Skip to main content
SpringerLink
Log in

Folding and Formation of Mesoglobules in Dilute Copolymer Solutions

  • Chapter
  • First Online:
Conformation-Dependent Design of Sequences in Copolymers I

Part of the book series: Advances in Polymer Science ((POLYMER,volume 195))

Abstract

It is known that linear homopolymer chains can undergo a coil-to-globule-to-precipitation transition when the solvent quality gradually changes from good to poor. It is also known that the observation of the coil-to-globule transition without any interchain association is extremely difficult if not impossible. On the other hand, the folding of individual amphiphilic copolymer chains, such as protein chains, in an extremely dilute solution is much easier. As the copolymer concentration increases, inevitable interchain association accompanied by intrachain folding can result in a stable mesoglobular phase (the aggregation of a limited number of chains), existing between single-chain globules and macroscopic phase separation (precipitation). In this article, we mainly review what we have accomplished in the last ten years by starting with a brief discussion of the folding of linear poly(N -isopropylacrylamide) (PNIPAM) homopolymer chains in water. Our focus is the folding of different hydrophilically or hydrophobically modified PNIPAM copolymer chains in extremely dilute solutions as well as the formation of stable mesoglobules made of amphiphilic copolymer chains in dilute solutions. The discoveries of the molten globular state and the “ordered-coil” state between the random-coil and compacted globular states will be illustrated. The effects of both the comonomer composition and distribution on the folding of individual copolymer chains into some unique core-shell nanostructures as well as the formation of the mesoglobular phase are discussed. The double roles of hydrophobic interaction in the formation and stabilization of stable mesoglobules will be explained in terms of the viscoelastic effect.

This is a preview of subscription content, log in via an institution to check access.

Access this chapter

Log in via an institution

Institutional subscriptions

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. Stryer L (1988) Biochemistry. Freeman WH, New York

    Google Scholar 

  2. Zhou YQ, Karplus M (1999) Nature 401:400

    Article  CAS  Google Scholar 

  3. Nelson ED, Teneyck LF, Onuchic JN (1997) Phys Rev Lett 79:3534

    Article  CAS  Google Scholar 

  4. Klimov DK, Thirumalai D (1996) Phys Rev Lett 76:4070

    Article  CAS  Google Scholar 

  5. Camacho C, Thirumalai D (1993) Phys Rev Lett 71:2505

    Article  CAS  Google Scholar 

  6. Khokhlov AR, Khalatur PG (1998) Physica A 249:253

    Article  CAS  Google Scholar 

  7. Zheligovskaya EA, Khalatur PG, Khokhlov AR (1999) Phys Rev E 59:3071

    Article  CAS  Google Scholar 

  8. Khokhlov AR, Khalatur PG (1999) Phys Rev Lett 82:3456

    Article  CAS  Google Scholar 

  9. Timoshenko EG, Kuznetsov YA (2000) J Chem Phys 112:8163

    Article  CAS  Google Scholar 

  10. Schild HG (1992) Prog Polym Sci 17:163

    Article  CAS  Google Scholar 

  11. Fujishige S, Kubota K, Ando I (1989) J Phys Chem 93:3311

    Article  CAS  Google Scholar 

  12. Kubota K, Fujishige S, Ando I (1990) J Phys Chem 94:5154

    Article  CAS  Google Scholar 

  13. Meewes M, RickaJ, Nyffenegger R, Binkert T (1991) Macromolecules 24:5811

    Article  CAS  Google Scholar 

  14. Zhou SQ, Wu C (1995) Macromolecules 28:5225

    Article  CAS  Google Scholar 

  15. Tiktopulo EI, Bychkova VE, Ricka J, Ptitsyn OB (1994) Macromolecules 27:2879

    Article  CAS  Google Scholar 

  16. Virtenen J, Baron C, Tenhu H (2000) Macromolecules 33:336

    Article  CAS  Google Scholar 

  17. Stockmayer WH (1960) Makromol Chem 35:54

    Article  CAS  Google Scholar 

  18. Flory PJ (1953) Principles of Polymer Chemistry. Cornell University Press, Ithaca, NY

    Google Scholar 

  19. Ptitsyn OB, Kron AK, Eizner YY (1968) J Polym Sci Part C 16:3509

    Google Scholar 

  20. Yamakawa H (1971) Modern Theory of Polymer Solutions. Harper & Row, New York, NY

    Google Scholar 

  21. Grosberg AY, Kuznetsov DV (1992) Macromolecules 25:1996

    Article  CAS  Google Scholar 

  22. Yamakawa H (1993) Macromolecules 26:5061

    Article  CAS  Google Scholar 

  23. Post CB, Zimm BH (1979) Biopolymers 18:1487 and (1982) 21:2123

    Article  CAS  Google Scholar 

  24. Park IH, Wang QW, Chu B (1987) Macromolecules 20:1965

    Article  CAS  Google Scholar 

  25. Chu B, Park IH, Wang QW, Wu C (1987) Macromolecules 20:2833

    Article  CAS  Google Scholar 

  26. Chu B, Yu J, Wang ZL (1993) Prog Colloid Polym Sci 91:142

    Article  CAS  Google Scholar 

  27. Tanaka F (1985) J Chem Phys 82:4707

    Article  CAS  Google Scholar 

  28. Tanaka F, Ushiki H (1988) Macromolecules 21:1041

    Article  CAS  Google Scholar 

  29. Grosberg AY, Kuznetsov DV (1993) Macromolecules 26:4249

    Article  CAS  Google Scholar 

  30. Yu J, Wang ZL, Chu B (1992) Macromolecules 25:1618

    Article  CAS  Google Scholar 

  31. Chu B, Ying QC, Grosberg AY (1995) Macromolecules 28:180

    Article  CAS  Google Scholar 

  32. Wu C, Zhou SQ (1995) Macromolecules 28:5388, 8381

    Article  CAS  Google Scholar 

  33. Wu C, Zhou SQ (1996) Macromolecules 29:1574

    Article  CAS  Google Scholar 

  34. Wu C, Zhou SQ (1996) Phys Rev Lett 77:3053

    Article  CAS  Google Scholar 

  35. Gao J, Wu C (1997) Macromolecules 30:6873

    Article  CAS  Google Scholar 

  36. Hu TJ, Wu C (1999) Phys Rev Lett 83:4105

    Article  CAS  Google Scholar 

  37. Wu C, Wang XH (1998) Phys Rev Lett 79:4092

    Article  Google Scholar 

  38. Wang XH, Qiu XP, Wu C (1998) Macromolecules 31:2972

    Article  CAS  Google Scholar 

  39. Wang XH, Wu C (1999) Macromolecules 32:4299

    Article  CAS  Google Scholar 

  40. Zhang GZ, Wu C (2001) Phys Rev Lett 86:822

    Article  CAS  Google Scholar 

  41. Zhang GZ, Wu C (2001) J Am Chem Soc 123:1376

    Article  CAS  Google Scholar 

  42. Zhou SQ, Fan SY, Au-yeung SCF, Wu C (1995) Polymer 36:1341

    Article  CAS  Google Scholar 

  43. Zimm BH (1948) J Chem Phys 16:1099

    Article  CAS  Google Scholar 

  44. Wu C, Xia KQ (1994) Rev Sci Instrum 65:587

    Article  CAS  Google Scholar 

  45. Chu B (1991) Laser Light Scattering. Academic Press, New York, NY

    Google Scholar 

  46. Berne B, Pecora R (1976) Dynamic Light Scattering. Plenum Press, New York, NY

    Google Scholar 

  47. Stockmayer WH, Schmidt M (1982) Pure Appl Chem 54:407

    Article  CAS  Google Scholar 

  48. Wu C (1998) Polymer 39:4609

    Article  CAS  Google Scholar 

  49. Yamamoto I, Iwasaki K, Hirotsu S (1989) J Phys Soc Jpn 58:210

    Article  CAS  Google Scholar 

  50. de Gennes P-G (1975) J Phys Lett 36:L55

    Article  Google Scholar 

  51. Sanchez IC (1979) Macromolecules 12:276

    Article  Google Scholar 

  52. Okada Y, Tanaka F (2005) Macromolecules 38:4465

    Article  CAS  Google Scholar 

  53. Baulin VA, Halperin A (2002) Macromolecules 35:6432

    Article  CAS  Google Scholar 

  54. Marchetti M, Prager S, Cussler EL (1990) Macromolecules 23:3445

    Article  CAS  Google Scholar 

  55. Birshtein TM, Pryamitsyn VA (1991) Macromolecules 24:1554

    Article  CAS  Google Scholar 

  56. Siu MH, Zhang GZ, Wu C (2002) Macromolecules 35:2723

    Article  CAS  Google Scholar 

  57. Zhang L, Eisenberg A (1995) Science 268:1728 and references therein

    Article  CAS  Google Scholar 

  58. Antonietti M, Heinz S, Schmidt M (1994) Macromolecules 27:3276

    Article  CAS  Google Scholar 

  59. Henselwood F, Liu G (1997) Macromolecules 30:488

    Article  CAS  Google Scholar 

  60. Wu C, Akashi M, Chen MQ (1997) Macromolecules 30:2187

    Article  CAS  Google Scholar 

  61. Li M, Jiang M, Zhu L, Wu C (1997) Macromolecules 30:2201

    Article  CAS  Google Scholar 

  62. Berlinova IV, Amzil A, Tsvetkova S, Panayotov IMJ (1994) Polym Sci Polym Chem 32:1523

    CAS  Google Scholar 

  63. Kawaguchi S, Winnik MA, Ito K (1995) Macromolecules 28:1159

    Article  CAS  Google Scholar 

  64. Gref R, Minamitake Y, Peracchia MT, Trubetskoy V, Torchilin V, Langer R (1994) Science 263:1600

    Article  CAS  Google Scholar 

  65. Fessi H, Puisieux F, Devissaguet J Ph, Ammoury N, Benita S (1989) Int J Pharm 55:R1

    Article  CAS  Google Scholar 

  66. Eckert AR, Webber SE (1996) Macromolecules 29:560

    Article  CAS  Google Scholar 

  67. Wu C, Qiu XP (1998) Phys Rev Lett 80:620

    Article  CAS  Google Scholar 

  68. Virtanen J, Tenhu H (2000) Macromolecules 33:5970

    Article  CAS  Google Scholar 

  69. Chen HW, Li JF, Ding YW, Zhang GZ, Zhang QJ, Wu C (2005) Macromolecules 38:4403

    Article  CAS  Google Scholar 

  70. Hu TJ, Wu C (2001) Macromolecules 34:6802

    Article  CAS  Google Scholar 

  71. Ostrovsky B, Bar-Yam Y (1994) Europhys Lett 25:409

    Article  CAS  Google Scholar 

  72. Cohen-Stua MA, Waajen FHWH, Cosgrove T, Vincent B, Crowley TL (1984) Macromolecules 17:1825

    Article  Google Scholar 

  73. Wagner M, Brochard-Wyart F, Hervert H, de Gennes P-G (1993) Colloid Polym Sci 271:621

    Article  CAS  Google Scholar 

  74. Cook RL, King HE Jr, Peiffer DG (1992) Phys Rev Lett 69:3072

    Article  CAS  Google Scholar 

  75. Polik WF, Burchard W (1983) Macromolecules 16:978

    Article  CAS  Google Scholar 

  76. Devanand K, Selser JC (1990) Nature 343:739

    Article  CAS  Google Scholar 

  77. Tanford C (1980) The Hydrophobic Effect: Formation of Micelles and Biological Membranes. Wiley, New York, NY

    Google Scholar 

  78. Bekiranov S, Bruinsma R, Pincus P (1993) Europhys Lett 24:183

    Article  CAS  Google Scholar 

  79. Martin JI, Wang Z-G (1995) J Phys Chem 99:2833

    Article  CAS  Google Scholar 

  80. Milner ST (1991) Science 251:905

    Article  CAS  Google Scholar 

  81. Auroy P, Auvray L, Leger L (1991) Phys Rev Lett 66:719

    Article  CAS  Google Scholar 

  82. László K, Kosik K, Geissler E (2004) Macromolecules 37:10067

    Article  CAS  Google Scholar 

  83. Ding YW, Ye XD, Zhang GZ (2005) Macromolecules 38:904

    Article  CAS  Google Scholar 

  84. Glass JE (1989) Polymers in Aqueous Media: Performance through Association. American Chemical Society, Washington, DC

    Book  Google Scholar 

  85. McCormick CL, Bock J, Schulz DN (1989) In: Mark HF, Bikales NM, Overberg CG, Menges G (eds) Encyclopedia of Polymer Science and Engineering. Wiley-Interscience, New York, NY, vol 17

    Google Scholar 

  86. Halperin A (1991) Macromolecules 24:1418; Borisov OV, Halperin A (1995) Langmuir 11:2911 and (1996) Macromolecules 29:2612

    Article  CAS  Google Scholar 

  87. Urakami N, Takasu M (1996) J Phys Soc Jpn 65:2694; Urakami N, Takasu M (1997) Prog Theor Phys Suppl 126:329

    Article  CAS  Google Scholar 

  88. Semenov AN, Joanny J-F, Khokhlov AR (1995) Macromolecules 28:1066

    Article  CAS  Google Scholar 

  89. de Gennes P-G (1995) Isr J Chem 35:33

    Google Scholar 

  90. Halperin A (2000) In: Ciferri A (ed) Supramolecular Polymers. Marcel Dekker, New York, NY

    Google Scholar 

  91. Hu Y, Armentrout RS, McCormick CL (1997) Macromolecules 30:3538

    Article  CAS  Google Scholar 

  92. Noda T, Morishima Y (1999) Macromolecules 32:4631

    Article  CAS  Google Scholar 

  93. Kikuchi A, Nose T (1996) Macromolecules 29:6770

    Article  CAS  Google Scholar 

  94. Zhang GZ, Winnik FM, Wu C (2003) Phys Rev Lett 90:35506

    Article  CAS  Google Scholar 

  95. Biggs S, Hill A, Selb J, Candau F (1992) J Phys Chem 96:1505

    Article  CAS  Google Scholar 

  96. Dowling KC, Thomas JK (1990) Macromolecules 23:1059

    Article  CAS  Google Scholar 

  97. Cui SX, Liu CJ, Zhang WK, Zhang X, Wu C (2003) Macromolecules 36:3779

    Article  CAS  Google Scholar 

  98. Hugel T, Seitz M (2001) Macromol Rapid Commun 22:989

    Article  CAS  Google Scholar 

  99. Oesterhelt F, Rief M, Gaub HE (1999) New J Phys 1:61

    Article  Google Scholar 

  100. Buchard W (1996) In: Brown W (ed) Light Scattering Principles and Development. Clarendon Press, Oxford

    Google Scholar 

  101. Qiu XP, Li M, Kwan CMS, Wu C (1998) J Polym Sci Polym Phys Ed 36:1501

    Article  CAS  Google Scholar 

  102. Wu C, Chan KK, Woo KF, Qian R, Li X, Chen L, Napper DH, Tan G, Hill AJ (1995) Macromolecules 28:1592

    Article  CAS  Google Scholar 

  103. Ricka J, Meewes M, Nyffenegger R, Binkert Th (1990) Phys Rev Lett 65:657

    Article  CAS  Google Scholar 

  104. Meewes M, Ricka J, Nyffenegger R, Binkert Th (1991) Macromolecules 24:5811

    Article  CAS  Google Scholar 

  105. Wu C (1994) Macromolecules 27:298

    Article  CAS  Google Scholar 

  106. Antonietti M, Bremser W, Schmidt M (1990) Macromolecules 23:3796

    Article  CAS  Google Scholar 

  107. Antonietti M, Heinz S, Schmidt M, Rosenauer C (1994) Macromolecules 27:3276

    Article  CAS  Google Scholar 

  108. Wu C, Akashi M, Chen MQ (1997) Macromolecules 30:2187

    Article  CAS  Google Scholar 

  109. Li M, Jiang M, Zhu L, Wu C (1997) Macromolecules 30:2201

    Article  CAS  Google Scholar 

  110. Li M, Jiang M, Zhang YB, Wu C (1999) Macromolecules 31:6841

    Article  Google Scholar 

  111. Gao J, Wu C (2000) Macromolecules 33:645

    Article  CAS  Google Scholar 

  112. Gao J, Wu C (2005) Langmuir 21:782

    Article  CAS  Google Scholar 

  113. Jordan DS, Green DW, Terry RE, Willhite GP (1982) J Soc Petrol Eng 8:463

    Google Scholar 

  114. Flory PJ, Osterheld JE (1954) J Phys Chem 58:653

    Article  CAS  Google Scholar 

  115. Ohmine I, Tanaka T (1982) J Chem Phys 77:5725

    Article  CAS  Google Scholar 

  116. Ben Jar PY, Wu YS (1997) Polymer 38:2557

    Article  CAS  Google Scholar 

  117. Ikegami A, Imai N (1962) J Polym Sci 56:133

    Article  CAS  Google Scholar 

  118. Dubin P, Bock J, Davies RM, Schulz DN, Thies C (1994) Macromolecular Complexes in Chemistry and Biology. Springer, Berlin Heidelberg New York

    Google Scholar 

  119. Narh KA, Keller A (1993) J Polym Sci Polym Phys 31:231

    Article  CAS  Google Scholar 

  120. Michaeli I (1960) J Polym Sci 48:291

    Article  CAS  Google Scholar 

  121. Family F, Landau DP (1984) Kinetics of Aggregation and Gelation. North-Holland, Amsterdam

    Google Scholar 

  122. Burns JL, Yan YD, Jameson GJ, Biggs S (1997) Langmuir 13:6413

    Article  CAS  Google Scholar 

  123. Kolb M, Botet R, Jullien R (1983) Phys Rev Lett 51:1123

    Article  Google Scholar 

  124. Meakin P (1983) Phys Rev Lett 51:1119

    Article  Google Scholar 

  125. von Schulthess GK, Benedek GB, Deblois RW (1980) Macromolecules 13:939

    Article  Google Scholar 

  126. Schaefer DW, Martin JE, Wiltzius P, Cannell DS (1984) Phys Rev Lett 52:2371

    Article  CAS  Google Scholar 

  127. Jullien R, Kolb M (1984) J Phys A 17:L693

    Google Scholar 

  128. Brown WD, Ball RC (1985) J Phys A 18:L517

    Article  CAS  Google Scholar 

  129. Ball RC, Weitz DA, Written TA, Leyvraz F (1987) Phys Rev Lett 58:274

    Article  Google Scholar 

  130. Peng SF, Wu C (1999) Macromolecules 32:585

    Article  CAS  Google Scholar 

  131. Ji HJ, Sun ZW, Zhan WX, Li ZH (1994) Acta Polym Sinica 11:559

    Google Scholar 

  132. Tanaka T, Nishio I, Ueno-Nishio ST (1982) Science 218:467

    Article  CAS  Google Scholar 

  133. Yuko I, Michael B, Manfred S, Klaus H (1998) Macromolecules 31:728

    Article  Google Scholar 

  134. Martin TA, Joost HJ, van Opheusden X (1996) Phys Rev E 53:5044

    Article  Google Scholar 

  135. Lin MY, Lindsay HM, Weitz DA, Ball RC, Klein R, Meakin P (1990) Phys Rev A 41:2005

    Article  CAS  Google Scholar 

  136. Timoshenko EG, Kuznetsov YA (2000) J Chem Phys 112:8163

    Article  CAS  Google Scholar 

  137. Timoshenko EG, Basovsky R, Kuznetsov YA (2001) Coll Surf A 190:129

    Article  CAS  Google Scholar 

  138. Timoshenko EG, Kuznetsov YA (2001) Europhys Lett 53:322

    Article  CAS  Google Scholar 

  139. Siu MH, Liu HY, Zhu XX, Wu C (2003) Macromolecules 36:2103

    Article  CAS  Google Scholar 

  140. Halsey TC (2000) Phys Today 53:36

    Article  CAS  Google Scholar 

  141. Siu MH, Cheng H, Wu C (2003) Macromolecules 36:6588

    Article  CAS  Google Scholar 

  142. Wu C, Li W, Zhu XX (2004) Macromolecules 37:4989

    Article  CAS  Google Scholar 

  143. Picarra S, Martinho JMG (2001) Macromolecules 34:53

    Article  CAS  Google Scholar 

  144. Tanaka H (1993) Phys Rev Lett 71:3158 (1992) Macromolecules 25:6377

    Google Scholar 

  145. Qiu X, Wu C (1997) Macromolecules 30:7921

    Article  CAS  Google Scholar 

Download references

Acknowledgments

The financial support from the Hong Kong Special Administration Region Earmarked Grants and the National Science Foundation of China over the last ten years is gratefully acknowledged. We are also indebted to many of our students, postdoctorals and collaborators, particularly to Professors Jiang M in Fudan University and Zhou SQ in the City University of New York, to Drs. Qiu XP, Wang XH, Li M, Hu TJ, Peng SF, and to Mr. Li W and Miss Siu MH.

Author information

Authors and Affiliations

  1. Laboratory of Macromolecular Colloids and Solutions, The Hefei National Laboratory for Physical Sciences at Micro-scale, Hefei, 230026, Anhui, China

    Guangzhao Zhang

  2. Department of Chemical Physics, University of Science and Technology of China, Hefei, 230026, Anhui, China

    Guangzhao Zhang

  3. Department of Chemistry, The Chinese University of Hong Kong, Shatin, N.T., Hongkong, China

    Chi Wu

Authors
  1. Guangzhao Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Chi Wu
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Chi Wu .

Editor information

Alexei R. Khokhlov

Rights and permissions

Reprints and permissions

About this chapter

Cite this chapter

Zhang, G., Wu, C. Folding and Formation of Mesoglobules in Dilute Copolymer Solutions. In: Khokhlov, A.R. (eds) Conformation-Dependent Design of Sequences in Copolymers I. Advances in Polymer Science, vol 195. Springer, Berlin, Heidelberg. https://doi.org/10.1007/12_050

Download citation

Publish with us

Policies and ethics

Search

Navigation