7016 Macromolecules 1995,28, 7016-7018 Notes Stiff Chains and Filaments under Tension Theo Odijk Faculty of Chemical Engineering and Materials Science, Delft University of Technology, P.O. Box 5045, 2600 GA Delft, The Netherlands Received April 4, 1995 Revised Manuscript Received July 11, 1995 There is an interesting class of problems in the physics of polymeric materials which one may group under the heading “semiclassical elasticity”. Herein, the question is raised how the deformational behavior of the material changes from entropy-dominated to elasticity- dominated as one increases the level of stress exerted on it. Chain fluctuations and undulations are gradually frozen out during this process. Thus, the connotation “semiclassical” applies to an evaluation of the partition function in the limit of weak fluctuations, which may remain influential nonetheless. A simple example of this effect is the elongation of stiff microfilaments under tensions that are of practical interest. Both the fluctua- tions and material extension in this problem were already addressed qualitatively by Oosawal two decades ago, but a straightforward quantitative analysis is apparently lacking. Let us suppose it is possible to associate a center curve with the macromolecule or filament in a particular configuration. The center curve is described by the radius vector 7%) = (ds), y(s), z(s)), where s is the contour distance from one_end. The contour length L is a function of the tension f exerted at both ends of the chain (Figure 1). The consour length is LO in the state without external stress cf = 01, referred to here and below by index 0. The unstressed reference configuration without ther- mal undulations is assumed to be a straight line. A fairly general, effective Hamiltonian may be written as the sum of three terms Su=6+%+5q (1) The bending energy2 valid for an extendible wormlike chain may be approximated by where kg is Boltzmann’s constant, Tis the temperature, and P(L,s) is the persistence length, which will generally depend on the material elongation and hence implicitly on the tension. At the same level of approximation, we have for the energy of material elongation (3) \ -f. - - \ -- / I-- /-- f. c-i LA Figure 1. Stiff chain under a gradually increasing tension: (a) undulation-dominated elongation; (b) at the crossover; (c) elasticity-dominated regime. extension are nonuniform. According to eqs 2 and 3, the filament behaves locally like an elastic medium. The tensile energy follows from considering the displacement of the two ends .5g= -?.(7(L) - 3(0)) (4) The statistical physics of a filament or chain defined by %is obviously complicated but one limit is readily soluble. I consider the case of small elongations and weak undulations (AL L - LO << LO; &Ids = 8, *: 1 gnd dy/ds 8, << 1 iff = fiz is in the z direction and 8 = (8,(s), 8Js)) is the angle between the tangential vector Glds and Zz. All quantities in eqs 1-4 are noy expanded systematically in AL and the small angle 8- (s) and only the leading terms are retained. The resulting harmonic approximation reads At this stage the canonical variables &) and AL are completely separable and the statistics becomes a mat- ter of quadrature. For instance, a quantity of experi- mental relevance is the elongation where K(L,s) is an elastic modulus and S/SO signifies an extension ratio at s (presumably, there is a one-to-one correspondence between SO and s). In principle, both P and K depend on s because both the bending and 0024-9297/95/2228-7016$09.00/0 where ( ) denotes canonical averaging and higher order terms are consistently deleted in the harmonic ap- proximation. The first average in eq 6 involves es- sentially Gaussian integrals since AL << LO 0 1995 American Chemical SocietyMacromolecules, Vol. 28, No. 20, 1995 Notes 7017 (7) The second average has been computed in a different context for finite contour lengths (see eq M.8 of ref 3). The general form of this expression was first derived by Fixman and Kovac4 although with different numer- ical coefficients because they employed an approxima- tion, Gaussian in the extension vector, which was forced to mimic a wormlike chain. Their formula also de- scribes the approach to the fully flexible limit. A convenient closed expression valid for sufficiently long contour lengths has been presented re~ently.~ Let us now focus on chains longer than the deflection lex~gth~,~ ,I = Po(@)h so that eqs 6 and 8 reduce to (9) The extension ratio e is defined with respect to the reference state. Equation 10 at zero material elongation (i.e., with KO = -1 has been discussed bef~re~,~ and expresses the manner in which undulations are frozen out as we increase the tension. Here, the curve of e against In f has a point of inflection given by - i(kBTK:)113 *-475- (11) It effectively demarcates the regime dominated by entropy (f < f*) from that dominated by energy cf > f*), loosely speaking (in practice, the entropy and energy terms are not pure). In general, there need not be a simple relation between the empirical constants KO and PO. We gain more insight into the magnitude and nature of the crossover given by eq 11 by supposing the macromol- ecules behaves like a cylindrical rod of homogeneous elasticity. Sometimes this may be a realistic model; often it must be regarded as a convenient idealization. The quantities KO and PO are now related2,8 through Young‘s modulus E and the rod diameter DO. ZD;E = 64K,T (12) (13) These equations yield a numerically transparent for- mula for the tension at the crossover k,T 4Po 113 113 f * - Do (Do) = kBT(&) (14) It is surprising, perhaps, that f* is independent of the diameter. In addition, we have the following relations valid at the point of inflection (16) Hence, for stiff filaments these ratios are indeed much smaller than unity as is required for the applicability of the harmonic approximation. Equation 15 yields the deflection length3f’t7,9 at the crossover Accordingly, at f = f* the transverse distance the filament wanders at mostg is then DO so, for higher tensions (f > fi), it looks progressively more like a straight, smooth rod on the scale of DO (Figure 1). If the elastic rod model is indeed realistic for biofila- ments, Young‘s modulus E would range from 10 to lo2 kBT nm-3 judging from the dimensions and persistence lengths of