Natural Nanotube-Based Biomimetic Porous Microspheres for Significantly Enhanced Biomolecule Immobilization

Inorganic nanostructures and their assemblies play important roles in immobilizing biomolecules. Herein, we developed a facile and green methodology to assemble natural halloysite nanotubes (1D building blocks) into nest-like porous microspheres (3D architecture). We further modified the microspheres with dopamine to form a biomimetic entity. The interconnected and hierarchical pores within the microspheres provide larger pore volume to entrap biomolecules, and the abundant functional groups on the pore surface bond covalently with enzyme to enhance the immobilization ability. The porous microspheres showed excellent loading capacity for laccase immobilization as high as 311.2 mg/g, around 30 times higher than the individual halloysite nanotubes (11.3 mg/g). The specific activity above 80% was retained for the immobilized laccase compared to the free laccase. In addition, the immobilized enzyme exhibited remarkable thermal and recycle use stability. The biomimetic microspheres are expected to be biologica...

[1]  G. Bayramoglu,et al.  Immobilization of laccase onto spacer-arm attached non-porous poly(GMA/EGDMA) beads: application for textile dye degradation. , 2009, Bioresource technology.

[2]  Nelson Durán,et al.  Applications of laccases and tyrosinases (phenoloxidases) immobilized on different supports: a review , 2002 .

[3]  D. Shantz,et al.  Biomimetic Silica Formation: Effect of Block Copolypeptide Chemistry and Solution Conditions on Silica Nanostructure , 2007 .

[4]  V. Vergaro,et al.  Cytocompatibility and uptake of halloysite clay nanotubes. , 2010, Biomacromolecules.

[5]  Qiang Sun,et al.  Weak Acid–Base Interaction Induced Assembly for the Synthesis of Diverse Hollow Nanospheres , 2011 .

[6]  S. Wen,et al.  Preparation and characterization of polystyrene/Ag core-shell microspheres--a bio-inspired poly(dopamine) approach. , 2012, Journal of colloid and interface science.

[7]  Huifang Xu,et al.  Morphological and Chemical/Physical Characterization of Fe‐Doped Synthetic Chrysotile Nanotubes , 2005 .

[8]  H. Möhwald,et al.  Halloysite clay nanotubes for controlled release of protective agents. , 2008, ACS nano.

[9]  P B Deasy,et al.  Characterisation of halloysite for use as a microtubular drug delivery system. , 2002, International journal of pharmaceutics.

[10]  H. Möhwald,et al.  Application of Inhibitor‐Loaded Halloysite Nanotubes in Active Anti‐Corrosive Coatings , 2009 .

[11]  M. King,et al.  Use of naturally occurring halloysite nanotubes for enhanced capture of flowing cells. , 2010, Langmuir : the ACS journal of surfaces and colloids.

[12]  A. Bengueddach,et al.  Intercalation of halloysite from Djebel Debagh (Algeria) and adsorption of copper ions , 2009 .

[13]  J. P. de Mesquita,et al.  Biobased nanocomposites from layer-by-layer assembly of cellulose nanowhiskers with chitosan. , 2010, Biomacromolecules.

[14]  H. Chang,et al.  A magnetically separable, highly stable enzyme system based on nanocomposites of enzymes and magnetic nanoparticles shipped in hierarchically ordered, mesocellular, mesoporous silica. , 2005, Small.

[15]  N Claffey,et al.  Formulation and preliminary in vivo dog studies of a novel drug delivery system for the treatment of periodontitis. , 2004, International journal of pharmaceutics.

[16]  M. in het Panhuis,et al.  Assembling carbon nanotubosomes using an emulsion-inversion technique. , 2005, Chemical communications.

[17]  A. Takahara,et al.  Selective modification of halloysite lumen with octadecylphosphonic acid: new inorganic tubular micelle. , 2012, Journal of the American Chemical Society.

[18]  H. Zou,et al.  Ultrafast enzyme immobilization over large-pore nanoscale mesoporous silica particles. , 2006, Chemical communications.

[19]  J. Waite,et al.  Cross-linking in adhesive quinoproteins: studies with model decapeptides. , 2000, Biochemistry.

[20]  Chunhua Wang,et al.  Influence of palygorskite on the structure and thermal stability of collagen , 2012 .

[21]  Xuebin B. Yang,et al.  Clay Gels For the Delivery of Regenerative Microenvironments , 2011, Advanced materials.

[22]  Y. Lvov,et al.  Clay nanotubes for corrosion inhibitor encapsulation: release control with end stoppers , 2010 .

[23]  Haeshin Lee,et al.  Mussel-Inspired Surface Chemistry for Multifunctional Coatings , 2007, Science.

[24]  R. Prakasham,et al.  Novel Synthesis of Ferric Impregnated Silica Nanoparticles and Their Evaluation as a Matrix for Enzyme Immobilization , 2007 .

[25]  G. Zhu,et al.  Halloysite Nanotubes, a Multifunctional Nanovehicle for Anticancer Drug Delivery , 2012 .

[26]  D. Ramón,et al.  Hierarchical bimodal porous silicas and organosilicas for enzyme immobilization , 2005 .

[27]  F. Caruso,et al.  Dopamine-Mediated Continuous Assembly of Biodegradable Capsules , 2011 .

[28]  Kvar C. L. Black,et al.  A novel technique for in situ aggregation of Gluconobacter oxydans using bio‐adhesive magnetic nanoparticles , 2012, Biotechnology and bioengineering.

[29]  Joseph J. Richardson,et al.  Multivalent directed assembly of colloidal particles. , 2013, Angewandte Chemie.

[30]  Jingtao Wang,et al.  Bioinspired fabrication of high performance composite membranes with ultrathin defect-free skin layer , 2009 .

[31]  Yufang Zhu,et al.  Immobilization of Trametes versicolor Laccase on Magnetically Separable Mesoporous Silica Spheres , 2007 .

[32]  F. Plou,et al.  Decolorization of synthetic dyes by laccase immobilized on epoxy-activated carriers , 2008 .

[33]  Jin-dun Liu,et al.  Immobilization of enzyme biocatalyst on natural halloysite nanotubes , 2010 .

[34]  Chen Guo,et al.  Magnetic mesoporous silica nanoparticles: fabrication and their laccase immobilization performance. , 2010, Bioresource technology.

[35]  K. Tazaki.  Microbial Formation of a Halloysite-Like Mineral , 2005 .

[36]  Junhui He,et al.  Facile Synthesis of Monodisperse Manganese Oxide Nanostructures and Their Application in Water Treatment , 2008 .

[37]  Haeshin Lee,et al.  Facile Conjugation of Biomolecules onto Surfaces via Mussel Adhesive Protein Inspired Coatings , 2009, Advanced materials.

[38]  Atsushi Takahara,et al.  Biomimetic dopamine derivative for selective polymer modification of halloysite nanotube lumen. , 2012, Journal of the American Chemical Society.

[39]  Daliang Zhang,et al.  Novel mesoporous silica spheres with ultra-large pore sizes and their application in protein separation , 2009 .

[40]  P. Gao,et al.  Immobilization of Laccase on Nanoporous Gold: Comparative Studies on the Immobilization Strategies and the Particle Size Effects , 2009 .

[41]  Norbert F Scherer,et al.  Single-molecule mechanics of mussel adhesion , 2006, Proceedings of the National Academy of Sciences.

[42]  Jin-dun Liu,et al.  The removal of dye from aqueous solution using alginate-halloysite nanotube beads. , 2012 .

[43]  Jungbae Kim,et al.  Highly Efficient Enzyme Immobilization and Stabilization within Meso-Structured Onion-Like Silica for Biodiesel Production , 2012 .

[44]  Feng Zhou,et al.  Bioinspired catecholic chemistry for surface modification. , 2011, Chemical Society reviews.

[45]  F. Caruso,et al.  Immobilization and intracellular delivery of an anticancer drug using mussel-inspired polydopamine capsules. , 2012, Biomacromolecules.

[46]  Hélio A. Duarte,et al.  Imogolite nanotubes: stability, electronic, and mechanical properties. , 2007, ACS nano.

[47]  M. V. D. Leeden.  Are conformational changes, induced by osmotic pressure variations, the underlying mechanism of controlling the adhesive activity of mussel adhesive proteins? , 2005 .