Supramolecular electrostatic

A poly(propylenamine) dendrimer (11, Fig. 6.37) functionalised with poly-(N-isopropylacrylamide) (PIPAAm) (see Section 4.1.2) was used as dendritic host for anionic cobalt(II)-phthalocyanine complexes (a, b) as guests, which are held together by supramolecular (electrostatic and hydrophobic) interactions [57]. These dendritic complexes were investigated as catalysts in the above-mentioned oxidation of thiols, where they show a remarkable temperature dependence the reaction rate suddenly increases above 34°C. One attempted explanation assumes that the dendritic arms undergo phase separation and contraction above the Lower Critical Solubility Temperature (LCST). At this temperature the phthalocyanine complex site is more readily accessible for substrates and the reaction rate is therefore higher. 

Oshovsky GV, Reinhoudt DN, Verboom W. Self-assembled hemicapsules with inherent Functionalities modeling of a supramolecular electrostatic self-assembly. J Org Chem. 2006 71 7441-7448. 

Supramolecular electrostatically driven assembly of the L-alanine-functionalized calix[4]arene... 

The following sections contain a review of many of the varied synthetic systems that have been developed to date utilising noncovalent interactions to form assembhes of molecules. These sections are loosely demarcated according to the most important type of noncovalent interactions utilized in conferring supramolecular order (ie, van der Waal s interactions, electrostatic interactions, and hydrogen bonds). For extensive reviews, see References 1,2,4—6,22,46,49,110—112. Finally, the development of self-assembling, self-replicating synthetic systems is noted. 

It is well known the tendency of polysaccharides to associate in aqueous solution. These molecular associations can deeply affect their function in a particular application due to their influence on molecular weight, shape and size, which determines how molecules interact with other molecules and water. There are several factors such as hydrogen bonding, hydrophobic association, an association mediated by ions, electrostatic interactions, which depend on the concentration and the presence of protein components that affect the ability to form supramolecular complexes. 

DNA is ideally suited as a structural material in supramolecular chemistry. It has sticky ends and simple rules of assembly, arbitrary sequences can be obtained, and there is a profusion of enzymes for modification. The molecule is stiff and stable and encodes information. Chapter 10 surveys its varied applications in nanobiotechnology. The emphasis of Chapter 11 is on DNA nanoensembles, condensed by polymer interactions and electrostatic forces for gene transfer. Chapter 12 focuses on proteins as building blocks for nanostructures. 

Although non-covalent interactions of anions are one of the most actively explored areas of supramolecular chemistry [15], the anion sensing and recognition have up to now relied primarily on electrostatic binding or hydrogen bonding to the receptor [16,54-61]. However, recent UV-Vis and NMR spectral studies clearly reveal that complex formation takes place in the solutions between halides and neutral olefinic and aromatic it-acceptors such as those in Fig. 3 [23,62],... 

All of these interactions involve a host and a guest as well as their surroundings like solvation, crystal lattice, and gas phase. Electrostatic interactions are the driving force behind the ion pairing (ion-ion, ion-dipole, dipole-dipole, etc.) interactions, which are undeniably important in natural and supramolecular systems. The electrostatic interaction energy E is given by... 

Fluorescence lifetime measurements on the aggregate have shown that the rate constant of the intermolecular energy transfer from the zinc porphyrin unit to the free-base porphyrin unit has been evaluated to be 3.0 x 109 s-1. This value is reasonable from a model in which dendritic donor 6b and acceptor 5a contact each other directly at their exterior surfaces (Scheme 2). Therefore, electrostatic assembly of positively and negatively charged dendrimers provides a promising supramolecular approach to construct photofunctional materials with nanometric precision. 

The general chemistry used in this approach involves the combination of a limited amount of an amine-terminated dendrimer core reagent with an excess of carboxylic acid terminated dendrimer shell reagent [31]. These two charge differentiated species are allowed to self-assemble into the electrostatically driven supramolecular core-shell tecto(dendrimer) architecture. After equilibration, covalent bond formation at these charge neutralized dendrimer contact sites is induced with carbodiimide reagents (Scheme 1). 

Noncovalent interactions in metal complexes of biomolecules may play an important role in the creation of supramolecular structures around the metal center. For instance, extensive three-dimensional hydrogen-bonded stmcmres grow around metal complexes of barbiturates, recognized as the most widely used drugs for the treatment of epilepsy.Electrostatic interactions between a cation and the Trring of an aromatic molecule (cation-tt interactions) are common motifs in protein structures. Little is known about alkali and alkali-earth cation-tt inter-... 

However, the DLVO model cannot completely explain the stabiUzation properties of imidazoUum ILs towards the lr(0) nanoparticles as it treats counterions as mono-ionic point charges and was not designed to account for sterically stabiUzed systems. Together with the electrostatic stabilization provided by the intrinsic high charge of the IL, a steric type of stabilization can also be envisaged. This is due to the presence of anionic and cationic supramolecular aggregates of the type [(BMl),t(X),( ] [(BMl),t (X)J"T where BMl is the l- -butyl-3-methyUmidazoUum cation and X is the anion. 

Fabrication of organic thin films based on sponfaneous molecular assembly has been considered as one of fhe powerful approaches to create novel supramolecular systems. In this context, multilayer films were fabricated by layer-by-layer electrostatic deposition techniques based on the electrostatic interaction between dsDNA and the positively charged polymer poly(diallyldimethylammonium chloride) (PDDA) on GC surfaces. A uniform assembly of PDDA/DNA multilayer films was achieved, based on the adsorption of the negatively charged DNA molecules on the positively charged substrate [55]. 

Studies on molecular recognition by artificial receptors are thus one of the most important approaches to such characterization in relation to supramolecular chemistry [4]. Functional simulation of intracellular receptors in aqueous media has been actively carried out with attention to various noncovalent host-guest interactions, such as hydrophobic, electrostatic, hydrogen-bonding, charge-transfer, and van der Waals modes [5-10]. On the other hand, molecular recognition by artificial cell-surface receptors embedded in supramolecular assemblies has been scarcely studied up to the present time, except for channel-linked receptors [11-13]. 

Controlled self-assembly allows exo-active surfaces to be viable supramolecular building blocks for constructing nanostructure assemblies. These nanostructure assemblies can be used to modify electrodes for sensing applications. Willner and coworkers have constructed nanostructure assemblies on electrodes through electrostatic cross-linking of citrate stabilized gold NPs and bipyridinium cyclophane (3,5-... 

Another method for the analysis of aptamer-protein complexes involved the use of a positively charged ferrocene-tethered polythiophene, (19), as redox label reporting unit (Fig. 12.19). The antithrombin aptamer was immobilized on an electrode surface, and the electrostatic binding of the redox polymer (19) to the aptamer monolayer resulted in a supramolecular complex that revealed electrical contact between the polymer and the electrode.74 The formation of the aptamer-thrombin complex removed the polymer from the surface and blocked the electrical contact between the polymer label and the electrode. As a result, higher concentrations of thrombin increased the surface coverage of the aptamer-thrombin complex on the electrode, and this decreased the amperometric responses of the sensing device. 

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