Self‐Rupturing and Hollow Microcapsules Prepared from Bio‐polyelectrolyte‐Coated Microgels

This paper reports on microcapsules obtained by layer-by-layer deposition of bio-polyelectrolyte multilayers at the surface of biodegradable dextran microgels. The behavior of the layer-by-layer coating upon degradation of the microgel core strongly depends on the bio-polyelectrolytes used. Two types of microcapsules, “self-rupturing” microcapsules and “hollow” microcapsules, are presented. Self-rupturing microcapsules are obtained when the swelling pressure of the degrading microgel core is strong enough to rupture the surrounding bio-polyelectrolyte membrane. Self-rupturing microcapsules could be of interest as a pulsed drug delivery system. Hollow microcapsules are obtained after applying multiple layers of bio-polyelectrolyte that can withstand the swelling pressure of the degrading microgel core. Biomacromolecules (such as albumin and dextran) spontaneously accumulate in the hollow microcapsules prepared from dex-HEMA microgels, which could be of interest for drug-encapsulation purposes.

[1]  Jia-cong Shen,et al.  Spontaneous deposition of horseradish peroxidase into polyelectrolyte multilayer capsules to improve its activity and stability. , 2002, Chemical communications.

[2]  N. Kotov,et al.  Nanorainbows: graded semiconductor films from quantum dots. , 2001, Journal of the American Chemical Society.

[3]  Christopher J. Barrett,et al.  Fabrication of Microporous Thin Films from Polyelectrolyte Multilayers , 2000 .

[4]  Gleb B. Sukhorukov,et al.  Urease encapsulation in nanoorganized microshells. , 2001 .

[5]  H. Möhwald,et al.  Polyelectrolyte multilayer capsule permeability control , 2002 .

[6]  B. Vainshtein,et al.  Successive deposition of alternate layers of polyelectrolytes and a charged virus , 1994 .

[7]  Gleb B. Sukhorukov,et al.  Influence of Shell Structure on Stability, Integrity, and Mesh Size of Polyelectrolyte Capsules: Mechanism and Strategy for Improved Preparation , 2005 .

[8]  A. Voigt,et al.  Scanning force microscopy investigation of polyelectrolyte nano- and microcapsule wall texture. , 2000 .

[9]  H. Möhwald,et al.  Hollow polyelectrolyte shells: Exclusion of polymers and Donnan equilibrium. , 1999 .

[10]  Alain M. Jonas,et al.  Ultrathin polymer coatings by complexation of polyelectrolytes at interfaces: suitable materials, structure and properties , 2000 .

[11]  Gleb B. Sukhorukov,et al.  Intracellularly Degradable Polyelectrolyte Microcapsules , 2006 .

[12]  A. Voigt,et al.  Polyelectrolyte complexes and layer-by-layer capsules from chitosan/chitosan sulfate. , 2002, Biomacromolecules.

[13]  W. Hennink,et al.  The use of aqueous PEG/dextran phase separation for the preparation of dextran microspheres. , 1999, International journal of pharmaceutics.

[14]  F. Horkay,et al.  Tailoring the swelling pressure of degrading dextran hydroxyethyl methacrylate hydrogels. , 2003, Biomacromolecules.

[15]  Wim E. Hennink,et al.  Degradation and release behavior of dextran-based hydrogels , 1997 .

[16]  J. E. Hennink,et al.  A new class of polymerizable dextrans with hydrolyzable groups: hydroxyethyl methacrylated dextran with and without oligolactate spacer , 1997 .

[17]  Gero Decher,et al.  Fuzzy Nanoassemblies: Toward Layered Polymeric Multicomposites , 1997 .

[18]  R. Srivastava,et al.  Spontaneous loading of positively charged macromolecules into alginate-templated polyelectrolyte multilayer microcapsules. , 2005, Biomacromolecules.

[19]  H. Möhwald,et al.  Resealing of polyelectrolyte capsules after core removal , 2002 .

[20]  G. Creasy,et al.  Pulsatile Delivery Systems , 1991, Annals of the New York Academy of Sciences.

[21]  G. Sukhorukov,et al.  Defined Picogram Dose Inclusion and Release of Macromolecules using Polyelectrolyte Microcapsules , 2005 .

[22]  Catherine Picart,et al.  Buildup Mechanism for Poly(l-lysine)/Hyaluronic Acid Films onto a Solid Surface , 2001 .

[23]  Michael F. Rubner,et al.  Controlling Bilayer Composition and Surface Wettability of Sequentially Adsorbed Multilayers of Weak Polyelectrolytes , 1998 .

[24]  H. Möhwald,et al.  Controlled Permeability of Polyelectrolyte Capsules via Defined Annealing , 2002 .

[25]  J. Cheung,et al.  Molecular self-assembly of conjugated polyions: a new process for fabricating multilayer thin film heterostructures , 1994 .

[26]  M. Mcshane,et al.  Macromolecule encapsulation in diazoresin-based hollow polyelectrolyte microcapsules. , 2005, Langmuir : the ACS journal of surfaces and colloids.

[27]  Gleb B. Sukhorukov,et al.  LAYER-BY-LAYER SELF ASSEMBLY OF POLYELECTROLYTES ON COLLOIDAL PARTICLES , 1998 .

[28]  Langer,et al.  New advances in microsphere-based single-dose vaccines. , 1997, Advanced drug delivery reviews.

[29]  P. Lazzerini,et al.  Reduction in plasma homocysteine level in patients with rheumatoid arthritis given pulsed glucocorticoid treatment , 2003, Annals of the rheumatic diseases.

[30]  W. Hennink,et al.  A novel preparation method for polymeric microparticles without the use of organic solvents , 1998 .

[31]  Jia-cong Shen,et al.  Spontaneous deposition of water-soluble substances into microcapsules: phenomenon, mechanism, and application. , 2002, Angewandte Chemie.

[32]  Lars Dähne,et al.  Smart Micro‐ and Nanocontainers for Storage, Transport, and Release , 2001 .

[33]  K. Braeckmans,et al.  Self‐Rupturing Microcapsules , 2005 .

[34]  R. Georgieva,et al.  Permeability and conductivity of red blood cell templated polyelectrolyte capsules coated with supplementary layers. , 2004, Langmuir : the ACS journal of surfaces and colloids.

[35]  M. Cima,et al.  A controlled-release microchip , 1999, Nature.

[36]  F. Horkay,et al.  Swelling Pressure Observations on Degrading Dex-HEMA Hydrogels , 2002 .

[37]  Andreas Voigt,et al.  pH-controlled macromolecule encapsulation in and release from polyelectrolyte multilayer nanocapsules. , 2001 .

[38]  G. Sukhorukov,et al.  Microgel-based engineered nanostructures and their applicability with template-directed layer-by-layer polyelectrolyte assembly in protein encapsulation. , 2005, Macromolecular bioscience.

[39]  Robert Langer,et al.  Multi-pulse drug delivery from a resorbable polymeric microchip device , 2003, Nature materials.

[40]  N. Kotov,et al.  Two modes of linear layer-by-layer growth of nanoparticle--polylectrolyte multilayers and different interactions in the layer-by-layer deposition. , 2001, Journal of the American Chemical Society.

[41]  C. Christiansen,et al.  Pulsed estrogen therapy in prevention of postmenopausal osteoporosis. A 2-year randomized, double blind, placebo-controlled study , 2004, Osteoporosis International.

[42]  G. Sukhorukov,et al.  Polyelectrolyte multilayer capsules as vehicles with tunable permeability. , 2004, Advances in colloid and interface science.

[43]  R. Langer,et al.  Designing materials for biology and medicine , 2004, Nature.

[44]  H. Möhwald,et al.  Lipid Coating on Polyelectrolyte Surface Modified Colloidal Particles and Polyelectrolyte Capsules , 2000 .

[45]  Wim E Hennink,et al.  Self-gelling hydrogels based on oppositely charged dextran microspheres. , 2005, Biomaterials.

[46]  E. Stein,et al.  Synthesis of size-controlled monodisperse manganese carbonate microparticles as templates for uniform polyelectrolyte microcapsule formation , 2005 .

[47]  H. Möhwald,et al.  Carbonate microparticles for hollow polyelectrolyte capsules fabrication , 2003 .

[48]  G. Prestwich,et al.  Molecular basis for the explanation of the exponential growth of polyelectrolyte multilayers , 2002, Proceedings of the National Academy of Sciences of the United States of America.

[49]  Michael F. Rubner,et al.  pH-Dependent Thickness Behavior of Sequentially Adsorbed Layers of Weak Polyelectrolytes , 2000 .

[50]  G. Sukhorukov,et al.  pH-responsive properties of hollow polyelectrolyte microcapsules templated on various cores. , 2004, Langmuir : the ACS journal of surfaces and colloids.

[51]  Nicholas A. Kotov,et al.  Free-Standing Layer-by-Layer Assembled Films of Magnetite Nanoparticles , 2000 .

[52]  H. Möhwald,et al.  Layer-by-layer engineering of biocompatible, decomposable core-shell structures. , 2003, Biomacromolecules.