Conformational disordering

Here, the second term describes the change of the hopping amplitudes due to the displacement of the atoms parallel to the chain [cf. Eq. (3.5)] and the third term is a random contribution resulting from the conformational disorder (chain twists). While the lattice displacements u are dynamic variables, the fluctuations dl +t due to disorder are assumed to be frozen ( quenched disorder). 

Figure 3-7. A simplified picture of a //wi-v-polyacelylcne chain with conformational disorder the right part of the chain is rotated with respect to its left part over the angle .

As an example of the second case, we may have conformationally disordered chains, but long-range order in the positions of the chain axes (condis crystals [5]). Fiber spectrum features are the occurrence of sharp reflections on the equator only and diffuse reflections on the other layer lines. 

A conformationally disordered mesomorphic form is present, for instance, in the high-temperature phase I of PTFE. In this form, a long-range 3-D order is present only in the periodic pseudohexagonal placement of the chain axes [49]. In fact intramolecular helix reversals would produce the conformational disorder [50-52] and a complete intermolecular rotational disorder would be also present [49, 52,53]. 

The atomic temperature factors obtained after crystallographic refinement are significantly higher for cys530 than for the other site cysteine residues. This is also true when the Ni ion is compared to the Fe center. This may reflect conformational disorder due to the fact that the crystals are made of a mixture of different Ni states (40% Ni-A, 10% Ni-B, and 50% of an EPR-silent species) (52). 

The conformational disorder and packing structure of diazirine 91N2 is shown on the left of Scheme 7.25. The formation of azine 92 can easily be explained by the head-to-head crystallization of the chloro-diazirine, which experiences close N---C1 interactions that ultimately bring the carbene carbon close to the diazirine nitrogen... 

DLAM) is in the region of 200 cm-1 and gives a measure of the long-range conformational disorder [100-103]. 

Experimental Data from Polymer Thermotropic Mesophases and Conformationally Disordered Crystals... 

The high-temperature polymorphic form of trans-1,4-poly(1,3-butadicne) (form II) provides another example of conformational disorder.111 At... 

This kind of conformational disorder has also been suggested for poly(methyl sorbate).105 It is therefore not unusual and also explains some properties of these polymers, as, for instance, the low entropy of melting.114... 

In the crystal structures of many other isotactic polymers, with chains in threefold or fourfold helical conformations, disorder in the up/down positioning of the chains is present. Typical examples are isotactic polystyrene,34,179 isotactic poly(l-butene),35 and isotactic poly(4-methyl-l-pentene).39,40,153,247... 

A particular kind of disorder, characterized by maintaining three-dimensional long-range periodicity only for some points of the structure, has been found in samples of syndiotactic polypropylene having a relatively low degree of stereoregularity.189 190 In these samples the chains present conformational disorder, which produces defects frozen in the crystals. 

Figure 2.46 Model of packing of conformationally disordered chains of sPP in disordered modifications of form II presenting kink bands.189,190 Chains drawn with thick and thin fines are at 0 and 0.5 along b. In the ordered portion of crystal chains are in ordered twofold (T2G2)B helical conformation, whereas in the defective portion (delimited by dashed lines) chains are in T2G2T6 conformation.

Figure 2.47 Models of packing in limit-ordered forms (a) II and (c) IV of sPP and (b) model of conformationally disordered modification, presenting kink bands, intermediate between limit-ordered models of form II and form IV. In defective region of model (b), delimited by dashed lines, chains are packed as in form IV, whereas in ordered regions chains are packed as in the form II.

Conformational disorder and kink-bands structures have recently been found also in random copolymers of syndiotactic polypropylene with small amounts of ethylene.192 193 The ethylene units are included in the crystalline regions193 and induce the crystallization of the metastable form II of sPP with conformationally disordered chains characterized by kink bands. Portions of chains containing the ethylene units tend, indeed, to assume a trans planar conformation, producing the kink-band defects in chains in the prevailing twofold helical conformation.192193... 

Another example of a conformationally disordered mesomorphic form is the high-temperature phase of trans-1,4-poly(1,3-butadiene).111112 As discussed in Section 2.6, in this phase the disorder corresponds to a statistical succession... 

This implies a modification of the chain direction and, finally, a generation of a helix with a larger cross section than that of the trans planar chain.218 Such phase transitions are often associated with the onset of some conformational disorder characterized by the occurrence of kink bands (Figure 2.48b), similar to those found in sPP samples quench crystallized from solutions189,190 (Figures 2.46 and 2.47) or in polyethylene.219 It is apparent from Figure 2.48... 

Figure 2.48 Possible cooperative mechanism of crystal-crystal transition from (a) trans planar form III of sPP into (c) isochiral helical form II. Transition occurs through formation of (b) intermediate conformationally disordered modifications containing kink bands, characterized by helical sequences having same chirality (R = right-handed helix). Formation of helical sequences of opposite chirality (right- and left-handed) produces (if) steric interactions between neighboring chains.

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