Role of environmental factors on the structure and spectroscopic response of 5′-DNA-porphyrin conjugates caused by changes in the porphyrin-porphyrin interactions

Angela Mammana, Gennaro Pescitelli, Tomohiro Asakawa, Steffen Jockusch, Ana G. Petrovic, Regina R. Monaco, Roberto Purrello, Nicholas J. Turro, Koji Nakanishi, George A. Ellestad, Milan Balaz, Nina Berova

Research output: Contribution to journalArticle

62 Citations (Scopus)

Abstract

We have explored the utility, strength, and limitation of throughspace exciton-coupled circular dichroism in determination of the secondary structure of optically active chromophoric nanoarrays using the example of end-capped porphyrin-and metalloporphyrin-oligodeoxynucleotide conjugates. We put special emphasis on the explanation of the origin and significance of the distinctive multiple bands in the CD spectra (trisignate and tetrasignate CD bands). Such CD profiles are often observed in chiral aggregates or multichromophoric arrays but have never before been studied in detail. We found that variation of temperature and ionic strength has a profound effect on the geometry of the porphyrin-DNA conjugates and thus the nature of electronic interactions. At lower temperatures and in the absence of NaCl all three 5′-DNA-porphyrin conjugates display negative bisignate CD exciton couplets of variable intensity in the Soret region resulting from through-space interaction between the electric transition dipole moments of the two end-capped porphyrins. As the temperature is raised these exciton couplets are transformed into single positive bands originating from the porphyrin-single-strand DNA interactions. At higher ionic strengths and low temperatures, multisignate CD bands are observed in the porphyrin Soret region. These CD signature bands originate from a combination of intermolecular, end-to-end porphyrin-porphyrin stacking between duplexes and porphyrin-DNA interactions. The intermolecular aggregation was confirmed by fluorescence and absorption spectroscopy and resonance light scattering. DeVoe theoretical CD calculations, in conjunction with molecular dynamics simulations and Monte Carlo conformational searches, were used to mimic the observed bisignate exciton-coupled CD spectra as well as multiple CD bands. Calculations correctly predicted the sign and shape of the experimentally observed CD spectra. These studies reveal that the exciton-coupled circular dichroism is a very useful technique for the determination of the structure of optically active arrays.

Original languageEnglish
Pages (from-to)11853-11866
Number of pages14
JournalChemistry - A European Journal
Volume15
Issue number44
DOIs
Publication statusPublished - 2009 Dec 1

Fingerprint

Porphyrins
DNA
Excitons
Dichroism
Ionic strength
Metalloporphyrins
Temperature
Oligodeoxyribonucleotides
Dipole moment
Fluorescence spectroscopy
Absorption spectroscopy
Light scattering
Molecular dynamics
Agglomeration
LDS 751
Geometry
Computer simulation

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Organic Chemistry

Cite this

Mammana, Angela ; Pescitelli, Gennaro ; Asakawa, Tomohiro ; Jockusch, Steffen ; Petrovic, Ana G. ; Monaco, Regina R. ; Purrello, Roberto ; Turro, Nicholas J. ; Nakanishi, Koji ; Ellestad, George A. ; Balaz, Milan ; Berova, Nina. / Role of environmental factors on the structure and spectroscopic response of 5′-DNA-porphyrin conjugates caused by changes in the porphyrin-porphyrin interactions. In: Chemistry - A European Journal. 2009 ; Vol. 15, No. 44. pp. 11853-11866.
@article{7642c58c8164498c921ce69a7f0d795a,
title = "Role of environmental factors on the structure and spectroscopic response of 5′-DNA-porphyrin conjugates caused by changes in the porphyrin-porphyrin interactions",
abstract = "We have explored the utility, strength, and limitation of throughspace exciton-coupled circular dichroism in determination of the secondary structure of optically active chromophoric nanoarrays using the example of end-capped porphyrin-and metalloporphyrin-oligodeoxynucleotide conjugates. We put special emphasis on the explanation of the origin and significance of the distinctive multiple bands in the CD spectra (trisignate and tetrasignate CD bands). Such CD profiles are often observed in chiral aggregates or multichromophoric arrays but have never before been studied in detail. We found that variation of temperature and ionic strength has a profound effect on the geometry of the porphyrin-DNA conjugates and thus the nature of electronic interactions. At lower temperatures and in the absence of NaCl all three 5′-DNA-porphyrin conjugates display negative bisignate CD exciton couplets of variable intensity in the Soret region resulting from through-space interaction between the electric transition dipole moments of the two end-capped porphyrins. As the temperature is raised these exciton couplets are transformed into single positive bands originating from the porphyrin-single-strand DNA interactions. At higher ionic strengths and low temperatures, multisignate CD bands are observed in the porphyrin Soret region. These CD signature bands originate from a combination of intermolecular, end-to-end porphyrin-porphyrin stacking between duplexes and porphyrin-DNA interactions. The intermolecular aggregation was confirmed by fluorescence and absorption spectroscopy and resonance light scattering. DeVoe theoretical CD calculations, in conjunction with molecular dynamics simulations and Monte Carlo conformational searches, were used to mimic the observed bisignate exciton-coupled CD spectra as well as multiple CD bands. Calculations correctly predicted the sign and shape of the experimentally observed CD spectra. These studies reveal that the exciton-coupled circular dichroism is a very useful technique for the determination of the structure of optically active arrays.",
author = "Angela Mammana and Gennaro Pescitelli and Tomohiro Asakawa and Steffen Jockusch and Petrovic, {Ana G.} and Monaco, {Regina R.} and Roberto Purrello and Turro, {Nicholas J.} and Koji Nakanishi and Ellestad, {George A.} and Milan Balaz and Nina Berova",
year = "2009",
month = "12",
day = "1",
doi = "10.1002/chem.200902029",
language = "English",
volume = "15",
pages = "11853--11866",
journal = "Chemistry - A European Journal",
issn = "0947-6539",
publisher = "Wiley-VCH Verlag",
number = "44",

}

Mammana, A, Pescitelli, G, Asakawa, T, Jockusch, S, Petrovic, AG, Monaco, RR, Purrello, R, Turro, NJ, Nakanishi, K, Ellestad, GA, Balaz, M & Berova, N 2009, 'Role of environmental factors on the structure and spectroscopic response of 5′-DNA-porphyrin conjugates caused by changes in the porphyrin-porphyrin interactions', Chemistry - A European Journal, vol. 15, no. 44, pp. 11853-11866. https://doi.org/10.1002/chem.200902029

Role of environmental factors on the structure and spectroscopic response of 5′-DNA-porphyrin conjugates caused by changes in the porphyrin-porphyrin interactions. / Mammana, Angela; Pescitelli, Gennaro; Asakawa, Tomohiro; Jockusch, Steffen; Petrovic, Ana G.; Monaco, Regina R.; Purrello, Roberto; Turro, Nicholas J.; Nakanishi, Koji; Ellestad, George A.; Balaz, Milan; Berova, Nina.

In: Chemistry - A European Journal, Vol. 15, No. 44, 01.12.2009, p. 11853-11866.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Role of environmental factors on the structure and spectroscopic response of 5′-DNA-porphyrin conjugates caused by changes in the porphyrin-porphyrin interactions

AU - Mammana, Angela

AU - Pescitelli, Gennaro

AU - Asakawa, Tomohiro

AU - Jockusch, Steffen

AU - Petrovic, Ana G.

AU - Monaco, Regina R.

AU - Purrello, Roberto

AU - Turro, Nicholas J.

AU - Nakanishi, Koji

AU - Ellestad, George A.

AU - Balaz, Milan

AU - Berova, Nina

PY - 2009/12/1

Y1 - 2009/12/1

N2 - We have explored the utility, strength, and limitation of throughspace exciton-coupled circular dichroism in determination of the secondary structure of optically active chromophoric nanoarrays using the example of end-capped porphyrin-and metalloporphyrin-oligodeoxynucleotide conjugates. We put special emphasis on the explanation of the origin and significance of the distinctive multiple bands in the CD spectra (trisignate and tetrasignate CD bands). Such CD profiles are often observed in chiral aggregates or multichromophoric arrays but have never before been studied in detail. We found that variation of temperature and ionic strength has a profound effect on the geometry of the porphyrin-DNA conjugates and thus the nature of electronic interactions. At lower temperatures and in the absence of NaCl all three 5′-DNA-porphyrin conjugates display negative bisignate CD exciton couplets of variable intensity in the Soret region resulting from through-space interaction between the electric transition dipole moments of the two end-capped porphyrins. As the temperature is raised these exciton couplets are transformed into single positive bands originating from the porphyrin-single-strand DNA interactions. At higher ionic strengths and low temperatures, multisignate CD bands are observed in the porphyrin Soret region. These CD signature bands originate from a combination of intermolecular, end-to-end porphyrin-porphyrin stacking between duplexes and porphyrin-DNA interactions. The intermolecular aggregation was confirmed by fluorescence and absorption spectroscopy and resonance light scattering. DeVoe theoretical CD calculations, in conjunction with molecular dynamics simulations and Monte Carlo conformational searches, were used to mimic the observed bisignate exciton-coupled CD spectra as well as multiple CD bands. Calculations correctly predicted the sign and shape of the experimentally observed CD spectra. These studies reveal that the exciton-coupled circular dichroism is a very useful technique for the determination of the structure of optically active arrays.

AB - We have explored the utility, strength, and limitation of throughspace exciton-coupled circular dichroism in determination of the secondary structure of optically active chromophoric nanoarrays using the example of end-capped porphyrin-and metalloporphyrin-oligodeoxynucleotide conjugates. We put special emphasis on the explanation of the origin and significance of the distinctive multiple bands in the CD spectra (trisignate and tetrasignate CD bands). Such CD profiles are often observed in chiral aggregates or multichromophoric arrays but have never before been studied in detail. We found that variation of temperature and ionic strength has a profound effect on the geometry of the porphyrin-DNA conjugates and thus the nature of electronic interactions. At lower temperatures and in the absence of NaCl all three 5′-DNA-porphyrin conjugates display negative bisignate CD exciton couplets of variable intensity in the Soret region resulting from through-space interaction between the electric transition dipole moments of the two end-capped porphyrins. As the temperature is raised these exciton couplets are transformed into single positive bands originating from the porphyrin-single-strand DNA interactions. At higher ionic strengths and low temperatures, multisignate CD bands are observed in the porphyrin Soret region. These CD signature bands originate from a combination of intermolecular, end-to-end porphyrin-porphyrin stacking between duplexes and porphyrin-DNA interactions. The intermolecular aggregation was confirmed by fluorescence and absorption spectroscopy and resonance light scattering. DeVoe theoretical CD calculations, in conjunction with molecular dynamics simulations and Monte Carlo conformational searches, were used to mimic the observed bisignate exciton-coupled CD spectra as well as multiple CD bands. Calculations correctly predicted the sign and shape of the experimentally observed CD spectra. These studies reveal that the exciton-coupled circular dichroism is a very useful technique for the determination of the structure of optically active arrays.

UR - http://www.scopus.com/inward/record.url?scp=72949102708&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=72949102708&partnerID=8YFLogxK

U2 - 10.1002/chem.200902029

DO - 10.1002/chem.200902029

M3 - Article

C2 - 19844929

AN - SCOPUS:72949102708

VL - 15

SP - 11853

EP - 11866

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

SN - 0947-6539

IS - 44

ER -