Abstract
Nanoengineered polymer carriers assembled by the layer-by-layer technique are being increasingly investigated as nano- to millimeter-sized, semi-permeable reactors. The reactors are assembled by the sequential adsorption of polymers that interact primarily via electrostatic forces, hydrogen bonding, or covalent bond formation onto a sacrificial colloidal template. Controlled permeability of molecular species is key to the functioning of these reactors and a number of techniques have been developed for measuring and controlling their permeability to both small molecules and larger macromolecules. The encapsulation of enzyme “machinery” into the carriers has produced a number of reactor examples capable of small molecule conversion. Advanced assembly techniques have been used to generate reactors with relevance to biomedicine, including biosensing, controlled drug release, and biopolymer synthesis.
Keywords
This is a preview of subscription content, log in via an institution.
Buying options
Tax calculation will be finalised at checkout
Purchases are for personal use only
Learn about institutional subscriptionsReferences
Kiick K (2007) Polymer therapeutics. Science 317:1182–1183
Duncan R (2003) The dawning era of polymer therapeutics. Nat Rev Drug Discov 2:347–360
Lensen D, Vriezema DM, van Hest JCM (2008) Polymeric microcapsules for synthetic applications. Macromol Biosci 8:991–1005
Decher G, Hong JD (1991) Buildup of ultrathin multilayer films by a self-assembly process. II. Consecutive absorption of anionic and cationic bipolar amphiphiles and polyelectrolytes on charged surfaces. Ber Bunsen Ges Phys Chem 95:1430–1434
Quinn JF, Johnston APR, Such GK, et al. (2007) Next generation, sequentially assembled ultrathin films: beyond electrostatics. Chem Soc Rev 36:707–718
Caruso F, Caruso RA, Moehwald H (1998) Nanoengineering of inorganic and hybrid hollow spheres by colloidal templating. Science 282:1111–1114
Donath E, Sukhorukov GB, Caruso F, et al. (1998) Novel hollow polymer shells by colloid-templated assembly of polyelectrolytes. Angew Chem Int Ed 37:2202–2205
Kurth DG, Volkmer D, Klitzing RV (2003) Multilayers on solid planar substrates: from structure to function. In: Decher G, Schlenoff JB (eds) Multilayer thin films. Wiley-VCH, Weinberg
Caruso F, Sukhorukov G (2003) Coated colloids: preparation, characterization, assembly and utilization. In: Decher G, Schlenoff JB (eds) Multilayer thin films. Wiley-VCH, Weinberg
Shiratori SS, Rubner R (2000) pH-dependent thickness behavior of sequentially absorbed layers of weak polyelectrolytes. Macromolecules 33:4213–4219
Tong W, Gao C (2008) Multilayer microcapsules with tailored structures for bio-related applications. J Mater Chem 18:3799–3812
Tong W, Gao C, Möhwald H (2005) Manipulating the properties of polyelectrolyte capsules by glutaraldehyde cross-linking. Chem Mater 4610–4616
Harris JJ, DeRose PM, Bruenig ML (1999) Synthesis of passivating, nylon-like coatings through cross-linking of ultrathin polyelectrolyte films. J Am Chem Soc 121:1978–1980
Sun J, Wu T, Sun J, et al. (1998) Fabrication of covalently attached multilayer via photolysis of layer-by-layer self-assembled films containing diazo-resins. Chem Commun 17:1853–1855
Pastoriza-Santos I, Schöler B, Caruso F (2001) Core-shell colloids and hollow polyelectrolyte capsules based on diazoresins. Adv Funct Mater 11:122–128
Tong W, Gao C, Möhwald H (2006) Stable weak polyelectrolyte microcapsules with pH-responsive permeability. Macromolecules 39:335–340
Stockton WB, Rubner MF (1997) Molecular-level processing of conjugated polymers. 4. Layer-by-layer manipulation of polyaniline via hydrogen-bonding interactions. Macromolecules 30:2717–2725
Wang L, Wang ZQ, Zhang X, et al. (1997) A new approach for the fabrication of an alternating multilayers film of poly(4-vinylpyridine) and poly(acrylic acid) based on hydrogen bonding. Macromol Rapid Commun 18:509–514
Kharlampieve E, Sukhishvili SA (2006) Hydrogen-bonded layer-by-layer polymer films. Macromol Sci Part C: Polymer Rev 46:377–395
Kozlovskaya V, Kharlampieva E, Erel I, et al. (2009) Multilayer-derived, ultrathin, stimuli-responsive hydrogels. Soft Matter 5:4077–4087
Kozlovskaya VA, Shamaev A, Sukhishvili SA (2008) Tuning swelling pH and permeability of hydrogel multilayer capsules. Soft Matter 4:1499–1507
Wattendorf U, Kreft O, Textor M, et al. (2008) Stable stealth function for hollow polyelectrolyte microcapsules through a poly(ethylene glycol) grafted polyelectrolyte adlayer. Biomacromolecules 9:100–108
Zelikin AN, Such GK, Postma A, et al. (2007) Poly(vinylpyrrolidone) for bioconjugation and surface ligand immobilization. Biomacromolecules 8:2950–2953
Quinn JF, Caruso F (2004) Facile tailoring of film morphology. Langmuir 20:20–22
Huang C-J, Chang F-C (2009) Using click chemistry to fabricate ultrathin thermoresponsive microcapsules through direct covalent layer-by-layer assembly. Macromolecules 42: 5155–5166
Johnston APR, Read ES, Caruso F (2005) DNA multilayer films on planar and colloidal supports: sequential assembly of like-charged polyelectrolytes. Nano Lett 5:953–956
Johnston APR, Mitomo H, Read ES, et al. (2006) Compositional and structural engineering of DNA multilayer films. Langmuir 22:3251–3258
Lee L, Johnston APR, Caruso F (2008) Manipulating the salt and thermal stability of DNA multilayer films via oligonucleotide length. Biomacromolecules 9:3070–3078
Johnston APR, Lee L, Wang Y, et al. (2009) Controlled degradation of DNA capsules with engineered restriction-enzyme cut sites. Small 5:1418–1421
Yang SY, Rubner MF (2002) Micropatterning of polymer thin films with pH-sensitive cross-linkable hydrogen-bonded polyelectrolyte multilayers. J Am Chem Soc 124:2100–2101
Yang SY, Lee D, Cohen RE, et al. (2004) Bioinert solution-cross-linked-hydrogen-bonded multilayers on colloidal particles. Langmuir 20:5978–5981
Kozlovskaya VA, Kharlampieva EP, Mansfield ML, et al. (2006) Poly(methacrylic acid) hydrogel films and capsules: response to pH and ionic strength, and encapsulation of macromolecules. Chem Mater 5:328–336
Connal LA, Kinnane CR, Zelikin AN, et al. (2009) Stabilization and functionalization of polymer multilayers and capsules via thiol-ene click chemistry. Chem Mater 21:27–30
Zelikin AN, Quinn JF, Caruso F (2006) Disulfide cross-linked polymer capsules: en route to biodeconstructible systems. Biomacromolecules 7:27–30
Zelikin AN, Li Q, Caruso F (2006) Degradable polyelectrolyte capsules filled with oligonucleotide sequences. Angew Chem Int Ed 45:7743–7745
Becker AL, Zelikin AN, Johnston APR, et al. (2009) Tuning the formation and degradation of layer-by-layer assembled polymer hydrogel microcapsules. Langmuir. doi:10.1021/la901687a
De Rose R, Zelikin AN, Johnston APR, et al. (2008) Binding, internalization, and antigen presentation of vaccine-loaded nanoengineered capsules in blood. Adv Mater 20:4698–4703
Sivakumar S, Bansal V, Cortez C, et al. (2009) Degradable, surfactant-free, monodisperse polymer-encapsulated emulsions as anticancer drug carriers. Adv Mater 21:1820–1824
Kinnane CR, Such GK, Antequera-Garcia G, et al. (2009) Low-fouling poly(N-vinyl pyrollidone) capsules with engineered degradable properties. Biomacromolecules 10:2839–2846
Kohli P, Blanchard GJ (2000) Applying polymer chemistry to interfaces: layer-by-layer and spontaneous growth of covalently bound multilayers. Langmuir 16:4655–4661
Serizawa T, Nanemeki K, Yamanoto K, et al. (2002) Thermoresponsive ultrathin hydrogels prepared by sequential chemical reactions. Macromolecules 35:2184–2189
Such GK, Quinn JF, Quinn A, et al. (2006) Assembly of ultrathin polymer multilayer films by click chemistry. J Am Chem Soc 128:9318–9319
Such GK, Tjipto E, Postma A, et al. (2007) Ultrathin, responsive polymer click capsules. Nano Lett 7:1706–1710
Ochs CJ, Such GK, Stadler B, et al. (2008) Low-fouling, biofunctionalized and biodegradable click capsules. Biomacromolecules 9:3389–3396
Kinnane CR, Wark K, Such GK, et al. (2009) Peptide-functionalized, low-biofouling click multilayers for promoting cell adhesion and growth. Small 5:444–448
Tong W, Gao C, Möhwald H (2006) Single polyelectrolyte microcapsules fabricated by glutaraldehyde-mediated covalent layer-by-layer assembly. Macromol Rapid Commun 27:2078–2083
Ibarz G, Dahne L, Donath E, et al. (2002) Resealing of polyelectrolyte capsules after core removal. Macromol Rapid Commun 23:474–478
Ibarz G, Dahne L, Donath E, et al. (2002) Controlled permeability of polyelectrolyte capsules via defined annealing. Chem Mater 14:4059–4062
Köhler K, Sukhorukov GB (2007) Heat treatment of polyelectrolyte multilayer capsules: a versatile method for encapsulation. Adv Funct Mater 17:2053–2061
Antipov AA, Sukhorukov GB, Leporatti S, et al. (2002) Polyelectrolyte multilayer capsule permeability control. Colloids Surf A 198:535–541
Berth G, Voigt A, Dautzenberg H, et al. (2002) Polyelectrolyte complexes and layer-by-layer capsules from chitosan/chitosan sulfate. Biomacromolecules 3:517–524
White JA, Deen WM (2002) Agarose-dextran gels as synthetic analogs of glomerular basement membrane: water permeability. Biophys J 82:2081–2089
Petrov AI, Volodkin DV, Sukhorukov GB (2005) Protein-calcium carbonate coprecipitation: a tool for protein encapsulation. Biotechnol Progr 21:918–925
Angelatos AS, Johnston APR, Wang Y, et al. (2007) Probing the permeability of polyelectrolyte multilayer capsules via a molecular beacon approach. Langmuir 23:4554–4562
Johnston APR, Caruso F (2005) A molecular beacon approach to measuring the DNA permeability of thin films. J Am Chem Soc 127:10014–10015
Tyagi S, Kramer FR (1996) Molecular beacons: probes that fluoresce upon hybridization. Nat Biotechnol 14:303–308
Lee JF, Stovall GM, Ellington AD (2006) Aptamer therapeutics advance. Curr Opin Chem Biol 10:282–289
Chong SF, Sexton A, De Rose R, et al. (2009) A paradigm for peptide vaccine delivery using viral epitopes encapsulated in degradable polymer hydrogel capsules. Biomaterials 30:5178–5186
Hagerman PJ (1988) Flexibility of DNA. Annu Rev Biophys Biophys Chem 17:265–286
Levicky RL, Herne TM, Tarlov MJ, et al. (1998) Using self-assembly to control the structure of DNA monolayers on gold: a neutron reflectivity study. J Am Chem Soc 120:9787–9792
Zelikin AN, Becker AL, Johnston APR, et al. (2007) A general approach for DNA encapsulation in degradable polymer miocrocapsules. ACS Nano 1:63–69
De Rose R, Zelikin AN, Johnston APR, et al. (2008) Binding, internalization, and antigen presentation of vaccine-loaded nanoengineered capsules in blood. Adv Mater 20:4698–4703
Kozlovskaya VA, Kharlampieva EP, Erel-Unal I, et al. (2009) Single-component layer-by-layer weak polyelectrolyte films and capsules: loading and release of functional molecules. Polym Sci Ser A 51:719–729
Tong W, Gao C, Mohwald H (2008) pH-responsive protein microcapsules fabricated via glutaraldehyde mediated covalent layer-by-layer assembly. Colloid Polym Sci 286:1103–1109
Bédard MF, Braun D, Sukhorukov GB, et al. (2008) Toward self-assembly of nanoparticles on polymeric microshells: near-IR release and permeability. ACS Nano 2:1807–1816
Park MK, Deng S, Advincula R (2004) Permeability and permselectivity control in photo-cross-linkable polyelectrolyte ultrathin films containing ph-switchable and benzophenone functional groups. Polym Mater Sci Eng 90:133–134
Johnston APR, Cortez C, Angelatos AS, et al. (2006) Layer-by-layer engineered capsules and their applications. Curr Opin Colloid Interface Sci 11:203–209
Lvov Y, Antipov AA, Mamedov A, et al. (2001) Urease encapsulation in nanoorganized microshells. Nano Lett 1:125–128
Tiourina OP, Antipov AA, Sukhorukov GB, et al. (2001) Entrapment of alpha-chymotrypsin into hollow polyelectrolyte microcapsules. Macromol Biosci 1:209–214
Caruso F, Trau D, Mohwald H, et al. (2000) Enzyme encapsulation in layer-by-layer engineered polymer multilayer capsules. Langmuir 16:1485–1488
Balabushevitch NG, Sukhorukov GB, Moroz NA, et al. (2001) Encapsulation of proteins by layer-by-layer adsorption of polyelectrolytes onto protein aggregates: factors regulating the protein release. Biotechnol Bioeng 76:207–213
Volodkin DV, Balabushevitch NG, Sukhorukov GB, et al. (2003) Inclusion of proteins into polyelectrolyte microparticles by alternative adsorption of polyelectrolytes on protein aggregates. Biochem-Moscow 68:236–241
Wang Y, Angelatos AS, Caruso F (2008) Template synthesis of nanostructured materials via layer-by-layer assembly. Chem Mater 20:848–858
Wang Y, Price AD, Caruso F (2009) Nanoporous colloids: building blocks for a new generation of structured materials. J Mater Chem 19:6451–6464
Wang Y, Caruso F (2005) Mesoporous silica spheres as supports for enzyme immobilization and encapsulation. Chem Mater 17:953–961
Yu AM, Wang Y, Barlow E, et al. (2005) Mesoporous silica particles as templates for preparing enzyme-loaded biocompatible microcapsules. Adv Mater 17:1737–1741
Yu AM, Gentle I, Lu GQ, et al. (2006) Nanoassembly of biocompatible microcapsules for urease encapsulation and their use as biomimetic reactors. Chem Commun 2150–2152
Volodkin DV, Petrov AI, Prevot M, et al. (2004) Matrix polyelectrolyte microcapsules: new system for macromolecule encapsulation. Langmuir 20:3398–3406
Volodkin DV, Larionova NI, Sukhorukov GB (2004) Protein encapsulation via porous CaCO3 microparticles templating. Biomacromolecules 5:1962–1972
Zhi ZL, Haynie DT (2006) High-capacity functional protein encapsulation in nanoengineered polypeptide microcapsules. Chem Commun 147–149
Srivastava R, Brown JQ, Zhu HG, et al. (2005) Stable encapsulation of active enzyme by application of multilayer nanofilm coatings to alginate microspheres. Macromol Biosci 5:717–727
Mak WC, Bai J, Chang XY, et al. (2009) Matrix-assisted colloidosome reverse-phase layer-by-layer encapsulating biomolecules in hydrogel microcapsules with extremely high efficiency and retention stability. Langmuir 25:769–775
Ciobanu M, Heurtault B, Schultz P, et al. (2007) Layersome: development and optimization of stable liposomes as drug delivery system. Int J Pharm 344:154–157
Germain M, Grube S, Carriere V, et al. (2006) Composite nanocapsules: lipid vesicles covered with several layers of crosslinked polyelectrolytes. Adv Mater 18:2868–2871
Stadler B, Chandrawati R, Goldie K, et al. (2009) Capsosomes: subcompartmentalizing polyelectrolyte capsules using liposomes. Langmuir 25:6725–6732
Stadler B, Chandrawati R, Price AD, et al. (2009) A microreactor with thousands of subcompartments: enzyme-loaded liposomes within polymer capsules. Angew Chem Int Ed 48:4359–4362
Chandrawati R, Stadler B, Postma A, et al. (2009) Cholesterol-mediated anchoring of enzyme-loaded liposomes within disulfide-stabilized polymer carrier capsules. Biomaterials 30:5988–5998
Stein EW, Volodkin DV, McShane MJ, et al. (2006) Real-time assessment of spatial and temporal coupled catalysis within polyelectrolyte microcapsules containing coimmobilized mucose oxiase and peroxidase. Biomacromolecules 7:710–719
Kreft O, Prevot M, Mohwald H, et al. (2007) Shell-in-shell microcapsules: a novel tool for integrated, spatially confined enzymatic reactions. Angew Chem Int Ed 46: 5605–5608
Borodina T, Markvicheva E, Kunizhev S, et al. (2007) Controlled release of DNA from self-degrading microcapsules. Macromol Rapid Commun 28:1894–1899
Price AD, Zelikin AN, Wang Y, et al. (2009) Triggered enzymatic degradation of DNA within selectively permeable polymer capsule microreactors. Angew Chem Int Ed 48:329–332
Ghan R, Shutava T, Patel A, et al. (2004) Enzyme-catalyzed polymerization of phenols within polyelectrolyte microcapsules. Macromolecules 37:4519–4524
Mak WC, Cheung KY, Trau D (2008) Diffusion controlled and temperature stable microcapsule reaction compartments for high-throughput microcapsule-PCR. Adv Funct Mater 18:2930–2937
Price AD, Zelikin AN, Wark KL, et al. (2010) A biomolecular “ship in a bottle”: continuous RNA synthesis within hollow polymer hydrogel assemblies. Adv Mater. 22: 720–723
Stadler B, Price AD, Chandrawati R, et al. (2009) Polymer hydrogel capsules: en route toward synthetic cellular systems. Nanoscale 1:68–73
Wiemann LO, Buthe A, Klein M, et al. (2009) Encapsulation of synthetically valuable biocatalysts into polyelectrolyte multilayer systems. Langmuir 25:618–623
Author information
Authors and Affiliations
Corresponding author
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2010 Springer
About this chapter
Cite this chapter
Price, A.D., Johnston, A.P.R., Such, G.K., Caruso, F. (2010). Reaction Vessels Assembled by the Sequential Adsorption of Polymers. In: Caruso, F. (eds) Modern Techniques for Nano- and Microreactors/-reactions. Advances in Polymer Science, vol 229. Springer, Berlin, Heidelberg. https://doi.org/10.1007/12_2009_44
Download citation
DOI: https://doi.org/10.1007/12_2009_44
Published:
Publisher Name: Springer, Berlin, Heidelberg
Print ISBN: 978-3-642-12872-1
Online ISBN: 978-3-642-12873-8
eBook Packages: Chemistry and Materials ScienceChemistry and Material Science (R0)