Viscosity Measurements of the Freeze Concentration Solution Confined in the Space Surrounded by Ice Crystals

  • Arinori InagawaEmail author
Part of the Springer Theses book series (Springer Theses)


In this chapter, the viscosities of the FCS in frozen glycerol/water solutions are evaluated by two spectrometric methods of different principles: (1) the reaction rate of the diffusion-controlled emission quenching and (2) fluorescence correlation (FCor) spectroscopy (Inagawa et al. in J Phys Chem C 121:12321–12328, 2017 [1]). Thermodynamics indicates that the concentration of glycerol in the FCS is constant at a constant temperature, regardless of the glycerol concentration in the original solution before freezing (\(c_{\text{gly}}^{\text{ini}}\)). However, the viscosity of the FCS measured at a given temperature increases with decreasing \(c_{\text{gly}}^{\text{ini}}\) and becomes more pronounced with decreasing measurement temperature. Further, the viscosity of the FCS in a rapidly frozen solution is higher than that observed in a slowly frozen solution. These results suggest that the viscosity of the FCS depends on the size of the space in which the FCS is confined and increases in smaller spaces. This result agrees well with several reports of anomalous phenomena in a microspace confined in ice. These phenomena originate from the fluctuation of the ice/FCS interface, which is macroscopically stable but microscopically dynamic and undergoes continuous freezing and thawing. Thus, the FCS near the interface displays ice-like physicochemical properties and structures, thereby affording higher viscosity than the corresponding bulk solution.


Viscosity Freeze-concentrated solution Ruthenium complex Quenching Fluorescence correlation spectroscopy Rhodamine 6G Phase transition Interfacial fluctuation 


  1. 1.
    Inagawa A, Ishikawa T, Kusunoki T, Harada M, Otsuka T, Okada T (2017) Viscosity of freeze-concentrated solution confined in micro/nanospace surrounded by ice. J Phys Chem C 121:12321–12328Google Scholar
  2. 2.
    Liu L, Faraone A, Mou CY, Yen CW, Chen SH (2004) Slow dynamics of supercooled water confined in nanoporous silica materials. J Phys Condens Matter 16(45):S5403–S5436Google Scholar
  3. 3.
    Suzuki A, Yui H (2014) Crystallization of confined water pools with radii greater than 1 nm in AOT reverse micelles. Langmuir 30(25):7274–7282PubMedGoogle Scholar
  4. 4.
    Rasaiah JC, Garde S, Hummer G (2008) Water in nonpolar confinement: from nanotubes to proteins and beyond. Annu Rev Phys Chem 59:713–740PubMedGoogle Scholar
  5. 5.
    Yamaguchi A, Namekawa M, Itoh T, Teramae N (2012) Microviscosity of supercooled water confined within aminopropyl-modified mesoporous silica as studied by time-resolved fluorescence spectroscopy. Anal Sci 28(11):1065–1070PubMedGoogle Scholar
  6. 6.
    Koga K, Zeng XC, Tanaka H (1998) Effects of confinement on the phase behavior of supercooled water. Chem Phys Lett 285:278–283Google Scholar
  7. 7.
    Bergman R, Swenson J (2000) Dynamics of supercooled water in confined geometry. Nature 403:283–286 PubMedGoogle Scholar
  8. 8.
    Giovambattista N, Rossky PJ, Debenedetti PG (2006) Effect of pressure on the phase behavior and structure of water confined between nanoscale hydrophobic and hydrophilic plates. Phys Rev E 73:0401604Google Scholar
  9. 9.
    Bai J, Zeng XC (2012) Polymorphism and polyamorphism in bilayer water confined to slit nanopore under high pressure. Proc Natl Acad Sci 109(52):21240–21245PubMedGoogle Scholar
  10. 10.
    Kimmel GA, Matthiesen J, Baer M, Mundy CJ, Petrik NG, Smith RS, Dohnálek Z, Kay BD (2009) No confinement needed: observation of a metastable hydrophobic wetting two-layer ice on graphene. J Am Chem Soc 131(35):12838–12844PubMedGoogle Scholar
  11. 11.
    Tsukahara T, Hibara A, Ikeda Y, Kitamori T (2007) NMR study of water molecules confined in extended nanospaces. Angew Chem Int Ed 46:1180–1183Google Scholar
  12. 12.
    Tsukahara T, Mizutani W, Mawatari K, Kitamori T (2009) NMR studies of structure and dynamics of liquid molecules confined in extended nanospaces. J Phys Chem B 113(31):10808–10816PubMedGoogle Scholar
  13. 13.
    Ponjavic A, Dench J, Morgan N, Wong JSS (2015) In situ viscosity measurement of confined liquids. RSC Adv 5(121):99585–99593Google Scholar
  14. 14.
    Han J, Herzfeld J (1993) Macromolecular diffusion in crowded solutions. Biophys J 65(3):1155–1161PubMedPubMedCentralGoogle Scholar
  15. 15.
    Luby-Phelps K (1994) Physical properties of cytoplasm. Curr Opin Cell Biol 6(1):3–9PubMedGoogle Scholar
  16. 16.
    Shawn Goodwin J, Drake KR, Remmert CL, Kenworthy AK (2005) Ras diffusion is sensitive to plasma membrane viscosity. Biophys J 89(2):1398–1410PubMedPubMedCentralGoogle Scholar
  17. 17.
    Deliconstantinos G, Villiotou V, Stavrides J (1995) Modulation of particulate nitric-oxide synthase activity and peroxynitrite synthesis in cholesterol-enriched endothelial-cell membranes. Biochem Pharmacol 49(11):1589–1600PubMedGoogle Scholar
  18. 18.
    Nadiv O, Shinitzky M, Manu H, Hecht D, Roberts CT, LeRoith D, Zick Y (1994) Elevated protein tyrosine phosphatase activity and increased membrane viscosity are associated with impaired activation of the insulin receptor kinase in old rats. Biochem J 298(Pt 2):443–450PubMedPubMedCentralGoogle Scholar
  19. 19.
    Zubenko G, Kopp U, Seto T, Firestone L (1999) Platelet membrane fluidity individuals at risk for Alzheimer’s disease: a comparison of results from fluorescence spectroscopy and electron spin resonance spectroscopy. Psychopharmacol 145(2):175–180Google Scholar
  20. 20.
    Scheuer K, Maras A, Gattaz WF, Cairns N, Förstl H, Müller WE (1996) Cortical NMDA receptor properties and membrane fluidity are altered in Alzheimer’s disease. Dement Geriatr Cogn Disord 7:210–214Google Scholar
  21. 21.
    Sakuma H, Otsuki K, Kurihara K (2006) Viscosity and lubricity of aqueous NaCl solution confined between mica surfaces studied by shear resonance measurement. Phys Rev Lett 96:046104PubMedGoogle Scholar
  22. 22.
    Fukushi D, Kasuya M, Sakuma H, Kurihara K (2011) Fluorescent dye probe for monitoring local viscosity of confined liquids. Chem Lett 40:776–778Google Scholar
  23. 23.
    Kasuya M, Hino M, Yamada H, Mizukami M, Mori H, Kajita S, Ohmori T, Suzuki A, Kurihara K (2013) Characterization of water confined between silica surfaces using the resonance shear measurement. J Phys Chem C 117(26):13540–13546Google Scholar
  24. 24.
    Hibara A, Saito T, Kim HB, Tokeshi M, Ooi T, Nakao M, Kitamori T (2002) Nanochannels on a fused-silica microchip and liquid properties investigation by time-resolved fluorescence measurements. Anal Chem 74(24):6170–6176 PubMedGoogle Scholar
  25. 25.
    Hashimoto T, Tasaki Y, Harada M, Okada T (2011) Electrolyte-doped ice as a platform for atto- to femtoliter reactor enabling zeptomol detection. Anal Chem 83(10):3950–3956PubMedGoogle Scholar
  26. 26.
    Hansler M, Jakubke H (1996) Nonconventional protease catalysis in frozen aqueous solutions. J Pept Sci 2:279–289PubMedGoogle Scholar
  27. 27.
    Langford VS, Mckinley AJ, Quickenden TI (2000) Luminescent photoproducts in UV-irradiated ice. Acc Chem Res 33(10):665–671PubMedGoogle Scholar
  28. 28.
    Terefe NS, Loey A, Van Hendrickx M (2004) Modelling the kinetics of enzyme-catalysed reactions in frozen systems : the alkaline phosphatase catalysed hydrolysis of di-sodium-p-nitrophenyl phosphate. Innov Food Sci Emerg Technol 5:335–344Google Scholar
  29. 29.
    Bogdan A, Molina MJ, Tenhu H, Mayer E, Loerting T (2010) Formation of mixed-phase particles during the freezing of polar stratospheric ice clouds. Nat Chem 2:197–201PubMedGoogle Scholar
  30. 30.
    Kahan TF, Zhao R, Donaldson DJ (2009) Hydroxyl radical reactivity at the air-ice interface. Atmos Chem Phys Discuss 10:843–854Google Scholar
  31. 31.
    Stӓhler J, Gahl C, Wolf M (2012) Dynamics and reactivity of trapped electrons on supported ice crystallites. Acc Chem Res 45(1):131–138Google Scholar
  32. 32.
    Tasaki Y, Okada T (2006) Ice chromatography. Characterization of water-ice as a chromatographic stationary phase. Anal Chem 78(12):4155–4160PubMedGoogle Scholar
  33. 33.
    Shamoto T, Tasaki Y, Okada T (2010) Chiral Ice chromatography. J Am Chem Soc 132(38):13135–13137PubMedGoogle Scholar
  34. 34.
    Inagawa A, Harada M, Okada T (2015) Fluidic grooves on doped-ice surface as size-tunable channels. Sci Rep 5:17308PubMedPubMedCentralGoogle Scholar
  35. 35.
    Qu H, Harada M, Okada T (2017) Voltammetry of viologens revealing reduction of hydrophobic interaction in frozen aqueous electrolyte solutions. ChemElectroChem 4(1):35–38Google Scholar
  36. 36.
    Tasaki Y, Okada T (2012) Up to 4 orders of magnitude enhancement of crown ether complexation in an aqueous phase coexistent with ice. J Am Chem Soc 134(14):6128–6131PubMedGoogle Scholar
  37. 37.
    Takenaka N, Ueda A, Maeda Y (1992) Acceleration of the rate of nitrite oxidation by freezing in aqueous solution. Nature 358:736–738Google Scholar
  38. 38.
    Takenaka N, Ueda A, Daimon T, Bandow H, Dohmaru T, Maeda Y (1996) Acceleration mechanism of chemical reaction by freezing: the reaction of nitrous acid with dissolved oxygen. J Phys Chem 100(32):13874–13884Google Scholar
  39. 39.
    Anzo K, Harada M, Okada T (2013) Enhanced kinetics of pseudo first-order hydrolysis in liquid phase coexistent with ice. J Phys Chem A 117(41):10619–10625PubMedGoogle Scholar
  40. 40.
    Tokumasu K, Harada M (2017) Freezing-facilitated dehydration allowing deposition of ZnO from aqueous electrolyte. ChemPhysChem 18:329–333PubMedGoogle Scholar
  41. 41.
    Sakai K, Hirano T, Hosoda M (2010) Electromagnetically spinning sphere viscometer. Appl Phys Express 3(1):16602Google Scholar
  42. 42.
    Srivastava N, Burns MA (2006) Analysis of non-newtonian liquids using a microfluidic capillary viscometer. Anal Chem 78(5):1690–1696PubMedGoogle Scholar
  43. 43.
    DeLaMarre M, Keyzer A, Shippy SA (2015) Development of a simple droplet-based microfluidic capillary viscometer for low-viscosity Newtonian fluids. Anal Chem 87(9):4649–4657 150331162924006PubMedGoogle Scholar
  44. 44.
    Pipe CJ, McKinley GH (2009) Microfluidic rheometry. Mech Res Commun 36(1):110–120Google Scholar
  45. 45.
    Nelson WC, Kavehpour HP, Kim C-J “CJ” (2011) A miniature capillary breakup extensional rheometer by electrostatically assisted generation of liquid filaments. Lab Chip 11(14):2424PubMedGoogle Scholar
  46. 46.
    Levitt JA, Kuimova MK, Yahioglu G, Chung P, Suhling K, Phillips D (2009) Membrane-bound molecular rotors measure viscosity in live cells via fluorescence lifetime imaging. J Phys Chem C 113:11634–11642Google Scholar
  47. 47.
    Chen S, Hong Y, Zeng Y, Sun Q, Liu Y, Zhao E, Bai G, Qu J, Hao J, Tang BZ (2015) Mapping live cell viscosity with an aggregation-induced emission fluorogen by means of two-photon fluorescence lifetime imaging. Chem A Eur J 21(11):4315–4320Google Scholar
  48. 48.
    Liang L, Wang X, Xing D, Chen T, Chen WR (2009) Noninvasive determination of cell nucleoplasmic viscosity by fluorescence correlation spectroscopy. J Biomed Opt 14(2):24013Google Scholar
  49. 49.
    Watanabe H, Otsuka T, Harada M, Okada T (2014) Imbalance between anion and cation distribution at ice interface with liquid phase in frozen electrolyte as evaluated by fluorometric measurements of pH. J Phys Chem C 118(29):15723–15731Google Scholar
  50. 50.
    Takayasu S, Suzuki T, Shinozaki K (2013) Intermolecular interactions and aggregation of fac-tris(2-phenylpyridinato-C2, N)Iridium(III) in nonpolar solvents. J Phys Chem B 117(32):9449–9456PubMedGoogle Scholar
  51. 51.
    Kim SW, Lee JR (2011) Measurement of the diffusion coefficients of single molecules using fluorescence correlation spectroscopy with a software correlator. J Korean Phys Soc 59(51):3171–3176Google Scholar
  52. 52.
    Uyama M, Harada M, Tsukahara T, Okada T (2013) Behavior of polyhydric alcohols at ice/liquid interface. J Phys Chem C 117(47):24873–24882Google Scholar
  53. 53.
    Chiorboli C, Indelli MT, Scandola AMR, Scandola F (1998) Salt effects on nearly diffusion controlled electron-transfer reactions. Bimolecular rate constants and cage escape yields in oxidative quenching of tris(2,2′-bipyridine)ruthenium(II). J Phys Chem 92(1):156–163Google Scholar
  54. 54.
    Iwamura M, Otsuka T, Kaizu Y (2002) Specific cation effect on quenching reactions of excited tris(α, α′-diimine)ruthenium(II) and chromium(III) complexes by cyanide complexes in aqueous solutions. Inorg Chim Acta 333:57–62Google Scholar
  55. 55.
    Smoluchowski MZ (1917) Smoluchowski. Phys Chem Streochiom Verwandtschatsl 92:129Google Scholar
  56. 56.
    Sutin N (1982) Nuclear, electronic, and frequency factors in electron transfer reactions. Acc Chem Res 15(9):275–282Google Scholar
  57. 57.
    Debye P (1942) Reaction rates in ionic solutions. J Electrochem Soc 82(1):265–272Google Scholar
  58. 58.
    Iwamura M, Otsuka T, Kaizu Y (2004) Specific cation effect on quenching reactions of excited tris(α,α′-diimine)ruthenium(II) and tris(2,2′-bipyridine)chromium(III) by tris(oxalato)- and tris(malnato)chromates(III) in aqueous solutions. Inorg Chim Acta 357:1565–1570Google Scholar
  59. 59.
    Conde MM, Rovere M, Gallo P (2017) Spontaneous NaCl-doped ice at seawater conditions: focus on the mechanisms of ion inclusion. Phys Chem Chem Phys 19(14):9566–9574PubMedGoogle Scholar
  60. 60.
    Nada H, Furukawa Y (2005) Anisotropy in growth kinetics at interfaces between proton-disordered hexagonal ice and water: a molecular dynamics study using the six-site model of H2O. J Cryst Growth 283(1–2):242–256Google Scholar
  61. 61.
    Bullock G, Molinero V (2013) Low-density liquid water is the mother of ice: on the relation between mesostructure, thermodynamics and ice crystallization in solutions. Faraday Discuss 167:371–388PubMedGoogle Scholar
  62. 62.
    Banerjee D, Bhat SN, Bhat SV, Leporini D (2012) Molecular probe dynamics reveals suppression of ice-like regions in strongly confined supercooled water. PLoS ONE 7(9):44382Google Scholar
  63. 63.
    Rigler R, Mets Ü, Widengren J, Kask P (1993) Fluorescence correlation spectroscopy with high count rate and low background: analysis of translational diffusion. Eur Biophys J 22(3):169–175Google Scholar
  64. 64.
    Fradin C, Luzet D, Braslau A, Alba M, Muller F, Daillant J, Petit JM, Rieutord F (1998) X-ray study of the fluctuations and the interfacial structure of a phospholipid monolayer at an alkane-water interface. Langmuir 14(26):7327–7330Google Scholar
  65. 65.
    Schlossman ML (2002) Liquid–liquid interfaces: studied by X-ray and neutron scattering. Curr Opin Colloid Interface Sci 7:235–243Google Scholar
  66. 66.
    Doerr AK, Tolan M, Seydel T, Press W (1998) The interface structure of thin liquid hexane films. Phys B 248(1–4):263–268Google Scholar

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© Springer Nature Singapore Pte Ltd. 2019

Authors and Affiliations

  1. 1.Graduate School of Regional Development and CreativityUtsunomiya UniversityUtsunomiyaJapan

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