Disordered conformations order

Xanthan is reported to undergo a chiroptically detected temperature or salt-driven conformational change from an ordered conformation at high salt and low temperature to a disordered conformation either associated with lowering the salt concentration, or with increasing the temperature (2-5). The primary structure of xanthan has been known for about a decade (6,7), but different structures have been suggested both for the ordered and disordered conformation. Some workers (8-13) conclude that the ordered conformation is double-stranded or double-helix, whereas others (14-17) claim that a single stranded description can account for the observed data under... 

In this study we use electron microscopy (EM) to study xanthan strandedness and topology both in the ordered and disordered conformation. Correlation of data obtained from electron micrographs to physical properties of dilute aqueous solution on the same sample will be used to provide a working hypothesis of the solution configuration of xanthan. Electron micrographs obtained from xanthan of different origins will be compared to assess similarities and differences in secondary structure at the level of resolution in the used EM technique. 

Examples of mesomorphic forms characterized by disorder in the conformation of the chains have already been described in Section 2.6. For instance, a mesomorphic form is present in the high-temperature form I of polytetrafluoro-ethylene.106,107 In this phase the chains are in disordered conformation due to the presence of helix reversals along the chains.108-110 Moreover, intermolec-ular disorder is also present due to the random rotations of the chains around the chain axes.109 A long-range three-dimensional order is present only in the pseudohexagonal placement of the chain axes.107,109... 

Mesomorphic forms characterized by conformationally ordered polymer chains packed in lattices with different kinds of lateral disorder have been described for various isotactic and syndiotactic polymers. For instance, for iPP,706 sPP,201 sPS,202 syndiotactic poly(p-methylstyrene) (sPPMS),203 and syndiotactic poly(m -methylstyrene),204 mesomorphic forms have been found. In all of these cases the X-ray fiber diffraction patterns show diffraction confined in well-defined layer lines, indicating order in the conformation of the chains, but broad reflections and diffuse haloes on the equator and on the other layer lines, indicating the presence of disorder in the arrangement of the chain axes as well as the absence of long-range lateral correlations between the chains. 

Hjerde, T., Smidsrad, O., Christensen, B.E. (1998b). Acid hydrolysis of k- and i-carra-geenan in the disordered and ordered conformations characterization of partially hydrolyzed samples and single-stranded oligomers released from the ordered structures. Macromolecules, 31, 1842-1851. 

The different conformational behavior of the azobenzoyl- and the azobenzenesul-fonyl-L-lysine polymers was explained on the basis that the monomeric units VI may interact with HFP differently than units V do (Scheme 4). The strongly proto-nating solvent HFP (pKa = 9.30) 36 is known to form electrostatic complexes with various organic compounds, including amines and dimethylsulfoxide 1371 on the other hand, sulfonamides are significantly protonated in acid media 38 so it may be presumed that protonation and formation of electrostatic complexes can occur for azobenzenesulfonyl-L-lysine residues, as well. In HFP therefore, polypeptides of structure V can adopt the ordered a-helix structure, while polypeptides of structure VI should be forced by the electrostatic interactions arising from complexation with HFP to adopt a disordered conformation. 

From this point of view, polypeptides containing photochromic units in the side chains are quite special polymers. They can exist in ordered or disordered conformations, and photoisomerization of their photochromic side chains can produce order = disorder conformational changes. These photostimulated structural variations, such as random coil a-helix, take place as highly cooperative transitions therefore photochromic polypeptides actually work as amplifiers and transducers of the primary photochemical events occurring in the photosensitive side chains. 

DPPC/Gramicidin D Mixtures. Experiments to determine the effects of Gramicidin D insertion on lipid conformational order, also illustrate one of the important advantages of the CD2 probe method namely, the ability to discern betveen various sources of disorder (Table V). Spectra of DPPC/Gramicidin mixtures at various... 

In hot, dilute dichlorobenzene solutions (>50 °C) broad absorption at Amax 480 nm is apparent in the UV-visible spectrum of PQT-12 (Fig. 4.8a), but the absorption is slightly red-shifted with the concomitant appearance of weak absorption at A max 610 nm (Fig. 4.8b) when the solution is cooled to room temperature. This is obviously because of the migration of PQT-12 molecules from the twisted disordered conformation in hot solution to an ordered coplanar conformation at lower temperatures. Because the HOMO level of PQT-12 in the solid state, esti-... 

Several research groups are currently investigating the inherent thermochromism of various polymers. Certain polysiloxanes exhibit reversible thermochromic activity [59, 60]. The thermochromic behavior of these macromolecules is due to order-disorder conformational changes that accompany a particular temperature change. This transition perturbs the electron delocalization of the silicone backbone and results in a shift in the absorption maxima in the UV-visible range. 

Whereas atactic PS is an amorphous polymer with a Tg of 100 CC, syndio-tactic PS is semicrystalline with a Tg similar to aPS and a Tm in the range 255-275 °C. The crystallization rate of sPS is comparable to that of polyethylene terephthalate). sPS exhibits a polymorphic crystalline behavior which is relevant for blend properties. In fact, it can crystallize in four main forms, a, (3, -y and 8. Several studies [8] based on FTIR, Raman and solid-state NMR spectroscopy and WAXD, led the a and (3 forms to be assigned to a trans-planar zig-zag molecular chain having a (TTTT) conformation, whereas the y and 8 forms contain a helical chain with (TTG G )2 or (G+G+TT)2 conformations. In turn, on the basis of WAXD results, the a form is said to comply with a unitary hexagonal cell [9] or with a rhombohedral cell [10]. Furthermore, two distinct modifications called a and a" were devised, and assigned to two limiting disordered and ordered forms, respectively [10]. 

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