Electrostatic interactions monomers

Tacticity of products. Most solid catalysts produce isotactic products. This is probably because of the highly orienting effect of the solid surface, as noted in item (1). The preferred isotactic configuration produced at these surfaces is largely governed by steric and electrostatic interactions between the monomer and the ligands of the transition metal. Syndiotacticity is mostly produced by soluble catalysts. Syndiotactic polymerizations are carried out at low temperatures, and even the catalyst must be prepared at low temperatures otherwise specificity is lost. With polar monomers syndiotacticity is also promoted by polar reaction media. Apparently the polar solvent molecules compete with monomer for coordination sites, and thus indicate more loosely coordinated reactive species. 

Because the monomer units in p(acrylic acid) can be ionized, the possibility of electrostatic interaction between groups within the same chain, as well as between the chain and the stationary phase, needs to be considered. 

Morishima et al. [75, 76] have shown a remarkable effect of the polyelectrolyte surface potential on photoinduced ET in the laser photolysis of APh-x (8) and QPh-x (12) with viologens as electron acceptors. Decay profiles for the SPV (14) radical anion (SPV- ) generated by the photoinduced ET following a 347.1-nm laser excitation were monitored at 602 nm (Fig. 13) [75], For APh-9, the SPV- transient absorption persisted for several hundred microseconds after the laser pulse. The second-order rate constant (kb) for the back ET from SPV- to the oxidized Phen residue (Phen+) was estimated to be 8.7 x 107 M 1 s-1 for the APh-9-SPV system. For the monomer model system (AM(15)-SPV), on the other hand, kb was 2.8 x 109 M-1 s-1. This marked retardation of the back ET in the APh-9-SPV system is attributed to the electrostatic repulsion of SPV- by the electric field on the molecular surface of APh-9. The addition of NaCl decreases the electrostatic interaction. In fact, it increased the back ET rate. For example, at NaCl concentrations of 0.025 and 0.2 M, the value of kb increased to 2.5 x 108 and... 

In the same manner, the rc-electron densities of the monomer and the cation are affected. Substituents, which decrease the electron density at the P-C-atom, that is, the place of the primary attack on the double bond, increase the positive charge at the a-C-atom of the cation and therefore its electrostatic interaction with a negative reaction centre (qa(cation) = —2.08 + 2.53qp(monomer) r = 0.93 n = 13). The previous equation shows that the electron density of the cation is more influenced than that of the monomer (Aqp(monomer) = 0.1 and Aqjcation) = 0.25).. 

Price i was the first to suggest that the factor of specificity in monomer addition is owing to electrostatic interaction of net charges on the monomer double bond and on the radical arising from polarization by the substituent. Alfrey and Price proposed that the rate constant be written, in analogy with Hammett s equation for the effects of nuclear substituents on the reactivity of aromatic compounds, as follows ... 

Electrostatic interactions play a dominant role in weak molecular clusters between components, like arenes, exhibiting quadrupole momenta q. The global minimum of the benzene dimer corresponds to structure with monomers located in perpendicular planes (T-shape structure). " This structure is favored by attractive... 

Cui et al. performed similar analyses to fhose of Dupuis and co-workers. The side chain-side chain radial disfribufion functions (RDFs) reported by Cui et al. show remarkable qualitative deviation from fhose in Zhou et al. i It is of note that the united atom approach used by Cui and co-workers ignored electrostatic interactions between CP2 groups of the polymeric backbone. This can lead to a poor description of fhe hydrated structure in the regions close to the polymeric backbones, unlike the all-atom force field used in Zhou et al. ° For the sake of limited computational resources, Cui et al. used a relatively short representation of Nation ionomer chains consisting of three monomers as compared to the ten monomers used by Vishnyakov and Neimark or Urata et al. It can be expected that structural correlations will strongly depend on this choice. 

The driving force for isoselective propagation results from steric and electrostatic interactions between the substituent of the incoming monomer and the ligands of the transition metal. The chirality of the active site dictates that monomer coordinate to the transition metal vacancy primarily through one of the two enantiofaces. Actives sites XXI and XXII each yield isotactic polymer molecules through nearly exclusive coordination with the re and si monomer enantioface, respectively, or vice versa. That is, we may not know which enantio-face will coordinate with XXI and which enantioface with XXII, but it is clear that only one of the enantiofaces will coordinate with XXI while the opposite enantioface will coordinate with XXn. This is the catalyst (initiator) site control or enantiomorphic site control model for isoselective polymerization. 

Several studies have dealt with the influence of lipids on conformational equilibria in cytochrome c via hydrophobic and electrostatic interactions. The binding of sodium dodecyl sulfate monomers and micelles was reported to cause a transition of cytochrome c to a state B2 which is of potential physiological relevance. The interplay between heme only state changes and secondary structure changes was analyzed by freeze-quench and stopped-flow experiments.276 The response of the heme spin state to lipid acyl chains in cytochrome c was... 

Approximate conformational energy estimates are utilized to evaluate the RIS model of PVDF, Occasional 10-20%) head to head tail to tail (H-H T-T) addition of monomer units in a random fashion is accounted for In the calculation of these conformational properties. In general it is found that the calculated conformational properties are relatively insensitive to the amount of H-H T-T addition assumed, but are instead markedly dependent upon the value of the dielectric constant Is) selected to mediate the electrostatic interactions encountered along a PVDF chain. 

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