The biomimetic synthesis of CaCO3 biomaterials


Here we propose a biomimetic strategy aiming at CaCO3-based biomaterials of which the properties are controlled through the crystallinity and morphology of the inorganic phase using precisely defined macromolecular templates. These macromolecular architectures will be designed such as to mimic three important aspects of biomineralization: a) the controlled nucleation and growth of crystals by precisely defined interactions between the template and the growing crystal, b) the shaping and localisation of mineral particles by restricting their growth to a confined space, and c) the formation of composites with good mechanical and biomaterials properties through the inclusion of macromolecular templates.
In order to arrive at a stage where this challenge can be met we have defined three topics:
· Crystallization templates with well-defined and stable surface structures will be developed based on peptide-derived diblock copolymers. We will use the variation of the peptide sequences to stabilise specific crystal faces and to develop correlations between the template structure and the crystal habits of specific polymorphs. By the construction of aggregates at surfaces and in solution we intend to investigate the relation between templating in two and three dimensions.
· We intend to use hydrophobically modified dendrimers to construct tubular bicontinuous macromolecular architectures with macroscale porosity based on water-in-oil microemulsions. Within the confines of these tubes (amorphous) calcium carbonate will be grown. The resulting materials will be evaluated as possible scaffolds for tissue engineering.
· Hydrophobically modified dendrimers will be complexed with terminally alkylated oligo-peptides to form templates with dynamic self-ordering surfaces. This modular approach can be applied to induce the (oriented) nucleation of specific crystal habits in solution, as well as in gels, aiming at the inclusion of the template in the developing inorganic phase. The mechanical properties will be related to the nature of both the organic and inorganic components


Hoofdstuk in boek

  • D.C. Popescu, S. Cavalli, A. Kros, M.S. FERNANDEZ, J.L. Arias, N.A.J.M. Sommerdijk(2007): Biomineralization: from Paleontology to Materials Science pp. 495 - 508

Wetenschappelijk artikel

  • E.G. Vrieling, N.A.J.M. Sommerdijk, R.A. van Santen, Q. Sun(2004): Bioinspired Synthesis of Mesoporous Silicas, Current Opinion in Solid State and Materials Science pp. 111
  • B. Mezari, R.A. van Santen, P.C.M.M. Magusin, P. Panine, Q. Sun, N.A.J.M. Sommerdijk(2005): The formation of gigantic hollow silica spheres from an EO76-PO29-EO76-Butanol-Ethanol-H2O quaternary system J. Mater Chem. pp. 256
  • N.A.J.M. Sommerdijk, M.O.M. Overhand, E. Tellers, S. Cavalli, D.C. Popescu, A. Kros(2005): b-Sheet forming lipopeptides as templates for the mineralization of CaCO3 Polym Prep.s pp. 118
  • W.W.C. Gieskes, Q. Sun, S. Hazelaar, R.A. van Santen, T.P.M. Beelen, E.G. Vrieling, N.A.J.M. Sommerdijk(2005): Controlled silica synthesis inspired by diatom silicon biomineralisation J. Nanosci. Nanotechn pp. 68
  • M.J.A. van Luyn, A.J.H. Spiering, M.C. Harmsen, L.A. Brouwer, E.W. Meijer, E. Wisse, R.A.E. Renken, N.A.J.M. Sommerdijk, E.N.M. van Leeuwen, P.Y.W. Dankers(2006): Molecular recognition in biodegradable thermoplastic elastomers Biomacromolecules pp. 3385
  • E.E. Tellers, K. Kjaer, M.O.M. Overhand, A. Kros, N.A.J.M. Sommerdijk, D.C. Popescu, J.W. Handgraaf, V. Vaiser, H. Rapaport, S. Cavalli(2006): Two-Dimensional Ordered β?Sheet lipopeptide Monolayers, J. Am. Chem. Soc., pp. 13959
  • E.N.M. van Leeuwen, S.J. Holder, N.A.J.M. Sommerdijk, N.A.A. Rossi, D.C. Popescu, J.A. Jansen(2006): Shaping amorphous calcium carbonate films into 2D model substrates for bone cell culture Angew. Chem. Int. Ed pp. 1762
  • B. Pichon, M.O.M. Overhand, M.R.J. Vos, A. Kros, H. Rapaport, N.A.J.M. Sommerdijk, D.C. Popescu, S. Cavalli, E.E. Tellers(2006): Self-organizing ß-sheet lipopeptide monolayers as template for the mineralization of CaCO3 Angew. Chem. Int. Ed pp. 739
  • M.O.M. Overhand, S. Cavalli, N.A.J.M. Sommerdijk, D.C. Popescu, E. Tellers, A. Kros(2006): Beta-sheet forming lipopeptides as templates for the mineralization of CaCO3 PMSE Preprints pp. 577
  • P.C.M.M. Magusin, Q. Sun, N.A.J.M. Sommerdijk, N.E. Papen-Botterhuis, R.A. van Santen(2006): Hollow silica spheres with ordered pore structure and their application in controlled release studies Chem. Eur. J. pp. 1448
  • A. Kros, N.A.J.M. Sommerdijk, E.N.M. van Leeuwen, H. Robson Marsden, A.V. Korobko(2007): Amphiphilic supramolecular polymers based on coiled-coil peptide mediated self-assembly PMSE Preprints pp. 765
  • N.A.J.M. Sommerdijk, J.J.J.P. van den Beucken, R.J.M. Nolte, X.F. Walboomers, J.A. Jansen, M.R.J. Vos(2007): Biological responses to multilayered DNA-coatings. J. Biomed. Mater. Res. B. pp. 231
  • M. Surin, Q. Sun, Ph. Leclere, R. Lazzoroni, J. Cornil, E.W. Meijer, N.A.J.M. Sommerdijk, F. Brustolin, G. Romanazzi, V. Lemaur(2007): The self-assembly of amphphilic oligothiophenes: Hydrogen bonding and poly(glutamate) complextion. Bull. Chem. Soc. Jpn. pp. 1703
  • J.A. Jansen, E.N.M. van Leeuwen, N.A.J.M. Sommerdijk, M.R.J. Vos(2007): Calcium carbonate thin films as biomaterials coatings using DNA as crystallization inhibitor Cryst. Eng. Comm. pp. 1209 - 1214
  • G. Fytas, N.A.J.M. Sommerdijk, B. Mezari, P.C.M.M. Magusin, M.A.C. Broeren, P.A.J. Hilbers, A.F. Smeijers, E.W. Meijer, M.H.P. van Genderen, M.R.J. Vos, T.M. Hermans, E.N.M. van Leeuwen, N. Gomopoulos(2007): Stepwise Non-Covalent Synthesis Leading to Dendrimer-Based Assemblies in Water J. Am. Chem. Soc pp. 15631 - 15638
  • D.C. Popescu, F. Perrot, S. Cantin, N. Chebotareva, M.R.J. Vos, O. van Asselen, B.P. Pichon, R. Sijbesma, M.M.J. Smulders, N.A.J.M. Sommerdijk(2007): Molecular recognition controls the organization of mixed self-organized bis-urea based mineralization templates for CaCO3 Langmuir pp. 12655 - 12662
  • M.R.J. Vos, T.H. van Kuppenveld, J.A. Jansen, N.A.J.M. Sommerdijk, R.J.M. Nolte, X.F. Walboomers, S.T.M. Nillesen, J.J.J.P. van den Beucken(2007): In vitro and in vivo effects of deoxyribonucleic acid-based coatings functionalized with vascular endothelial growth factor. Tissue. Eng. pp. 711
  • B. Pichon, N.A.J.M. Sommerdijk, S.-Y. Kwak, E. DiMasi(2007): Structural adaptability in an organic template for mineralization Cryst. Eng. Comm. pp. 1192 - 1204
  • R.A.J. Janssen, S.C.J. Meskers, P.T.K. Chin, C. de Melloega, N.A.J.M. Sommerdijk, S.S. van Bavel(2007): Highly Luminescent CdTe/CdSe colloidal heteronanocrystals with temperature dependent emission color J. Am. Chem. Soc. pp. 14880 - 14886
  • R.P. Sijbesma, D.C. Popescu, M.M.J. Smulders, B. Pichon, P.H.H. Bomans, P. Frederik, N. Chebotareva, N.A.J.M. Sommerdijk(2007): Self-organized surfactants as templates for the mineralization of CaCO3. PMSE Preprints pp. 123 - 124
  • N.A.J.M. Sommerdijk, J.J.L.M. Cornelissen, J.C. Maan, A.E. Rowan, H. Engelkamp, P.C.M. Christianen, V.I. Claessen, M. Comellas-Aragones, R.J.M. Nolte, B.J.M. Verduin(2007): A virus-based single-enzyme nanoreactor Nature Nanotechn. pp. 635 - 639
  • M.M.J. Smulders, B.P. Pichon, N.A.J.M. Sommerdijk, O.L.J. van Asselen, E. DiMasi, D.C. Popescu, R.P. Sijbesma, S.-Y. Kwak, N. Cheboatareva(2007): Template Adaptability is Key in the Oriented Crystallization of CaCO3 J. Am. Chem. Soc. pp. 14058 - 14067
  • N.A.J.M. Sommerdijk, P.H.H. Bomans, J.A. Jansen, F. de Haas, M.R.J. Vos, P.M. Frederik, R.J.M. Nolte(2007): Insights in the Organization of DNA-surfactant monolayers using cryo-electon tomography J. Am. Chem. Soc pp. 11894 - 11895
  • S.C.G. Leeuwenburgh, M.R.J. Vos, R.J.M. Nolte, J.A. Jansen, X.F. Walboomers, J.J.J.P. van der Beucken, N.A.J.M. Sommerdijk(2007): Multilayered DNA-Coatings: In vitro bioactivity studies and effects on osteoblast-like cell behaviour. Acta Biomaterialia pp. 587 - 596
  • A.P.H. Schenning, N.A.J.M. Sommerdijk, A. Ajayaghosh, E.W. Meijer, J. van Herrikhuyzen, M.R.J. Vos, R.A.J. Janssen, S.C.J. Meskers, S.J. George(2007): OPV Tapes as a scaffold for inorganic nanoparticles: Engineering photophysical properties. Angew. Chem. Int. Ed. pp. 1825
  • Q. Sun, W.W.C. Gieskes, P.J. Kooyman, M. Tian, R.A. van Santen, E.G. Vrieling, N.A.J.M. Sommerdijk(2007): Salinity-Dependent Diatom Silica Nanostructuring Implies A Direct Role Of External Ionic Strength Proc. Nat. Acad. Sci USA pp. 10441 - 10446
  • J.A. Jansen, M.R.J. Vos, J.J.J.P. van der Beucken, N.A.J.M. Sommerdijk, X.F. Walboomers, R.J.M. Nolte(2007): Macrophage behavior on multilayered DNA-coating in vitro. J. Biomed. Mater. Res.A. pp. 612
  • N.A.J.M. Sommerdijk, E.M. Pouget, A. Kros, A.V. Korobko, S.J. Veen, E.N.M. van Leeuwen, H. Robson Marsden(2008): Non-covalent Triblock Copolymers Based on a Coiled-Coil Peptide Motif J. Am. Chem. Soc. pp. 9386 - 9393
  • P.H.H. Bomans, M.R. Vos, P.M. Frederik, N.A.J.M. Sommerdijk(2008): The development of a glove-box/Vitrobot combination: Air-water interface events visualized by cryo-TEM Ultramicroscopy pp. 1478 - 1483
  • N.A.J.M. Sommerdijk, G. de With(2008): Biomimetic CaCO3 Mineralization Using Designer Molecules and Interfaces Chem. Rev pp. 4499 - 4550
  • G. Portale, P.C.M. Christianen, J. van Herrikhuyzen, A.P.H.J. Schenning, S.C.J. Meskers, J.C. Gielen, N.A.J.M. Sommerdijk(2008): Disk Micelles from amphiphilic Janus gold nanoparticles. Chem. Commun. pp. 697 - 699
  • S.C.G. Biagini, S.J. Holder, P.H.H. Bomans, N.A.J.M. Sommerdijk, A.L. Parry(2008): Cryo-Electron Tomography reveals Confined Complex Morphologies from Tripeptide-containing Amphiphilic Double Comb Diblock Copolymers Angew. Chem. Int. Ed. pp. 8859 - 8862
  • M.R.J. Vos, N.A.J.M. Sommerdijk, R.J.M. Nolte, J.J.J.P. van den Beucken, S.C.G. Leeuwenburgh, X.F. Walboomers, J.A. Jansen(2008): DNA-Coatings: Bioactive properties and effects on osteoblast-like cells. Key Eng. Mater. pp. 361 - 363
  • E.W. Meijer, D.W.P.M. Lowik, J. Gielen, J.T. Heldens, S.J. George, R. Matmour, P. Christianen, J.C.M. van Hest, P.E.L.G. Leclere, W. Adriaens, I. de Cat, S. de Feyter, N.A.J.M. Sommerdijk, A.P.H.J. Schenning, P.H.H. Bomans(2008): Oligo(p-phenylenevinylene)-peptide conjugates: synthesis and self-assembly in solution and at the solid-liquid interface J. Am. Chem. Soc. pp. 14576 - 14583
  • E.M. Pouget, W.J.M. Mulder, G.J. Strijkers, K. Nicolay, N.A.J.M. Sommerdijk, C.P.M. Reutelingsperger, G.A.F. van Tilborg(2008): Kinetics of avidin-induced clearance of biotinylated bimodal liposomes for improved MR molecular imaging. NMR in Biomedicine pp. 1444 - 1456
  • P.H.H. Bomans, B. Pichon, P.M. Frederik, N.A.J.M. Sommerdijk(2008): A quasi-time resolved cryo-TEM study of the nucleation of CaCO3 under Langmuir monolayers J. Am. Chem. Soc pp. 4034 - 4040
  • M. Breurken, J.A. Jansen, P.H.H. Bomans, F. de Haas, M.R.J. Vos, N.A.J.M. Sommerdijk, P.M. Frederik, R.J.M. Nolte, P.E.L.G. Leclere(2008): Electron tomography shows molecular within a layer-by-layer film. J. Am. Chem. Soc. pp. 12608 - 12609
  • N.A.J.M. Sommerdijk, G. de With, J.A.C.M. Goos, P.M. Frederik, P.H.H. Bomans, E.M. Pouget(2009): The initial stages of template controlled CaCO3 formation revealed by CryoTEM. Science pp. 1455 - 1458
  • Nico A.J.M Sommerdijk, M.A.C. Broeren, E.W. Meijer, T.M. Hermans, N. Gomopoulos, P. van der Schoot, G. Fytas, M.H.P. van Genderen(2009): Self-assembly of soft nanoparticles with tunable patchiness Nature Nanotechnology pp. 721 - 726
  • Z.A. Fayad, S. Aime, F. Arena, E. Leupold, H.M.H.F. Sanders, W.J.M. Mulder, K. Nicolay, M. Dathe, N.A.J.M. Sommerdijk, E. Terreno, E. Vucic(2009): Well-defined, multifunctional nanostructures of a paramagnetic lipid and a lipopeptide for macrophage imaging. J. Am. Chem. Soc. pp. 406
  • E. Violante, D.D. Castelli, E. Terreno, N.A.J.M. Sommerdijk, S. Aime, H.M.H.F. Sanders(2009): Osmotically shrunken LIPOCEST agents: an innovative class of magnetic resonance imaging contrast media based on chemical exchange saturation transfer. Chen. Eur. J. pp. 1440
  • N.A.J.M. Sommerdijk, P.G.A. Jansen, J.C. Gielen, P.H.H. Bomans, A.P.H.J. Schenning, P.C.M. Christianen, M.R.J. Vos, R. Lazzaroni, T.F.A de Greef, E.W. Meijer, Ph. Leclere, M. Surin, S. Jabbari-Farouji, X. Vila, P. van der Schoot(2009): Insights into templated supramolecular polymerization: binding of naphthalene derivatives to ssDNA templates of different lengts. J. Am. Chem. Soc. pp. 1222 - 1231
  • E.W. Meijer, T.M. Hermans, P. van der Schoot, G. Fytas, M.A.C. Broeren, N. Gomopoulos, M.H.P. van Genderen, N.A.J.M. Sommerdijk(2009): Dilution-induced self-assembly of soft patchy nanoparticles. Nature Nanotech. pp. 721
  • A. Kros, N.A.J.M. Sommerdijk, N.A. Elbers, P.H.H. Bomans, H. Robson Marsden(2009): A minimal model for membrane fusion. Angew. Chem. Int. Ed. pp. 2330
  • G.J. Strijkers, H.M.H.F. Sanders, Nico A.J.M Sommerdijk, W.J.M. Mulder, S.J.F. Erich, H.P. Huinink, K. Nicolay, O.C.G. Adan, M. Merkx(2009): Morphology, binding behaviour and MR-properties of paramagnetic collagen-binding liposomes. Contrast Media & Molecular Imaging pp. 81 - 88
  • Z. Shao, B. Leng, L.J. Brylka, G. de With, P.H.H. Bomans, W. Ming, Nico A.J.M Sommerdijk(2010): Cryogenic electron tomography reveals the template effect of chitosan in biomimetic silicification. Chemical Communications pp. 1703 - 1705
  • Nico A.J.M Sommerdijk, P.M. Frederik, G. de With, P.H.H. Bomans, A. Dey, E.M. Pouget(2010): The development of morphology and structure in hexagonal vaterite. J. American Chemical Society pp. 11560 - 11565
  • G. de With, F. Nudelman, P.A.J. Hilbers, A. George, P.H.H. Bomans, H. Friedrich, L.J. Brylka, K. Pieterse, Nico A.J.M Sommerdijk(2010): The role of collagen in bone apatite formation in the presence of hydroxyapatite nucleation inhibitors. Nature Materials pp. 1004 - 1009
  • G.J. Strijkers, G. de With, Nico A.J.M Sommerdijk, E.M. Pouget, H.M.H.F. Sanders, M. Iafisco, P.H.H. Bomans, F. Nudelman, K. Nicolaij, M. Merkx, G. Falini(2011): The binding of CNA35 contrast agents to collagen fibrils. Chemical Communications pp. 1503 - 1505





Prof. dr. N.A.J.M. Sommerdijk

Verbonden aan

Technische Universiteit Eindhoven, Faculteit Scheikundige Technologie, Laboratorium voor Materiaal en Grensvlakchemie


Mw. L.J. Brylka, Ir. E.N.M. van Leeuwen, Dr. F. Nudelman, Dr. B. Pichon, Dr. E.M. Pouget, Ir. E. Wisse


01/01/2004 tot 26/05/2011