously described for MMT based SSRF were observed, with the replacement of the well-defined signals by a broad chemical environment, shifted to the orthophosphate region (δ = 2.5 ppm) (Figure Cc), probably involving Mg–O–P bonds. Obviously, the solid state NMR results were in good agreement with the results obtained by PXRD and further evidenced the formation of amorphous materials due to mechanochemical activation by milling. − Thermogravimetric analyses (Figure ) were performed for all precursors and milled samples in order to investigate the effect of mechanochemical treatment on composition.…”

Section: Resultssupporting

confidence: 70%

Design and Kinetic Study of Sustainable Potential Slow-Release Fertilizer Obtained by Mechanochemical Activation of Clay Minerals and Potassium Monohydrogen Phosphate

Borges

Prevot

Forano

et al. 2017

Ind. Eng. Chem. Res.

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Sustainable slow-release fertilizers have been reported as environmentally friendly alternatives to highly soluble commercial products. Their main advantages are that they dissolve and release nutrients into soils in a way that assures bioavailability of nutrients to plants over a long period of growth. In addition, novel formulations can reduce or eliminate environmental problems caused by excess use of conventional fertilizers, such as eutrophication and atmospheric pollution. In this study, the solid-state mechanochemical activation method was used to prepare potential fertilizers by milling montmorillonite (MMT) or talc with K2HPO4. Characterizations by several instrumental techniques evidenced phase transformations, while kinetic studies and modeling indicated promising release performance. Even though the potassium release behavior was similar for both systems, the kinetic studies showed that phosphorus release profiles were different. Since potassium struvite (K-struviteMgKPO4·6H2O) was formed during the release experiments, talc based potential slow-release fertilizers displayed slower release behavior compared to MMT.

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Section: Resultssupporting

confidence: 70%

Design and Kinetic Study of Sustainable Potential Slow-Release Fertilizer Obtained by Mechanochemical Activation of Clay Minerals and Potassium Monohydrogen Phosphate

Borges

Prevot

Forano

et al. 2017

Ind. Eng. Chem. Res.

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“…The spectral deconvolution allows for calculation of the proportions of these three components, as gathered in Table 2 , made on spectra with a similar signal/noise ratio. The silica condensation degree obtained is representative of an overall well-condensed silica network, in agreement with that was usually obtained for such siliceous sponge material [ 17 , 62 ]. More precisely, D was assessed as 0.92 for the AL and 0.91 for the PG.…”

Section: Resultssupporting

confidence: 88%

“…As a result of 29 Si HPDec-MAS ssNMR and 1 H MAS ssNMR, FTIR and X-ray analyses we demonstrated that the spicules are composed of well condensed silica [cf. 17 , 62 ] with the outermost AL characterized by slightly more condensed silica, with less water, than the rest of the spicule. Etching in NaOH revealed that the silica is permeated by homogenous organics of protein character, most probably collagen, silicatein and/or galectins, as indicated by 13 C CP-MAS ssNMR analyses.…”

Section: Discussionmentioning

confidence: 99%

Insights into the structure and morphogenesis of the giant basal spicule of the glass sponge Monorhaphis chuni

et al. 2021

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Background A basal spicule of the hexactinellid sponge Monorhaphis chuni may reach up to 3 m in length and 10 mm in diameter, an extreme case of large spicule size. Generally, sponge spicules are of scales from micrometers to centimeters. Due to its large size many researchers have described its structure and properties and have proposed it as a model of hexactinellid spicule development. Thorough examination of new material of this basal spicule has revealed numerous inconsistencies between our observations and earlier descriptions. In this work, we present the results of detailed examinations with transmitted light and epifluorescence microscopy, SEM, solid state NMR analysis, FTIR and X-ray analysis and staining of Monorhaphis chuni basal spicules of different sizes, collected from a number of deep sea locations, to better understand its structure and function. Results Three morphologically/structurally different silica layers i.e. plain glassy layer (PG), tuberculate layer (TL) and annular layer (AL), and an axial cylinder (AC) characterize adult spicules. Young, immature spicules display only plain glassy silica layers which dominate the spicule volume. All three layers i.e. PG, TL and AL can substitute for each other along the surface of the spicule, but equally they are superimposed in older parts of the spicules, with AL being the most external and occurring only in the lower part of the spicules and TL being intermediate between AL and PG. The TL, which is composed of several thinner layers, is formed by a progressive folding of its surface but its microstructure is the same as in the PG layer (glassy silica). The AL differs significantly from the PG and TL in being granular and porous in structure. The TL was found to display positive structures (tubercles), not depressions, as earlier suggested. The apparent perforated and non-perforated bands of the AL are an optical artefact. The new layer type that we called the Ripple Mark Layer (RML) was noted, as well as narrow spikes on the AL ridges, both structures not reported earlier. The interface of the TL and AL, where tubercles fit into depressions of the lower surface of the AL, represent tenon and mortise or dovetail joints, making the spicules more stiff/strong and thus less prone to breaking in the lower part. Early stages of the spicule growth are bidirectional, later growth is unidirectional toward the spicule apex. Growth in thickness proceeds by adding new layers. The spicules are composed of well condensed silica, but the outermost AL is characterized by slightly more condensed silica with less water than the rest. Organics permeating the silica are homogeneous and proteinaceous. The external organic net (most probably collagen) enveloping the basal spicule is a structural element that bounds the sponge body together with the spicule, rather than controlling tubercle formation. Growth of various layers may proceed simultaneously in different locations along the spicule and it is sclerosyncytium that controls formation of silica layers. The growth in spicule length is controlled by extension of the top of the axial filament that is not enclosed by silica and is not involved in further silica deposition. No structures that can be related to sclerocytes (as known in Demospongiae) in Monorhaphis were discovered during this study. Conclusions Our studies resulted in a new insight into the structure and growth of the basal Monorhaphis spicules that contradicts earlier results, and permitted us to propose a new model of this spicule’s formation. Due to its unique structure, associated with its function, the basal spicule of Monorhaphis chuni cannot serve as a general model of growth for all hexactinellid spicules.

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Section: Sio2mentioning

confidence: 99%

Section: Sio2mentioning

confidence: 99%

Interactions between Metal Oxides and Biomolecules: from Fundamental Understanding to Applications

et al. 2018

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Metallo-oxide (MO)-based bioinorganic nanocomposites promise unique structures, physicochemical properties, and novel biochemical functionalities, and within the past decade, investment in research on materials such as ZnO, TiO 2 , SiO 2 , and GeO 2 has significantly increased. Besides traditional approaches, the synthesis, shaping, structural patterning, and postprocessing chemical functionalization of the materials surface is inspired by strategies which mimic processes in nature. Would such materials deliver new technologies? Answering this question requires the merging of historical knowledge and current research from different fields of science. Practically, we need an effective defragmentation of the research area. From our perspective, the superficial accounting of material properties, chemistry of the surfaces, and the behavior of biomolecules next to such surfaces is a problem. This is particularly of concern when we wish to bridge between technologies in vitro and biotechnologies in vivo. Further, besides the potential practical technological efficiency and advantages such materials might exhibit, we have to consider the wider long-term implications of material stability and toxicity. In this contribution, we present a critical review of recent advances in the chemistry and engineering of MO-based biocomposites, highlighting the role of interactions at the interface and the techniques by which these can be studied. At the end of the article, we outline the challenges which hamper progress in research and extrapolate to developing and promising directions including additive manufacturing and synthetic biology that could benefit from molecular level understanding of interactions occurring between inanimate (abiotic) and living (biotic) materials.

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A Solid State NMR Investigation of Recent Marine Siliceous Sponge Spicules

Cited by 6 publications

References 28 publications

Design and Kinetic Study of Sustainable Potential Slow-Release Fertilizer Obtained by Mechanochemical Activation of Clay Minerals and Potassium Monohydrogen Phosphate

Design and Kinetic Study of Sustainable Potential Slow-Release Fertilizer Obtained by Mechanochemical Activation of Clay Minerals and Potassium Monohydrogen Phosphate

Insights into the structure and morphogenesis of the giant basal spicule of the glass sponge Monorhaphis chuni

Interactions between Metal Oxides and Biomolecules: from Fundamental Understanding to Applications

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