Mismatch branching

There was still some room for uncertainty on this retention-retention mechanism. The argument was, if the unobserved tt-allyl Mo complex (such as 77 or B in Scheme 2.18) was more highly reactive towards sodium malonate than experimentally observed tt-allyl Mo complexes (such as 71, 74, and 80), the reaction should proceed through inversion (since there is an equilibrium between the two tt-allyl Mo complexes via the o-allyl complex.) If so, when the isolated Mo-complex 71 was subjected to the reaction, 71 must be equilibrated to the enantiomer of 71 via the o-allyl complex prior to reaction with a nucleophile. Therefore, reaction from the Mo complex 71 should proceed with less stereoselectivity than that from a mismatched branched carbonate. This hypothesis was examined, as shown in Scheme 2.26. 

Cladistics for Products and Manufacturing, Fig. lO Imperfect coevoliition of products and manufacturing system causing mismatching branches (Adapted from (AlGeddawy andElMaraghy 2012))... 

The pattern formation of fiber networks to be discussed as follows is controlled by a completely new mechanism, the so-called crystallographic mismatch branching mechanism. The patterns produced by this mechanism can have both the microscopic interfacial anisotropy and the characteristic of fractals, hi particular, the evolution of the pattern is supersaturation- and impurity-dependent. 

As to be discussed in Sect. 4.1, the crystallographic mismatch branching can be utilized to construct self-organized interconnecting fiber network structures/patterns, so as to engineer supramolecular fimctional soft materials. 

In this section, we will focus on the formation of fibrous networks/patterns via the (wide angle) crystallographic mismatch branching. Actually, the typical patterns that occurred owing to the (wide angle) crystallographic mismatch branching are shown in Fig. 5b and c. 

The key question to be addressed is why and how crystallographic mismatch branching takes place. Obviously, the crystallographic mismatch branching takes place via the supersatmation-driven interfacial structural mismatch or the crystallographic mismatch nucleation and growth (Fig. 5). 

The occurrence of crystallographic mismatch branching is controlled by the following two steps (1) the growth of the surface of parent crystals (2) the crystallographic mismatch nucleation on the surface. 

Fig. 8 The correlation between ln[ )(A/r/ r)" ] and l/ Afi/kT) for a lanosta-8,24-dien-3/3-ol 24,25-dihydrolanosterol = 56 44 (L-Dffl,)/di-(2-ethylhex)d phthalate) (C8Hi7COO)2 (C6H4) (DIOP) system with 0.01% ethylene/vinyl acetate copolymer (EVACP) at 20 °C. The linear relationship confirms the governing role of the crystallographic mismatch branching mechanism in the formation of organized interconnecting fiber networks. T = 298.15 K, X = 0.026. The supersaturation difference A/x/kT is obtained by changing the molar fraction of the solute in the solutions [18]...

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