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.
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References
Stryer L (1988) Biochemistry. Freeman WH, New York
Zhou YQ, Karplus M (1999) Nature 401:400
Nelson ED, Teneyck LF, Onuchic JN (1997) Phys Rev Lett 79:3534
Klimov DK, Thirumalai D (1996) Phys Rev Lett 76:4070
Camacho C, Thirumalai D (1993) Phys Rev Lett 71:2505
Khokhlov AR, Khalatur PG (1998) Physica A 249:253
Zheligovskaya EA, Khalatur PG, Khokhlov AR (1999) Phys Rev E 59:3071
Khokhlov AR, Khalatur PG (1999) Phys Rev Lett 82:3456
Timoshenko EG, Kuznetsov YA (2000) J Chem Phys 112:8163
Schild HG (1992) Prog Polym Sci 17:163
Fujishige S, Kubota K, Ando I (1989) J Phys Chem 93:3311
Kubota K, Fujishige S, Ando I (1990) J Phys Chem 94:5154
Meewes M, RickaJ, Nyffenegger R, Binkert T (1991) Macromolecules 24:5811
Zhou SQ, Wu C (1995) Macromolecules 28:5225
Tiktopulo EI, Bychkova VE, Ricka J, Ptitsyn OB (1994) Macromolecules 27:2879
Virtenen J, Baron C, Tenhu H (2000) Macromolecules 33:336
Stockmayer WH (1960) Makromol Chem 35:54
Flory PJ (1953) Principles of Polymer Chemistry. Cornell University Press, Ithaca, NY
Ptitsyn OB, Kron AK, Eizner YY (1968) J Polym Sci Part C 16:3509
Yamakawa H (1971) Modern Theory of Polymer Solutions. Harper & Row, New York, NY
Grosberg AY, Kuznetsov DV (1992) Macromolecules 25:1996
Yamakawa H (1993) Macromolecules 26:5061
Post CB, Zimm BH (1979) Biopolymers 18:1487 and (1982) 21:2123
Park IH, Wang QW, Chu B (1987) Macromolecules 20:1965
Chu B, Park IH, Wang QW, Wu C (1987) Macromolecules 20:2833
Chu B, Yu J, Wang ZL (1993) Prog Colloid Polym Sci 91:142
Tanaka F (1985) J Chem Phys 82:4707
Tanaka F, Ushiki H (1988) Macromolecules 21:1041
Grosberg AY, Kuznetsov DV (1993) Macromolecules 26:4249
Yu J, Wang ZL, Chu B (1992) Macromolecules 25:1618
Chu B, Ying QC, Grosberg AY (1995) Macromolecules 28:180
Wu C, Zhou SQ (1995) Macromolecules 28:5388, 8381
Wu C, Zhou SQ (1996) Macromolecules 29:1574
Wu C, Zhou SQ (1996) Phys Rev Lett 77:3053
Gao J, Wu C (1997) Macromolecules 30:6873
Hu TJ, Wu C (1999) Phys Rev Lett 83:4105
Wu C, Wang XH (1998) Phys Rev Lett 79:4092
Wang XH, Qiu XP, Wu C (1998) Macromolecules 31:2972
Wang XH, Wu C (1999) Macromolecules 32:4299
Zhang GZ, Wu C (2001) Phys Rev Lett 86:822
Zhang GZ, Wu C (2001) J Am Chem Soc 123:1376
Zhou SQ, Fan SY, Au-yeung SCF, Wu C (1995) Polymer 36:1341
Zimm BH (1948) J Chem Phys 16:1099
Wu C, Xia KQ (1994) Rev Sci Instrum 65:587
Chu B (1991) Laser Light Scattering. Academic Press, New York, NY
Berne B, Pecora R (1976) Dynamic Light Scattering. Plenum Press, New York, NY
Stockmayer WH, Schmidt M (1982) Pure Appl Chem 54:407
Wu C (1998) Polymer 39:4609
Yamamoto I, Iwasaki K, Hirotsu S (1989) J Phys Soc Jpn 58:210
de Gennes P-G (1975) J Phys Lett 36:L55
Sanchez IC (1979) Macromolecules 12:276
Okada Y, Tanaka F (2005) Macromolecules 38:4465
Baulin VA, Halperin A (2002) Macromolecules 35:6432
Marchetti M, Prager S, Cussler EL (1990) Macromolecules 23:3445
Birshtein TM, Pryamitsyn VA (1991) Macromolecules 24:1554
Siu MH, Zhang GZ, Wu C (2002) Macromolecules 35:2723
Zhang L, Eisenberg A (1995) Science 268:1728 and references therein
Antonietti M, Heinz S, Schmidt M (1994) Macromolecules 27:3276
Henselwood F, Liu G (1997) Macromolecules 30:488
Wu C, Akashi M, Chen MQ (1997) Macromolecules 30:2187
Li M, Jiang M, Zhu L, Wu C (1997) Macromolecules 30:2201
Berlinova IV, Amzil A, Tsvetkova S, Panayotov IMJ (1994) Polym Sci Polym Chem 32:1523
Kawaguchi S, Winnik MA, Ito K (1995) Macromolecules 28:1159
Gref R, Minamitake Y, Peracchia MT, Trubetskoy V, Torchilin V, Langer R (1994) Science 263:1600
Fessi H, Puisieux F, Devissaguet J Ph, Ammoury N, Benita S (1989) Int J Pharm 55:R1
Eckert AR, Webber SE (1996) Macromolecules 29:560
Wu C, Qiu XP (1998) Phys Rev Lett 80:620
Virtanen J, Tenhu H (2000) Macromolecules 33:5970
Chen HW, Li JF, Ding YW, Zhang GZ, Zhang QJ, Wu C (2005) Macromolecules 38:4403
Hu TJ, Wu C (2001) Macromolecules 34:6802
Ostrovsky B, Bar-Yam Y (1994) Europhys Lett 25:409
Cohen-Stua MA, Waajen FHWH, Cosgrove T, Vincent B, Crowley TL (1984) Macromolecules 17:1825
Wagner M, Brochard-Wyart F, Hervert H, de Gennes P-G (1993) Colloid Polym Sci 271:621
Cook RL, King HE Jr, Peiffer DG (1992) Phys Rev Lett 69:3072
Polik WF, Burchard W (1983) Macromolecules 16:978
Devanand K, Selser JC (1990) Nature 343:739
Tanford C (1980) The Hydrophobic Effect: Formation of Micelles and Biological Membranes. Wiley, New York, NY
Bekiranov S, Bruinsma R, Pincus P (1993) Europhys Lett 24:183
Martin JI, Wang Z-G (1995) J Phys Chem 99:2833
Milner ST (1991) Science 251:905
Auroy P, Auvray L, Leger L (1991) Phys Rev Lett 66:719
László K, Kosik K, Geissler E (2004) Macromolecules 37:10067
Ding YW, Ye XD, Zhang GZ (2005) Macromolecules 38:904
Glass JE (1989) Polymers in Aqueous Media: Performance through Association. American Chemical Society, Washington, DC
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
Halperin A (1991) Macromolecules 24:1418; Borisov OV, Halperin A (1995) Langmuir 11:2911 and (1996) Macromolecules 29:2612
Urakami N, Takasu M (1996) J Phys Soc Jpn 65:2694; Urakami N, Takasu M (1997) Prog Theor Phys Suppl 126:329
Semenov AN, Joanny J-F, Khokhlov AR (1995) Macromolecules 28:1066
de Gennes P-G (1995) Isr J Chem 35:33
Halperin A (2000) In: Ciferri A (ed) Supramolecular Polymers. Marcel Dekker, New York, NY
Hu Y, Armentrout RS, McCormick CL (1997) Macromolecules 30:3538
Noda T, Morishima Y (1999) Macromolecules 32:4631
Kikuchi A, Nose T (1996) Macromolecules 29:6770
Zhang GZ, Winnik FM, Wu C (2003) Phys Rev Lett 90:35506
Biggs S, Hill A, Selb J, Candau F (1992) J Phys Chem 96:1505
Dowling KC, Thomas JK (1990) Macromolecules 23:1059
Cui SX, Liu CJ, Zhang WK, Zhang X, Wu C (2003) Macromolecules 36:3779
Hugel T, Seitz M (2001) Macromol Rapid Commun 22:989
Oesterhelt F, Rief M, Gaub HE (1999) New J Phys 1:61
Buchard W (1996) In: Brown W (ed) Light Scattering Principles and Development. Clarendon Press, Oxford
Qiu XP, Li M, Kwan CMS, Wu C (1998) J Polym Sci Polym Phys Ed 36:1501
Wu C, Chan KK, Woo KF, Qian R, Li X, Chen L, Napper DH, Tan G, Hill AJ (1995) Macromolecules 28:1592
Ricka J, Meewes M, Nyffenegger R, Binkert Th (1990) Phys Rev Lett 65:657
Meewes M, Ricka J, Nyffenegger R, Binkert Th (1991) Macromolecules 24:5811
Wu C (1994) Macromolecules 27:298
Antonietti M, Bremser W, Schmidt M (1990) Macromolecules 23:3796
Antonietti M, Heinz S, Schmidt M, Rosenauer C (1994) Macromolecules 27:3276
Wu C, Akashi M, Chen MQ (1997) Macromolecules 30:2187
Li M, Jiang M, Zhu L, Wu C (1997) Macromolecules 30:2201
Li M, Jiang M, Zhang YB, Wu C (1999) Macromolecules 31:6841
Gao J, Wu C (2000) Macromolecules 33:645
Gao J, Wu C (2005) Langmuir 21:782
Jordan DS, Green DW, Terry RE, Willhite GP (1982) J Soc Petrol Eng 8:463
Flory PJ, Osterheld JE (1954) J Phys Chem 58:653
Ohmine I, Tanaka T (1982) J Chem Phys 77:5725
Ben Jar PY, Wu YS (1997) Polymer 38:2557
Ikegami A, Imai N (1962) J Polym Sci 56:133
Dubin P, Bock J, Davies RM, Schulz DN, Thies C (1994) Macromolecular Complexes in Chemistry and Biology. Springer, Berlin Heidelberg New York
Narh KA, Keller A (1993) J Polym Sci Polym Phys 31:231
Michaeli I (1960) J Polym Sci 48:291
Family F, Landau DP (1984) Kinetics of Aggregation and Gelation. North-Holland, Amsterdam
Burns JL, Yan YD, Jameson GJ, Biggs S (1997) Langmuir 13:6413
Kolb M, Botet R, Jullien R (1983) Phys Rev Lett 51:1123
Meakin P (1983) Phys Rev Lett 51:1119
von Schulthess GK, Benedek GB, Deblois RW (1980) Macromolecules 13:939
Schaefer DW, Martin JE, Wiltzius P, Cannell DS (1984) Phys Rev Lett 52:2371
Jullien R, Kolb M (1984) J Phys A 17:L693
Brown WD, Ball RC (1985) J Phys A 18:L517
Ball RC, Weitz DA, Written TA, Leyvraz F (1987) Phys Rev Lett 58:274
Peng SF, Wu C (1999) Macromolecules 32:585
Ji HJ, Sun ZW, Zhan WX, Li ZH (1994) Acta Polym Sinica 11:559
Tanaka T, Nishio I, Ueno-Nishio ST (1982) Science 218:467
Yuko I, Michael B, Manfred S, Klaus H (1998) Macromolecules 31:728
Martin TA, Joost HJ, van Opheusden X (1996) Phys Rev E 53:5044
Lin MY, Lindsay HM, Weitz DA, Ball RC, Klein R, Meakin P (1990) Phys Rev A 41:2005
Timoshenko EG, Kuznetsov YA (2000) J Chem Phys 112:8163
Timoshenko EG, Basovsky R, Kuznetsov YA (2001) Coll Surf A 190:129
Timoshenko EG, Kuznetsov YA (2001) Europhys Lett 53:322
Siu MH, Liu HY, Zhu XX, Wu C (2003) Macromolecules 36:2103
Halsey TC (2000) Phys Today 53:36
Siu MH, Cheng H, Wu C (2003) Macromolecules 36:6588
Wu C, Li W, Zhu XX (2004) Macromolecules 37:4989
Picarra S, Martinho JMG (2001) Macromolecules 34:53
Tanaka H (1993) Phys Rev Lett 71:3158 (1992) Macromolecules 25:6377
Qiu X, Wu C (1997) Macromolecules 30:7921
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.
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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
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