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We report a very selective and sensitive spectroscopic detection of Z-DNA embedded in B-DNA in condensed as well as non-condensed DNA using anionic Ni(II) meso-tetrakis(4-sulphonatophenyl)porphyrin, NiTPPS. A combination of micromolar concentrations of Ni(II) and spermine(4+) allowed us to prepare left-handed Z-DNA in short oligonucleotides without DNA condensation. A strong induced circular dichroism (ICD) signal was observed in the visible absorption region when NiTPPS was added to BZ DNA (Z-DNA fragment located at the end of a B-DNA tract with one B/Z DNA junction) and BZB DNA (Z-DNA sequence embedded in B-DNA having two B/Z DNA junctions). Almost no ICD signal was detected when NiTPPS was added to B-DNA. NiTPPS showed different binding modes with condensed and non-condensed Z-DNAs and allowed the distinction between condensed Z-DNA (positive bisignate CD couplet) and non-condensed Z-DNA (negative bisignate CD couplet)., (Copyright © 2012 Elsevier Inc. All rights reserved.)

For the first time it has been shown by spectroscopic studies such as circular dichroism and UV/Vis that cationic zinc porphyrin serves as a selective spectroscopic sensor that is able to recognize short left-handed Z-DNA tracts embedded in the B-Z-B sequences., (Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Here, we report a highly sensitive and specific chiroptical detection method of condensed left-handed Z-DNA in the presence of canonical right-handed B-DNA. The selective formation of a left-handed cytosine-guanine oligonucleotide (CG ODN) in the presence of a right-handed adenine-thymine oligonucleotide (AT ODN) was induced by millimolar concentrations of NiCl(2) and confirmed by electronic circular dichroism. The nickel(II) induced B- to Z-DNA transition of the CG ODN was accompanied by the concurrent condensation of the Ni(II)-Z-DNA, as confirmed by resonance light scattering, transmission spectroscopy, and centrifugation. The selective condensation of the CG ODN allowed its separation from the AT ODN using centrifugation. No structural changes were observed for the AT ODN upon addition of Ni(II). Anionic nickel(II) meso-tetra(4-sulfonatophenyl) porphyrin (NiTPPS) spectroscopically detected the left-handed Z-DNA in the Z-DNA/B-DNA mixture via a strong exciton coupled circular dichroism (ECCD) signal induced in the porphyrin Soret band absorption region. The bisignate ECCD signal originates from the assembly of achiral porphyrins into helical arrays by intermolecular interactions with the condensed Z-DNA scaffold. No induced CD signal was observed for the Ni(II)-B-DNA-NiTPPS complex. Hence, an unambiguous spectroscopic recognition of Ni(II) induced condensed Z-DNA in the presence of B-DNA is possible. The sensitivity of this chiroptical method was as low as 5% of the Z-DNA (4.4 μmol base pair concentration) in the presence of 95% B-DNA (80 μmol). Thus, NiTPPS is a highly sensitive probe for applications in biosensing via the CD signal amplification., (© 2011 American Chemical Society)

Using exciton-coupled circular dichroism (ECCD) spectroscopy, our lab was able to differentiate between the two enantiomers of methamphetamine using a commercially available porphyrin tweezer as an achiral host. The host-guest complex formed with (+)-(S)-methamphetamine produced a negative bisignate-shaped ECCD spectrum, whereas the complex formed with (-)-(R)-methamphetamine produced a positive one. This sensitive technique could serve as an alternative method for the enantiodiscrimination of chiral methamphetamine, a commonly abused drug in the United States., (2009 Wiley-Liss, Inc.)

Porphyrinmaleimides were synthesized and characterized. The thiol-containing amino acid L-cysteine reacted with 58% yield with these porphyrins to form bioconjugate adducts. The new thiol-active reagents were labeled cytoplasmic cysteine 140 and 316 in rhodopsin (Rh), a G protein coupled receptor (GPCR).

Thymidine phosphoramidites containing trispyridylphenyl and tetraphenylporphyrin chromophores attached via a short amide linker in the 3'-position have been synthesized and used as building blocks in solid-phase synthesis of self-complementary 8-mer oligonucleotides 3'-T-5'-GCGCGCA-3' and 5'-ACGCGCGT-3'. To our knowledge, these are the first porphyrin-oligonucleotide conjugates carrying the porphyrin chromophores in the 3'-position. Chain assembly was achieved by automated solid-phase synthesis and by inexpensive straightforward 'in flask' modification of commercially available solid supported oligonucleotides. This approach allows the synthesis of modified oligonucleotides without using costly instrumentation for automated DNA synthesis. Porphyrin-containing self-complementary oligonucleotides are expected to be a valuable model for drug binding studies and determination of conformational changes in DNA sequences using circular dichroism.

The preparation and circular dichroic (CD) studies of self-complimentary 8-mer DNA sequences with a porphyrin at the 3' end are presented. Electronic interaction between the two porphyrins (the interchromophoric distance is in the range of 28-40 A), attached to both ends of the double-stranded helix, gives rise to a long-range exciton-coupled CD in the visible region (400-450 nm). The porphyrin chromophores act as sensitive probes of geometrical changes in the DNA backbone and sensitively reflect the double-strand to single-strand transition. This study demonstrates the possibility of using exciton-coupled porphyrin CDs for conformational studies of DNA.

The article presents a study which examines the interactions of a tetranionic porphyrin with DNA. It explores the interactions of Z-DNA sensor to a versatile supramolecular device. The study found that cationic zinc porphyrin can selectively detect the left-handed Z-form of DNA. It notes that spectroscopic properties of metallo-porphyrins are very attractive for sensing Z-DNA.