4 research outputs found
Enhancing DNA-Mediated Assemblies of Supramolecular Cage Dimers through Tuning Core Flexibility and DNA LengthA Combined Experimental–Modeling Study
Two complementary
small-molecule–DNA hybrid (SMDH) building
blocks have been combined to form well-defined supramolecular cage
dimers at DNA concentrations as high as 102 μM. This was made
possible by combining a flexible small-molecule core and three DNA
arms of moderate lengths (<20 base pairs). These results were successfully
modeled by coarse-grained molecular dynamics simulations, which also
revealed that the formation of ill-defined networks in the case of
longer DNA arms can be significantly biased by the presence of deep
kinetic traps. Notably, melting point studies revealed that cooperative
melting behavior can be used as a means to distinguish the relative
propensities for dimer versus network formation from complementary
flexible three-DNA-arm SMDH (fSMDH<sub>3</sub>) components: sharp,
enhanced melting transitions were observed for assemblies that result
mostly in cage dimers, while no cooperative melting behavior was observed
for assemblies that form ill-defined networks
Enhancing DNA-Mediated Assemblies of Supramolecular Cage Dimers through Tuning Core Flexibility and DNA LengthA Combined Experimental–Modeling Study
Two complementary
small-molecule–DNA hybrid (SMDH) building
blocks have been combined to form well-defined supramolecular cage
dimers at DNA concentrations as high as 102 μM. This was made
possible by combining a flexible small-molecule core and three DNA
arms of moderate lengths (<20 base pairs). These results were successfully
modeled by coarse-grained molecular dynamics simulations, which also
revealed that the formation of ill-defined networks in the case of
longer DNA arms can be significantly biased by the presence of deep
kinetic traps. Notably, melting point studies revealed that cooperative
melting behavior can be used as a means to distinguish the relative
propensities for dimer versus network formation from complementary
flexible three-DNA-arm SMDH (fSMDH<sub>3</sub>) components: sharp,
enhanced melting transitions were observed for assemblies that result
mostly in cage dimers, while no cooperative melting behavior was observed
for assemblies that form ill-defined networks
Enhancing DNA-Mediated Assemblies of Supramolecular Cage Dimers through Tuning Core Flexibility and DNA LengthA Combined Experimental–Modeling Study
Two complementary
small-molecule–DNA hybrid (SMDH) building
blocks have been combined to form well-defined supramolecular cage
dimers at DNA concentrations as high as 102 μM. This was made
possible by combining a flexible small-molecule core and three DNA
arms of moderate lengths (<20 base pairs). These results were successfully
modeled by coarse-grained molecular dynamics simulations, which also
revealed that the formation of ill-defined networks in the case of
longer DNA arms can be significantly biased by the presence of deep
kinetic traps. Notably, melting point studies revealed that cooperative
melting behavior can be used as a means to distinguish the relative
propensities for dimer versus network formation from complementary
flexible three-DNA-arm SMDH (fSMDH<sub>3</sub>) components: sharp,
enhanced melting transitions were observed for assemblies that result
mostly in cage dimers, while no cooperative melting behavior was observed
for assemblies that form ill-defined networks
Charge Transport across DNA-Based Three-Way Junctions
DNA-based molecular electronics will
require charges to be transported
from one site within a 2D or 3D architecture to another. While this
has been shown previously in linear, π-stacked DNA sequences,
the dynamics and efficiency of charge transport across DNA three-way
junction (3WJ) have yet to be determined. Here, we present an investigation
of hole transport and trapping across a DNA-based three-way junction
systems by a combination of femtosecond transient absorption spectroscopy
and molecular dynamics simulations. Hole transport across the junction
is proposed to be gated by conformational fluctuations in the ground
state which bring the transiently populated hole carrier nucleobases
into better aligned geometries on the nanosecond time scale, thus
modulating the π–π electronic coupling along the
base pair sequence