Porphyrin-DNA conjugates: Porphyrin induced adenine-guanine homoduplex stabilization and interduplex assemblies

Gevorg Sargsyan, Milan Balaz

Research output: Contribution to journalArticle

23 Citations (Scopus)

Abstract

DNA has found widespread uses as a nanosized scaffold for assembly of patterned multichomophoric nanostructures. Herein we report the synthesis, self-assembly, stability, and spectroscopic studies of short alternating non-self-complementary DNA sequences 5′-(dGdA)4 and 5′-(dAdG)4 with non-charged tetraarylporphyrins covalently linked to the 5′ position of deoxyadenosine or deoxyguanosine via a phosphate or amide linker. The linker, the metal in the porphyrin coordination center, and the neighboring nucleobase have very distinct effects on the duplex formation of porphyrin-deoxyguanosine-deoxyadenosine oligodeoxynucleotides. At ionic strength between 5 mM and 40 mM, free base trispyridylphenylporphyrin appended to the 5′ termini of 5′-(dAdG)4 oligonucleotide via short non-polar amide linker served as a hydrophobic molecular cap inducing deoxyadenosine-deoxyguanosine antiparallel homoduplex. At ionic strength of ≥60 mM, the free base porphyrin functioned as a molecular 'glue' and induced the formation of porphyrin-DNA inter-homoduplex assemblies with characteristic tetrasignate CD Cotton effects in the porphyrin Soret band region. When the porphyrin cap was covalently attached to 5′ position of deoxyguanosine or deoxyadenosine via charged phosphate linker, no significant deoxyadenosine- deoxyguanosine hybridization was observed even at elevated ionic strengths.

Original languageEnglish
Pages (from-to)5533-5540
Number of pages8
JournalOrganic and Biomolecular Chemistry
Volume10
Issue number29
DOIs
Publication statusPublished - 2012 Aug 7

Fingerprint

guanines
adenines
Porphyrins
Guanine
Adenine
Deoxyguanosine
porphyrins
assemblies
deoxyribonucleic acid
Stabilization
stabilization
DNA
Ionic strength
Osmolar Concentration
caps
Amides
amides
phosphates
Phosphates
complementary DNA

All Science Journal Classification (ASJC) codes

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry

Cite this

@article{44da6ba2f7014fc3b455cbdf8e094ed0,
title = "Porphyrin-DNA conjugates: Porphyrin induced adenine-guanine homoduplex stabilization and interduplex assemblies",
abstract = "DNA has found widespread uses as a nanosized scaffold for assembly of patterned multichomophoric nanostructures. Herein we report the synthesis, self-assembly, stability, and spectroscopic studies of short alternating non-self-complementary DNA sequences 5′-(dGdA)4 and 5′-(dAdG)4 with non-charged tetraarylporphyrins covalently linked to the 5′ position of deoxyadenosine or deoxyguanosine via a phosphate or amide linker. The linker, the metal in the porphyrin coordination center, and the neighboring nucleobase have very distinct effects on the duplex formation of porphyrin-deoxyguanosine-deoxyadenosine oligodeoxynucleotides. At ionic strength between 5 mM and 40 mM, free base trispyridylphenylporphyrin appended to the 5′ termini of 5′-(dAdG)4 oligonucleotide via short non-polar amide linker served as a hydrophobic molecular cap inducing deoxyadenosine-deoxyguanosine antiparallel homoduplex. At ionic strength of ≥60 mM, the free base porphyrin functioned as a molecular 'glue' and induced the formation of porphyrin-DNA inter-homoduplex assemblies with characteristic tetrasignate CD Cotton effects in the porphyrin Soret band region. When the porphyrin cap was covalently attached to 5′ position of deoxyguanosine or deoxyadenosine via charged phosphate linker, no significant deoxyadenosine- deoxyguanosine hybridization was observed even at elevated ionic strengths.",
author = "Gevorg Sargsyan and Milan Balaz",
year = "2012",
month = "8",
day = "7",
doi = "10.1039/c2ob25710f",
language = "English",
volume = "10",
pages = "5533--5540",
journal = "Organic and Biomolecular Chemistry",
issn = "1477-0520",
publisher = "Royal Society of Chemistry",
number = "29",

}

Porphyrin-DNA conjugates : Porphyrin induced adenine-guanine homoduplex stabilization and interduplex assemblies. / Sargsyan, Gevorg; Balaz, Milan.

In: Organic and Biomolecular Chemistry, Vol. 10, No. 29, 07.08.2012, p. 5533-5540.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Porphyrin-DNA conjugates

T2 - Porphyrin induced adenine-guanine homoduplex stabilization and interduplex assemblies

AU - Sargsyan, Gevorg

AU - Balaz, Milan

PY - 2012/8/7

Y1 - 2012/8/7

N2 - DNA has found widespread uses as a nanosized scaffold for assembly of patterned multichomophoric nanostructures. Herein we report the synthesis, self-assembly, stability, and spectroscopic studies of short alternating non-self-complementary DNA sequences 5′-(dGdA)4 and 5′-(dAdG)4 with non-charged tetraarylporphyrins covalently linked to the 5′ position of deoxyadenosine or deoxyguanosine via a phosphate or amide linker. The linker, the metal in the porphyrin coordination center, and the neighboring nucleobase have very distinct effects on the duplex formation of porphyrin-deoxyguanosine-deoxyadenosine oligodeoxynucleotides. At ionic strength between 5 mM and 40 mM, free base trispyridylphenylporphyrin appended to the 5′ termini of 5′-(dAdG)4 oligonucleotide via short non-polar amide linker served as a hydrophobic molecular cap inducing deoxyadenosine-deoxyguanosine antiparallel homoduplex. At ionic strength of ≥60 mM, the free base porphyrin functioned as a molecular 'glue' and induced the formation of porphyrin-DNA inter-homoduplex assemblies with characteristic tetrasignate CD Cotton effects in the porphyrin Soret band region. When the porphyrin cap was covalently attached to 5′ position of deoxyguanosine or deoxyadenosine via charged phosphate linker, no significant deoxyadenosine- deoxyguanosine hybridization was observed even at elevated ionic strengths.

AB - DNA has found widespread uses as a nanosized scaffold for assembly of patterned multichomophoric nanostructures. Herein we report the synthesis, self-assembly, stability, and spectroscopic studies of short alternating non-self-complementary DNA sequences 5′-(dGdA)4 and 5′-(dAdG)4 with non-charged tetraarylporphyrins covalently linked to the 5′ position of deoxyadenosine or deoxyguanosine via a phosphate or amide linker. The linker, the metal in the porphyrin coordination center, and the neighboring nucleobase have very distinct effects on the duplex formation of porphyrin-deoxyguanosine-deoxyadenosine oligodeoxynucleotides. At ionic strength between 5 mM and 40 mM, free base trispyridylphenylporphyrin appended to the 5′ termini of 5′-(dAdG)4 oligonucleotide via short non-polar amide linker served as a hydrophobic molecular cap inducing deoxyadenosine-deoxyguanosine antiparallel homoduplex. At ionic strength of ≥60 mM, the free base porphyrin functioned as a molecular 'glue' and induced the formation of porphyrin-DNA inter-homoduplex assemblies with characteristic tetrasignate CD Cotton effects in the porphyrin Soret band region. When the porphyrin cap was covalently attached to 5′ position of deoxyguanosine or deoxyadenosine via charged phosphate linker, no significant deoxyadenosine- deoxyguanosine hybridization was observed even at elevated ionic strengths.

UR - http://www.scopus.com/inward/record.url?scp=84863624852&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84863624852&partnerID=8YFLogxK

U2 - 10.1039/c2ob25710f

DO - 10.1039/c2ob25710f

M3 - Article

C2 - 22692698

AN - SCOPUS:84863624852

VL - 10

SP - 5533

EP - 5540

JO - Organic and Biomolecular Chemistry

JF - Organic and Biomolecular Chemistry

SN - 1477-0520

IS - 29

ER -