Biomedical applications of electrostatic layer-by-layer nano-assembly of polymers, enzymes, and nanoparticles

Cell Biochemistry and Biophysics

Volumn 39, Issue 1, 2003, Pages 23-43

  Ai, Hua ^a,b   Jones, Steven A ^a   Lvov, Yuri M ^a  

^a Louisiana Tech University   (United States)

^b Case Western Reserve University   (United States)

Author keywords

Layer by layer; Microencapsulation; Micropatterning; Self assembly; Shell; Silicone rubber; Thin films

Indexed keywords

BIOMATERIAL; BIOMIMETIC MATERIAL; DRUG VEHICLE; ENZYME; MICROSPHERE; POLYMER;

ARTIFICIAL MEMBRANE; CHEMISTRY; DRUG DELIVERY SYSTEM; ELECTRICITY; ELECTROCHEMISTRY; GENETIC PROCEDURES; INSTRUMENTATION; METHODOLOGY; NANOTECHNOLOGY; PARTICLE SIZE; PROSTHESES AND ORTHOSES; REVIEW; SYNTHESIS; TRANSDUCER; VEHICLES;

BIOMIMETIC MATERIALS; BIOSENSING TECHNIQUES; COATED MATERIALS, BIOCOMPATIBLE; DRUG DELIVERY SYSTEMS; ELECTROCHEMISTRY; ELECTROSTATICS; ENZYMES; MEMBRANES, ARTIFICIAL; MICROSPHERES; NANOTECHNOLOGY; PARTICLE SIZE; POLYMERS; PROSTHESES AND IMPLANTS; TRANSDUCERS; VEHICLES;

EID: 2142766802     PISSN: 10859195     EISSN: None     Source Type: Journal    
DOI: 10.1385/CBB:39:1:23     Document Type: Review

References (109)

1. Decher, G. (1997) Fuzzy nanoassemblies: Toward layered polymeric multicomposites. Science 227, 1232-1237.
2. Bertrand, P., Jonas, A., Laschevsky, A., and Legras, R. (2000) Ultrathin polymer coating by complexation of polyelectrolytes at interfaces: suitable materials, structure and properties. Macromol. Rapid Commun. 21, 319-348.
3. Lvov, Y. Electrostatic layer-by-layer assembly of proteins and polyions. In Protein Architecture: Interfacial Molecular Assembly and Immobilization Biotechnology (Lvov, Y., and Möhwald, H. M., eds.). Dekker, New York, 2000, pp. 125-167.
4. Lvov, Y., Decher, G., and Möhwald, H. (1993) Assembly, structural characterization and thermal behavior of layer-by-layer deposited ultrathin films of polyvinylsulfate and polyallylamine. Langmuir 9, 481-486.
5. Decher, G., Essler, F., Hong, J. D. Lowack, K., Schmitt, J., and Lvov, L. (1993) Layer-by-layer adsorbed films of polyelectrolytes, proteins or DNA. Polymer Preprints 34, 745-746.
6. Mendelsohn, J. D., Yang, S., Hiller, J., Hochbaum, A. I., and Rubner, M. F. (2003) Rational design of cytophilic and cytophobic polyelectrolyte multilayer thin films. Biomacromolecules 4, 96-106.
7. Elbert, D., Herbert, C., and Hubbell, J. (1999) Thin polymer layers formed by polyelectrolyte multilayer techniques on biological surfaces. Langmuir 15, 5355-5362.
8. Schlenoff, J. Dubas, S., and Farhat, T. (2000) Sprayed polyelectrolyte multilayers. Langmuir 16, 9968-9969.
9. Hua, F., Cui, T., and Lvov, Y. (2002) Lithographic approach to pattern self-assembled nanoparticle multilayers. Langmuir 18, 67123-#6715.
10. Zheng, H., Lee, I., Rubner, M., and Hammond, P. Two component particle arrays on patterned polyelectrolyte multilayer templates. Adv. Mat. 14, 681.
11. Ai, H., Lvov, Y. M., Mills, D. K., Alexander, J. S., and Jones, S. A. (2003) Coating and selective deposition of nanofilm on silicone rubber for endothelial cell adhesion and growth. Cell. Biochem. Biophys., 38, 103-114.
12. Lvov, Y. and Caruso, F. (2001) Biocolloids with ordered urease multilayer shells as enzymatic reactors. Anal. Chem. 73(17), 4212-4217.
13. Fang, M., Grant, P. S., McShane, M., Sukhorukov, G., Golub, V., and Lvov, Y. (2002) Magnetic bio/nanoreactor with multilayer shells of glucose oxidase and inorganic nanoparticles. Langmuir 18, 6338-6344.
14. Ai, H., Fang, M., Jones, S. A., and Lvov, Y. (2002) electrostatic layer-by-layer nanoassembly on biological microtemplates. Platelets Biomacromolecules 3, 560-564.
15. Qiu, X., Leporatti, S., Donath, E., and Möhwald, H. (2001) Studies on the drug release properties of polysaccharide multilayers encapsulated ibuprofen microparticles. Langmuir 17, 5375-5380.
16. Ai, H., Jones, S. A., de Villiers, M. M., and Lvov, Y. (2003) Nano-encapsulation of furosemide microcrystals for controlled drug release. J. Control. Release 89, 59-68.
17. Ho, P., Kim, J., Burroughes, J. H., et al. (2000) Molecular-scale interface engineering for polymer light-emitting diodes. Nature 404, 481-484.
18. Lee, J-K., Mattoussi, H., Yoo, D., Wu, A., and Rubner, M. (1997) Thin film light emitting heterostructures: from conjugated polymers to ruthenium complexes to inorganic nanocrystallites. Polymer Prep. 38, 351-352.
19. Gao, M., Richter, B., and Kirstein, S. (1997) White-light electroluminescent from self-assembled Q-CdS/PPV multilayer structures. Adv. Mater. 9, 802-805.
20. Lvov, Y., Antipov, A. A., Mamedov, A., Möhwald, H., and Sukhorukov G. B. (2001) Urease encapsulation in nanoorganized microshells. Nano. Lett. 1, 125-128.
21. Mao, G., Tsao, Y., Tirrell, M., Davis, H. T., Hessel, V., and Ringsdorf, H. (1995) Interaction, structure, and stability of photoreactive bolaform amphiphile multilayers. Langmuir 11, 942-952.
22. Cheung, J., Fou, A., and Rubner, M. (1994) Molecular self-assembly of conducting polymers. Thin Solid Films 244, 985-989.
23. Kleinfeld, E., and Ferguson, G. (1994) Stepwise formation of multilayered nanostructural films from macromolecular precursors. Science 265, 370-373.
24. He, J-A., Samuelson, L., Li, L., Kumar, J., and Tripathy, S. (1998) Oriented bacteriorhodopsin/polycation multilayers by electrostatic layer-by-layer assembly. Langmuir 14, 1674-1679.
25. Ulman, A. An Introduction to Ultrathin Films, from Langmuir-Blodgett to Self-Assembly. Academic Press, Boston, 1991, pp. 1-440.
26. Sano, M. Lvov, Y. and Kunitake, T. (1996) Formation of ultrathin polymer layers on solid substrates by means of polymerization-induced epitaxy and alternate adsorption. Annu. Rev. Mater. Sci. 26, 153-187.
27. Lvov, Y., Ariga, K., Ichinose, I., and Kunitake, K. (1995) Assembly of multicomponent protein films by means of electrostatic layer-by-layer adsorption. J. Am. Chem. Soc. 117, 6117-6123.
28. Decher, G., Lvov, Y. and Schmitt, J. (1994) Proof of multilayer structural organization of polycation/polyanion self-assembled films. Thin Solid Films 244, 772-777.
29. Yoo, D., Shiratori, S., and Rubner, M. (1998) Controlling bilayer composition and surface wettability of sequentially adsorbed multilayers of weak polyelectrolytes. Macromolecules 31, 4309-4318.
30. Ratner, B. D. (1995) Surface modification of polymers: chemical, biological and surface analytical challenges. Biosens. Bioelectron 10(9-10), 797-804.
31. Ratner, B. D. (1993) New ideas in biomaterials science - a path to engineered biomaterials. J. Biomed. Mater. Res. 27, 837-850.
32. Lvov. Y. and Decher. G. (1994) Assembly of multilayer ordered films by alternating adsorption of oppositely charged macromolecules. Crystallog. Rep. 39, 628-647.
33. Schmitt, J., Grünewald, T., Krajer, K., Pershan, P., Decher, G., and Löshe, M. (1993) The internal structure of layer-by-layer adsorbed polyelectrolyte films: a neutron and X-ray reflectivity study. Macromolecules 26, 7058-7063.
34. Cima, L. G. (1994) Polymer substrates for controlled biological interactions. J. Cell. Biochem. 56, 155-161.
35. Osterberg, E., Bergström, K., Holmberg, K., et al. (1995) Protein-rejecting ability of surface-bound dextran in end-on and side-on configurations: comparison to PEG. J. Biomed. Mater. Res. 29, 741-747.
36. Lvov, Y. Onda, M. Ariga, K., and Kunitake, T. (1998) Ultrathin films of charged polysaccharides assembled alternately with linear polyions. J. Biomater. Sci. Polym. Ed. 9, 345-355.
37. Serizawa, T., Yamaguchi, M., and Akashi, M. (2002) Alternating bioactivity of polymeric layer-by-layer assemblies: anticoagulation vs procoagulation of human blood. Biomacromolecules 3, 724-731.
38. Hogt, A. H., Dankert, J., de Vries, J. A., and Feijen, J. (1983) Adhesion devices of coagulase-negative staphylococci to biomaterials. J. Gen. Microbiol. 129, 1959-1968.
39. An, Y. H., and Friedman, R. J. (1998) Concise review of mechanisms of bacterial adhesion to biomaterial surfaces. J. Biomed. Mater. Res. 43, 338-348.
40. An, Y. H., Bradley, J., Powers, D. L., and Friedman, R. J. (1997) In vivo study of preventing prosthetic infection using cross-linked albumin coating. J. Bone. Joint. Surg. 79, 816-819.
41. Brynda, E. and Houska, M. Ordered multilayer assemblies: albumin/heparin for biocompatible coating and monoclonal antibodies for optical immunosensors. In Protein Architecture: Interfacial Molecular Assembly and Immobilization Biotechnology (Lvov, Y. and Möhwald, H., eds.). Dekker, New York, 2000, pp. 251-286.
42. Willoughby, D. A. ed. First International Workshop on Hyaluronan in Drug Delivery. Windsor, UK, Royal Society of Medicine Press, 1994.
43. Ai, H., Lvov, Y., Mills, D. K., et al. Coating bio-nanofilm on PDMS through layer-by-layer self-assembly. Proceedings of the Second Joint EMBS/BMES Conference, Houston, TX, 2002, pp. 608-609.
44. Verheye, S., Markou, C. P., Salame, M. Y., et al. (2000) Reduced thrombus formation by hyaluronic acid coating of endovascular devices. Arterioscler. Thromb. Vasc. Biol. 20, 1168-1172.
45. Bickel, C., Rupprecht, H. J., Darius, H., et al. (2001) Substantial reduction of platelet adhesion by heparin-coated stents. J. Intervent. Cardiol. 14, 407-413.
46. Maalej, N., Albrecht, R., Loscalzo, J., and Folts, J. D. (1999) The potent platelet inhibitory effects of S-nitrosated albumin coating of artificial surfaces. J. Am. Coll. Cardiol. 33, 1408-1414.
47. Carrozza, J. P. and Baim, D. S. (1995) Thrombotic and hemorrhagic complications of stenting coronary arteries: incidence, management, and prevention. J. Thromb. Thrombolysis 1, 289-297.
48. Galeska, I., Hickey, T., Moussy, F., Kreutzer, D., and Papadimitrakopoulos, F. Characterization and biocompatibility studies of novel humic acids based films as membrane material for an implantable glucose sensor. Biomacromolecules 2, 1249-1255.
49. Bontempo, A. R. and Rapp, J. (1997) Protein-lipid interaction on the surface of a hydrophilic contact lens in vitro. Curr. Eye. Res. 16, 776-781.
50. Maissa, C., Franklin, V., Guillon, M., and Tighe, B. (1998) Influence of contact lens material surface characteristics and replacement frequency on protein and lipid deposition. Optometry Vision. Sci. 75, 697-705.
51. Acton, C., Hoffman, G., McKenna, H., and Moloney, F. (1989) Silicone-induced foreign-body reaction after temporomandibular joint arthroplasty. Case report. Aust. Dent. J. 34, 228-232.
52. Adams, W. P. J., Robinson, J. B. J., and Rohrich, R. J. (1998) Lipid infiltration as a possible biologic cause of silicone gel breast implant aging. Plast. Reconstr. Surg. 101, 64-68.
53. Carmen, R. and Mutha, S. C. (1972) Lipid absorption by silicone rubber heart valve poppets - in-vivo and in-vitro results. J. Biomed. Mater. Res. 6, 327-346.
54. Klemic, K., Klemic, J., Reed, M., and Sigworth, F. (2002) Micromolded PDMS planar electrode allows patch clamp electrical recordings from cells. Biosens. Bioelectron 17, 597-604.
55. Ai, H., Fang, M., Lvov, Y., Mills, D., Alexander, J., and Jones, S. (2002) Coating poly-D-lysine nano-film on PDMS for endothelial cell adhesion and growth. FASEB J. 16(4), A36.
56. Chen, W. and McCarthy, T. J. (1997) Layer-by-layer deposition: a tool for polymer surface modification. Macromolecules 30, 78-86.
57. Levasalmi, J. and McCarthy, T. J. (1997) Poly(4-methyl-1-pentene)- supported polyelectrolyte multilayer films: preparation and gas permeability. Macromolecules 30, 1752-1757.
58. Deutsch, J., Motlagh, D., Russell, B., and Desai, T. A. (2000) Fabrication of microtextured membranes for cardiac myocyte attachment and orientation. J. Biomed. Mater. Res. 53, 267-275.
59. Mata, A., Boehm, C., Fleischman, A. J., Muschler, G., and Roy, S. (2002) Growth of connective tissue progenitor cells on microtextured polydimethylsiloxane surfaces. J. Biomed. Mater. Res. 62, 499-506.
60. Lvov, Y., Decher, G., and Sukhorukov, G. (1993) Assembly of thin films by means of successive deposition of alternate layers of DNA and poly(allylamine). Macromolecules 26, 5396-5399.
61. Decher, G., Lehr, B., Lowack, K., Lvov, Y., and Schmitt, J. New nanocomposite films for biosensors: layer-by-layer adsorbed films of polyelectrolytes, proteins or DNA. Biosens. Bioelectron 9, 677-684.
62. Sukhorukov, G., Möhwald, H., Decher, G., and Lvov, Y. (1996) Layer-by-layer assembly of DNA and polynucleotides films by means of alternate adsorption with polycations. Thin Solid Films 284, 220-223.
63. Kayushina, R., Lvov, Y., Stepina, N., and Khurgin, Y. (1996) Construction and X-ray reflectivity study of self-assembled lysozyme/polyions multilayers. Thin Solid Films 284, 246-248.
64. Onda, M., Lvov, Y., Ariga, K., and Kunitake, T. (1996) Sequential reactions by glucose oxidase/peroxidase molecular films assembled by layer-by-layer alternate adsorption. Biotechnol. Bioeng. 51, 163-166.
65. Onda, M., Lvov, Y., Ariga, K., and Kunitake, T. Sequential reaction and product separation on molecular films of glucoamylase and glucose oxidase assembled on an ultrafilter. J. Ferment. Bioengin. 82, 502-506.
66. Lvov, Y. and Sukhorukov, G. B. (1997) Protein architecture: assembly of ordered films by means of alternated adsorption of oppositely charged macromolecules. Membr. Cell. Biol. 11, 277-303.
67. Kong, W., Wang, L., Gao, M., Zhou, H., Zhang, X., Li, W., and Shen, J. (1994) Immobilized bilayer glucose isomerase in porous trimethylamine polystyrene based on molecular deposition. J. Chem. Soc. Chem. Comm. 11, 1297-1298.
68. Lvov, Y., Ariga, K., and Kunitake, T. (1994) Layer-by-layer assembly of alternate protein/polyion ultrathin films. Chem. Lett. 2323-2326.
69. Kong, J., Lu, Z., Lvov, Y., Desamero, R., Frank, H., and Rusling, J. (1998) Direct electrochemistry of cofactor redox sites in bacterial photosynthetic reaction center protein. J. Am. Chem. Soc. 120, 7371-7372.
70. Kong, J., Sun, W., Wu, X., Deng, J., Lvov, Y., Desamero, R., Frank, H., and Rusling, J. (1999) Fast reversible electron transfer from photosynthetic reaction center from wild type Rhodobacter spheroids reconstituted in polycation sandwiched monolayer film. Bioelectrochem. Bioeng. 48, 101-107.
71. Caruso, F., Niikura, K., Furlong, N., and Okahata, Y. (1997) Assembly of alternating polyelectrolyte and protein multilayer films for immunosensing. Langmuir 13, 3427-3433.
72. Onda, M., Ariga, K., and Kunitake, T. (1999) Activity and stability of glucose oxidase in molecular films assembled alternately with polyions. J. Biosci. Bioeng. 87, 69-75.
73. Singhvi, R., Kumar, A., Lopez, G. P., et al. (1994) Engineering cell shape and function. Science 264, 696-698.
74. Biebuyck, H. A., and Whitesides, G. M. (1994) Self-organization of organic liquids on patterned self-assembled monolayers of alkanethiolates on gold. Langmuir 10, 2790-2793.
75. Chen, K., Jiang, X., Kimerling, L., and Hammond, P. (2000) selective self-organization of coll oids on patterned polyelectrolyte templates. Langmuir 16, 7825-7834.
76. Inerowicz, H. D., Howell, S., Regnier, F. E., and Reifenberger, R. (2002) Multiprotein immunoassay arrays fabricated by microcontact printing. Langmuir 18, 5263-5268.
77. Langer, R. (1998) Drug delivery and targeting. Nature 392, 5-10.
78. Jalil, R., and Nixon, J. R. (1990) Biodegradable poly(lactic acid) and poly(lactide-co-glycolide) microcapsules - problems associated with preparative techniques and release properties. J. Microencapsul. 7(3), 297-325.
79. Wu, X. S. Preparation, characterization, and drug delivery applications of microspheres based on biodegradable lactic/glycolic acid polymers. In Encyclopedic Handbook of Biomaterials and Bioengineering (Wise, et al., eds.). New York: Marcel Dekker, 1995, pp. 1151-1200.
80. Arshady, R. (1991) Preparation of biodegradable microspheres and microcapsules: 2. Polylactides and related polyesters. J. Control. Rel. 17, 1-22.
81. Park, J. W., Hong, K., Kirpotin, D., Papahajopoulos, D., and Benz, C. C. (1997) Immunoliposomes for cancer treatment. Adv. Pharmacol. 40, 399-435.
82. Moya, S., Donath, E., Sukhorukov, G. B., et al. (2000) Lipid coating on polyelectrolyte surface modified colloidal particles and polyelectrolyte capsules. Macromolecules 33, 4538-4544.
83. LaVan, D. A., Lynn, D. M., and Langer, R. (2002) Moving smaller in drug discovery and delivery. Nat. Rev. Drug. Disc. 1, 77-84.
84. Antipov, A., Sukhorukov, G., Donath, E., and Möhwald, H. (2001) Sustained release properties of polyelectrolyte multilayer capsules. J. Phys. Chem. Biol B. 105(12), 2281-2284.
85. Junyaprasert, V., Mitrevej, A., Sinchaipanid, N., Boonme, P., and Wurster, D. (2001) Effect of process variables on the microencapsulation of vitamin A palmitate by gelatin-acacia coacervation. Drug. Dev. Ind. Pharmacol. 27(6), 561-566.
86. Dubin, P., Block, J., Davies, R., Schulz, D., Thies, C., eds. (1995) Macromolecular Complexes in Chemistry and Biology. Springler-Verlag, Berlin, pp. 285-324.
87. Balabushevitch, N. G., Sukhorukov, G. B., Moroz, N. A., et al. (2001) Encapsulation of proteins by layer-by-layer adsorption of polyelectrolytes onto protein aggregates: factors regulating the protein release. Biotechnol. Bioeng. 76(3), 207-213.
88. Donath, E., Sukhorukov, G. B., Caruso, F., Davis, S. A., and Möhwald, H. (1998) Novel hollow polymer shells by colloid-templated assembly of polyelectrolytes. Angew. Chem. Int. Ed. 37(16), 2201-2205.
89. Caruso, F., Caruso, R. A., and Möhwald, H. (1998) Nanoengineering of inorganic and hybrid hollow spheres by colloidal templating. Science 282, 1111-1114.
90. Discher, B. M., Won, Y., Ege, D. S., Lee, J., Bates, F. S., Discher, D. E., and Hammer, D. A. (1999) Polymersomes: tough vesicles made from diblock copolymers. Science 284, 1143-1146.
91. Dinsmore, A., Hsu, M., Nikolaides, M., Marquez, M., Bausch, A., and Weitz, D. (2002) Colloidosomes: selectively permeable capsules composed of colloidal particles. Science 298, 1006-1009.
92. Klitzing, R. V. and Möhwald, H. (1996) A realistic diffusion model for ultrathin polyelectrolyte films. Macromolecules 29, 6901-6906.
93. Ibarz, G., Dahne, L., Donath, E., and Möhwald, H. (2002) Controlled permeability of polyelectrolyte capsules via defined annealing. Chem. Mater. 14, 4059-4062.
94. Sukhorukov, G., Brumen, M., Donath, E., and Möhwald, H. (1999) Hollow polyelectrolyte shells: exclusion of polymers and donnan equilibrium. J. Phys. Chem. Biol. 103, 6434-6440.
95. Sukhorukov, G., Donath, E., Moya, S., Susha, A. S., Voigt, A., Hartmann, J., and Möhwald, H. (2000) Microencapsulation by means of step-wise adsorption of polyelectrolytes. J. Microencapsul. 17, 177.
96. Sukhorukov, G. B., Antipov, A. A., Voigt, A., Donath, E., and Möhwald, H. (2001) pH-controlled macromolecule encapsulation in and release from polyelectrolyte multilayer nanocapsules. Macromol. Rapid Commun. 22, 44-46.
97. Tiourina, O., Antipov, A., Sukhorukov, G., Larionova, N., Lvov, Y., and Möhwald, H. (2001) Entrapment of α-chymotrypsin into hollow polyelectrolyte microcapsules. Macromol. Biosci. 1, 209-214.
98. Antipov, A. A., Sukhorukov, G., Leporatti, S., Radtchenko, I., Donath, E., and Möhwald, H. (2002) Polyelectrolyte multilayer capsule permeability control. Colloid Surface A. 198-200, 535-541
99. Mendelson, J., Barret, C., Chan, V., Pal, A., Mayes, A., and Rubner, M. (2000) Fabrication of microporous thin films from polyelectrolyte multilayers. Langmuir 16, 5017-5023.
100. Tiourina, O. and Sukhorukov, G. (2002) Multilayer alginate / protamine microsized capsules: encapsulation of α-chymotrypsin and controlled release study. Int. J. Pharmacol. 242, 155-161.
101. Bruni, S. and Chang, T. (1989) Hepatocytes immobilised by microencapsulation in artificial cells: effects on hyperbilirubinemia in Gunn rats. Biomater. Artif. Cells. Artif. Organs 17, 403-411.
102. Fremond, B., Joly, A., Desille, M., Desjardins, J., Campion, J., and Clement, B. Cell-based therapy of acute liver failure: the extracorporeal bioartificial liver. Cell. Biol. Toxicol. 12, 325-329.
103. Bader, A., Knop, E., Boker, K., et al. (1995) A novel bioreactor design for in vitro reconstruction of in vivo liver characteristics. Artif. Organs 19, 368-374.
104. Chia, S., Wan, A., Quek, C., et al. (2002) Multilayered microcapsules for cell encapsulation. Biomaterials 23, 849-856.
105. Ai, H., Fang, M., Lvov, Y., Mills, D., and Jones, S. Applications of the electrostatic layer-by-layer self-assembly technique in biomedical engineering. Proceedings of the Second Joint EMBS/BMES Conference, Houston, TX, 2002, pp. 502, 503.
106. Neu B, Voigt A, Mitlohner R, et al. (2001) Biological cells as templates for hollow microcapsules. J. Microencapsul. 18, 385-395.
107. Caruso, F. and Schuler, C. (2000) Enzyme multilayers on colloid particles: assembly, stability, and enzymatic activity. Langmuir 16, 9595-9603.
108. Sukhorukov, G. Designed nano-engineering polymer films on colloidal particles and capsules. In: Novel Methods to Study Interfacial Layers. (Möbius, D., Miller, R., eds.). Elsevier, Amsterdam, 2001, pp. 384-416.
109. Caruso, F., Trau, D., Möhwald, H., and Renneberg, R. (2000) Enzyme encapsulation in layer-by-layer engineered polymer multilayer capsules. Langmuir 16, 1485-1488.