The role of phosphopeptides in the mineralisation of silica

Daus, Fabian; Pfeifer, Erik; Seipp, Kevin; Hampp, Norbert; Geyer, Armin

doi:10.1039/c9ob02438g

Cited by 11 publications

(34 citation statements)

References 36 publications

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“…In contrastt ob iomineralization processes, these strategies requiret he presence of solution-borne phosphate ions, which are thought to increaset he condensation kinetics. [9,27,28] Carefully tuning the chemical conditions, such as ionicstrength and scaffold concentration,g rants control over the morphology of the silica materials. [4] An impressiven umber of innovative routes to produce silica in ac ontrolled manner has been developed using ah andful of bio(macro)moleculara nalogs.…”

Section: Introductionmentioning

confidence: 99%

“…This method is advantageous because the amine‐rich polymers not only serve as a scaffold but also act as a catalyst to promote the condensation of silicic acid. In contrast to biomineralization processes, these strategies require the presence of solution‐borne phosphate ions, which are thought to increase the condensation kinetics [9, 27, 28] . Carefully tuning the chemical conditions, such as ionic strength and scaffold concentration, grants control over the morphology of the silica materials [4] …”

Section: Introductionmentioning

confidence: 99%

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Bioinspired Scaffolding by Supramolecular Amines Allows the Formation of One‐ and Two‐Dimensional Silica Superstructures

Magana

Gumí-Audenis

Tas

et al. 2020

Chemistry A European J

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Silica materials attract an increasing amount of interest in (fundamental) research, and find applications in, for example, sensing, catalysis, and drug delivery.A st he properties of these (nano)materials not only depend on their chemistry but also their size, shape,a nd surface area, the controllable synthesis of silica is essential for tailoringt he materials to specific applications. Advantageously,b ioinspired routes for silica production are environmentally friendly ands traightforward since the formation process is spontaneousa nd proceeds under mild conditions. These strategies mostly employ amine-bearing phosphorylated (bio)polymers. In this work, we expand this principle to supramolecular polymers based on the water-soluble cationic cyanine dye Pinacyanol acetate. Upon assembly in water, these dye molecules form large, polyaminated, supramolecular fibers.T he surfaces of these fibers can be used as ascaffold for the condensation of silicic acid. Controlo ver the ionic strength, dye concentration, and silicic acid saturation yielded silica fibers with ad iameter of 25 nm and as ingle, 4nmp ore. Unexpectedly,o ther unusual superstructures, namely,n ummulites and spherulites, are also observed depending on the ionic strength and dye concentration.T ransmission and scanning electronm icroscopy (TEM and SEM) showedt hat these superstructures are formed by aligned silica fibers. Close examination of the dye scaffold prior silicification using small-angle X-ray scattering (SAXS), and UV/Vis spectroscopy revealed minor influence of the ionic strength and dye concentration on the morphologyo ft he supramolecular scaffold.T otal internal reflection fluorescence (TIRF) during silicification unraveledt hat if the reaction is kept under static conditions, only silica fibers are obtained. Experiments performed on the dye scaffold and silica superstructures evidenced that the marked structurald iversity originates from the arrangemento fs ilica/dye fibers. Under these mild conditions, external force fields can profoundly influence the morphologyo ft he produced silica.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Bioinspired Scaffolding by Supramolecular Amines Allows the Formation of One‐ and Two‐Dimensional Silica Superstructures

Magana

Gumí-Audenis

Tas

et al. 2020

Chemistry A European J

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“…pH was measured for the equilibrium (8 days) and kinetic (1 h) experiments only after the separation of the precipitate and the supernatant, and was not measured thereafter (Data available in Supplementary Table S1 ). For the biomimetic experiment, R5 was added to each sample at 0.01 g/ml (5 mM) before the addition of sodium silicate to ensure that the peptide is active 16 . The supernatant was sampled and separated from the precipitate at different times to evaluate the precipitation rates, solution/solid exchanges and the effect of the R5 peptide on the precipitation reactions and Si isotopic fractionation.…”

Section: Methodsmentioning

confidence: 99%

“…Previous studies have attempted to understand the role of SDV-localised biomolecules by studying their ability to influence the formation of silica in vitro 14 – 16 . An attractive model system in this regard is the peptide known as ‘R5’, which has the sequence NH2-SSKKSGSYSGSKGSKRRIL-CO2H and was derived from the sequence of a silaffin peptide from Cylindrotheca fusiformis 17 .…”

Section: Introductionmentioning

confidence: 99%

A biomimetic peptide has no effect on the isotopic fractionation during in vitro silica precipitation

Cassarino

Curnow

Hendry

2021

Sci Rep

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The stable isotopic composition of diatom silica is used as a proxy for nutrient utilisation in natural waters. This approach provides essential insight into the current and historic links between biological production, carbon cycling and climate. However, estimates of isotopic fractionation during diatom silica production from both laboratory and field studies are variable, and the biochemical pathways responsible remain unknown. Here, we investigate silicon isotopic fractionation through a series of chemical precipitation experiments that are analogous to the first stages of intracellular silica formation within the diatom silicon deposition vesicle. The novelty of our experiment is the inclusion of the R5 peptide, which is closely related to a natural biomolecule known to play a role in diatom silicification. Our results suggest that the presence of R5 induces a systematic but non-significant difference in fractionation behaviour. It thus appears that silicon isotopic fractionation in vitro is largely driven by an early kinetic fractionation during rapid precipitation that correlates with the initial amount of dissolved silica in the system. Our findings raise the question of how environmental changes might impact silicon isotopic fractionation in diatoms, and whether frustule archives record information in addition to silica consumption in surface water.

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“…1 Left: Structure of native silaffin-1A 1 extracted from marine diatoms. 1 There have been various studies on modifications to the structure of native silaffin-1A 1 to investigate the role of particular amino acid residues on the oligomerization reaction to generate silica, namely modifications of the primary amino acid sequence and post-translational modifications (PTM) such as the addition of polyamine side chains to lysine residues (blue), phosphorylation of serine residues (gold), 2,3 and the methylation of lysine residues (green). 3 Top left inset: Structure of orthosilicic acid.…”

Section: Introductionmentioning

confidence: 99%

Elucidating the role of catalytic amino acid residues in the peptide-mediated silica oligomerization reaction mechanism

Hare

Pfaendtner

2022

Phys. Chem. Chem. Phys.

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The role of phosphopeptides in the mineralisation of silica

Abstract: We describe the synthesis of hyperphosphorylated peptides and the investigation of their in vitro silicification activity in combination with long-chain polyamines (LCPA) at high dilution and mildly acidic conditions.

Cited by 11 publications

References 36 publications

Bioinspired Scaffolding by Supramolecular Amines Allows the Formation of One‐ and Two‐Dimensional Silica Superstructures

Bioinspired Scaffolding by Supramolecular Amines Allows the Formation of One‐ and Two‐Dimensional Silica Superstructures

A biomimetic peptide has no effect on the isotopic fractionation during in vitro silica precipitation

Elucidating the role of catalytic amino acid residues in the peptide-mediated silica oligomerization reaction mechanism

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