Affine chain behaviour

The absolute values of the reductions in moduli, or increases in Mj, can be Interpreted in terms of small, inelastic loops. The small-strain, static moduli measured are consistent with affine chain behaviour, showing, on the basis of one-membered loops, that between about 10 and 20% of groups react to form inelastic loops by the end of a polymerisation. For the more concentrated systems a significant proportion of this comes from post-gel intramolecular reaction (Pr,e Pr,c) ... 

Note In reality, affine chain behaviour can apply only at small deformations. 

To evaluate Pj. g from modulus measurements, a value of A has to be assumed and used together with the experimental value of Mg/AM. Accordingly, Figures 4 and 5 show pj- g plotted versus Pr.c affine (A=l) and phantom (A = 1 - 2/t) chain behaviour using the results in Figure 1. One condition that should be obeyed in the plots is that Pr e Pr c Pr e includes pre-gel and post-gel reaction. 

Tables 6.8-6.11 illustrate the wide range of C3 side-chain modified A -THC analogues that have been reported in the literature, together with associated in vitro and in vivo data. The affinity of classical cannabinoid analogues for the CBi receptor has been shown to correlate with depression of spontaneous activity and the production of antinociception, hypothermia and catalepsy in mice, and with psychomimetic activity in humans [93]. However, in some cases, there were unexplained differences between the observed trends in binding affinity and the trends in activity in mouse behavioural models. This may point to differences in efficacy among full agonists, partial agonists and antagonists/inverse agonists, or may reflect differences in in vivo metabolism or blood-brain barrier penetration or a combination of these factors.

The phantom network behaviour corresponding to volumeless chains which can freely interpenetrate one through the other and thus to unrestricted fluctuations of crosslinks should be approached in swollen systems or at high strains (proportionality to the Mooney-Rivlin constant C-j). For suppressed fluctuations of crosslinks, which then are displaced affinely with the strain, A for the small-strain modulus (equal to C1+C2) approaches unity. This situation should be characteristic of bulk systems. The constraints arising from interchain interactions important at low strains should be reflected in an increase of Aabove the phantom value and no extra Gee contribution to the modulus is necessary. The upper limit of the predicted equilibrium modulus corresponds therefore, A = 1. 

From the examination of structure-activity relationships, it has been concluded that a phenyl moiety at C-6 as well as a 4-hydroxypiperidine side-chain attached to C-3 of the pyridazine system is essential for anticonvulsant activity in this class of compounds [184], Compounds (54) and (55) have been found to have similar anticonvulsant profiles in animals (mice, rats and baboons) [165, and literature cited therein] and to represent potent broad-spectrum antiepileptic drugs. Their potency with regard to antagonizing seizures (induced by electro-shock or various chemicals) has been compared with standard anticonvulsants like carbamazepine and phenobarbitone [185, 186], A quantitative electroencephalographic analysis of (55) has been published [187]. From in vitro studies it has been concluded that the anticonvulsant activities of these compounds are not mediated by an enhancement of GABAergic transmission or by an interaction with benzodiazepine receptor sites [ 165,186,187], On the other hand, in vivo experiments showed that (54), at anticonvulsant doses, increases the affinity of flunitrazepam for its central receptor site [ 186], Investigations of (54) and (55) in a behavioural test predictive of antianxiety activity revealed a marked difference in the pharmacological profiles of these structurally closely related compounds the dichloro compound SR 41378 (55) has also been found to possess anxiolytic (anticonflict) properties [165],... 

O is the stress per unit unstrained area, G the shear modulus, A the deformation ratio, p the density of the dry network. iJ>2 volume fraction of polymer present in the network, V the volume at formation. A=1 for affine behaviour (expected) and 1-2/f for phantom behaviour(1,3). is the molar mass for the perfect network, essentially the molar mass of a chain of v bonds, the number which can form the smallest loop (5-7) see Figure 2. is equal to the... 

In PB networks, the variation of the line shape as a function of the applied stress was interpreted in terms of a chain length distribution. Shorter chains may be more oriented than longer ones, at a given elongation [18], which may lead to a non-affine behaviour at the chain scale. The question of the spatial scale to which the deformation is affinely transmitted, has been investigated intensively by small angle neutron scattering [64]. However, it may happen as well that the chain portions close to junction points are more oriented (have a more restricted mobility) than those in the middle of the chains [19]. 

The work from Sheldon s group [10] was the first to present the use of ionic liquids in the enzymatic synthesis of esters. Since then, there have been many reports on biosynthesis of esters in ionic liquids. De los Rios et al. [64,65] synthesised a wide range of aliphatic organic esters, commonly used in the perfumery, flavour and pharmaceutical industries, by transesteriflcation from vinyl esters and alcohols catalysed by free CaLB in different 1,3-dialkylimidazolium-based ILs (Fig. 7.2). They analysed the effects of the alkyl chain lengths of the acyl donor and the alcohol. The optimum (C6 for acyl donor and C4 for alcohol) chain lengths were found because the activity decreased with further increase in alkyl chain length. The authors attributed the enzyme behaviour to a substrate modulation mainly due to the different affinity of the lipase towards the different substrates and steric hindrance and denaturalisation by small alcohol molecules. 

Figure 3.66 shows the steady-shear viscosity for a polymer system at three molar masses. Note the plateau in viscosity at low shear rates (or the zero-shear viscosity). Also note how the zero-shear viscosity scales with to the power 3.4. (This is predicted by Rouse theory (Rouse, 1953).) Figure 3.67 shows the viscosity and first normal-stress difference for a high-density polyethylene at 200 C. Note the decrease in steady-shear viscosity with increasing shear rate. This is termed shear-thinning behaviour and is typical of polymer-melt flow, in which it is believed to be due to the polymer chain orientation and non-affine motion of polymer chains. Note also that the normal-stress difference increases with shear rate. This is also common for polymer melts, and is related to an increase in elasticity as the polymer chain motion becomes more restricted normal to flow at higher shearing rates. 

Another group tried to explain the Mooney-Rivlin-like stress-strain behaviour by different non-affine network chain deformation mechanisms... 

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