Abstract
Analytical ultracentrifugation is a powerful tool for the determination of thermodynamic, elastic and molecular parameters and structural properties of gels. Although gelling systems are an important class of mixtures, only a few researchers have studied their properties by means of analytical ultracentrifugation. This might be due to the extreme experimental difficulties concerning the detection of the polymer concentration in turbid gels, adhesion problems, etc. Nevertheless, the potential benefit of such experiments has led to several investigations in this field during recent years. These resulted in the introduction of a theoretical treatment of the sedimentation of even multicomponent gels and an improved experimental set-up which allows the characterization of a gel/solvent system in a limited concentration range in a single sedimentation equilibrium experiment. For microgels prepared and crosslinked in emulsions, an interesting rapid sedimentation velocity technique is available for their characterization. This review article describes the capabilities of the experimental method and what has been achieved with it in the past. Furthermore, it gives an outlook on applications which may be possible in the future.
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References
Hinsken H, presented at the 9th Symposium on Analytical Ultracentrifugation, March 1995 in Berlin-Buch (to be published)
Steensgaard J, Humphries S, Spragg P (1992) Measurement of sedimentation coefficients' in Rickwood D. (ed.); Preparative Centrifugation, A practical Approach; Oxford University Press 193
Mc Bain JW, Stuewer RF (1936) Anwendungen des einfachen luftgetriebenen Zentrifugenkreisels auf kolloidchemische Probleme Kolloid-Zeitschrift 74 Heft 1: 10–16
Svedberg T, Pedersen KO (1940) The Ultracentrifuge. Oxford University Press, London pp 29–33 or Svedberg T, Pedersen KO (1940) Die Ultrazentrifuge. Steinkopff Verlag Dresden 26–29
Posnjak E, Freundlich HS (1912) 442–456 in the publication Über den Quellungsdruck; Kolloidchem-Beih 3:417–456
Shaskoua VE, van Holde KE (1958) Graft Copolymers: Synthesis and Characterization; J Polymer Sci 28:395–411
Shaskoua VE, Beaman RG (1958) Microgel: An Idealized Polymer Molecule; J Polymer Sci 33:101–117
Kegeles G, Sia CL (1963) An ultracentrifugal field relaxation method for molecular weights, Biochemistry 2:906–909
Buchdahl R, Ende HA, Peebles LH (1963) Detection of structureal differences in polymers by density gradient ultracentrifugation II: Detection of Microgel; J Polymer Sci Part C No. 1:143–152
Johnson P (1964) A sedimentation study on gel systems; Proc Royal Soc A 278:527–542
Borchard W (1975) Zur Thermodynamik von elastischen Mischphasen; Habilitation, Clausthal 108
Cölfen H, Harding SE (1994) unpublished
Johnson P, Metcalfe JC (1963) Sedimentation studies of gelatin gels; J Photograph Sci 11:214–224
Flory PJ, Garrett RR (1958) Phase transitions in collagen and gelatin systems; J Am Chem Soc 80:4836–4845
Metcalfe JC (1965) A physico-chemical study of gelatin gels. Phd thesis, Cambridge
King RW (1967) Physical and Chemical Studies on Gelatin Gels and Sols. Phd thesis, Cambridge
Johnson P, Metcalfe JC (1967) Physicochemical studies on gelatin gels from soluble and insoluble collagens. Eur Polym J 3:423–447
Johnson P, King RW (1968) Sedimentation studies on gelatin gels; J Photograph Sci 16:82–88
Kegeles G (1968) Reversible pressure-induced gel formation in T-2 bacteriophage DNA, Fed Proc 27:799
Johnson P (1968) Physicochemical studies on strongly interacting systems in Solution properties of natural polymers; Chem Soc Special publication No. 23, Burlington House, London 243–262
Johnson P (1971) Velocity and equilibrium aspects of the sedimentation of agar gels; J Photograph Sci 19:49–54
Johnson P (1972) Velocity and equilibrium aspects of the sedimentation of agar gels in Cox RJ (Ed.) Photographic gelatin; Academic press London, New York 13–27
Cölfen H, Borchard W (1994) Determination of the partial specific volumes of thermoreversible gelatin/water and κ-carrageenan/water gels; Makromol Chem Phys 195:1165–1175
Johnson P, Rainsford KD (1972) The physical properties of mucus: Preliminary observations on the sedimentation behaviour of porcine gastric mucus; Biochim Biophys Acta 286:72–78
Chun PW, Richard AJ, Herschler WP, Krista ML (1973) Ultracentrifugal field relaxation behavior off d-DNA; Biopolymers 12:1931–1935
Borchard W (1975) Über das Quellungsverhalten von Polystyrol verschiedener Netzwerkdichte in Cyclohexan. Progr Colloid Polym Sci 57:39–47
Bloomfield VA (1976) Ultracentrifugal compression of gels. Biopolymers 15: 1243–1249
Babskij VG, S'edin AA (1977) Investigation of gel forming structures by means of Analytical Ultracentrifugation. Khim Biol Nauki 10:926–929
Brian AA, Frisch HL, Lerman LS (1981) Thermodynamics and equilibrium sedimentation analysis of the close approach of DNA molecules and a molecular ordering transition; Biopolymers 20:1305–1328
Richard AJ (1983) Centrifugal field relaxation and ionic strength effects on calf thymus DNA gels; Biopolymers 22:935–943
Scholte TG (1970) Determination of Thermodynamic Parameters of Polymer-Solvent Systems from Sedimenation-Diffusion Equilibrium in the Ultracentrifuge; J Polymer Sci 8, Part A2 841–868
Trohalaki S, Brian AA, Frisch HL, Lerman LS (1984) Scaling of the equilibrium sedimentation distribution in dense DNA solutions Biophys J 45:777–782
Richard AJ (1984) The effects of alkalimetal chlorides and of spermidine and spermine on the swelling pressures of DNA gels in the ultracentrifuge; Biopolymers 23:1307–1313
Richard AJ, Westkaemper RB (1986) Scaled particle theory applied to gels of high molecular weight DNA in the ultracentrifuge; Biopolymers 25:2017–2026
Lange H (1986) Determination of the degree of swelling and crosslinking of extremely small polymer gel quantities by Analytical Ultracentrifugation, Colloid Polym Sci 264:488–493
Flory PJ, Rehner JR (1943) Statistical mechanics of cross-linked polymer networks II: Swelling. J Chem Phys 11:521–526
Holtus G, Borchard W (1989) Swelling pressure equilibrium of physical networks in the field of an analytical ultracentrifuge. Colloid Polym Sci 267: 1133–1138
Holtus G (1990) Untersuchung der Quellungsdruckgleichgewichte von wäßrigen Gelatine-Gelen in einer Analytischen Ultrazentrifuge. Phd thesis, Duisburg
Floßdorf J, Schillig H, Schindler KP (1978) Intermittierende Laserbeleuchtung für die Interferenz und Schlierenoptik einer analytischen Ultrazentrifuge; Makromol Chem 179:1617–1621
Klodwig U, Mächtle W (1989) On-line digitization of Schlieren pictures inside the analytical ultracentrifuge; Colloid Polym Sci 267:1117–1126
Borchard W, Luft B, Reutner P (1986) Mixed Crystal Formation and Glassy Solidification in the System Gelatin-Water; J Photograph Sci 34:132–137
Cölfen H (1991) Untersuchung der thermoreversiblen Gelierung mit Hilfe der Analytischen Ultrazentrifuge; Diploma thesis, Duisburg
Borchard W (1991) Swelling pressure equilibrium of swollen crosslinked systems in an external field. I: Theory; Progr Colloid Polym Sci 86:84–91
Holtus G, Cölfen H, Borchard W (1991) Swelling pressure equilibrium of swollen crosslinked systems in an external field. II: The determination of molecular parameters of gelatin/water gels from the swelling pressure-concentration curves; Progr Colloid Polym Sci 86:92–101
Flory PJ (1942) Thermodynamics of high polymer solutions J Chem Phys 10:51–61
Huggins ML (1943) Thermodynamic properties of solutions of high polymers: The empirical constant in the activity equation; Ann NY Acad Sci 44:431–443
Pouradier J, Venet AM (1950) The structure of gelatin II: Variation of the physical and mechanical properties with molecular weight J Chim Phys 47:391–398
Keese AS (1978) Untersuchungen der thermodynamischen Eigenschaften von wäßrigen Gelatinelösungen mit Hilfe osmotischer Messungen; Diplomarbeit, Clausthal, 49
Pezron I, Herning T, Djabourov M, Leblond J (1990) Scattering from a Biopolymer Solution in the Sol and Gel States: The Gelatin Example In Burchard W and Ross Murphy SB (Eds.) Physical Networks, Polymers and Gels, Elsevier Science Publishers Ltd., London, New York 231–252
Cölfen H, Borchard W (1994) Soluble parts in gelatin/water gels; Acta Polymer 45:325–329
Cölfen H, Borchard W (1991) Swelling pressure equilibrium of swollen crosslinked systems in an external field. III: Unsolved problems concerning the systems gelatin/water and κ-carrageenan/water; Progr Colloid Polym Sci 86:102–110
Müller HG, Schmidt A, Kranz D (1991) Determination of the degree of swelling and crosslinking of latex particles by Analytical Ultracentrifugation; Progr Colloid Polym Sci 86:70–75
Mächtle W (1992) Analysis of Polymer Dispersions with an Eight-Cell-AUC-Multiplexer: High Resolution Particle Size Distribution and Density Gradient Techniques in Harding SE, Rowe AJ and Horton JC. Analytical Ultracentrifugation in Biochemistry and Polymer Science; Royal Society of Chemistry, Cambridge, 147–175
Borchard W, Cölfen H (1992) Characterization of thermoreversible gels by means of sedimentation equilibria; Macromol Chem. Macromol Symp 61:143–164
Michalczyk A (1993) Zeitabhängigkeit des komplexen Schubmoduls und der optischen Drehung während der Gelierung des Systems Gelatine/Wasser im Zusammenhang mit kritischen. Exponenten; Phd thesis, Duisburg, Verlag Köster, Berlin 1994
Hinsken H (1992) Untersuchung der thermoreversiblen Gelierung des Systems κ-Carrageenan/Wasser mit Hilfe der Analytischen Ultrazentrifuge; Diploma thesis, Duisburg
Gilbert GA (1959) Sedimentation and electrophoresis of interacting substances I: Idealized boundary shape for a single substance aggregating reversibly; Proc Roy Soc A 250:377–388
Gilbert GA, Jenkins RCL (1959) Sedimentation and electrophoresis of interacting substances II: Asymptotic boundary shape for two substances interacting reversibly; Proc Roy Soc A253:420–437
De Gennes PG (1975) Scaling concepts in Polymer Physics, Cornell University Press, London
Hinsken H, Borchard W (1995) Continuous swelling pressure equilibria of the system κ-carrageenan/water; Colloid Polym Sci 273:913–925
Borchard W (1994) The sedimentation diffusion equlibrium of a ternary gel; Progr Colloid Polym Sci 94:82–89
Boyer RF, Spencer RS (1948) Some thermodynamic properties of slightly crosslinked Styrene-Divinylbenzene gels; J Polym Sci 3:97–127
Yphantis DA (1964) Equilibrium ultracentrifugation of dilute solutions; Biochemistry 3:297–317
Cölfen H, Borchard W (1994) A modified experimental set-up for sedimentation equilibrium experiments with gels. Part 1: The instrumentation; Progr Colloid Polym Sci 94:90–101
Cölfen H, Borchard W (1994) A modified experimental set-up for sedimentation equilibrium experiments with gels. Part 2: Technical developments; Anal Biochem 219:321–334
Ortlepp B, Panke D (1991) Analytical ultracentrifuges with multiplexer and video systems for measuring particle size and molar mass distributions; Progr Colloid Polym Sci 86:57–61
Yphantis DA (1960) Rapid determination of molecular weights of peptides and proteins; Ann NY Acad Sci 88: 586–601
Cölfen H (1993) Bestimmung thermodynamischer und elastischer Eigenschaften von Gelen mit Hilfe von Sedimentationsgleichgewichten in einer Analytischen Ultrazentrifuge am Beispiel des Systems Gelatine/Wasser; Phd thesis, Duisburg, 1. Auflage Verlag Köster, Berlin 1994
Schuck P (1994) Simultaneous radial and wavelength analysis with the Optima XL-A analytical ultracentrifuge; Progr Colloid Polym Sci 94:1–13
Borchard W, Hermanns B (1984) A new Temperature Measuing Device for Rotating Systems; Angew Makromol Chem 128:189–201
Cölfen H, Holtus G, Borchard W (1993) Multifunctional cell for measurements of temperature, distance, and refractive index as for determining optical calibration factors in rotating systems, Rev Sci Instrum 64(10):2999–3005
Cölfen H, Borchard W (1995) Influence of soluble parts in gelatin/water gels on their network structure in an ultracentrifugal field; Makromol Chem Phys 196 in press
Hinsken H, Selic E, Borchard W (1995) Formation of reversible concentration gradients during the centrifugation of gels; Progr Colloid Polym Sci 99:154–162
Mächtle W, Ley G, Streib J (1995) Studies of microgel formation in aqueous and organic solvents by light scattering and analytical ultracentrifugation; Progr Colloid Polym Sci 99:144–153
Flory PJ (1953) Principles of Polymer Chemistry; Cornell University Press, Ithaka, New York 576
Rowe AJ, Wynne Jones S, Thomas DG, Harding SE (1992) Methods for Off-line Analysis of Sedimentation Velocity and Sedimentation Equilibrium Patterns; In: Harding SE, Rowe AJ, Horton JC (Eds.) Analytical Ultracentrifugation in Biochemistry and Polymer Science; The Royal Society of Chemistry, Cambridge 49–62
Tombs MP, Harding SE (1988) Protein transport processes in the water-water interface in incompatible two phase systems In: Fisher D, Sutherland IA (Eds.) Advances in Separations using Aqueous Phase Systems in Cell Biology and Biotechnology; Plenum Press, New York 229–232
Harding SE, Tombs MP (1989) Protein diffusion through interfaces In: Schwenke KD, Raab B (Eds.) Interactions in Protein Systems, Abhandlungen der Akademie der Wissenschaften der DDR, Akademie-Verlag, Berlin (1989)
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Dedicated to Prof. Dr. W. Borchard on occasion of his 60th birthday
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Cölfen, H. Analytical ultracentrifugation of gels. Colloid Polym Sci 273, 1101–1137 (1995). https://doi.org/10.1007/BF00653080
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DOI: https://doi.org/10.1007/BF00653080