Chain packing order

By an order parameter S =Sqd thus the residual anisotropy, which is not averaged by fast local motions, is characterised. This is the main information obtained for partially ordered systems, and can be considered a characterisation of the mobility of the C-2H bond, which on the other hand describes the chain packing order in oriented aggregates. 

The effect of the substituents on chain mobility and chain packing has been related to the gas transport properties [209]. Role of symmetry of methyl group placement on bisphenol rings in PES shows the permeability coefficients in the following order ... 

Differently from the cases of ETFE, PTFE, 1,4-trans-polybutadiene, and PE, in the mesomorphic form of i-PP it is believed that there is a nearly complete conformational order, in the chains packed with parallel axes, (intrachain long range 3-D order) and only short-range lateral order in the positioning of the chain axes [60, 61]. 

By and NMR, the occurrence of conformational changes of the AOT molecules with R has been emphasized [13]. An increase of the lateral packing order of the surfactant alkyl chains located in the micellar palisade layer due to water addition has also been pointed out by FT-IR [58,92]. 

With decreasing temperature, the density oscillation becomes very pronounced and grows into a deeper melt region. At 300 K, for example, we can see at least 5 layers after 1.28 ns. Within the layers, as will be shown later, definite order in chain orientation and chain packing is observed suggesting the growth of polymer crystals. 

The membrane is a dynamic assembly and things are diffusing rapidly in the plane of the bilayer. The middle of the bilayer has been likened to olive oil. As with oil, cooling the lipid bilayer will cause the hydrocarbons to become more ordered (structured). The side chains pack closer to each other, and the fluidity of the membrane is lower. Things that disrupt the ability of the side chains to pack in a regular fashion make the membrane more fluid (Fig. 3-4). These include high temperature, lipids with shorter chains (double bonds. The shorter lipids and the m-double bonds cause the occurrence of holes (packing defects). 

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. 

Many conformations were sampled by the usual MC procedure. The result is of course that there is no preferred orientation of the molecule. Each conformation can, however, be characterised by an instantaneous main axis this is the average direction of the chain. Then this axis is defined as a director . This director is used to subsequently determine the orientational order parameter along the chain. The order is obviously low at the chain ends, and relatively high in the middle of the chain. It was found that the order profile going from the centre of the molecules towards the tails fell off very similarly to corresponding chains (with half the chain length) in the bilayer membrane. As an example, we reproduce here the results for saturated acyl chains, in Figure 10. The conclusion is that the order of the chains found for acyl tails in the bilayer is dominated by intramolecular interactions. The intermolecular interactions due to the presence of other chains that are densely packed around such a chain,... 

Natural biological membranes consist of lipid bilayers, which typically comprise a complex mixture of phospholipids and sterol, along with embedded or surface associated proteins. The sterol cholesterol is an important component of animal cell membranes, which may consist of up to 50 mol% cholesterol. As cholesterol can significantly modify the bilayer physical properties, such as acyl-chain orientational order, model membranes containing cholesterol have been studied extensively. Spectroscopic and diffraction experiments reveal that cholesterol in a lipid-crystalline bilayer increases the orientational order of the lipid acyl-chains without substantially restricting the mobility of the lipid molecules. Cholesterol thickens a liquid-crystalline bilayer and increases the packing density of lipid acyl-chains in the plane of the bilayer in a way that has been referred to as a condensing effect. 

From previous discussion it is clear that this behavior must be ascribed to crystallization phenomena or at least to segmental motions which result in an increase of order in the polymer and hence a more efficient chain packing. 

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