Charge separation and recombination pathways in diblock dna hairpins

Jacob H. Olshansky, Ryan M. Young, Michael R Wasielewski

Research output: Contribution to journalArticle

1 Citation (Scopus)

Abstract

Achieving high-yielding photoinduced charge separation through the I-stacked bases of DNA is a critical requirement for realizing numerous DNA-based technologies. In the current work, we combine two strategies for achieving high-yield charge separation. First, a chromophore with a high driving force for charge injection, naphthalenediimide (NDI), is used because it generates hot carriers that enhance charge-Transfer rates. Second, a diblock DNA sequence is used with two or three adenines followed by a series of guanines to implement an energy landscape that accelerates charge separation while retarding charge recombination. The photoinduced dynamics of these NDI diblock oligomers with and without a terminal hole acceptor are probed by femtosecond transient absorption spectroscopy. The measured rate constants for various charge separation and recombination processes are interpreted within the context of a full kinetic model of these systems. We find that the A 2 and A 3 oligomers achieve similar charge separation yields (as high as 20-25%) for a given length, yet the critical recombination process that determines these yields occurs at different distances from the NDI chromophore and on different time scales. This type of analysis could be used to predict charge separation efficiencies in candidate DNA structures.

Original languageEnglish
Pages (from-to)1545-1553
Number of pages9
JournalJournal of Physical Chemistry B
Volume123
Issue number7
DOIs
Publication statusPublished - Feb 21 2019

Fingerprint

polarization (charge separation)
deoxyribonucleic acid
DNA
Chromophores
oligomers
Oligomers
chromophores
Charge injection
Hot carriers
guanines
DNA sequences
adenines
Guanine
Adenine
Absorption spectroscopy
Charge transfer
Rate constants
absorption spectroscopy
charge transfer
retarding

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films
  • Materials Chemistry

Cite this

Charge separation and recombination pathways in diblock dna hairpins. / Olshansky, Jacob H.; Young, Ryan M.; Wasielewski, Michael R.

In: Journal of Physical Chemistry B, Vol. 123, No. 7, 21.02.2019, p. 1545-1553.

Research output: Contribution to journalArticle

Olshansky, Jacob H. ; Young, Ryan M. ; Wasielewski, Michael R. / Charge separation and recombination pathways in diblock dna hairpins. In: Journal of Physical Chemistry B. 2019 ; Vol. 123, No. 7. pp. 1545-1553.
@article{40dca5f8baea4cd484a889da4e003307,
title = "Charge separation and recombination pathways in diblock dna hairpins",
abstract = "Achieving high-yielding photoinduced charge separation through the I-stacked bases of DNA is a critical requirement for realizing numerous DNA-based technologies. In the current work, we combine two strategies for achieving high-yield charge separation. First, a chromophore with a high driving force for charge injection, naphthalenediimide (NDI), is used because it generates hot carriers that enhance charge-Transfer rates. Second, a diblock DNA sequence is used with two or three adenines followed by a series of guanines to implement an energy landscape that accelerates charge separation while retarding charge recombination. The photoinduced dynamics of these NDI diblock oligomers with and without a terminal hole acceptor are probed by femtosecond transient absorption spectroscopy. The measured rate constants for various charge separation and recombination processes are interpreted within the context of a full kinetic model of these systems. We find that the A 2 and A 3 oligomers achieve similar charge separation yields (as high as 20-25{\%}) for a given length, yet the critical recombination process that determines these yields occurs at different distances from the NDI chromophore and on different time scales. This type of analysis could be used to predict charge separation efficiencies in candidate DNA structures.",
author = "Olshansky, {Jacob H.} and Young, {Ryan M.} and Wasielewski, {Michael R}",
year = "2019",
month = "2",
day = "21",
doi = "10.1021/acs.jpcb.8b11782",
language = "English",
volume = "123",
pages = "1545--1553",
journal = "Journal of Physical Chemistry B",
issn = "1520-6106",
number = "7",

}

TY - JOUR

T1 - Charge separation and recombination pathways in diblock dna hairpins

AU - Olshansky, Jacob H.

AU - Young, Ryan M.

AU - Wasielewski, Michael R

PY - 2019/2/21

Y1 - 2019/2/21

N2 - Achieving high-yielding photoinduced charge separation through the I-stacked bases of DNA is a critical requirement for realizing numerous DNA-based technologies. In the current work, we combine two strategies for achieving high-yield charge separation. First, a chromophore with a high driving force for charge injection, naphthalenediimide (NDI), is used because it generates hot carriers that enhance charge-Transfer rates. Second, a diblock DNA sequence is used with two or three adenines followed by a series of guanines to implement an energy landscape that accelerates charge separation while retarding charge recombination. The photoinduced dynamics of these NDI diblock oligomers with and without a terminal hole acceptor are probed by femtosecond transient absorption spectroscopy. The measured rate constants for various charge separation and recombination processes are interpreted within the context of a full kinetic model of these systems. We find that the A 2 and A 3 oligomers achieve similar charge separation yields (as high as 20-25%) for a given length, yet the critical recombination process that determines these yields occurs at different distances from the NDI chromophore and on different time scales. This type of analysis could be used to predict charge separation efficiencies in candidate DNA structures.

AB - Achieving high-yielding photoinduced charge separation through the I-stacked bases of DNA is a critical requirement for realizing numerous DNA-based technologies. In the current work, we combine two strategies for achieving high-yield charge separation. First, a chromophore with a high driving force for charge injection, naphthalenediimide (NDI), is used because it generates hot carriers that enhance charge-Transfer rates. Second, a diblock DNA sequence is used with two or three adenines followed by a series of guanines to implement an energy landscape that accelerates charge separation while retarding charge recombination. The photoinduced dynamics of these NDI diblock oligomers with and without a terminal hole acceptor are probed by femtosecond transient absorption spectroscopy. The measured rate constants for various charge separation and recombination processes are interpreted within the context of a full kinetic model of these systems. We find that the A 2 and A 3 oligomers achieve similar charge separation yields (as high as 20-25%) for a given length, yet the critical recombination process that determines these yields occurs at different distances from the NDI chromophore and on different time scales. This type of analysis could be used to predict charge separation efficiencies in candidate DNA structures.

UR - http://www.scopus.com/inward/record.url?scp=85060809500&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85060809500&partnerID=8YFLogxK

U2 - 10.1021/acs.jpcb.8b11782

DO - 10.1021/acs.jpcb.8b11782

M3 - Article

VL - 123

SP - 1545

EP - 1553

JO - Journal of Physical Chemistry B

JF - Journal of Physical Chemistry B

SN - 1520-6106

IS - 7

ER -