Organoclay Layered Nanocomposites

Hybrid Nanostructures Based on Organociay Wrapping of Single Biomolecules 

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The enzymatic activities of intercalated GOx-AM P layered nanocomposites at various pH values and temperatures were compared with the native enzyme in aqueous solution. In both cases, characteristic linear plots consistent with Michalis-Menton kinetics were obtained. The Lineweaver-Burk plots indicated that the reaction rates (Vmax) for free and intercalated GOx (3.3 and 4.0 pM min 1 respectively), were comparable, suggesting that the turnover rate at substrate saturation was only marginally influenced by entrapment between the re-assembled organoclay sheets. However, the dissociation constant (Km) associated with the activity of the enzyme was higher for intercalated GOx (6.63 mM) compared to native GOx (2.94 mM), suggesting... 

Fig. 8.18 Schematic diagram showing the potential scope of organically functionalized magnesium phyllosilicate (shown in top centre of figure) for the preparation of functional bioinorganic nanomaterials. (A) biomolecule-induced co-assembly of exfoliated aminopro-pyl-functionalized organoclay sheets to produce layered nanocomposites containing functional protein molecules (top left) or DNA (bottom left). (B) molecular wrapping...

Nanohybrids can be prepared in the form of intercalated layered nanocomposites produced by co-assembly of guest biomolecules in the presence of exfoliated organoclay sheets (Section 8.4), or by wrapping single biomolecules in ultrathin layers of condensed organoclay oligomers (Section 8.5). Such approaches should provide new general routes towards the development of functional biomaterials with numerous applications. 

Fig. 17.24 TEM micrographs of nylon 6/organoclay/EOR-g-MA (76/4/20) ternary nanocomposite showing (a) submicron and nano-voids which are associated with intra-gallery delamination of some organoclay layers (note that the section is not selectively stained in order to clearly reveal delaminations of clay layers), (b) cavitation of EOR-g-MA particles which preferentially starts from the larger particles as indicated by arrows, and (c) extensive matrix shear yielding at the arrested crack tip which in turn causes the EOR-g-MA particles and delaminated clay layers to collapse within the matrix. A schematic of the arrested crack tip illustrating different locations from where TEM micrographs (a-c) were taken is also shown. Note that the schematic is not to scale (Lim et al. 2010)...

VanderHart and co-workers [37] used solid-state NMR ( H C) spectroscopy for the first time as a tool to study the morphology, surface chemistry and to a very limited extent the dynamics of exfoliated PCN. This method uses the reduction in the spin-spin relaxation time,, of a nanocomposite when compared with the neat system, as an indicator for the organoclay layer separation. It was shown that the paramagnetic Fe " ions in the crystal lattice of the montmorillonite provide an additional relaxation mechanism of the protons. The additional relaxation depends on average Fe - H distance, which is determined by clay concentration and dispersion of clay in the matrix. 

A typical shish-kebab crystalline structure has been foimd by Maiti and Okamoto (2003) and Kim et al. (2001) in polyamide/organoclay nanocomposite and by Choi and Kim (2004) in PP/EPR/talc nanocomposite where a preferential orientation of polymer lamellae perpendicular to the surface of organoclay layers was inspected by TEM measurements. The unique observation of lamellar orientation (Ml the clay layers was ascribed to nucleation and epitaxial crystallization at the interface between layered silicate and polymer matrix especially the surfaces of clay platelets acted as heterogeneous nucleation sites. Orientation of iPP crystals was also enhanced in rPP/PP-MA/o-MMT injection-moulded parts, especially manufactured by dynamic packing injection moulding (Wang et al. 2005). MMT... 

PBT/EVA-g-MAH/organoclay ternary nanocomposite also shows enhanced thermal stabilities compared to its pristine counterpart, due to the clay layer structure, which restricts the mobility of the small molecules produced during degradation. 

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