Poly persistence length

From disaccharide analysis, few authors predict the conformation of the poly a-D galacturonan as well as the role of the charge density [35,36] they determine the persistence length Ip that will allow us to explain the behaviour in solution. 

For many polymers K and a values can be found in the Polymer Handbook [23]. In a recent study by Vanhee et al. [30] the universal calibration has been applied using the polystyrene (PS) calibration curve to characterize rigid rod poly(p-phenylenes) (PPP). It turned out that due to its larger persistence length, PPP with a certain mass requires a much larger volume than PS for the same molecular weight. Ron et al. employed universal calibration for the characterization of erodible copolymers [58]. 

It is considered that, if ideal, optically active poly(alkyl(aryl)silane) homopolymer and copolymer systems could be obtained which had stiffer main-chain structures with longer persistence lengths, it should be possible to clarify the relationship between the gabs value and the chiral molar composition. The magnitude of the chirality of the polyisocyanates allowed precise correlations with the cooperativity models.18q In the theory of the cooperative helical order in polyisocyanates, the polymers are characterized by the chiral order parameter M, which is the fraction of the main chain twisting in one helical sense minus the fraction of the main chain twisting in the opposing sense. This order parameter is equal to the optical activity normalized by the value for an entirely one-handed helical polymer. The theory predicts... 

C.L. Gettinger, A.J. Heeger, J.H. Drake, and D.J. Pine, A photoluminescence study of poly (phenylene vinylene) derivatives the effect of intrinsic persistence length, J. Chem. Phys., 101 1673-1678, 1994. 

The persistence length of poly(dG-dC) was determined to be 800 A,(148) about 1.6 times the value characteristic of native DNAs. Possible long-term changes in these light scattering samples were not investigated. 

All this leads to the question of how DNA affects nucleosomal stability at the molecular level. DNA bendability has been repeatedly put forward as a candidate to play an important role [280-282]. This property is related to the persistence length of DNA [283]. A study on the characterization of nucleosomes reconstituted onto methylated DNA [poly(dG-m dC) poly (dG-m dC)] [284] provides support to this hypothesis. Poly(dG-m dC) poly (dG-m dQ DNA can be induced to change from its B to its Z conformation in the presence of millimolar amounts of divalent ions [285] such as MgCl2. The persistence length of poly(dG-m dC) poly (dG-m dC) in the Z form in high salt was found to be 208 nm (ca. 612 bp) [286], a value much lower than that of the same polymer in the B form (93.8 nm, 276 bp) at... 

Mills JB, Vacano E, Hagerman PJ (1999) Flexibility of single-stranded DNA use of gapped duplex helices to determine the persistence lengths of poly(dT) and poly(dA). J Mol Biol 285 245-257... 

The potential for novel phase behaviour in rod-coil block copolymers is illustrated by the recent work of Thomas and co-workers on poly(hexyl iso-cyanate)(PHIC)-PS rod-coil diblock copolymers (Chen etal. 1996). PHIC, which adopts a helical conformation in the solid state, has a long persistence length (50-60 A) (Bur and Fetters 1976) and can form lyotropic liquid crystal phases in solution (Aharoni 1980). The polymer studied by Thomas and co-workers has a short PS block attached to a long PHIC block. A number of morphologies were reported—wavy lamellar, zigzag and arrowhead structures—where the rod block is tilted with respect to the layers, and there are different alternations of tilt between domains (Chen et al. 1996) (Fig. 2.37). These structures are analogous to tilted smectic thermotropic liquid crystalline phases (Chen et al. 1996). 

The light-scattering behavior of those polysilanes studied indicates that they are slightly extended and stiffened compared with typical polyolefins. One measure of chain flexibility is the characteristic ratio C, which is also shown in the table. The values of C for most polysilanes of about 20 are larger than those for typical hydrocarbon polymers (—10), indicating that the polysilanes are somewhat less flexible than polyolefins. However, poly(diarylsilylene)s are much more rod-like and inflexible, with persistence lengths greater than 100 46... 

The sensitivity of the helical preference of polyisocyanates to small chiral influences is also observed in chiral solvents. Poly(n-hexyl isocyanate) was found experimentally to have a persistence length of 20— 40 nm depending on the solvent in which the measurements were carried out.66 It was hypothesized that in more polar solvents a local interaction of the solvent would give rise to larger torsional oscillations around the backbone bonds. It was indeed observed that dissolution of poly(n-hexyl isocyanate) in non-racemic chiral solvents, e.g., (5)-l-chloro-2-methyl-butane, changed the persistence length and in addition also resulted in an excess of one helical sense.67 The chiral bias favoring one helical sense by itself is miniscule, but due to the cooperativity, a chiral preference is observed. More recently it was noted that the circular dichroism of these polymers decreases upon the addition of an achiral or racemic... 

Figure 18. (Left) SFM images of poly(r -butylacrylate) brushes with varying degree of polymerization, n, of the polyfn-butylacrylate) side chains on mica (spin cast samples). (Right) Persistence length of a molecular brush as a function of the side chain length n. The continuous line describes the power function lp

Isocyanide polymerization has also been used to polymerize peptide-based monomers. Cornelissen et al. [31,32] prepared oligopeptides based on alanine and functionalized the N-terminus with an isocyanide moiety. These monomers were subsequently polymerized using a Ni catalyst into /3-helical poly isocyanopeptides with the dipeptides in the side chain. It was found that these polymers formed rigid rods, which were revealed by AFM to have extremely long persistence lengths. This rigidity was caused by the formation of /5-sheets between the alanines in the side chain. The same group... 

FIG. 21 Constitution formula for poly(p-phenylene). The fully aromatic backbone exhibits an excellent chemical stability and has a persistence length of approximately 20 nm. The degree of polymerization used in the studies in Refs. 34, 46 was located between 20 and 40, so that the contour length equals approximately one persistence length at most. The dominant contribution to the signal in small-angle x-ray scattering experiments stems from the iodine ions, since the excess electron density of the backbone is very low. 

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