Aqueous solutions of microbially produced sodium hyaluronate in phosphate buffered saline (, ) were characterized with regard to their molecular parameters and viscoelastic behavior. The weight-average molar mass , -average radius of gyration , and their distributions were determined using a hyphenated assembly of size exclusion chromatography, multi-angle light scattering, and a differential refractive index detector. Correlation of the obtained results with viscometric data enabled the establishment of and relationships (; ). Viscoelastic behavior was investigated by steady state shear experiments. The viscosity yield was determined for varying concentrations and molar masses using shear rates from to . The elastic behavior in shear flow, represented by the first normal stress difference , has been detected on one hand via rheo-mechanical experiments and on the other hand being correlated from the rheo-optical material functions flow birefringence and its orientation utilizing the stress-optical rule. This correlation enabled the extension of the measurement range toward lower absolute values of of more than two decades. The correlated values were in good agreement with the data obtained by rheo-mechanical measurements.
REFERENCES
1.
Altmann
, S.
, Zeidler
, H.
, Gaffga
, R.
, and Kulicke
, W.-M.
, “Rheology of pathological synovial-fluids. 2. Structural rheology of hyaluronic-acid
,” Rheol. Acta
19
, 642
–659
(1980
).2.
Andersson
, M.
, Wittgren
, B.
, and Wahlund
, K.-G.
, “Accuracy in multiangle light scattering measurements for molar mass and radius estimations. Model calculations and experiments
,” Anal. Chem.
75
, 4279
–4291
(2003
).3.
Berriaud
, N.
, Milas
, M.
, and Rinaudo
, M.
, “Rheological study on mixtures of different molecular weight hyaluronates
,” Int. J. Biol. Macromol.
16
, 137
–142
(1994
).4.
Bothner
, H.
, Waaler
, T.
, and Wik
, O.
, “Limiting viscosity number weight average melocular weight of hyaluronate samples produced by heat degradation
,” Int. J. Biol. Macromol.
10
, 287
–291
(1988
).5.
Brandt
, K. D.
, Block
, J. A.
, Michalski
, J. P.
, Moreland
, L. W.
, Caldwell
, J. R.
, and Lavin
, P. T.
, “Efficacy and safety of intraarticular sodium hyaluronate in knee osteoarthritis. ORTHOVISC study group
,” Clin. Orthop. Relat. Res.
385
, 130
–143
(2001
).6.
Calciu-Rusu
, D.
, Rothfuss
, E.
, Eckelt
, J.
, Haase
, T.
, Dick
, H. B.
, and Wolf
, B. A.
, “Rheology of sodium hyaluronate saline solutions for ophthalmic use
,” Biomacromolecules
8
, 1287
–1292
(2007
).7.
Chabrecek
, P.
, Soltes
, L.
, Kallay
, Z.
, and Novak
, I.
, “Gel permeation chromatographic characterization of sodium hyaluronate and its fractions prepared by ultrasonic degradation
,” Chromatographia
30
, 201
–204
(1990
).8.
Chong
, F. C.
, Blank
, L. M.
, Mclaughlin
, R.
, and Nielsen
, L. K.
, “Microbial hyaluronic acid production
,” Appl. Microbiol. Biotechnol.
66
, 341
–351
(2005
).9.
Clasen
, C.
, and W. M.
Kulicke
, “A convenient way of interpreting steady shear rheo-optical data of semi-dilute polymer solutions
,” Rheol. Acta
40
, 74
–85
(2001
).10.
Clasen
, C.
, and W. M.
Kulicke
, “Rheo-optical studies of barley -beta-glucan solution: Detection of the flow behavior of aggregates in the sol state
,” J. Rheol.
47
, 321
–335
(2003
).11.
Cleland
, R. L.
, and J. L.
Wang
, “Ionic polysaccharides. 3. Dilute solution properties of hyaluronic acid fractions
,” Biopolymers
9
, 799
–810
(1970
).12.
Dick
, B.
, Schwenn
, O.
, and Pfeiffer
, N.
, “Einteilung der viskoelastischen substanzen für die ophthalmochirugie
,” Ophthalmologe
96
, 193
–211
(1999
).13.
Dobrynin
, A. V.
, “Electrostatic persistence length of semiflexible and flexible polyelectrolytes
,” Macromolecules
38
, 9304
–9314
(2005
).14.
Eisner
, G.
, “Grundlage für die praktische Anwendung viskoelastischer Substanzen in der Augenchirugie
,” Fortschr. Ophthalmol.
86
, 19
–22
(1989
).15.
Flory
, P. J.
, and T. G.
, Fox
, Jr., “Treatment of intrinsic viscosities
,” J. Am. Chem. Soc.
73
, 1904
–1908
(1951
).16.
Fouissac
, E.
, Milas
, M.
, and Rinaudo
, M.
, “Shear-rate, concentration, molecular weight, and temperature viscosity dependences of hyaluronate, a wormlike polyelectrolyte
,” Macromolecules
26
, 6945
–6951
(1993
).17.
Fouissac
, E.
, Rinaudo
, M.
, and Borsali
, R.
, “Influence of the ionic strength on the dimensions of sodium hyaluronate
,” Macromolecules
25
, 5613
–5617
(1992
).18.
Fuller
, G. G.
, Optical Rheometry of Complex Fluids
(Oxford University Press
, London
, 1995
).19.
Fuller
, G. G.
, and K. J.
Mikkelsen
, “Optical rheometry using a rotary polarization modulator
,” J. Rheol.
33
, 761
–769
(1989
).20.
Gatej
, I.
, Popa
, M.
, and Rinaudo
, M.
, “Role of the pH on hyaluronan behavior in aqueous solution
,” Biomacromolecules
6
, 61
–67
(2005
).21.
Graessley
, W. W.
, “Entanglement concept in polymer rheology
,” Adv. Polym. Sci.
16
, 179
–226
(1974
).22.
Hamilton
, R. G.
, Strobos
, J.
, and Adkinson
, N. F.
, “Immunogenicity studies of cosmetically administered nonanimal-stabilized hyaluronic acid particles
,” Dermatol. Surg.
33
, 176
–185
(2007
).23.
Hascall
, V. C.
, and D.
Heinegard
, “Aggregation of cartilage proteoglycans. I. Role of hyaluronic acid
,” J. Biol. Chem.
249
, 4232
–4241
(1974a
).24.
Hascall
, V. C.
, and D.
Heinegard
, “Aggregation of cartilage proteoglycans. II. Oligosaccharide competitors of the proteoglycan-hyaluronic acid interaction
,” J. Biol. Chem.
249
, 4242
–4249
(1974b
).25.
Hayashi
, K.
, Tsutsumi
, K.
, Norisuye
, T.
, and Teramoto
, A.
, “Electrostatic contributions to chain stiffness and excluded-volume effects in sodium hyaluronate solutions
,” Polym. J. (Tokyo, Jpn.)
28
, 922
–928
(1996
).26.
Hokputsa
, S.
, Jumel
, K.
, Alexander
, C.
, and Harding
, S. E.
, “A comparison of molecular mass determination of hyaluronic acid using SEC/MALLS and sedimentation equilibrium
,” Eur. Biophys. J.
32
, 450
–456
(2003
).27.
Huggins
, M. L.
, “The viscosity of dilute solutions of long-chain molecules. IV. Dependence on concentration
,” J. Am. Chem. Soc.
64
, 2716
–2718
(1942
).28.
29.
Janeschitz-Kriegl
, H.
, “Flow birefrigence of elastic-viscous polymer systems
,” Adv. Polym. Sci.
6
, 170
(1969
).30.
Janeschitz-Kriegl
, H.
, Polymer Melt Rheology and flow birefringence
(Springer-Verlag
, Berlin
, 1981
).31.
Kogan
, G.
, Soltes
, L.
, Stern
, R.
, and Gemeiner
, P.
, “Hyaluronic acid: A natural biopolymer with a broad range of biomedical and industrial applications
,” Biotechnol. Lett.
29
, 17
–25
(2007
).32.
Krause
, W. E.
, Bellomo
, E. G.
, and Colby
, R. H.
, “Rheology of sodium hyaluronate under physiological conditions
,” Biomacromolecules
2
, 65
–69
(2001
).33.
Kulicke
, W. -M.
and N.
Böse
, “Bestimmung der molmassenverteilung sowie der stabilitätsgrenze von polyacrylamiden unter benutzung einer kombinierten ausschlußchromatographie-kleinwinkel-laser-streulichtphotometer-anlage
,” Colloid Polym. Sci.
262
, 197
–207
(1984
).34.
Kulicke
, W. -M.
, and C.
Clasen
, Viscosimetry of Polymers and Polyelectrolytes
(Springer
, Heidelberg
, 2004
).35.
Kulicke
, W. M.
, and R.
Kniewske
, “The shear viscosity dependence on concentration, molecular-weight, and shear rate of polystyrene solutions
,” Rheol. Acta
23
, 75
–83
(1984
).36.
Laurent
, T. C.
, Ryan
, M.
, and Pietruszkiewicz
, A.
, “Fractionation of hyaluronic acid. Polydispersity of hyaluronic acid from the bovine vitreous body
,” Biochim. Biophys. Acta
42
, 476
–485
(1960
).37.
Lee
, H.
, Kim
, H.
, and Moon
, M. H.
, “Field programming in frit inlet asymmetrical flow field-flow fractionation/multiangle light scattering: Application to sodium hyaluronate
,” J. Chromatogr. A
1089
, 203
–210
(2005
).38.
Li
, M.
, Rosenfeld
, L.
, Vilar
, R. E.
, and Cowman
, M. K.
, “Degradation of hyaluronan by peroxynitrite
,” Arch. Biochem. Biophys.
341
, 245
–250
(1997
).39.
Lodge
, A. S.
, “A network theory of flow birefrigence and stress in concentrated polymer solutions
,” Trans. Faraday Soc.
52
, 120
(1956
).40.
Mendichi
, R.
, Schieroni
, A. G.
, Grassi
, C.
, and Re
, A.
, “Characterization of ultra-high molar mass hyaluronan. 1. Off-line static methods
,” Polymer
39
, 6611
–6620
(1998
).41.
Mendichi
, R.
, Soltes
, L.
, and Schieroni
, A. G.
, “Evaluation of radius of gyration and intrinsic viscosity molar mass dependence and stiffness of hyaluronan
,” Biomacromolecules
4
, 1805
–1810
(2003
).42.
Meyer
, K.
, and J. W.
Palmer
, “The polysaccharide of the vitreous humor
,” J. Biol. Chem.
107
, 629
–634
(1934
).43.
O'Regan
, M.
, Martini
, I.
, Crescenzi
, F.
, DeLuca
, C.
, and Lansing
, M.
, “Molecular mechanisms and genetics of hyaluron biosynthesis
,” Int. J. Biol. Macromol.
16
, 283
–286
(1994
).44.
Orvisky
, E.
, Soltes
, L.
, Chabrecek
, P.
, Novak
, I.
, and Stancikova
, M.
, “Size-exclusion chromatographic characterization of sodium hyaluronate fractions prepared by high energetic sonication
,” Chromatographia
37
, 20
–22
(1993
).45.
Reinhardt
, U.
, “Rheo-optical characterization of the tobacco-mosaic-virus
,” Macromol. Chem. Phys.
196
, 63
–74
(1995
).46.
Rinaudo
, M.
, Roure
, I.
, Milas
, M.
, and Malovikova
, A.
, “Electrostatic interactions in aqueous solutions of ionic polysaccharides
,” Int. J. Polym. Anal. Charact.
4
, 57
–69
(1997
).47.
Rousseaux
, G.
, A.
de Wit
, and M.
Martin
, “Viscous fingering in packed chromatographic columns: Linear stability analysis
,” J. Chromatogr. A
1149
, 254
–273
(2007
).48.
Schittenhelm
, N.
, and W. M.
Kulicke
, “Producing homologous series of molar masses for establishing structure-property relationships with the aid of ultrasonic degradation
,” Macromol. Chem. Phys.
201
, 1976
–1984
(2000
).49.
Soltes
, L.
, Mendichi
, R.
, Lath
, D.
, Mach
, M.
, and Bakos
, D.
, “Molecular characteristics of some commercial high-molecular-weight hyaluronans
,” Biomed. Chromatogr.
16
, 459
–462
(2002
).50.
Terbojevich
, M.
, Cosani
, A.
, Palumbo
, M.
, and Pregnolato
, F.
, “Structural properties of hyaluronic acid in moderately concentrated solutions
,” Carbohydr. Res.
149
, 363
–377
(1986
).51.
Weissmann
, B.
, and K.
Meyer
, “The structure of hyalobiuronic acid and of hyaluronic acid from umbilical cord
,” J. Am. Chem. Soc.
76
, 1753
–1757
(1954
).52.
Wyatt
, P. J.
, “Light scattering and the absolute characterization of macromolecules
,” Anal. Chim. Acta
272
, 1
–40
(1993
).53.
Yanaki
, T.
, and M.
Yamaguchi
, “Shear-rate dependence of the intrinsic viscosity of sodium hyaluronate in 0.2M sodium chloride solution
,” Chem. Pharm. Bull. (Tokyo)
42
, 1651
–1654
(1994
).54.
Zeidler
, H.
, Altmann
, S.
, John
, B.
, Gaffga
, R.
, and Kulicke
, W.-M.
, “Rheologie pathologischer gelenkflüssigkeiten. 1. Weitere ergebnisse zur viskoelastizität
,” Rheol. Acta
18
, 151
–167
(1979
).55.
Zimm
, B. H.
, “The scattering of light and the radial distribution function of high-polymer solutions
,” J. Chem. Phys.
16
, 1093
–1099
(1948
).© 2009 The Society of Rheology.
2009
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