**1. Introduction**

280 Soybean – Genetics and Novel Techniques for Yield Enhancement

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Today's research worlds try to bring everything in nanosize and the tremendous development on nanosize and technology introduced numbers of molecules with immense applications. Though nanostructures from numbers of metals and materials are being synthesized, supramolecular structures attracts the research group at increasing level, because of the interest and urge to know the origin of life. Hence, research groups at global level are making attempts on how the self-assembly and the supramolecular structures have been formed from the single and /or from the combination molecules.

Thus the design and the construction of supramolecular assembly/structures are quite interesting and various hypothetical theories have been developed to substantiate the origin of life. Supramolecular structures are large molecules fashioned by binding of smaller molecules mutually and it often to develop molecules of preferred form including 2D triangles, squares, pentagons, hexagons and 3D octahedrons, cubes and some irregular shapes. Self-assembly is the most prevailing methodology in the design of large, distinct, ordered structures.

The objects of supramolecular chemistry are defined on one hand by the nature of the molecular components and on the other by the type of interactions that hold them together. Three major steps are involved in supramolecular systems; (i) selective binding, (ii) growth of the components in the correct relative orientation and (iii) termination requiring a built in feature which signifies the end process. The chemistry of supramolecular structure is a constitutional dynamic chemistry due to the reversibility of the connecting events. The kinetic liability confers the self-assembling systems to undergo annealing and self-healing of defects and to manifest tunable degree of polymerization and cohesive properties. In contrast, covalent linked, nonlabile type cannot heal spontaneously and the defects are permanent (Lehn, 2005).

According to Murakami, synthesis of supramolecular structure is based on the principle of molecular recognition and molecular self-assembly realized due to the formation of noncovalent interaction towards the cooperation of many weak bonds including electrostatic interaction, Van der Waals forces, dipole interaction, hydrogen bonding, hydrophobic interaction, and π–π interaction. Recently the interest was drawn to a new topological form of supramolecular structures by self-assembly and also by weak interactions.

Transformation of Soybean Oil to Various Self-Assembled Supramolecular Structures 283

iodanes, 18 crown-6 (Ochiai et al., 2003) and etc. Similarly, semisynthetic or the combinational substrates such as galactocerebroside containing long chain unsaturated fatty acids, tris(hydroxylmethyl)- aminomethane based biosurfactant, hyperbranched polyethelenimine and fatty acids, glycolipid derivative with hydrogenated fluorinated

In addition, a complete bio-based supramolecular structures from milk fat protein, lipids, DNA, RNA complex, nucleotides, aminoacids or doublechain aminoacids, phospholipids, glycolipids, peptides, gluconamides, bolamphiphilies, lipopeptide and biological

Even though supramolecular assemblies from above said molecules are in reports with varied hypothetical explanation, however, still the story behind the assembly of biological molecule is unclear. To understand the theory of self-assembly and supramolecular formation, researchers initiated the self-assembly studies using fatty acids and its derivatives. Montarnal et al., (2008) reported self-healing supramolecular rubber like material using vegetable oil, unsaturated fatty acid derivatives, combined with diethylene triamine and urea. Vegetable oil based supramolecular organogel is synthesized by Rogers et al., (2007). Chen et al., (2005) prepared supramolecular nanocapsules by electrostatic interaction between fatty acids palmitic acid and polyethylenimine. A mixture of fatty diacid and triacid is condensed first with diethylene triamine and then reacted with urea giving an oligomeric supramolecular self-assembled thermoreversible rubber having selfhealing property (Cordier et al. 2008). Novales et al., (2008) reported self-assembly of fatty

Maximum reported supramolecular assemblies involve complete synthetic or hybrid systems and or semi biological system. Complete biological means of supramolecular

The present chapter covers the formation of various supramolecular structures from vegetable oils by microbial product mediated process. The experiments conducted in our laboratory revealed *in situ* transformation of vegetable oils to self-assembled different supramolecular structures viz., vesicle, stable vesicle, supramolecular capsules, colloidosomes, self-healing material, supramolecular rubber like material, organogels, sheet/ flims, bioadhesives, etc., mediated through microbial products. Three different experimental setups were run. In the first set of experiments, microbes were directly used for the transformation of vegetable oil to supramolecular structures. For the second set up, instead of microbes, microbial products were used. The third sets of experiments were executed without any microbes and microbial products but prior to exposure to the

Soybean and sunflower oil are directly procured from the manufacturers and used as a source for triglycerides. Microbes used in the present study are from the varied sources; marine and clinical origin. Microbial products are also from media suppliers; HiMedia Laboratories Pvt. Ltd and MERCK Ltd. The media used for present study are (i) mineral medium comprises of 1 g NH4NO3; 2.55 g NaH2PO4; 0.5 g MgSO4·7H2O; 0.1 g CaCl2·H2O; 0.02 g MnSO4·H2O; 1 g Peptone; 0.5 g Glucose; Zobell marine broth containing 5g Peptic

assemblies demand more time and the process of synthesize is a challenging task.

**2. Transformation of soybean oil to supramolecular structures-**

**a biomediated process** 

medium, the oil was heated at 100 C.

mixed lipid tail, synthetic spingolipids, block copolymers and etc., are also in use.

amphiphilies compounds are also introduced by various researchers.

acids and hydroxyl derivative salts to form supramolecular assembly.

**1.2 Vegetable oil / fatty acid based supramolecular structures** 

Generally, supramolecular solid structures are commonly prepared by different templates; polymers, polystyrene, silica and some other metal nanoparticles. Vesicles and microemulsions are used as template to develop on an attractive and stable supramolecular structure. However, in the soft template approach, the control on the size and mechanical stability of the supramolecular structures could become a problem. Further, as pointed out by Shelnutt and his co-workers, it is not easy to prepare stable or large sized (e.g., > 100 nm in diameter) and thickly walled supramolecular spheres based on the soft template approach. Therefore, a new protocol using biological materials through which the rigid structure with controllable size and thickness can be made easily is of great interesting.

Amphiphilic and/or non-polar components further increase the structural diversity to include sponge and microemulsion phases, and even stable multiphase colloidal dispersions of one complex fluid in another – cubosomes and hexosomes. Many aspects of these nanostructures remain under exploited because self-assembled structures exist in dynamic equilibrium, and hence respond to changes in solution conditions. A great deal could potentially be achieved if amphiphilic self-assemblies could be rendered more robust *in situ.* One method for achieving this is to "lock-in" the self-assembled structure using polymerizable surfactants.

Simple, single-chain fatty acids have long been known to self-assemble into supramolecular structures such as micelles and vesicles (Gebicki & Hicks, 1973; Gebicki & Hicks, 1976). Fatty acids in a bilayer membrane are in rapid exchange with the aqueous environment (Walde et al., 1994). Such amphiphiles can also interact with solid surfaces. The interaction of amphiphiles with solid surfaces often involves adsorption due to chemical or physicochemical forces through covalent bonds, hydrogen bonds, ion exchange, Van der Waals forces, and hydrophobic effects (Giles, 1982; Evans, 1986).

The interactions of simple, single-chain amphiphiles with many different surfaces results in the organization of membranes and the formation of vesicles. This effect could have played a key role in the organization and formation of the first cell-like structures on the early earth. Since mineral particles have been implicated in very early chemistries and polymerization reactions (Bernal, 1951; Wachtershauser, 1988; Ferris and Hill et al., 1996; Sowerby et al., 2001; Sowerby et al., 2002; Monnard, 2005), it is intriguing that minerals might have also been involved in the formation of yet another essential component of lifethe cellular membrane. Mineral-mediated vesicle formation occurs with many disparate types of minerals and is therefore a more general property than clay-catalyzed RNA polymerization.
