Current Opinion in Solid State and Materials Science 8 (2004) 111120

Bioinspired synthesis of mesoporous silicas

Qianyao Sun
a

a,b

, Engel G. Vrieling c,1, Rutger A. van Santen b, Nico A.J.M. Sommerdijk a,*

Laboratory of Macromolecular and Organic Chemistry, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven, The Netherlands b Schuit Institute of Catalysis, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven, The Netherlands c Department of Marine Biology, Center for Ecological and Evolutionary Studies, University of Groningen, P.O. Box 14, 9750 AA Haren, The Netherlands Received 23 June 2003; accepted 30 January 2004

Abstract Recent years have witnessed rapid growth in the number of new investigations at the interface of materials chemistry and biology. This review highlights the recent developments in the studies of protein-mediated silica biomineralization in diatoms and the downscaling and upscaling models derived thereof, as well as the recent progress in the fabrication of articial silicas with novel pore structures and morphologies at dierent length scales based on these new insights into biosilica formation. 2004 Elsevier Ltd. All rights reserved.

1. Introduction Silica and silica-based materials have found widespread application for industrial, technological and domestic purposes. The demand for improved silica types with specic properties such as mechanical strength, pore volume, pore-size distribution, specic surface area or surface reactivity [13] is fueling the search for innovative production of such materials [4,5]. Indeed, extensive work has been undertaken to prepare mesoporous silica and to understand the complicated physical chemistry accompanying the relatively simple condensation reaction in which silica monomers are used to build the large polymeric structures typical for such porous silicas. In contrast to the chemically produced silicas that generally are prepared under harsh conditions, e.g. at elevated temperatures, high pressures and/or strongly acidic or alkaline media, in Nature silica architectures

* Corresponding author. Tel.: +31-40-2475870; fax: +31-402451036. E-mail address: n.a.j.m.sommerdijk@tue.nl (N.A.J.M. Sommerdijk). 1 Current address: Groningen Biomolecular Sciences and Biotechnology Institute, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The Netherlands.

with delicate morphologies are generated in aqueous medium under ambient conditions [*6]. Unicellular organisms, such as diatoms use structuring and templating biomolecules to produce silica shells that not only contain hierarchically ordered pore structures with dimensions ranging from the nanometer to the micrometer domain, but also possess remarkable mechanical and structural [*7,8,9] properties. It is these intriguing architectures that have inspired many scientists not only to investigate the processes underlying their formation, but also to mimic these processes in order to obtain better control over the structure and morphology of chemically produced silica [1012,*13,*14]. The introduction in 1992 of MCM-type materials [15], using surfactants as structure-directing agents, brought the development of methods to prepare mesoporous silicas forward with a great leap. In this approach dierent lyotropic phases of a large variety of surfactants and amphiphilic polymers have been used to structure the developing silica phase that grows around these self-assembled organic templates, resulting in numerous new mesophases [**16,*17]. Although the pore sizes of as-made porous silica range from a few to tens of nanometers using this method, the large welldened pore dimensions observed in diatoms are still out of reach. For this reason natural silica production (i.e. silica biomineralization) receives increasing attention, since it holds the key to the formation of silica

1359-0286/$ - see front matter 2004 Elsevier Ltd. All rights reserved. doi:10.1016/j.cossms.2004.01.005

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morphologies with a dedicated organization of hierarchically structured elements and the ability to synthesize such silicas under ambient conditions. This review gives a brief overview of recent developments in the eld of silica biomineralization in diatoms, and the progress in the biomimetic fabrication of silica with hierarchical structure and morphology at dierent length scales.

2. Protein-mediated silica formation In unicellular photosynthesizing diatoms, biopolymer-mediated silica formation proceeds via a dierent ger et al. [*18,19], mechanism. As was shown by Kro small proteins and polyamines could be liberated from diatomaceous silica by hydrouoric acid (HF)-assisted dissolution. The proteins best studied from this series are the Silan-1A isoforms, which are small (2.43.1 kDa) polycationic proteins with highly modied amino acid residues in their native state. Particularly interesting is the fact that the lysine groups of this protein are modied with oligo-N-methylpropyleneamines, as it was demonstrated that only silans bearing these side chains are able to precipitate silica [*18]. This is consistent with the observation that polyamines induce fast silica precipitation and occulation to larger aggregates instead of gel formation [**21]. Recently, Noll et al. [*22] demonstrated that the use of tripropylenetetramine, as an analog of the native oligo-N-methylpropyleneamines present in silan-1A, resulted in the formation of smooth silica spheres. These spheres exhibit a surface structure that reasonably agrees with the surface of the exoskeleton of diatoms from the genus Coscinodiscus,

although the size of the formed particles was appreciably larger than of those observed in other diatoms [*23]. More recently it was found that, apart from the oligoN-methylpropyleneamine modications of the lysine residues, the native silan-1A is also characterized by ger et al. multiple phosphorylated serine residues. Kro [**20] developed a mild method for the dissolution of biosilica that allowed the isolation of the associated silans in their native state. This method employed a solution of ammonium uoride of pH 5 rather than the normally used hydrouoric acid. Based on 31 P NMR and mass spectroscopy it was concluded that silan-1A from the diatom Cylindotheca fusiformis contained seven phosphorylated serine residues and one phosphorylated trimethylhydroxy lysine moiety. This eightfold phosphorylated protein showed even higher ability to induce the precipitation of silica than the previously reported silan-1A, although the dimensions of the resulting spheres suggested that these do not represent biologically relevant silica structures. Importantly, however, it was realized that the zwitter ionic structure of the native silans leads to the self-assembly of these molecules and may explain their extremely ecient induction of silica precipitation [**20]. Following up on this model Sumper proposed, on the basis of simulations, a new model that consists of multiple steps in which phase separation processes occur [**24]. At the initial stage phase separation enables the formation of the large, for diatoms characteristic, honeycomb structures, followed by several intermitted steps of silica formationeach mediated by phase separation processesto create smaller structures (Fig. 1). In this downscaling model, the largest

Fig. 1. Schematic drawing of the templating mechanism by a downscaling phase separation model [(A)(D)] in comparison with scanning electron micrographs of the valves from the diatom Coscinodiscus wailesii [(E)(H)]. (A) The monolayer of polyamine-containing droplets in close-packed arrangement guides silica deposition. (B and C) Consecutive segregations of smaller (about 300 nm) droplets open new routes for silica precipitation. (D) Dispersion of 300-nm droplets into 50-nm droplets guides the nal stage of silica deposition. Silica precipitation occurs only within the water phase (white areas). The repeated phase separations produce a hierarchy of self-similar patterns. (EH) SEM images of valves at the corresponding stages of development. Modied from Ref. [**24] with kind permission of Prof. Dr. M. Sumper and the American Association for the Advancement of Science.

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structures are formed at the start (Fig. 1A) followed by the formation of the smaller ones (Fig. 1B and C) and nally the more delicate details (Fig. 1D). In contrast, Vrieling et al. [**21] derived an upscaling model based on experimental data obtained from in situ timeresolved ultrasmall angle X-ray scattering analysis of silica transformations mediated by synthetic polymers (polyethyleneglycol, polyethyleneimidine) and proteins (myoglobin, horseradish peroxidase). In the course of the polymerization and transformation reactionthe latter induced by agingphase separation occurred and led to discrimination of silica-rich and templaterich phases, which continuously interact during the transformation of silica from smaller aggregates to the larger structures (Fig. 2). Ultimately removal of the template-rich phase would account for the creation of porous network.

3. Bioinspired synthesis of silica 3.1. Silica structure control by (bio)polymers As mentioned above, studies on biomineralization have highlighted the role of proteins in mediating the formation of biogenic silica. Inspired by these ndings important progress has been made in the biomimetic preparation of a variety of silica morphologies. Naik et al. [*25] examined the role in silicication of a 19 amino acid peptide derived from silan-1A and showed that through careful manipulation of the environment and the use of mechanical force, the formation of several silica nano-morphologies could be achieved, ranging from common spheres to organized and complex brils. It was found that silica spheres, the lowest free energy structures, are formed in a static environment, whereas

c
10 nm

Aggregation

Densification

2 nm Precursor Input

10 nm

Aggregation

Phase separation

50 nm

d
> 100nm

2-D expansion

3-D Growth

Removal of proteinrich mesophase

Casing formation

> 5m

Fig. 2. Schematic presentation of the described upscaling model. At the onset of valve formation (a) silica precursors and peptides are imported into the silica deposition vesicle (SDV), where precipitation of silica is induced by small organic molecules (e.g., silans and/or polyamines indicated by the red curved structures to form silica sols shown as grey spheres (b). These sols further densify and grow to larger silica particles (bluish spheres), while larger peptides (green ellipsoids) start to interact with the silica (c). When aggregation continues (d), silica forms larger particles (up to 50 nm). At this stage silica and protein aggregates become transferred to silica- and protein-rich mesophases (bluegreen ovals) by phase separation (e). This process proceeds until the SDV has reached it nal two-dimensional and three-dimensional size (f) and the protective casing has been formed (g). In order to leave pores, the protein-rich mesophase is somehow removed prior to assembly of a protective casing before the wall leaves the cell. Reproduced from Vrieling et al. [**21] with permission of WileyVCH. (For interpretation of the references in colour in this gure legend, the reader is referred to the web version of this article.)

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elongated strands occur when the polymerization front is in motion. Patwardhan et al. [26] showed that using poly-L -lysine as the template, ber-like and laddershaped silica morphologies with periodic voids could be observed by owing the reaction mixture through a tube or by stirring during the reaction, respectively. The observations of Naik et al. and Patwardhan et al. demonstrate that in vitro biocatalysis may be employed in order to form tailor-made silica structures. In addition Livage and coworkers studied the inuence of amine-containing peptides (such as polylysine, polyarginine [*27] and arginine-based surfactants [28]) on silica condensation. Their results indicated that these (bio)polymers act as gelating agents of silica oligomers in the case of silicic acid, and as occulation agents in silica sols. The generation of porous materials with ordered nanostructure is inevitably coupled to the detailed characterization of those materials following transformation of intermediates during the reaction, as well as to the analysis of the product with various techniques. The use of any single analytical technique cannot adequately reveal the detailed pore structure of such materials [**29,30]. With in situ (ultra) small-angle X-ray scattering, scanning electron microscopy and nitrogen physisorption Sun et al. [*31] investigated the silica aggregation behavior and pore formation controlled by polyethylene glycol (PEG). This model system allows the in situ monitoring of the silicication process as PEG induces a slower precipitation than is observed in the case of for example polyethylene imine. It was shown that PEG plays three dierent roles in silica aggregation: (1) it serves as a occulation agent in silica sols, (2) the hydrophobic silicaPEG interactions steer the silica polymerization, and (3) it induces phase separation, where a phase rich in both PEG and silica is formed in

the formerly homogeneous aqueous solution. It was demonstrated that PEG chains of dierent lengths, but also dierent PEG/silica ratios can be used to create by choice silicas with a variety of pore dimensions of approximately 220 nm (Fig. 3). In the biomimetic preparation of silica structures, PEG may therefore well be a promising, cheap and versatile substitute for the biomolecules involved in silica biomineralization. 3.2. Silica morphology control Inorganic materials, although diverse in composition, lack the structural and morphological variety that is one of the characteristics of polymeric, supramolecular and self-assembled structures [*32,*33,*34,*35,*36]. A great deal of research eort has been devoted towards the development of ecient and innovative fabrication methods to obtain inorganic materials with well-dened morphologies, because of their potential applications in e.g. catalysis, chromatography, absorbance, drug-delivery, etc. To develop novel inorganic materials closely resembling these organic architectures, supramolecular structures such as organogels based on low molecular mass amines, and amphiphilic mesophases have been transcribed into inorganic materials [37,38]. 3.3. Fibrillar silica prepared from amine-containing organogels Increasing attention has been focused on the selfassembly of low molecular mass gelators into ber-like structures that can eciently gelate organic solvents via physical interactions, including hydrogen-bonding, pp-stacking and solvophobic eects [*32,*33]. Cholesterol- and cyclohexane-based organogel templates have enabled the formation of hollow silica bers with linear, helical, and multilayered morphologies through transcription mediated by electrostatic or hydrogen-bonding interactions. Recently silica brils with a double stranded helical structure were prepared through mineralization of twisted bilayer ribbons formed from a cationic gemini surfactant with chiral tartrate counter ions [*39], whereas hollow silica bers with a monodisperse inner diameter of 45 nm were obtained from a sugar-appended porphyrin gelator [*40]. Silica nanotubes with adjustable meso- or macroscale inner diameters were obtained using a sugar-appended azonaphthol gelator [41]. It has been shown that the presence of positive charges or hydrogen-bonding sites (e.g. amine groups) is indispensable for a successful transcription of the organogel template into the silica structure. In the case of the sugar-appended azonaphthol gelator, an azohydrazone tautomeric form provides a secondary amino group that is thought to play a major role in the successful solgel transcription, mimicking the silica biomineralization process. In addition, the rst example of

Fig. 3. A general overview of PEGsilicas as a function of PEG/silica ratio and size of PEG polymers. At a PEG/silica ratio of 0.5 (upper row), the increase of the length of the PEG chains leads to a replacement of the fractal silicas (dimension D 2:5) composed of fractal particles D 2:3 found for PEG 600 by smooth silica spheres (PEG2000), and by silica spheres covered by fractal particles (D 2:7, PEG20000). At a high PEG/silica ratio of 2.0 (lower row), if hydrophobicity is simultaneously low, the homogeneous porous silicas are composed of fractal particles, whereas they are covered with particles (when hydrophobicity is high). Reproduced from Sun et al. [*31] with permission of American Chemical Society 2002.

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Fig. 4. Schematic representation of the creation of the helically structured silica from the organogel based on azobenzene-appended cholesterol derivative 1: (a) gelator, (b) incipient organogel ber, (c) silica adsorption (lower) and aggregation of organogel ber (upper), and (d) the inner helical structure of the silica formed after calcinations. Reproduced from Jung et al. [**42] with permission of American Chemical Society 2003.

silica nanotubes with a helical inner channel with an internal diameter of 7.5 nm was reported [**42], using an organogel from a dimeric azobenzene-appended cholesterol derivative (Fig. 4). Such chiral silica nanotubes have potential for applications in chiral separation and catalysis. In addition to the well-accepted mechanism for the catalyst mediated formation of silica in solution, a surface mechanism was also proposed by van Bommel [43]. This new mechanism allows the transcription process to take place exclusively on the surface of the template. Further growth of inorganic materials takes place solely on this surface, resulting in an inorganic product containing only templated silica. Interestingly this process resembles the one observed for silicication in marine sponges. It has been established that inside siliceous spines of these sponges a welldened lamentous proteinaceous structure is present, consisting of oligomers of silicatein [4446]. Silicatein resembles the structure of cathepsin and has been demonstrated to be active in the hydrolysis of silicon

alkoxides such as TEOS, thereby inducing silica polymerization at the surface of the protein [46]. These intriguing results indicate that the use of sol-gel transformation mediated by organogelators may well lead to synthesis of novel materials that possess elaborate complex architectures. 3.4. Nanotubular silica in a condensed statemesoporous silica It was already mentioned that since the discovery of surfactant-mediated syntheses of mesoporous silica nanostructures, several mesophases e.g. hexagonal, cubic, lamellar have been dened [**16]. These materials, synthesized by a cooperative assembly of surfactants and associated inorganic species, unlike microporous zeolitic materials, that usually show well-dened crystal morphology corresponding to ordering at the atomic level, possess signicant ordering on the mesoscopic scale. The short-range ordering at the nanoscale level,

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Fig. 5. TEM images, electron diraction patterns and the resulting structural model of mesoporous benzenesilica. (A) Image and pattern taken with [0 0 1] incidence, parallel to the channels. Uniform mesopores with a diameter of 3.8 nm are arranged in a hexagonal manner. (B) Image and pattern taken with [1 0 0] incidence, perpendicular to the channels. Many lattice fringes with a spacing of 0.76 nm are observed in the pore walls. The electron diraction pattern also shows diused spots due to the 0.76 nm periodicity (large arrow) in the perpendicular direction to the spots due to channel arrangement with d 4:55 nm (small arrow). (C) Schematic model of as-made benzenesilica. Reproduced from Inagaki et al. [**48] with permission of Nature 2002.

however, is generally poor, which dramatically limits their practical utility [*47]. Although eorts to prepare highly crystalline materials continue, some major progress has been made recently. Inagaki et al. [**48] presented a benzenesilica hybrid mesoporous material, comprising a hexagonal array of mesopores, with crystal-like pore walls that exhibit surface structural periodicity along the channel direction (Fig. 5). Further characterization revealed that the pore walls were made of a covalently bonded network composed of O1:5 Si C6 H4 SiO1:5 units; the sharp signals observed in the 29 Si NMR spectra indicated a unique and uniform environment surrounding the Si atoms in the walls. Furthermore, Yu et al. [*49] reported the synthesis of mesoporous silica single crystals with a body-centered cubic space group, making use of a nonionic block copolymer EO132 PO50 EO132 as a template. Inorganic salts such as K2 SO4 were employed to increase the interaction of the silicate species with hydrophilic head groups of the nonionic block copolymers, resulting in long-range ordered domains of the silica-surfactant mesostructures and eventually in the formation of mesoporous single crystals. The preparation of ordered mesoporous carbon materials has been achieved, which mirror the pore structure of periodic silica templates after removing the silica matrix from silicacarbon composites [*47,50]. Such synthesis routes rely on the fact that ordered mesoporous silica can be lled with a carbon precursor

that is subsequently pyrolyzed, after which the silica is removed by HF or alkaline leaching. For a successful transformation from mesoporous silica templates to mesoporous carbon, the thermal and hydrothermal stability of mesoporous silica templates has to be high enough to withstand the harsh high-temperature treatment, and the yield of silica templates with desired morphology should be high. Yu et al. [52] addressed this matter by an inorganic salts synthesis approach. Highly ordered and condensed mesoporous SBA-15 rods were obtained using the triblock copolymer EO20 PO70 EO20 as the template, in the presence of large amounts of the inorganic salts. From the resulting silica scaold, hexagonally ordered mesoporous carbon rods could then be prepared, which were characterized by a very large surface area (up to 1823 m2 /g) and a pore volume up to 2.23 cm3 /g. This technique, however, implies the possibility of silica leaching/dissolution that also aects the material that is lled into the silica pore system or replaces silicon. Lu et al. [*53] were able to circumvent the problem of silica leaching eects by going one step further and using mesoporous ordered carbons as a matrix for the production of an ordered mesoporous silica, from which carbon then could be removed easily by combustion or possibly by high-temperature hydrogenation techniques for materials not stable enough against oxidation. This innovative approach may well be extended to other inorganic framework compositions, if only they can be

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Fig. 6. Scanning electron microscopy images of the same exoskeletons of the diatom species Aulacoseira. (a) Before and (b) after reaction with Mgg for 4 h at 900 C. Ten specic protuberances can be seen to be retained after reaction, along with the larger hole (H) and ner pores and ridges on the surfaces of the frustules. The solidied MgSi is a product of the reaction of reduced silicon with Mgg . Reproduced from Sandhage et al. [51] with permission of WileyVCH 2002.

introduced in the carbon matrix and retain the integrity during carbon removal. Sandhage et al. [51] demonstrated that silica-based diatom frustules could be converted into new metal oxide compositions using the technique of shape-preserving displacement. In this process uid/solid displacement (oxidation reduction) reactions have been employed for the conversion of diatomaceous silica into magnesium oxide while retaining the morphology and architecture of the exoskeleton (Fig. 6). With this approach they show that the displacement procedure has a potential for the development of hybrid, bioprocessing routes i.e. genetic engineering of cell wall shapes, of the biological silica assembly, and of chemical conversion. It can be easily envisaged how the feature of biological replication of complex-shaped biosilicas with welldened meso/nanoscale features can be coupled to processing of uid/solid displacement reactions to yield

large numbers of chemically tailored, complex-shaped, 3-D meso- or nanodevices. 3.5. Hierarchically structured silicas Various structuring agents such as block copolypeptides, nonionic block copolymers, diamines, and gemini surfactants, have been used to mediate the specic shapes of the mesoporous silica. Mesoporous silica with hollow morphologies has attracted a lot of attention because of its low-density, as well as of its thermal and mechanical stability that allows possible application as e.g. insulators, catalysts, sorbents, and containers for chemically active or vulnerable agents (e.g. in controlled drug-delivery). Previous preparation methods have involved various templating approaches using lyotropic liquids [15,54,*55], block copolymer mesophases [56,57], bicontinuous (micro)emulsions [*58], emulsion foams

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[59], colloidal arrays [60], bacterial superstructures [*61], and even polystyrene latex spheres [62]. Most of the mesostructures reported possess non-uniform shapes, undesirable shell thickness, or a lack of structural stability and moreover often require high temperature routes. Recently some major progress has been reported in this eld. Sun et al. [**63] reported a facile and ecient single-step synthesis of hollow silica spheres with a well-dened multilamellar structure and with a high size-uniformity, using an EO76 PO29 EO76 triblock copolymer-based emulsion in combination with the inexpensive sodium silicate solution (Fig. 7). The hybrid materials could be obtained via a rapid (4 h) synthesis procedure at either a reaction temperature of 80 C or

room temperature. The rst route is suitable to produce thermally stable materials with a highly dened wall structure for applications, whereas the second route (at RT) provides a promising tool to enclose temperaturesensitive or volatile agents e.g. for drug-delivery application. In a dierent approach, Yu et al. [*64] reported the synthesis of hollow spheres with ultra large mesoporous wall structures from EO39 BO47 EO39 -based reverse emulsions. The silica wall of the product consists of uniform and hexagonally ordered ultra large mesopores with pore sizes up to 50 nm, which may be suitable for the storage, release and transport of biomolecules. In addition, Prouzet et al. [*65] showed that hollow nanoscaled mesoporous spherical silicas could be obtained by applying sonication to the reaction mixture of PEOpolymer Tergitol C15 (EO)12 and silicon alkoxide in order to form a stable emulsion. It was described that the cavitation bubbles created by ultrasonication become trapped in the solution, and are frozen by the subsequent hydrolysis of silicon alkoxide and condensation of silica. The striking feature of the formed silica is the large hysteresis loop in nitrogen physisorption, which corresponds to the retention of condensed nitrogen within the voids, suggesting that these nano-scaled hollow silica spheres may be applied in storing or stabilizing volatile compounds. Finally, Wong et al. [**66] reported a wet chemical synthesis procedure in which silica (1012 nm) and gold nanoparticles (1012 nm) were cooperatively assembled at room temperature with lysinecysteine diblock polypeptides into hollow spheres. In this system the L -lysine block of the copolypeptide provided preferential attachment sites for silica, while the L -cysteine block was used for binding to gold nanoparticles due to the strong anity of gold surfaces for sulde and disulde moieties resulting in the formation of hollow spheres with amorphous walls composed of two distinct layers of silicagold nanoparticles. Their results suggest that block copolypeptides designed with specic recognition sites for nanoparticles of various compositions may lead to development of a general approach for the hierarchical organization of nanoparticles into multidimensional composite arrays.

4. Conclusion and perspective The biomimetic approaches for silica formation as summarized above are very encouraging, as they strongly suggest that the use of principles learned from Nature and in particular from diatom biomineralization will enable the elaboration of novel silica-based materials such as silica brils with inner chiral nanochannels and well-dened multilamellar hollow spheres, presenting hierarchical structures and morphologies. The integration of biomineralization principles such as supramolecular template synthesis, phase separation and

Fig. 7. Electron microscopy of silica hollow spheres with a welldened multilamellar structure. (a) A SEM overview showing the size-uniformity of the synthesized particles prepared from PEOPPO PEO-based emulsions (bar represents 10 lm). In the inset a detailed view clearly indicate the hollowness of spheres (bar represents 1 lm); (b) high resolution TEM micrograph demonstrating the multilamellar shell (arrows) of the hollow silica spheres (bar represents 33 nm). The images were reproduced from Sun et al. [**63] with permission of WileyVCH 2003.

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self-assembly into the strategy of materials fabrication opens up the great potential for the tailored structuring of materials from nanometer to micrometer scale. The application of these biological principles would allow the transfer of the superior structures, morphologies and properties of biogenic materials towards large scale synthetic materials. Meanwhile, the understanding of the bio-inspired novel materials could, vice versa, shed new light onto the understanding of the mechanisms of formation of complex architectures that are generated in Nature. As bioinspired silica synthesis is an intriguing eld of materials chemistry; the quick expansion of the further understanding of principles and the future application of these systems may be foreseen.

[10] [11]

[12]

[*13]

[*14]

[15]

Acknowledgements QS and EGV were supported by the Technology Foundation STW (grant GFc4983), the applied science division of NWO and the technology program of the Ministry of Economic Aairs. Dr. W.W.C. Gieskes (Department of Marine Biology, University of Groningen, NL) is thanked for contributive discussions.
[**16]

[*17]

[*18]

[19]

References The papers of particular interest have been highlighted as: * of special interest; ** of outstanding interest.
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