Is Gum Arabic a Good Emulsifier Due to CH...π Interactions? How Urea Effectively Destabilizes the Hydrophobic CH...π Interactions in the Proteins of Gum Arabic than Amides and GuHCl?

The photophysical studies of gum arabic (GA) in the presence of urea, 1,3-dimethylurea (DMU), tetramethylurea (TMU), guanidine hydrochloride (GuHCl), formamide (FA), acetamide (AA), and dimethyl formamide (DMF) were carried out by monitoring the emission, three-dimensional emission contour, and time-correlated fluorescence lifetime techniques. On addition of only 1 × 10-3 M urea, 75.0% of the fluorescence of GA is quenched, while the same occurs in GuHCl at 3.0 M. FA quenched 50% of the fluorescence of GA at 5.0 M. However, DMU, TMU, AA, and DMF resulted in a fluorescence enhancement. The unusual fluorescence trends reveal the existence of CH...π interactions in the proteins of GA. The experimental results and the structural aspects of proteins in GA led us to propose that the aggregation of polyproline helices in GA, through several CH...π interactions, would have a major role to play in the emulsification mechanism of GA.

Multicharacteristic Behavior of Tyrosine Present in the Microdomains of the Macromolecule Gum Arabic at Various pH Conditions.

Gum arabic (GA), the dried exudates of Acacia seyal and Acacia senegal trees, being a biopolymer, has found many applications in the food, pharmaceutical, cosmetic, and lithography industries. GA, a water-soluble food hydrocolloid, is a complex and variable mixture of arabinogalactan oligosaccharides, polysaccharides, and glycoproteins. It has been a subject of great interest and a wide range of research has been done on the polysaccharide structural aspects and the emulsifying properties only. In the present study, fluorescence spectral technique is employed as an analytical tool to understand the photophysics of GA. The tyrosine microenvironment of GA was explored by studying the steady-state absorption, emission, fluorescence lifetime, and three-dimensional (3D) emission contour spectra of GA at various pH conditions in aqueous solution. The multiple emissive states are attributed to the presence of intrinsic fluorophore tyrosine in a heterogeneous microenvironment. The study portrays the multicharacteristic behavior of tyrosine in various pH conditions and in different microdomains. The exposure of the buried tyrosine to the heterogeneous aqueous phase was authenticated by 3D emission contour spectral studies. An interesting visualization of tyrosine involving in hydrogen-bonding network with another tyrosine moiety at neutral pH was ascertained. The coexistence of hydrophilic carbohydrate and hydrophobic protein in GA enables its emulsification and stabilization properties. Hence, any advancement toward understanding the protein microenvironment of GA is of great significance for chemists, as the molecular modeling and biosynthesis of the gum with desired end product are underway in many research institutes.