Polyelectrolyte multilayer microcapsules: Self-assembly and toward biomedical applications

Over the past few years, many studies have been performed involving the application of the Layer-by-Layer (LbL) deposition of oppositely charged polyelectrolytes onto charged colloidal particles, followed by the dissolution of the templates, ultimately resulting in polyelectrolyte multilayer microcapsules. The ease of preparation of polyelectrolyte multilayer microcapsules afforded by the LbL self-assembly technique, as well as the advantages of accurate control over size, composition, and the thickness of the multilayer shell make these capsules very promising for a number of applications in materials and biomedical science. In this review, we describe the assembly and stimuli-responsive properties (“smart” capsules) of polyelectrolyte multilayer microcapsules, and also discuss the potential of this technique in regard to biomedical applications. In addition, we illustrate two measurement techniques for determining the mechanical properties of polyelectrolyte multilayer microcapsules—(i) osmotic swelling and (ii) AFM compression experiments. These capsules are believed to have great potential for future applications, including biosensors, bioreactors, and carriers for targeted drug delivery.

[1]  Superswollen ultrasoft polyelectrolyte microcapsules , 2005 .

[2]  Woochang Lee,et al.  Immunosensor for detection of Yersinia enterocolitica based on imaging ellipsometry. , 2004, Analytical chemistry.

[3]  Young's Modulus of Polyelectrolyte Multilayers from Microcapsule Swelling , 2003, cond-mat/0307622.

[4]  V. Lulevich,et al.  Effect of pH and salt on the stiffness of polyelectrolyte multilayer microcapsules. , 2004, Langmuir : the ACS journal of surfaces and colloids.

[5]  Gleb B. Sukhorukov,et al.  Stepwise Polyelectrolyte Assembly on Particle Surfaces: a Novel Approach to Colloid Design , 1998 .

[6]  B. Cho,et al.  "Grafting-from" polymerization inside a polyelectrolyte hollow-capsule microreactor. , 2005, Angewandte Chemie.

[7]  M. Mcshane,et al.  Synthesis and functionalization of monodisperse poly(ethylene glycol) hydrogel microspheres within polyelectrolyte multilayer microcapsules. , 2006, Chemical communications.

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

[9]  Olga I. Vinogradova,et al.  Mechanical properties of polyelectrolyte multilayer microcapsules , 2004 .

[10]  F. Caruso,et al.  Electrostatically assembled polyelectrolyte/dendrimer multilayer films as ultrathin nanoreservoirs , 2002 .

[11]  Woochang Lee,et al.  Application of complement 1q for the site-selective recognition of immune complex in protein chip. , 2006, Biosensors & bioelectronics.

[12]  G. Sukhorukov,et al.  Synthesis of nanosized magnetic ferrite particles inside hollow polyelectrolyte capsules , 2003 .

[13]  H. Möhwald,et al.  Thermosensitive hollow capsules based on thermoresponsive polyelectrolytes , 2003 .

[14]  Denis Andrienko,et al.  Elasticity of polyelectrolyte multilayer microcapsules. , 2004, The Journal of chemical physics.

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

[16]  J. Schlenoff,et al.  Factors Controlling the Growth of Polyelectrolyte Multilayers , 1999 .

[17]  G. Prestwich,et al.  Layer by layer buildup of polysaccharide films: physical chemistry and cellular adhesion aspects. , 2004, Langmuir : the ACS journal of surfaces and colloids.

[18]  D. Streich,et al.  pH‐Sensitive Nanocontainers , 2001 .

[19]  Frank Caruso,et al.  1. Ultrathin Multilayer Polyelectrolyte Films on Gold: Construction and Thickness Determination , 1997 .

[20]  G. Sukhorukov,et al.  Reversible swelling of polyanion/polycation multilayer films in solutions of different ionic strength , 1996 .

[21]  J. Hofmann,et al.  Defoliation and plasmid delivery with layer-by-layer coated colloids. , 2006, Macromolecular bioscience.

[22]  A. Voigt,et al.  Plastic behaviour of polyelectrolyte microcapsules derived from colloid templates. , 2000, Journal of microencapsulation.

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

[24]  M. Gu,et al.  Characterization ofgltA: luxCDABE fusion inEscherichia coli as a toxicity biosensor , 2006 .

[25]  Olga I. Vinogradova,et al.  MECHANICAL BEHAVIOR AND CHARACTERIZATION OF MICROCAPSULES , 2006 .

[26]  A. Voigt,et al.  Layer‐by‐Layer Self‐Assembly of Polyelectrolyte and Low Molecular Weight Species into Capsules , 2001 .

[27]  C. Barrett,et al.  pH-responsive properties of multilayered poly(L-lysine)/hyaluronic acid surfaces. , 2003, Biomacromolecules.

[28]  G. Decher Polyelectrolyte Multilayers, an Overview , 2003 .

[29]  M. Mcshane,et al.  Microcapsule biosensors using competitive binding resonance energy transfer assays based on apoenzymes. , 2005, Analytical chemistry.

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

[31]  M. Textor,et al.  Biofunctional Polyelectrolyte Multilayers and Microcapsules: Control of Non‐Specific and Bio‐Specific Protein Adsorption , 2005 .

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

[33]  F. Caruso,et al.  DNA multilayer films on planar and colloidal supports: sequential assembly of like-charged polyelectrolytes. , 2005, Nano letters.

[34]  G. Sukhorukov,et al.  Nanoassembly of biodegradable microcapsules for DNA encasing. , 2004, Journal of the American Chemical Society.

[35]  Frank Caruso,et al.  Layer-by-layer engineered capsules and their applications , 2006 .

[36]  G. Decher,et al.  From Functional Core/Shell Nanoparticles Prepared via Layer-by-Layer Deposition to Empty Nanospheres , 2004 .

[37]  V. Lulevich,et al.  Mechanical Properties of Polyelectrolyte Microcapsules Filled with a Neutral Polymer , 2003 .

[38]  A. Gliozzi,et al.  Encapsulated living cells on microstructured surfaces. , 2005, Langmuir : the ACS journal of surfaces and colloids.

[39]  G. Glasser,et al.  Effect of organic solvent on the permeability and stiffness of polyelectrolyte multilayer microcapsules , 2005 .

[40]  Amish J. Patel,et al.  Enzyme-catalyzed polymerization of phenols within polyelectrolyte microcapsules , 2004 .

[41]  G L Coté,et al.  A fluorescence-based glucose biosensor using concanavalin A and dextran encapsulated in a poly(ethylene glycol) hydrogel. , 1999, Analytical chemistry.

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

[43]  F. Caruso,et al.  Fabrication of polyelectrolyte multilayer films comprising nanoblended layers. , 2004, Journal of the American Chemical Society.

[44]  Caruso,et al.  Nanoengineering of inorganic and hybrid hollow spheres by colloidal templating , 1998, Science.

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

[46]  A. Fery,et al.  Salt softening of polyelectrolyte multilayer capsules. , 2005, Langmuir : the ACS journal of surfaces and colloids.

[47]  H. Möhwald,et al.  Fabrication of micro reaction cages with tailored properties. , 2001, Journal of the American Chemical Society.

[48]  G. Sukhorukov,et al.  Inorganic Particle Synthesis in Confined Micron-Sized Polyelectrolyte Capsules , 2002 .

[49]  Kurt Kremer,et al.  The nature of flexible linear polyelectrolytes in salt free solution: A molecular dynamics study , 1995 .

[50]  V. Lulevich,et al.  Deformation properties of nonadhesive polyelectrolyte microcapsules studied with the atomic force microscope , 2003 .

[51]  Byoung-Suhk Kim,et al.  Salt softening of polyelectrolyte multilayer microcapsules. , 2005, Journal of colloid and interface science.

[52]  Gleb B. Sukhorukov,et al.  Self‐Rupturing and Hollow Microcapsules Prepared from Bio‐polyelectrolyte‐Coated Microgels , 2007 .

[53]  Lars Dähne,et al.  Tailor-made polyelectrolyte microcapsules: from multilayers to smart containers. , 2004, Angewandte Chemie.

[54]  O. Rolinski,et al.  Molecular distribution sensing in a fluorescence resonance energy transfer based affinity assay for glucose. , 2001, Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy.

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

[56]  Jeong-Woo Choi,et al.  Nanoscale fabrication of biomolecular layer and its application to biodevices , 2004 .

[57]  Christopher J. Barrett,et al.  pH-Dependent Loading and Release Behavior of Small Hydrophilic Molecules in Weak Polyelectrolyte Multilayer Films , 2004 .

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

[59]  A. Dobrynin,et al.  Theory of polyelectrolytes in solutions and at surfaces , 2005 .

[60]  H. El-Shall,et al.  Atomic force microscopy measurement of the elastic properties of the kidney epithelial cells. , 2005, Journal of colloid and interface science.

[61]  G. Sukhorukov,et al.  Micron-scale hollow polyelectrolyte capsules with nanosized magnetic Fe3O4 inside , 2003 .

[62]  A. Fery,et al.  Elastic properties of polyelectrolyte capsules studied by atomic-force microscopy and RICM , 2003, The European physical journal. E, Soft matter.

[63]  Gleb B. Sukhorukov,et al.  Incorporation of macromolecules into polyelectrolyte micro- and nanocapsules via surface controlled precipitation on colloidal particles , 2002 .

[64]  G. Sukhorukov,et al.  Polyelectrolyte capsules modified with YF3 nanoparticles: An AFM study , 2004 .

[65]  R. Bashir,et al.  “Bottom-up” approach for implementing nano/microstructure using biological and chemical interactions , 2007 .

[66]  F. Caruso,et al.  Core-shell colloids and hollow polyelectrolyte capsules based on diazoresins. , 2001 .

[67]  Sohrab Mansouri,et al.  A Miniature Optical Glucose Sensor Based on Affinity Binding , 1984, Bio/Technology.

[68]  Dong Ha Kim,et al.  Assembly and mechanical properties of phosphorus dendrimer/polyelectrolyte multilayer microcapsules. , 2005, Langmuir : the ACS journal of surfaces and colloids.

[69]  Qi Liao,et al.  Molecular dynamics simulations of polyelectrolyte solutions: Osmotic coefficient and counterion condensation , 2003 .

[70]  Byoung-Suhk Kim,et al.  Multilayer DNA/poly(allylamine hydrochloride) microcapsules: assembly and mechanical properties. , 2005, Biomacromolecules.

[71]  Helmuth Möhwald,et al.  Novel Hollow Polymer Shells by Colloid-Templated Assembly of Polyelectrolytes. , 1998, Angewandte Chemie.

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

[73]  J Hartmann,et al.  Microencapsulation by means of step-wise adsorption of polyelectrolytes. , 2000, Journal of microencapsulation.