Alkyl Chain flexibility

Alk l chain. The increase in the alkyl chain length and linearity improves the efficiency of the plasticizer and the low-temperature flexibility of the plasticized polymers. 

Fig. 7. Snapshots from a smectic-A phase of liquid crystal dimer molecules composed of two Gay-Berne mesogens linked by a flexible alkyl chain. Data from [112] supplied by Dr M R Wilson, University of Durham...

On the theoretical side, Marcelja [26] was first to account explicitly for flexible tail chains in nematic ordering, using the Maier-Saupe model potential (Eq. 1) for each segment of the molecule. More complex models were proposed by Samulski et al. [27] and Emsley et al. [28]. In these approaches alkyl chains are assumed to exist in a discrete set of conformers described by... 

The use of ordered supramolecular assemblies, such as micelles, monolayers, vesicles, inverted micelles, and lyotropic liquid crystalline systems, allows for the controlled nucleation of inorganic materials on molecular templates with well-defined structure and surface chemistry. Poly(propyleneimine) dendrimers modified with long aliphatic chains are a new class of amphiphiles which display a variety of aggregation states due to their conformational flexibility [38]. In the presence of octadecylamine, poly(propyleneimine) dendrimers modified with long alkyl chains self-assemble to form remarkably rigid and well-defined aggregates. When the aggregate dispersion was injected into a supersaturated... 

As described above, the arrangement of the various functional moieties was controlled spatially across the films at molecular dimensions in the form of LB films. In a series of folded type of sensitizer (S) and electron-donor (D) dyads in a previous work, however, the dyad molecules in the LB films can take many conformations due to flexibility of the longer alkyl chain of the dyads so that clear dependence of the photoinduced electron transfer rate on the alkyl chain length, i.e. S-D distance, was not observed [2], By this reason, we are studying the chain length dependence by using a series of linear type S-D dyads, in which the S and D moieties were linked by a single alkyl chain. In the closely packed LB films, the alkyl chain was considered to be extended and the distance between S and D to be... 

This difficulty has been circumvented by the introduction of a modified concept [100]. Here, flexible alkyl chains are used as tethers that are incorporated in macrocyclic cyclo-[n]-malonates. In this way, the regioselectivity is not based on steric preorganization but on the avoidance of unequal strain in the alkyl chains. This has very important consequences for the symmetry of the product addition pattern and dictates selection rules (1) Cyclo-[n]-malonates containing alkyl chains... 

A hither facet of research has involved the structural characterisation of aluminium complexes which incorporate polydentate salen-type ligands. These have been noted in both neutral and monocationic (ion-separated) contexts (the latter requiring that the metal centre be stabilised by an external Lewis base) [35]. While such charged systems are invariably mononuclear the same is only usually true of their neutral analogues by virtue of the sterically demanding bis(aryloxide), chelating ligand. In the context of these latter complexes, dimerisation has been noted [251] while, more recently, the employment of flexible alkyl chains between two salen-coordinated aluminium ions has enabled the observation of dinuclear compounds [160, 161]. 

Position t if at terminal end of alkyl chain J. if interdispersed or attached to a rigid ring Higher molecular flexibility Low/no molecular flexibility... 

Avoid bifunctional or potentially bifunctional epoxides, especially when the epoxide groups are at the terminal end of an alkyl chain, as they are more reactive than epoxy groups interdispersed or attached to a rigid ring due to higher molecular flexibility to interact with DNA. 

Frequency-domain measurements of fluorescence energy transfer are used to determine the end-to-end distance distribution of donor-acceptor D-A) pairs linked by flexible alkyl chains. The length of the linker is varied from 11 to 2B atoms, and two different D-A pairs are used. In each case the D-A distributions are recovered from global analysis of measurements with different values for the FSrster distance, which are obtained by collislonal quenching of the donors. In all cases essentially the same distance distribution Is recovered from the frequency-domain data for each value of tha Ffirster distance. The experimentally recovered distance distributions are compared with those calculated from the RIS model. The experimentally recovered distance distributions for the largest chain molecules are In agreement with the predictions of the RIS model. However, the experimental and RIS distributions are distinct for the shorter D-A pairs. 

For many applications low-temperature flexibility of the plasticized composition is also important. Plasticizers of low viscosity and low viscosity-temperature gradient are usually effective at low temperature. There is also a close relationship betv/een rate of oil extraction and low-temperature flexibility plasticizers effective at low temperature are usually rather readily extracted from the resin. Plasticizers containing linear alkyl chains are generally more effective at low temperature than those containing rings. Low-temperature performance is evaluated by measuremen t of stiffness in flexure or torsion or by measurement of second-order transition point, brittle point or peak dielectric loss factor. 

The nematic phase (N) is the least ordered, and hence the most fluid liquid crystal phase. The order in this type of LC phases is based on a rigid and anisometric (in most cases rod-shaped or disc-shaped) molecular architecture. Such molecules tend to minimize the excluded volume between them, and this leads to long range orientational order. For rod-like molecules the ratio between molecular length and its broadness determines the stability of the nematic phase with respect to the isotropic liquid state and the stability rises with increase of this ratio. In most cases the rigid cores are combined with flexible chains, typically alkyl chains, which hinder crystallization and in this way retain fluidity despite of the onset of order. 

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