DNA demonstrates a remarkable capacity for creating designer nanostructures and devices. A growing number of these structures utilize Förster resonance energy transfer (FRET) as part of the device's functionality, readout or characterization, and, as device sophistication increases so do the concomitant FRET requirements. Here we create multi-dye FRET cascades and assess how well DNA can marshal organic dyes into nanoantennae that focus excitonic energy. We evaluate 36 increasingly complex designs including linear, bifurcated, Holliday junction, 8-arm star and dendrimers involving up to five different dyes engaging in four-consecutive FRET steps, while systematically varying fluorophore spacing by Förster distance (R0). Decreasing R0 while augmenting cross-sectional collection area with multiple donors significantly increases terminal exciton delivery efficiency within dendrimers compared with the first linear constructs. Förster modelling confirms that best results are obtained when there are multiple interacting FRET pathways rather than independent channels by which excitons travel from initial donor(s) to final acceptor.

The growing maturity of DNA-based architectures has raised considerable interest in applying them to create photoactive light harvesting and sensing devices. Toward optimizing efficiency in such structures, resonant energy transfer was systematically examined in a series of dye-labeled DNA duplexes where donor-acceptor separation was incrementally changed from 0 to 16 base pairs. Cyanine dyes were localized on the DNA using double phosphoramidite attachment chemistry. Steady state spectroscopy, single-pair fluorescence, time-resolved fluorescence, and ultrafast two-color pump-probe methods were utilized to examine the energy transfer processes. Energy transfer rates were found to be more sensitive to the distance between the Cy3 donor and Cy5 acceptor dye molecules than efficiency measurements. Picosecond energy transfer and near-unity efficiencies were observed for the closest separations. Comparison between our measurements and the predictions of Förster theory based on structural modeling of the dye-labeled DNA duplex suggest that the double phosphoramidite linkage leads to a distribution of intercalated and nonintercalated dye orientations. Deviations from the predictions of Förster theory point to a failure of the point dipole approximation for separations of less than 10 base pairs. Interactions between the dyes that alter their optical properties and violate the weak-coupling assumption of Förster theory were observed for separations of less than four base pairs, suggesting the removal of nucleobases causes DNA deformation and leads to enhanced dye-dye interaction.

Because of their ease of design and assembly, DNA scaffolds provide a valuable means for organizing fluorophores into complex light harvesting antennae. However, as the size and complexity of the DNA−fluorophore network grows, it can be difficult to fully understand energy transfer properties because of the large number of dipolar interactions between fluorophores. Here, we investigate simple DNA− fluorophore networks that represent elements of the more complex networks and provide insight into the Forster Resonance Energy Transfer (FRET) processes in the presence of multiple pathways. These FRET networks consist of up to two Cy3 donor fluorophores and two Cy3.5 acceptor fluorophores that are linked to a rigid dual-rail DNA scaffold with short interfluorophore separation corresponding to 10 DNA base pairs (∼34 Å). This configuration results in five FRET pathways: four hetero-FRET and one homo-FRET pathway. The FRET properties are characterized using a combination of steady-state and time-resolved spectroscopy and understood using Forster theory. We show that the multiple FRET pathways lead to an increase in FRET efficiency, in part because homo-FRET between donor fluorophores provides access to parallel pathways to the acceptor and thereby compensates for low FRET efficiency channels caused by a static transition dipole distribution. More generally, the results show that multiple pathways may be used in the design of artificial light harvesting devices to compensate for inhomogeneities and nonideal ensemble effects that degrade FRET efficiency.

An emerging trend with semiconductor quantum dots (QDs) is their use as scaffolds to assemble multiple energy transfer pathways. Examples to date have combined various competitive and sequential Förster resonance energy transfer (FRET) pathways between QDs and fluorescent dyes, luminescent lanthanide complexes, and bioluminescent proteins. Here, we show that the photoluminescence (PL) of QD bioconjugates can also be modulated by a combination of FRET and charge transfer (CT), and characterize the concurrent effects of these mechanistically different pathways using PL measurements at both the ensemble and the single particle level. Peptides were distally labeled with either a fluorescent dye that quenched QD PL through FRET or a ruthenium(II) phenanthroline complex that quenched QD PL through electron transfer. The labeled peptides were assembled around a central CdSe/ZnS QD at different ratios, tuning the relative rates of FRET and CT, which were competitive quenching pathways. The concurrent effects of FRET and CT were predictable from a rate analysis that was calibrated to the isolated effects of each of these pathways. Notably, the dye/QD PL intensity ratio reflected changes in the relative rate of FRET but was approximately independent of CT. In turn, the sum of the QD and dye PL intensities, when adjusted for quantum yields, reflected changes in the relative rate of CT quenching, approximately independent of FRET. The capacity for multiplexed sensing of protease activity was demonstrated using these two orthogonal detection channels. Combined CT-FRET configurations with QDs are thus promising for applications in bioanalysis, sensing, and imaging, and may prove useful in other photonic applications.

The wide bandgap semiconductors SiC and GaN are already commercialized as power devices that are used in the automotive, wireless, and industrial power markets, but their adoption into space and avionic applications is hindered by their susceptibility to permanent degradation and catastrophic failure from heavy-ion exposure. Efforts to space-qualify these wide bandgap power devices have revealed that they are susceptible to damage from the high-energy, heavy-ion space radiation environment (galactic cosmic rays) that cannot be shielded. In space-simulated conditions, GaN and SiC transistors have shown failure susceptibility at ∼50% of their nominal rated voltage. Similarly, SiC transistors are susceptible to radiation damage-induced degradation or failure under heavy-ion single-event effects testing conditions, reducing their utility in the space galactic cosmic ray environment. In SiC-based Schottky diodes, catastrophic single-event burnout (SEB) and other single-event effects (SEE) have been observed at ∼40% of the rated operating voltage, as well as an unacceptable degradation in leakage current at ∼20% of the rated operating voltage. The ultra-wide bandgap semiconductors Ga2O3, diamond and BN are also being explored for their higher power and higher operating temperature capabilities in power electronics and for solar-blind UV detectors. Ga2O3 appears to be more resistant to displacement damage than GaN and SiC, as expected from a consideration of their average bond strengths. Diamond, a highly radiation-resistant material, is considered a nearly ideal material for radiation detection, particularly in high-energy physics applications. The response of diamond to radiation exposure depends strongly on the nature of the growth (natural vs chemical vapor deposition), but overall, diamond is radiation hard up to several MGy of photons and electrons, up to 1015 (neutrons and high energetic protons) cm−2 and >1015 pions cm−2. BN is also radiation-hard to high proton and neutron doses, but h-BN undergoes a transition from sp2 to sp3 hybridization as a consequence of the neutron induced damage with formation of c-BN. Much more basic research is needed on the response of both the wide and ultra-wide bandgap semiconductors to radiation, especially single event effects.

The Breit-Wigner phase of a wave function was obtained by measuring the interference between two independent ionization paths of a molecule. The state of interest was present in only one of the paths, thereby producing a phase shift in the observed signal. An analytical theory was used to determine the phase of the wave function from the observable.

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Optical-optical double resonance was employed to study rotational energy transfer in collisions of selected rotational/fine-structure levels of CN(A2pi, v = 3) with N2. The CN radical was generated by 193 nm photolysis of BrCN in a slow flow of N2 at total pressures of 0.2-1.4 Torr. Specific fine-structure lambda-doublet levels of CN(A2pi, v = 3) were prepared by pulsed dye laser excitation on isolated lines in the CN A-X (3,0) band, while the initially excited and collisionally populated levels were observed after a short delay by laser-induced fluorescence in the B-A (3,3) band. Total removal rate constants for specified rotational/fine-structure levels involving total angular momentum J from 4.5 to 12.5 were determined. These rate constants decrease with increasing J, with no obvious dependence on the fine-structure/lambda-doublet label. State-to-state relative rate constants were determined for several initial levels and show a strikingly strong collisional propensity to conserve the fine-structure/lambda-doublet label. Comparison is made with the results of quantum scattering calculations based on potential energy surfaces averaged over the orientation of the N2 molecule. Reasonable agreement is found with experimentally determined total removal rate constants. However, the computed state-to-state rate constants show a stronger propensity for fine-structure and lambda-doublet changing transitions. These differences between experiment and theory could be due to the neglect of the N2 orientation and the correlation of the CN and N2 angular motions.