Noncovalent surfactants

The rate constants for micelle-catalyzed reactions, when plotted against surfactant concentration, yield approximately sigmoid-shaped curves. The kinetic model commonly used quantitatively to describe the relationship of rate constant to surfactant, D, concentration assumes that micelles, D , form a noncovalent complex (4a) with substrate, S, before catalysis may take place (Menger and Portnoy, 1967 Cordes and Dunlap, 1969). An alternative model... 

Many commercially important polymers are produced via emulsion polymerization. This is also one of the most common methods to produce dye-doped beads. A dye is added to the mixture of monomers prior to initiating the polymerization and is either noncovalently entrapped or is copolymerized. The second method ensures that no leaching will occur from the particle but requires modification of the dye (typically by providing it with a double bond). This method is most common for preparation of pH-sensitive beads where a pH indicator is entrapped inside cross-linked polyacrylamide particles. The size of the beads can be tuned over a wide range so that preparation of both nano- and microbeads is possible. Despite thorough washing the surfactants are rather difficult to remove completely and their traces can influence the performance of some biological systems. 

Purification is often required for the beads obtained by the techniques described above since undesired substances such as surfactants, coupling agents, etc. need to be removed. This is also valid for dye molecules noncovalently adsorbed on the surface of the beads since they usually have different properties (sensitivity, cross-talk to other analytes, leaching, etc.) compared to the molecules located in the core. The dye-doped beads can be purified by repeated precipitation which is achieved by adding salts (typically sodium chloride). In certain cases (typically for large beads) the addition of salts is not necessary so that the beads can be isolated by centrifugation. Washing with ethanol often helps remove lipophilic dye molecules adsorbed on the surface provided that the polymer is not swellable. Alternatively, dialysis can be useful especially if a hydrophilic water-soluble indicator is covalently coupled to the bead surface. 

An alternative efficient approach to disperse CNTs relies on the use of synthetic peptides. Peptides were designed to coat and solubilise the CNTs by exploiting a noncovalent interaction between the hydrophobic face of amphiphilic helical peptides and the graphitic surface of CNTs (Dieckmann et al., 2003 Zoibas et al., 2004 Dalton et al., 2004 Arnold et al., 2005). Peptides showed also selective affinity for CNTs and therefore may provide them with specifically labelled chemical handles (Wang et al., 2003). Other biomolecules, such as Gum Arabic (GA) (Bandyopadhyaya et al., 2002), salmon sperm DNA, chondroitin sulphate sodium salt and chitosan (Zhang et al., 2004 Moulton et al., 2005), were selected as surfactants to disperse CNTs (Scheme 2.1). 

Fig. 1.3 Functionalization pathways for SWNTs (a) defect-group functionalization, (b) covalent side-wall functionalization, (c) noncovalent exohedral functionalization with surfactants, (d) noncovalent exohedral functionalization with polymers, and (e) endohedral functionalization with, for example, C60. For methods (b)-(e), the tubes are drawn in idealized fashion, but defects are found in real situations. From [103] with kind permission of Wiley.

The alternative noncovalent functionalization does not rely on chemical bonds but on weaker Coulomb, van der Waals or n-n interactions to connect CNTs to surface-active molecules such as surfactants, aromatics, biomolecules (e.g. DNA), polyelectrolytes and polymers. In most cases, this approach is used to improve the dispersion properties of CNTs [116], for example via charge repulsion between micelles of sodium dodecylsulfate [65] adsorbed on the CNT surface or a large solvation shell formed by neutral molecule (e.g. polyvinylpyrrolidone) [117] around the CNTs. 

It is possible to divide the noncovalent functionalization according to the type of molecules used, thus four categories are found (1) surfactants, (2) polymers, (3) bio-... 

The majority of studies have used surfactants that wrap around nanocarbons via van der Waals interactions [37]. For instance, surfactants such as sodium dodecylsulfate (SDS) are commonly used to disperse CNTs in aqueous solutions [38,39] while other surfactants, such as Pluorinc-123, are used to mechanically exfoliate graphene from graphite flakes (Fig. 5.4(a)) [40,41]. The polar head group of the surfactant can be used to further hybridize the nanocarbon via a range of covalent or noncovalent interactions [42]. For example, nanoparticles of Pt [43,44] and Pd [45] have been decorated onto SDS-wrapped MWCNTs. Similarly, Whitsitt et al. evaluated various surfactants for their ability to facilitate the deposition of Si02 NPs onto SWCNTs [46,47]. As an exam-... 

Noncovalent interaction of SWNTs with organic molecules (pyrene and naphthalene) and surfactants of different types in aqueous solutions leads to the spectral shift of lines and its intensity redistribution in spectra in comparison with the spectra of pristine SWNT. 

Noncovalent approaches can usually preserve the structures and properties of carbon nanotubes after functionalization17 (though not necessarily the near-infrared absorption characteristics due to well-established doping effects), thus are equally important to the biocompatibilization and bioapplications of nanotubes.15 Among commonly employed noncovalent schemes are surfactant dispersion,18 tt-tt stacking with aromatic compounds,19 and polymer wrapping.20... 

Noncovalent functional strategies to modify the outer surface of CNTs in order to preserve the sp2 network of carbon nanotubes are attractive and represent an effective alternative for sidewall functionalization. Some molecules, including small gas molecules [195], anthracene derivatives [196-198] and polymer molecules [118, 199], have been found liable to absorb to or wrap around CNTs. Nanotubes can be transferred to the aqueous phase through noncovalent functionalization of surface-active molecules such as SDS or benzylalkonium chloride for purification [200-202]. With the surfactant Triton X-100 [203], the surfaces of the CNTs were changed from hydrophobic to hydrophilic, thus allowing the hydrophilic surface of the conjugate to interact with the hydrophilic surface of biliverdin reductase to create a water-soluble complex of the immobilized enzyme [203]. 

Noncovalent functionalization - incubation with surfactants and lipids A 1-mL aqueous solution of SDS [1 % by weight, concentration greater than the critical micellar concentration (CMC)], was sonicated with 1 mg of SWCNTs or MWCNTs. Similarly, an aqueous solution (1 mg mL-1) of an amphiphilic monochain lipid reagent, e.g. an octadecanoyl moiety linked with nitrilotriacetic acid, was sonicated with 1 mg of MWCNTs for 3 min [206]. 

Hence DOLPA reverse micelles recognize the Arg-rich proteins through specific phosphate-guanidinium groups. Such noncovalent bonds of surfactant molecules lead to alterations in the hydrophilic protein surface into sufficiently hydrophobic surfaces to be solubilized in a nonpolar solvent. Molecular recognition on the protein surface facilitates protein transfer, a significant characteristic for the specific separation of biomolecules. 

A recent and exciting area of research is the solubilization of enzymes in nonaqueous solvents. One way solubilization is achieved is through noncovalent complexes of lipid (surfactant) and protein, to be referred to here as enzyme-lipid aggregates, or ELAs. Such complexes are reported to be highly active and stable. Moreover, the activity of ELAs can be significantly higher than free, suspended enzyme (in the absence or presence of surfactant), enzymes solubilized in aqueous-organic biphasic systems, or reverse micellar solutions, and can approach catalytic rates in... 

Noncovalent functionalization with derivatives of pyrene, formation of micelles with various surfactants, wrapping in polymers (including starch, peptides)... 

Surfactant molecules can also be used as anchors for the immobilization of chemical species by noncovalent interactions [38], The hydrophobic part of the molecule interacts with the graphene sheets, whereas the hydrophilic head (charged) can interact with the metal complex by electrostatic interactions or covalent bonding. Polyelectrolytes can also act as spacers for charged chemical species, and in this case, strong electrostatic interactions with carbon materials occur [49,53],... 

An example of micellar oxidahon is a biomimetic system of cytochrome P450 investigated by Monh et al. [12], who foimd in the epoxidahon of styrene with NaOCl a significant influence of the type of surfactant cetylpyridinium chloride promoted the reachon more than cetyltrimethylammonium bromide. One explanahon could be a specific noncovalent interachon between catalyst, substrate and surfactant. 

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