CHEMOENZYMATIC FUNCTIONALIZATION OF RIBONUCLEIC ACID WITH AZOBENZENE CHROMOPHORES

In recent years, biological molecules have brought about a renaissance in the development of novel responsive materials. An example of this is the development of new photoresponsive materials for the artificial regulation of chemical and biological systems. Towards this we have developed a novel enzymatic synthetic approach for covalent attachment of photoresponsive units into the RNA backbone. This involves a lipase catalyzed acylation of the 2' hydroxyl group in the ribose sugars in the RNA molecule to incorporate photo-isomerizable azobenzene groups into the RNA strands. A reverse micellar approach was used for this RNA functionalization to maintain the solubility of the nucleic acid as well as to limit the preferred hydrolysis reaction in aqueous media. The azobenzene groups incorporated in the RNA molecule show photo-isomerization behavior and can serve as optical ‘handles’ for the manipulation of the conformation of RNA. This modification of RNA using covalently attached chromophores or fluorophores is a generic approach that can be extended to other biomacromolecular matrices leading to new opportunities for biophotonic device applications. †Deceased.

[1]  M. Komiyama,et al.  meta-Aminoazobenzene as a thermo-insensitive photo-regulator of DNA-duplex formation , 2000 .

[2]  M. Komiyama,et al.  Photo-responsive oligonucleotides carrying azobenzene at the 2′-position of uridine , 1999 .

[3]  T. Cech,et al.  RNA tertiary folding monitored by fluorescence of covalently attached pyrene. , 1999, Biochemistry.

[4]  M. Komiyama,et al.  PHOTO-RESPONSIVE OLIGONUCLEOTIDES CARRYING AZOBENZENE IN THE SIDE-CHAINS , 1998 .

[5]  I. Hamachi,et al.  Photoswitching of the Enzymatic Activity of Semisynthetic Ribonuclease S′ Bearing Phenylazophenylalanine at a Specific Site , 1998 .

[6]  J. Kumar,et al.  Enzymatically Synthesized Photodynamic Polyaniline Containing Azobenzene Groups , 1998 .

[7]  M R Chance,et al.  RNA folding at millisecond intervals by synchrotron hydroxyl radical footprinting. , 1998, Science.

[8]  T. Cech,et al.  Kinetic pathway for folding of the Tetrahymena ribozyme revealed by three UV-inducible crosslinks. , 1996, RNA.

[9]  K. Yamana,et al.  SYNTHESIS OF A NEW PHOTOISOMERIZABLE LINKER FOR CONNECTING TWO OLIGONUCLEOTIDE SEGMENTS , 1996 .

[10]  D. Turner,et al.  The time dependence of chemical modification reveals slow steps in the folding of a group I ribozyme. , 1995, Biochemistry.

[11]  P. Zarrinkar,et al.  Kinetic intermediates in RNA folding. , 1994, Science.

[12]  E. Gulari,et al.  Enzymatic Esterification of Diols in Reverse Micellar Media , 1994 .

[13]  E. Gulari,et al.  1‐Monoglyceride production from lipase‐catalyzed esterification of glycerol and fatty acid in reverse micelles , 1991, Biotechnology and bioengineering.

[14]  Shai Rubin,et al.  Photoregulation of papain activity through anchoring photochromic azo groups to the enzyme backbone , 1991 .

[15]  F. Ciardelli,et al.  Photoresponsive polymers: Azobenzene‐containing poly(L‐lysine) , 1987 .

[16]  N. Rosato,et al.  Azobenzene-containing poly(l-glutamates). Photochromism and conformation in solution , 1983 .

[17]  P. Luisi,et al.  Solubilization and condensed packaging of nucleic acids in reversed micelles. , 1982, Biochemical and biophysical research communications.

[18]  Nirmal K. Viswanathan,et al.  Surface relief structures on azo polymer films , 1999 .

[19]  M. Winnik.  Photophysical and Photochemical Tools in Polymer Science , 1986 .

[20]  S. Suzuki,et al.  Control of peptide chain conformation by photoisomerising chromophores: Enzymes and model compounds , 1983 .

[21]  G. Smets.  Photochromic phenomena in the solid phase , 1983 .