Evaluation of Internal Structure and Morphology of Poly(benzyl ether) Dendrimers by Molecular Dynamics Simulations

Taewan Hong; Hyung-Il Kim

Macromolecular Research, Vol.12, No.2, 178-188, April, 2004

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Evaluation of Internal Structure and Morphology of Poly(benzyl ether) Dendrimers by Molecular Dynamics Simulations

Taewan Hong, and Hyung-Il Kim^†

Department of Fine Chemicals Engineering and Chemistry, Chungnam National University, Daejeon 305-764, Korea

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We performed molecular dynamics (MD) simulations at 300 K on a series of poly(benzyl ether) (PBE) dendrimers having a different core functionalities. We used the rotational isomeric state Metropolis Monte Carlo (RMMC) method to construct the initial configuration in a periodic boundary cell (PBC) before the MD simulations were undertaken. To elucidate the effects that the structural features have on the chain dimension, the overall internal structure, and the morphology, we monitored the radii of gyration, R_g, and the conformational changes during the simulations. The PBE dendrimers in a glassy state adopted less-extended structures when compared with the conformations obtained from the RMMC calculations. We found that R_g of the PBE dendrimer depends on the molecular weight, M, according to the relation, R_g ~ M^0.22. The radial distributions of the dendrimers were developed identically in the PBC, irrespective of the core functionality. A gradual decrease in radial density resulted from the fact that the terminal branch ends are distributed all over the molecule, except for the core region.

Keywords:dendrimer;internal structure;molecular dynamics simulation;poly(benzyl ether).

[References]

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Zimm BH, Stockmayer WH, J. Chem. Phys., 17, 1301 (1949)

[Referenced By]

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[2] Tomalia DA, Baker H, Dewald J, Hall M, Martin S, Roeck J, Ryder J, Smith P, Polym. J., 17, 117 (1985)

[3] Tomalia DA, Wilson LR, U.S. Patent, 4,713,975 (1987)

[4] Winnik FM, Davidson AR, Breton MP, U.S. Patent, 5,120,361 (1992)

[5] Tomalia D, Dvornic PR, Nature, 372(6507), 617 (1994)

[6] Kim C, Koo BW, Lee SB, Song CK, Macromol. Res., 10(3), 178 (2002)

[7] Twyman LJ, Beezer AE, Esfand R, Hardy MJ, Mitchell JC, Tetrahedron Lett., 40, 1743 (1999)

[8] Wiener EC, Brechbiel MW, Brothers H, Magin RL, Gansow OA, Tomalia DA, Lauterbur PC, Magn. Reson. Med., 31, 1 (1994)

[9] Haensler J, Szoka FC, Bioconjugate Chem., 4, 372 (1993)

[10] Ottaviani MF, Furini F, Casini A, Turro NJ, Jockusch S, Tomalia DA, Messori L, Macromolecules, 33(21), 7842 (2000)

[11] Rao C, Tam JP, J. Am. Chem. Soc., 116, 975 (1994)

[12] Lescanec RL, Muthukumar M, Macromolecules, 23, 2280 (1990)

[13] Ballauff M, Top. Curr. Chem., 212, 177 (2001)

[14] Hecht S, Frechet JMJ, J. Am. Chem. Soc., 121(16), 4084 (1999)

[15] deGennes PG, Hervet H, J. Phys. Lett., 44, L351 (1983)

[16] Naidoo KJ, Hughes SJ, Moss JR, Macromolecules, 32(2), 331 (1999)

[17] Lee I, Athey BD, Wetzel AW, Meixner W, Baker JR, Macromolecules, 35(11), 4510 (2002)

[18] Zacharopoulos N, Economou LG, Macromolecules, 35(5), 1814 (2002)

[19] Yang SH, Yang JS, Jo WH, Korea Polym. J., 8(5), 224 (2000)

[20] Choi SS, Korea Polym. J., 8(3), 125 (2000)

[21] Honneycutt JD, Compt. Theor. Polym. Sci., 8, 1 (1998)

[22] Boris D, Rubinstein M, Macromolecules, 29(22), 7251 (1996)

[23] Murat M, Grest GS, Macromolecules, 29(4), 1278 (1996)

[24] Naylor AM, Goddard NA, Kiefer GE, Tomalia DA, J. Am. Chem. Soc., 111, 2339 (1989)

[25] Mansfield ML, Klushin LI, Macromolecules, 26, 4262 (1993)

[26] Mansfield ML, Macromolecules, 33(21), 8043 (2000)

[27] Wallace EJ, Buzza DMA, Read DJ, Macromolecules, 34(20), 7140 (2001)

[28] Jorgensen WL, Tiradorives J, J. Phys. Chem., 100(34), 14508 (1996)

[29] Sun H, J. Comput. Chem., 15, 752 (1994)

[30] Ribgy D, Sun H, Eichinger BE, Polym. Int., 44, 311 (1997)

[31] Sun H, Rigby D, Spectrochimica Acta Part A, 53, 1301 (1997)

[32] Mourey TH, Turner SR, Rubinstein M, Fretchet JMJ, Hawker CJ, Wooley KL, Macromolecules, 25, 2401 (1992)

[33] De Backer S, Prinzie Y, Verheijen W, Smet M, Desmedt K, Dehaen W, De Schryver FC, J. Phys. Chem. A, 102(28), 5451 (1998)

[34] Jung KY, Kim HI, Liu J, Korea Polym. J., 8(2), 59 (2000)

[35] Zimm BH, Stockmayer WH, J. Chem. Phys., 17, 1301 (1949)