Complex coacervation of proteins and anionic polysaccharides

Current Opinion in Colloid and Interface Science

Volumn 9, Issue 5, 2004, Pages 340-349

  De Kruif, Cornelus G ^a,b   Weinbreck, Fanny ^a   De Vries, Renko ^c  

^a NIZO FOOD RESEARCH   (Netherlands)

^b UTRECHT UNIVERSITY   (Netherlands)

^c WAGENINGEN UNIVERSITY   (Netherlands)

Author keywords

Complex coacervation; Composition; Microencapsulation; Phase behaviour; Protein polysaccharide interactions; Rheology; Structure

Indexed keywords

CHARGE DISTRIBUTION; COACERVATION; DELOCALIZATION;

COLLOIDS; ENCAPSULATION; ENTROPY; NEGATIVE IONS; PHASE SEPARATION; POLYMERS; POLYSACCHARIDES; VISCOSITY;

PROTEINS;

POLYSACCHARIDE; PROTEIN DERIVATIVE;

COACERVATION; COLLOID; CORRELATION ANALYSIS; DIFFUSION; DILUTION; ELASTICITY; ENCAPSULATION; ENTROPY; FLOW KINETICS; GAS; LIQUID; PHASE SEPARATION; PRECIPITATION; PROTEIN ANALYSIS; PROTEIN STRUCTURE; REVIEW; VISCOSITY;

EID: 9944250034     PISSN: 13590294     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.cocis.2004.09.006     Document Type: Review

References (90)

1. IUPAC compendium of Chemical Technology 1997.
2. H.G. Bungenberg de Jong, and H.R. Kruyt Coacervation (partial miscibility in colloid systems) Proc. K. Ned. Akad. Wet. 32 1929 849 856
3. F.W.Z. Tiebackx Gleichzeitige Ausflockung zweier Kolloide Chem. Ind. Kolloide 8 1911 198 201
4. J.T.G. Overbeek, and M.J. Voorn Phase separation in polyelectrolyte solutions. Theory of complex coacervation J. Cell. Comp. Physiol. 49 1 1957 7 26
5. A. Veis, and C. Aranyi Phase separation in polyelectrolyte systems. I. Complex coacervates of gelatine J. Phys. Chem. 64 1960 1203 1210
6. A. Veis Phase separation in polyelectrolyte solutions. II. Interaction effects J. Phys. Chem. 65 1961 1798 1803
7. A. Veis Phase separation in polyelectrolyte systems. III. Effect of aggregation and molecular weight heterogeneity J. Phys. Chem. 67 1963 1960 1964
8. A. Veis, E. Bodor, and S. Mussell Molecular weight fractionation and the self-suppression of complex coacervation Biopolymers 5 1967 37 59
9. A. Nakajima, and H. Sato Phase relationships of an equivalent mixture of sulfated polyninyl alcohol and aminoacetalyzed polyvinyl alcohol in microsalt aqueous solution Biopolymers 10 1972 1345 1355
10. K. Tainaka Study of complex coacervation in low concentration by virial expansion method. I. Salt free systems J. Phys. Soc. Jpn. 46 6 1979 1899 1906
11. K. Tainaka Effect of counterions on complex coacervation Biopolymers 19 1980 1289 1298
12. B.K. Green, L. Schleicher, Manifold Record Material, US Patent Application 2 730 456, The National Cash Register, 1956.
13. B.K. Green, L. Schleicher, Oil-Containing Microscopic Capsules and Method of Making Them. US Patent Application 2 800 457, The National Cash Register, 1957.
14. C. Schmitt, C. Sanchez, S. Desobry-Banon, and J. Hardy Structure and technofunctional properties of protein-polysaccharide complexes: a review Crit. Rev. Food Sci. Nutr. 38 8 1998 689 753
15. S.L. Turgeon, M. Beaulieu, C. Schmitt, and C. Sanchez Protein-polysaccharide interactions: phase-ordering kinetics, thermodynamic and structural aspects Curr. Opin. Colloid Interface Sci. 8 4-5 2003 401 414 Excellent review on the protein-polysaccharide interactions including complex coacervation and thermodynamic incompatibility. Important issues such as the kinetics and the structural transitions and characteristics of associative phase separation were addressed. A long list of references is available.
16. H.G. Bungenberg de Jong Crystallisation-coacervation-flocculation H.R. Kruyt Colloid Science vol. II 1949 Elsevier Publishing Amsterdam 232 258 Chapter VIII
17. V. Ball, M. Winterhalter, P. Schwinte, P. Lavalle, J.C. Voegel, and P. Schaaf Complexation mechanism of bovine serum albumin and poly(allylamine hydrocolloid) J. Phys. Chem. 106 2002 2357 2364 Interesting paper on the calorimetry of BSA and a synthetic polyamine. The authors discuss the origin of the measured endothermal heat of complexation, which disappears at high salt concentration.
18. H. Dautzenberg Polyelectrolyte complex formation and highly aggregating systems: methodical aspects and general tendencies T. Radeva Physical Chemistry of Polyelectrolytes Surfactant Science Series vol. 99 2001 Marcel Dekker New York 743 792 A review chapter that discusses several experimental techniques and summarizes in a systematical way many of the earlier findings and results.
19. M. Girard, S.L. Turgeon, and S.F. Gauthier Thermodynamic parameters of β-lactoglobulin-pectin complexes assessed by isothermal titration calorimetry J. Agric. Food Chem. 51 2003 4450 4455 The authors study the interaction free energy of complexation by analysing isothermal titration calorimetry results. The system used is at very low ionic strength. The measured heat of complexation is exothermal.
20. K. Kaibara, T. Okazaki, H.B. Bohidar, and P.L. Dubin pH-induced coacervation in complexes of bovine serum albumine and cationic polyelectrolytes Biomacromolecules 1 2000 100 107
21. F. Weinbreck, H. Nieuwenhuijse, G.W. Robijn, and C.G. de Kruif Complexation of whey proteins with carrageenan J. Agric. Food Chem. 52 2004 3550 3555
22. T. Matsudo, K. Ogawa, and E. Kokufuta Intramolecular complex formation of poly(N-isopropylacrylamide) with human serum albumin Biomacromolecules 4 2003 728 735 A light scattering study on the complex formation of HAS with a synthetic polyamide. The results clearly indicate the formation of intramolecular complexes. The polyamide is an uncharged polymer, but the results show that solvent quality is of importance as well and as a result complexation is temperature dependent.
23. T. Matsudo, K. Ogawa, and E. Kokufuta Complex formation of protein with different water-soluble synthetic polymers Biomacromolecules 4 2003 1794 1799
24. D.J. Burgess, and J.E. Carless Microelectrophoretic studies of gelatin and acacia for the prediction of complex coacervation J. Colloid Interface Sci. 98 1 1984 1 8
25. C. Schmitt, C. Sanchez, F. Thomas, and J. Hardy Complex coacervation between β-lactoglobulin and acacia gum in aqueous media Food Hydrocoll. 13 1999 483 496
26. S. Girod, M. Boissière, K. Longchambon, S. Begu, C. Tourne-Pétheil, and J.M. Devoiselle Polyelectrolyte complex formation between iota-carrageenan and poly(l-lysine) in dilute aqueous solutions: a spectroscopic and conformational study Carbohydr. Polym. 55 2004 37 45
27. E. Seyrek, P.L. Dubin, C. Tribet, and E.A. Gamble Ionic strength dependence of protein-polyelectrolyte interactions Biomacromolecules 4 2003 273 282
28. W. Poon, P. Pusey, and H. Lekkerkerker Colloids in suspense Phys. World 1996 (April)
29. K.W. Mattison, I.J. Brittain, and P.L. Dubin Protein-polyelectrolyte phase boundaries Biotechnol. Prog. 11 1995 632 637
30. F. Weinbreck, H.S. Rollema, R.H. Tromp, and C.G. de Kruif Diffusivity of whey protein and gum arabic in their coacervates Langmuir 20 2004 6389 6395 First paper dealing with the diffusion of the polymers inside the coacervate phase. Three complementary techniques were used (e.g. nuclear magnetic resonance, fluorescence recovery after photobleaching and diffusing wave spectroscopy) and showed that the diffusion of the polymer was the slowest at the pH of maximum electrostatic interaction. It was also found that the protein and the polysaccharide moved independently in the coacervate phase (the protein faster than the polysaccharide). With time, it seemed that the coacervate phase rearranged to form a more homogeneous and transparent phase.
31. F. Weinbreck, R.H. Tromp, and C.G. de Kruif Composition and structure of whey protein/gum arabic coacervates Biomacromolecules 5 2004 1437 1445
32. D. Leisner, and T. Imae Interpolyelectrolyte complex and coacervate formation of poly(glutamic acid) with a dendrimer studied by light scattering and SAXS J. Phys. Chem., B 107 2003 8078 8087
33. M. Girard, S.L. Turgeon, and S.F. Gauthier Interbiopolymer complexing between β-lactoglobulin and low- and high-methylated pectin measured by potentiometric titration and centrifugation Food Hydrocoll. 16 2002 585 591
34. M. Girard, S.L. Turgeon, and P. Paquin Emulsifying properties of whey protein-carboxymethylcellulose complexes J. Food Sci. 67 1 2002 113 119
35. M. Girard, S.L. Turgeon, and S.F. Gauthier Quantification of the interactions between β-lactoglobulin and pectin through capillary electrophoresis analysis J. Agric. Food Chem. 51 2003 6043 6049
36. M. Girard, C. Sanchez, S.I. Laneuville, S.L. Turgeon, and S.F. Gauthier Associative phase separation of β-lactoglobulin/pectin solutions: a kinetic study by small angle static light scattering Colloids Surf., B Biointerfaces 35 2004 15 22
37. F. Weinbreck, H. Nieuwenhuijse, G.W. Robijn, and C.G. de Kruif Complex formation of whey proteins-exocellular polysaccharide EPS B40 Langmuir 19 2003 9404 9410
38. A.B. Kayitmazer, E. Seyrek, P.L. Dubin, and B.A. Staggemeier Influence of chain stiffness on the interaction of polyelectrolyte with oppositely charged micelles and proteins J. Phys. Chem., B 107 2003 8158 8165
39. T.V. Burova, N.V. Grinberg, V.Ya. Grinberg, C.G. de Kruif, Conformational changes in κ- and ι-carrageenans induced by complexing with β-casein. Submitted for publication 2004.
40. D.J. Burgess Complex coacervation: microcapsule formation P.L. Dubin Macromolecular Complexes in Chemistry and Biology 1994 Springer Verlag Berlin 285 300 Chapter 17
41. A.N. Gurov, and P.V. Nuss Protein-polysaccharide complexes as surfactants Die Nahrung 30 3-4 1986 349 353
42. C. Thomassin, H.P. Merkle, and B.A. Gander Physico-chemical parameters governing protein microencapsulation into biodegradable polyesters by coacervation Int. J. Pharm. 147 1997 173 186
43. R.I. Baeza, D.J. Carp, O.E. Pérez, and A.M.R. Pilosof κ-Carrageenan-protein interactions: effect of proteins on polysaccharide gelling and textural properties Lebensm.-Wiss. Technol. 35 2002 741 747
44. M.M. Ould Eleya, and S.L. Turgeon Rheology of κ-carrageenan and β-lactoglobulin mixed gels Food Hydrocoll. 14 2000 29 40
45. M.M. Ould Eleya, and S.L. Turgeon The effects of pH on the rheology of β-lacglobulin/κ-carrageenan mixed gels Food Hydrocoll. 14 2000 245 251
46. I. Haug, M.A.K. Williams, L. Lundin, O. Smidsrød, and K.I. Draget Molecular interactions in, and rheological properties of, a mixed biopolymer system undergoing order/disorder transitions Food Hydrocoll. 17 2003 439 444
47. F. Weinbreck, R.H.W. Wientjes, H. Nieuwenhuijse, G.W. Robijn, and C.G. de Kruif Rheological properties of whey protein/gum arabic coacervates J. Rheol. 2004 (in press) One of the first papers dealing with the rheological properties of the coacervate phase itself. The effect of electrostatic interactions were investigated by comparing the viscosity of mixtures of biopolymers at the same concentration as in the coacervate phase but at pH=7 at which no interaction took place. The pH played a major role in the viscosity of the coacervate. The results showed that the coacervate phase was very viscous in nature, as compared to the blank that were elastic. The coacervate phase was only slightly shear thinning at low shear rates, but showed some hysteresis and thexotropic behavior. With time, the initial viscosity was completely recovered, showing the dynamics of the system. The viscosity of the coacervate could be directly related to the strength of the electrostatic interactions.
48. M.J. Voorn Complex coacervation Recl. Trav. Chim. Pays-Bas 75 4 1956 317 330
49. V. Yu Borue, and I. Ya Erukhimovich A Statistical theory of weakly charged polyelectrolytes: fluctuations, equation of state, and microphase separation Macromolecules 21 1988 3240 3249
50. V. Yu Borue, and I. Ya Erukhimovich A statistical theory of globular polyelectrolyte complexes Macromolecules 23 1990 3625 3632
51. M. Castelnovo, and J.-F. Joanny Complexation between oppositely charged polyelectrolytes: beyond the random phase approximation Eur. Phys. J., E Soft Matter 6 2001 377 386
52. A. Kudlay, and M. Olvera de la Cruz Precipitation of oppositely charged polyelectrolytes in salt solutions J. Chem. Phys. 120 2004 404 412
53. P.M. Biesheuvel, and M.A. Cohen Stuart Electrostatic free energy of weakly charged macromolecules in solution and intermolecular complexes consisting of oppositely charged polymers Langmuir 20 2004 2785 2791
54. P.M. Biesheuvel, and M.A. Cohen Stuart Cylindrical cell model for the electrostatic free energy of polyelectrolyte complexes Langmuir 20 2004 4764 4770 Poisson-Boltzmann cell model with separate cells for polycations and polyanions. Provided suitable boundary conditions can be found that accurately mimic the arrangement of the polycations and polyanions in the complex coacervates, this approach could lead to accurate predictions for phase behavior in other kinds of systems as well.
55. R.J Allen, and P.B. Warren Complexation and phase behavior of oppositely charged polyelectrolyte/macroion systems Langmuir 20 2004 1997 2009 Very clear discussion of phase behavior of systems with complex coacervation. Classic self-consistent field theory for polyelectrolyte adsorption is applied to compute phase diagrams for mixtures of spherical macroions and oppositely charged flexible polyelectrolytes.
56. T.T Nguyen, and B.I. Shklovskii Complexation of a polyelectrolyte with oppositely charged spherical macroions: giant inversion of charge J. Chem. Phys. 114 2001 5905 5916 For a single charged chain complexed with multiple oppositely charged spheres, the authors estimate the correlation attraction between complexed spheres that leads to chain collapse for nearly neutral complexes. The same attraction exists between single chain complexes and leads to complex coacervation.
57. R. de Vries Monte Carlo simulations of flexible polyanions complexing with whey proteins at their isoelectric point J. Chem. Phys. 120 2004 3475 3481
58. F. Xing, G. Cheng, B. Yang, and L. Ma Microencapsulation of capsaicin by the complex coacervation of gelatin, acacia and tannins J. Appl. Polym. Sci. 91 4 2004 2669 2675
59. K.S. Mayya, A. Bhattacharyya, and J.F. Argillier Micro-encapsulation by complex coacervation: influence of surfactant Polym. Int. 52 2003 644 647
60. G. Strauss, and S.M. Gibson Plant phenolics as cross-linkers of gelatine gels and gelatine-based coacervates for use as food ingredients Food Hydrocoll. 18 2004 81 89 Plant-derived polyphenols and flavonoids were found to be suitable for cross-linking gelatin and gelatin-based coacervates. This new food-grade cross-linker could be a good alternative to the use of glutaraldehyde in microencapsulation using complex coacervation.
61. J. Lazko, Y. Popineau, D. Renard, and J. Legrand Microcapsules based on glycinin-sodium dodecyl sulfate complex coacervation J. Microencapsul 21 1 2004 59 70 Systematic study on a new polymer system used for microencapsulation based on soy glycinin (a soybean storage protein)-sodium dodecyl sulfate (SDS). SDS formed a complex with glycinin and allowed precipitation of the protein at the oil surface. The precipitated state of the protein enhanced cross-linking efficiency with glutaraldehyde.
62. R.T. Thimma, and S. Tammishetti Study of complex coacervation of gelatin with sodium carboxymethyl guar gum: microencapsulation of clove oil and sulphamethoxazole J. Microencapsul 20 2 2003 203 210
63. V. Ducel, J. Richard, P. Saulnier, Y. Popineau, and F. Boury Evidence and characterization of complex coacervates containing plant proteins: applications to the microencapsulation of oil droplets Colloids Surf., A Physicochem. Eng. Asp. 232 2004 239 247 A first extensive study on complex coacervation involving plant proteins. The physicochemical conditions (pH and ratio) under which a coacervate was formed between protein (α gliadin or pea globulin)/polysaccharide (gum arabic or carboxymethyl cellulose) was investigated using pertinent tools like ζ potential and turbidity measurements. Optimum coacervation pH was found to be rather low (pH∼3) as compared to other proteins like gelatin or whey proteins. Encapsulation of oil was achieved using these systems and the morphology of the coacervate studied. The steric conformation of the biopolymers forming the complex was a key parameter determining the ability of the coacervates to encapsulate oil droplets. Coacervation should be promoted rather than precipitation for obtaining good capsules.
64. L. Zhang, J. Guo, X. Peng, and Y. Li Preparation and release behaviour of carboxymethylated chitosan/alginate microspheres encapsulating bovine serum albumin J. Appl. Polym. Sci. 92 2004 878 882
65. X. Yu, Y. Li, and D. Wu Microencapsulation of tannase by chitosan-alginate complex coacervate membrane: synthesis of antioxidant propyl gallate in biphasic media J. Chem. Technol. Biotechnol. 79 2004 475 479
66. C. Peniche, I. Howland, O. Carrillo, C. Zaldívar, and W. Argüelles-Monal Formation and stability of shark liver oil loaded chitosan/calcium alginate capsules Food Hydrocoll. 18 2004 865 871
67. D.J. Burgess, K.K. Kwok, and P.T. Megremis Characterization of albumin-acacia complex coacervation J. Pharm. Pharmacol. 43 1991 232 236
68. D.J. Burgess, and O.N. Singh Spontaneous formation of small sized albumin/acacia coacervate particles J. Pharm. Pharmacol. 45 1993 586 591
69. N.A. Elgindy, and M.A. Elegakey Carbopol-gelatin coacervation: influence of some variable Drug Dev. Ind. Pharm. 7 1981 587 603
70. 2+ Food Hydrocoll. 17 2003 723 737
71. C.Y. Lii, S.C. Liaw, V.M.F. Lai, and T. Tomasik Xanthan gum-gelatin complexes Eur. Polym. J. 38 2002 1377 1381
72. H.J.W. Peters, E.M.G. van Bommel, and J.G. Fokkens Effect of gelatin properties in complex coacervation processes Drug Dev. Ind. Pharm. 18 1 1992 123 134
73. M. Kazmiersi, L. Wicker, and M. Corredig Interactions of β-lactoglobulin and high-methoxyl pectins in acidified systems J. Food Sci. 68 5 2003 1673 1679
74. S.I. Laneuville, P. Paquin, and S.L. Turgeon Effect of preparation conditions on the characteristics of whey proteins-xanthan gum complexes Food Hydrocoll. 14 2000 305 314
75. C. Sanchez, S. Despond, C. Schmitt, and J. Hardy Effect of heat and shear on β-lactoglobulin-acacia gum complex coacervation E. Dickinson R. Miller Food Colloids, Fundamentals of Formulation 2001 Royal Society of Chemistry Cambridge 332 341
76. C. Sanchez, G. Mekhloufi, C. Schmitt, D. Renard, P. Robert, C.M. Lehr, A. Lamprecht, and J. Hardy Self-assembly of β-lactoglobulin and acacia gum in aqueous solvent: structure and phase-ordering kinetics Langmuir 18 2002 10323 10333
77. C. Sanchez, and D. Renard Stability and structure of protein- polysaccharide coacervates in the presence of protein aggregates Int. J. Pharm. 242 2002 319 324
78. C. Schmitt, C. Sanchez, D. Despond, D. Renard, F. Thomas, and J. Hardy Effect of protein aggregates on the complex coacervation between β-lactoglobulin and acacia gum at pH 4.2 Food Hydrocoll. 14 2000 403 413
79. C. Schmitt, C. Sanchez, D. Despond, D. Renard, P. Robert, and J. Hardy Structural modification of β-lactoglobulin as induced by complex coacervation with acacia gum E. Dickinson R. Miller Food Colloids, Fundamentals of Formulation 2001 Royal Society of Chemistry Cambridge 323 331
80. C. Schmitt, C. Sanchez, A. Lamprecht, D. Renard, C.M. Lehr, C.G. de Kruif, and J. Hardy Study of β-lactoglobulin/acacia gum complex coacervation by diffusing-wave spectroscopy and confocal scanning laser microscopy Colloids Surf., B Biointerfaces 20 2001 267 280
81. M. Vikelouda, and V. Kiosseoglou The use of carboxymethylcellulose to recover potato proteins and control their functional properties Food Hydrocoll. 18 2004 21 27
82. F. Weinbreck, R. de Vries, P. Schrooyen, and C.G. de Kruif Complex coacervation of whey proteins and gum arabic Biomacromolecules 4 2 2003 293 303
83. I.G. Plashchina, T.A. Mrachkovskaya, A.N. Danilenko, G.O. Kozhevnikov, N.Y. Starodubrovskaya, E.E. Braudo, and K.D. Schwenke Complex formation of Faba bean legumin with chitosan: surface activity and emulsion properties of complexes E. Dickinson R. Miller Food Colloids, Fundamentals of Formulation 2001 Royal Society of Chemistry Cambridge 332 341
84. X.L. Yan, E. Khor, and L.Y. Lim PEC films prepared from chitosan-alginate coacervates Chem. Pharm. Bull. 48 7 2000 941 946
85. X.L. Yan, E. Khor, and L.Y. Lim Chitosan-alginate films prepared with chitosan at different molecular weights J. Biomed. Mater. Res. 58 4 2001 358 365
86. E.V. Shumilina, and Y.A. Shchipunov Chitosan-carrageenan gels Colloid J. 64 2002 372 378
87. U.A. Antonov, and M.P. Gonçalves Phase separation in aqueous gelatin-κ carrageenan systems Food Hydrocoll. 13 1999 517 524
88. V.B. Galazka, D. Smith, D.A. Ledward, and E. Dickinson Complexes of bovine serum albumin with sulfated polysaccharides: effects of pH, ionic strength and high pressure treatment Food Chem. 64 1999 303 310
89. A.N. Gurov, N.V. Gurova, A.L. Leontiev, and V.B. Tolstoguzov Equilibrium and non-equilibrium complexes between bovine serum albumin and dextran sulphate: I. Complexing conditions and composition of non-equilibrium complexes Food Hydrocoll. 2 4 1988 267 283
90. M.V. Fogle, G. Hörger, Encapsulation process by complex coacervation using inorganic polyphosphates and organic hydrophilic polymeric material. US Patent 3, 697, 437. National Cash Register, 1972.