Copolymers cooperativity

Surfilcon-A copolymer of MMA, VP, and other methacrjiates 74 Permaflex Cooper Vision, Inc. 

Table 8. Parameters of cooperative bonding of lysozyme, haemoglobin and serum albumin (proteins) by a macroreticular MA-EDMA (2.5 mol%) copolymer...

Tabelle 9. Values of AG and AG for cooperative bonding of proteins by an MA-EDMA (2.5 mol %) macroreticular copolymer in the variation of the degree of ionization of carboxylic groups... 

The presence of a critical St content in ASt-x can also be seen in fluorescence spectra [29], This copolymer in aqueous solution shows an excimer emission peaking at 325 nra. As shown in Fig. 8, the intensity of the excimer emission increases, while the monomer emission decreases, with increasing St content. Eventually the excimer dominates the monomer emission at an St content of 72 mol%. The excimer emission becomes apparent at an St content of about 50 mol%, which agrees with the critical St content estimated by viscometry and NMR spectroscopy. The existence of the critical St content suggests the hydro-phobic self-aggregation to be a cooperative process. 

Kabanov et al.131) found that a copolymer of 4-vinylpyridine and acroleinoxime, 82 (PPox), is a powerful catalyst for the hydrolyses of PNPA, NABA, and 3-nitro-4-trimethyl-acetoxybenzoic acid 83 (NTBA). The activity of the copolymer was 103 times higher than that of the low-molecular-weight oxime, iso-butyraldoxime. They proposed the cooperative activation of the oxime- and pyridine-groups in the vicinity of pyridinium cation groups of the copolymer. 

FIGURE 5.7 Phase separation in styrene-butadiene-styrene (SBS) triblock copolymer. The isolated spherical styrene domains form the hard phase, which act both as intermolecular tie points and filler. The continuous butadiene imparts the elastomeric characteristics to this polymer. MW = molecular weight. (From Grady, B.P. and Cooper, S.L., Science and Technology of Rubber, Mark, J.E., Erman, B., and Eirich, F.R. (eds.). Academic Press, San Diego, CA, 1994. With permission.)... 

Miller J.A., Lin S.B., Hwang K.K.S., Wu K.S., Gibson P.E., and Cooper S.L. Properties of polyether-polyurethane block copolymers Effect of hard segment length distribution. Macromolecules, 18, 32, 1985. 

C(Q) and Q Q) are the characteristic frequencies attributed to the cooperative and the interdiffusion modes, respectively. In the case of the copolymer solvent system, the interdiffusion mode originates from the relative motion of one block with respect to the other. 

Time-resolved in situ Small Angle Neutron Scattering (SANS) investigations have provided direct experimental evidence for the initial steps in the formation of the SBA-15 mesoporous material, prepared using the non-ionic tri-block copolymer Pluronic 123 and TEOS as silica precursor. Upon time, three steps take place during the cooperative self-assembly of the Pluronic micelles and the silica species. First, the hydrolysis of TEOS is completed, without modifications of the Pluronic spherical micelles. Then, when silica species begin to interact with the micelles, a transformation from spherical to cylindrical micelles takes place before the precipitation of the ordered SBA-15 material. Lastly, the precipitation occurs and hybrid cylindrical micelles assemble into the two-dimensional hexagonal structure of SBA-15. 

In the primary structure of alternating block-copolymers the hydrophobic H-type blocks could be too short to facilitate the efficient cooperative hydrophobic interactions responsible for promoting the phase separation. 

A slight increase in the turbidity upon heating of aqueous solutions of the s-fractions of the NVCl/NVIAz-copolymers obtained from the feeds with initial comonomer molar ratios of 75 25 (Tcp 65 °C) and 80 20 (Tcp 66 °C) could be due to the micellization phenomena, although the absence of DSC peaks over the same temperature range testified to the non-cooperative character of the process. This could indicate that the chains of these s-type copolymers had, nevertheless, a certain amount of oligoNVCl blocks non-buried by the hydrophilic microenvironment sufficiently well and thus capable of participating in the hydrophobically-induced associative intermolecular processes at elevated temperatures. At the same time, the sequence of monomer units in the s-copolymers obtained from the feeds with the initial comonomer ratios of 85 15 and 90 10 (mole/mole) corresponded to the block-copolymers of another type. The basis for such a conclusion is the lack of macroscopic heat-induced phase separation at elevated temperatures (Fig. 3 a and b) and, simultaneously, the transi-... 

On the other hand, noticeable cooperative preferential screw sense induction was reported in rodlike polysilane copolymers bearing (.S )-2-mcthylbutyl and 2-methylpropyl groups (10) and (R)-2-melhylbutyl and 2-methylpropyl groups (11) in isooctane (Chart 4.3). Since the UV-CD spectral features of the polysilane copolymers are almost identical with those of 4-6 and the Xmax varies sensitively with changes in the molar fraction of chiral substituents and temperature,28 the copolymer systems are suitable for testing the sergeants-and-soldiers phenomenon by their CD-UV spectra. 

Another significant cooperativity effect in preferential helical screw sense optically active copolymers is the majority rule phenomenon.18bl8q In this case, the screw sense of a helical main chain with unequal proportions of opposite chirality enantiopure chiral side groups is controlled by the enantiomeric excess only. Since this phenomenon was first reported from poly-a-olefins made of vinyl co-monomers bearing nonenantiopure chiral moieties by Green et al.8b and Pino et al.,16b this majority rule has been established in... 

It is considered that, if ideal, optically active poly(alkyl(aryl)silane) homopolymer and copolymer systems could be obtained which had stiffer main-chain structures with longer persistence lengths, it should be possible to clarify the relationship between the gabs value and the chiral molar composition. The magnitude of the chirality of the polyisocyanates allowed precise correlations with the cooperativity models.18q In the theory of the cooperative helical order in polyisocyanates, the polymers are characterized by the chiral order parameter M, which is the fraction of the main chain twisting in one helical sense minus the fraction of the main chain twisting in the opposing sense. This order parameter is equal to the optical activity normalized by the value for an entirely one-handed helical polymer. The theory predicts... 

In this part, two series of 44 copolymers with coiled main-chain structures and 45 copolymers with stiff main-chain conformations were described. It was concluded that both optically inactive 42 and 43 adopt helical conformations with an equal proportion of P and M screw senses by means of UV and CD spectra as well as molecular mechanics calculations. A marked positive cooperative induction effect of the preferential screw sense in 44 and 45 copolymers was found. However, there is a marked difference in the helical cooperativity between 44 and 45, probably because of the differences in their global and local conformations. This difference can be related to the persistence of the helical conformation against defects allowing change of... 

To investigate cooperativity in these copolymers, the gabs ratios were evaluated. The dissymmetry ratio, gabs, is displayed as a function of chiral content for 47, 50, 51, and 53-58 at 20°C in Figure 4.40. It is evident that the absolute magnitudes of gabs (i.e., independent of sign) for the pa ra - phe n y I - su b stituted... 

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