Design of Cyclophanes: Synthesis and Study of Photophysical and Biomolecular Recognition Properties

Development of organic molecules that exhibit selective interactions with different biomolecules has immense significance in biochemical and medicinal applications. In this context, our main objective has been to design a few novel functionaIized molecules that can selectively bind and recognize nucleotides and DNA in the aqueous medium through non-covalent interactions. Our strategy was to design novel cycIophane receptor systems based on the anthracene chromophore linked through different bridging moieties and spacer groups. It was proposed that such systems would have a rigid structure with well defined cavity, wherein the aromatic chromophore can undergo pi-stacking interactions with the guest molecules. The viologen and imidazolium moieties have been chosen as bridging units, since such groups, can in principle, could enhance the solubility of these derivatives in the aqueous medium as well as stabilize the inclusion complexes through electrostatic interactions.We synthesized a series of water soluble novel functionalized cyclophanes and have investigated their interactions with nucleotides, DNA and oligonucIeotides through photophysical. chiroptical, electrochemical and NMR techniques. Results indicate that these systems have favorable photophysical properties and exhibit selective interactions with ATP, GTP and DNA involving electrostatic. hydrophobic and pi-stacking interactions inside the cavity and hence can have potential use as probes in biology.

" Studies on Laser induced Phatothermal Phenomena in Selected Organic Compounds and Fullerenes"

In the pre—laser era it was difficult to believe that the optical properties of a medium depend upon the intensity of the radiation incident on it. The basis for this conclusion is that the electric field strength associated with the conventional light sources used before the advent of lasers was much smaller than (103 V/cm) the field sttrengths of atomic or interatomic fields (2 107 —- 10” V/cm). The radiation with such low intensity is not able to affect atomic fields to the extent of changing optical parameters. The invention of laser in 1960 was a turning point. The high degree of coherence of the laser radiation provides high spatial concentration of optical power. With the availability of the femtosecond lasers it has become possible to get extremely high peak powers 2 1013 W/cmz). At such high fields, the relationship between electric ‘polarization P and the electric field strength E ceases to be linear and several nonlinear effects begin to occur. Nonlinear absorption, a branch of nonlinear optics, refers to the interaction between radiation and matter accompanied by absorption of more than one photon. Nonlinear absorption has acquired great importance after the invention of high power lasers. One of the objectives of the present work is to investigate the nonlinear absorption processes occurring in fullerene, selected organic solvents and laser dyes. Fullerenes and laser dyes were chosen because of their highly nonlinear behaviour. Fullerenes, the most beautiful among molecules, offer fascinating field of research owinglto their significant structural properties. As toluene, benzene and carbon disulphide are themost widely used solvents for fullerenes, it seems important to study the nonlinear properties of these liquids as well. Like fullerenes, laser dyes also possess highly delocalized 7r electrons which are responsible for their nonlinear absorption. Dye lasers were the fulfillment of an experimenter’s pipe dream - to have a laser that is easily tunable over a wide range of wavelengths. A better understandingof the photophysical properties of laser dyes can significantly enhance the development and technology of dye lasers. We studied the nonlinear absorption properties of two rhodamine dyes to have some insight into their nonlinear optical properties.

Synthesis and Study of Photophysical and Metal Ion Binding Properties of a Few Novel Semisquaraine and Croconaine Dyes

Photosciences & Photonics, Chemical Sciences & Technology Division, National Institute for Interdisciplinary Science & Technology

Design Of Metal Architectures: Synthesis And Study Of Their Photophysical And Biomolecular Recognition Properties

Design and study of molecular receptors capable of mimicking natural processes has found applications in basic research as well as in the development of potentially useful technologies. Of the various receptors reported, the cyclophanes are known to encapsulate guest molecules in their cavity utilizing various non–covalent interactions resulting in significant changes in their optical properties. This unique property of the cyclophanes has been widely exploited for the development of selective and sensitive probes for a variety of guest molecules including complex biomolecules. Further, the incorporation of metal centres into these systems added new possibilities for designing receptors such as the metallocyclophanes and transition metal complexes, which can target a large variety of Lewis basic functional groups that act as selective synthetic receptors. The ligands that form complexes with the metal ions, and are capable of further binding to Lewis-basic substrates through open coordination sites present in various biomolecules are particularly important as biomolecular receptors. In this context, we synthesized a few anthracene and acridine based metal complexes and novel metallocyclophanes and have investigated their photophysical and biomolecular recognition properties.