page_title: Host–guest chemistry
section_title: Nuclear magnetic resonance
hierarchical_section_title: Host–guest chemistry / Experimental techniques / Nuclear magnetic resonance
caption_attribution_description: English: PAMAM and drugs
context_page_description: In supramolecular chemistry, host–guest chemistry describes complexes that are composed of two or more molecules or ions that are held together in unique structural relationships by forces other than those of full covalent bonds. Host–guest chemistry encompasses the idea of molecular recognition and interactions through non-covalent bonding. Non-covalent bonding is critical in maintaining the 3D structure of large molecules, such as proteins and is involved in many biological processes in which large molecules bind specifically but transiently to one another.
  Although non-covalent interactions could be roughly divided into those with more electrostatic or dispersive contributions, there are few commonly mentioned types of non-covalent interactions: ionic bonding, hydrogen bonding, van der Waals forces and hydrophobic interactions.
context_section_description: Nuclear magnetic resonance (NMR) is one of the most powerful spectroscopic techniques in analytical chemistry. It is an important tool for the studies of host–guest complexes, for elucidating the structures of the various complexes existing in the form of aggregates, ion pair or encapsulated systems. As the name suggests, NMR identifies the different nuclei in the molecules (most commonly, proton), by measuring their chemical shift. The binding activity of two molecules causes a considerable change in their electronic environments. This leads to a shift in the signals in the NMR spectrum, and this basic principle is made use of to study the phenomena of host–guest chemistry. The driving forces for host–guest binding are the various secondary interactions between molecules, such as hydrogen bonding and pi–pi interaction. Thus, NMR also serves as an important technique to establish the presence of these interactions in a host–guest complex.
  Previous NMR studies have given useful information about the binding of different guest to hosts. Fox et al. calculated the hydrogen-bond interactions between pyridine molecules and poly(amido amine (PAMAM) dendrimer; on the basis of the chemical shift of the amine and the amide groups. In a similar study, Xu et al. titrated carboxylate based G4 PAMAM dendrimer (the host) with various amine based drugs (the guests) and monitored the chemical shifts of the dendrimer. In conjunction with the 2D-NOESY NMR techniques, they were able to precisely locate the position of the drugs on the dendrimers and the effect of functionality on the binding affinity of the drugs. They found conclusive evidence to show that the cationic drug molecules attach on the surface of anionic dendrimers by electrostatic interactions, whereas an anionic drug localizes both in the core and the surface of the dendrimers, and that the strength of these interactions are dependent on the pKa values of the molecules.
  In a different study, Sun et al. studied the host–guest chemistry of ruthenium trisbipyridyl-viologen molecules with cucurbituril. Whilst monitoring the change in the chemical shifts of the pyridine protons on viologen, they found that the binding modes for the 1:1 complexes are completely different for different cucurbituril molecules. 
  An important factor that has to be kept in mind while analyzing binding between the host and the guest is the time taken for data acquisition compared to the time for the binding event. In a lot of cases, the binding events are much faster than the time-scale of data acquisition, in which case the output is an averaged signal for the individual molecules and the complex. The NMR timescale is of the order of milliseconds, which in certain cases when the binding reaction is fast, limits the accuracy of the technique.
caption: Dendrimers used for drug delivery applications (only end groups shown for simplicity) and the common drugs. The nature of the binding between the drug and the dendrimer is important for efficient release of drugs in the body.
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