Enzymatic immobilization of organometallic species: biosilification of NCN- and PCP-pincer metal species using demosponge axial filaments

O’Leary, Patrick; Walree, Cornelis A. van; Mehendale, Nilesh C.; Sumerel, Jan L.; Morse, Daniel E.; Kaska, William C.; Koten, Gerard van; Gebbink, Robertus J. M. Klein

doi:10.1039/b900341j

Cited by 20 publications

(12 citation statements)

References 24 publications

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“…Purified filaments of silicatein can be converted to catalysts for processes as diverse as Heck reactions or binding of SO 2 gas; this occurs by incubating them with alkoxy silanes with metallated pincer complexes, integrating the pincer into silica [143]. In the first description of an enzymatically enhanced organometallic condensation, recombinant silicatein (modestly—only 2-fold) catalyzes the condensation of alkoxy silanes at neutral pH and ambient temperature to yield silicones like straight-chained dimethylsiloxane [144].…”

Section: Biotechnological Applications Of Silicifying Proteins Andmentioning

confidence: 99%

The Role of Proteins in Biosilicification

Otzen

2012

Scientifica

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Although the use of silicon dioxide (silica) as a constituent of living organisms is mainly restricted to diatoms and sponges, the ways in which this process is controlled by nature continue to inspire and fascinate. Both diatoms and sponges carry out biosilificiation using an organic matrix but they adopt very different strategies. Diatoms use small and heavily modified peptides called silaffins, where the most characteristic feature is a modulation of charge by attaching long chain polyamines (LCPAs) to lysine groups. Free LCPAs can also cooperate with silaffins. Sponges use the enzyme silicatein which is homologous to the cysteine protease cathepsin. Both classes of proteins form higher-order structures which act both as structural templates and mechanistic catalysts for the polycondensation reaction. In both cases, additional proteins are continuously being discovered which modulate the process further. This paper concentrates on the role of these proteins in the biosilification process as well as in various applications, highlighting areas where focus on specific protein properties may provide further insight. The field of biosilification is a crossroads of different disciplines, where insight into the energetics and mechanisms of molecular self-assembly combine with fundamental biology, complex multicomponent colloidal systems, and an impressive array of potential technological applications.

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Section: Biotechnological Applications Of Silicifying Proteins Andmentioning

confidence: 99%

The Role of Proteins in Biosilicification

Otzen

2012

Scientifica

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“…It was shown that (recombinant) silicatein is capable of precipitating various transition metal oxides from different solute precursors, e.g., gallium oxide from gallium nitrate [160] or anatase from a soluble lactato-titanium complex [161]. Silicatein is capable of processing not only metal-centred substrates, but also catalyzing polymerization to give biodegradable poly(L)-lactide [162], silicones [163], or gas-sensing pincer metal complexes [164]. Tremel and co-workers pushed this idea further, by binding silicatein on surfaces by various techniques to give functionalized metals, e.g., gold-thiolate surfaces by means of a nitrilotriacetic acid (NTA)-linker system, and metal oxide-surfaces by an NTA-bearing capping agent [165,166,167,168].…”

Section: From Creatures To Conceptsmentioning

confidence: 99%

Bioinspired Materials: From Living Systems to New Concepts in Materials Chemistry

et al. 2019

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Nature successfully employs inorganic solid-state materials (i.e., biominerals) and hierarchical composites as sensing elements, weapons, tools, and shelters. Optimized over hundreds of millions of years under evolutionary pressure, these materials are exceptionally well adapted to the specifications of the functions that they perform. As such, they serve today as an extensive library of engineering solutions. Key to their design is the interplay between components across length scales. This hierarchical design—a hallmark of biogenic materials—creates emergent functionality not present in the individual constituents and, moreover, confers a distinctly increased functional density, i.e., less material is needed to provide the same performance. The latter aspect is of special importance today, as climate change drives the need for the sustainable and energy-efficient production of materials. Made from mundane materials, these bioceramics act as blueprints for new concepts in the synthesis and morphosynthesis of multifunctional hierarchical materials under mild conditions. In this review, which also may serve as an introductory guide for those entering this field, we demonstrate how the pursuit of studying biomineralization transforms and enlarges our view on solid-state material design and synthesis, and how bioinspiration may allow us to overcome both conceptual and technical boundaries.

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“…Pt-silica prepared using this method were used for SO 2 sensing while Pd-silica hybrids were successfully tested for Heck reactions for carbon-carbon coupling. 214…”

Section: Supporting Metals and Functional Metallic Nanoparticlesmentioning

confidence: 99%

“…8c). 214 These complexes were condensed with an alkoxysilane in the presence of silicatein protein to produce metalsilica composites which demonstrated applications in sensors and catalysis. Pt-silica prepared using this method were used for SO 2 sensing while Pd-silica hybrids were successfully tested for Heck reactions for carbon-carbon coupling.…”

Section: Supporting Metals and Functional Metallic Nanoparticlesmentioning

confidence: 99%

Biomimetic and bioinspired silica: recent developments and applications

2011

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In a previous review of biological and bioinspired silica formation (S. V. Patwardhan et al., Chem. Commun., 2005, 1113 [ref. 1]), we have identified and discussed the roles that organic molecules (additives) play in silica formation in vitro. Tremendous progress has been made in this field since and this review attempts to capture, with selected examples from the literature, the key advances in synthesising and controlling properties of silica-based materials using bioinspired approaches, i.e. conditions of near-neutral pH, all aqueous environments and room temperature. One important reason to investigate biosilicifying systems is to be able to develop novel materials and/or technologies suitable for a wide range of applications. Therefore, this review will also focus on applications arising from research on biological and bioinspired silica. A range of applications such as in the areas of sensors, coatings, hybrid materials, catalysis and biocatalysis and drug delivery have started appearing. Furthermore, scale-up of this technology suitable for large-scale manufacturing has proven the potential of biologically inspired synthesis.

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Enzymatic immobilization of organometallic species: biosilification of NCN- and PCP-pincer metal species using demosponge axial filaments

Cited by 20 publications

References 24 publications

The Role of Proteins in Biosilicification

The Role of Proteins in Biosilicification

Bioinspired Materials: From Living Systems to New Concepts in Materials Chemistry

Biomimetic and bioinspired silica: recent developments and applications

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