DNA's charge transfer and self-assembly characteristics have made it a hallmark of molecular electronics for the past two decades. A fast and efficient charge transfer mechanism with programmable properties using DNA nanostructures is required for DNA-based nanoelectronic applications and devices. The ability to integrate DNA with inorganic substrates becomes critical in this process. Such integrations may affect the conformation of DNA, altering its charge transport properties. Thus, using molecular dynamics simulations and first-principles calculations in conjunction with Green's function approach, we explore the impact of the Au (111) substrate on the conformation of DNA and analyze its effect on the charge transport. Our results indicate that DNA sequence, leading to its molecular conformation on the Au substrate, is critical to engineer charge transport properties. We demonstrate that DNA fluctuates on a gold substrate, sampling various distinct conformations over time. The energy levels, spatial locations of molecular orbitals and the DNA/Au contact atoms can differ between these distinct conformations. Depending on the sequence, at the HOMO, the charge transmission differs up to 60 times between the top ten conformations. We demonstrate that the relative positions of the nucleobases are critical in determining the conformations and the coupling between orbitals. We anticipate that these results can be extended to other inorganic surfaces and pave the way for understanding DNA–inorganic interface interactions for future DNA-based electronic device applications. 
                        more » 
                        « less   
                    
                            
                            Nanofluidic charged-coupled devices for controlled DNA transport and separation
                        
                    
    
            Abstract Controlled molecular transport and separation is of significant importance in various applications. In this work, we presented a novel concept of nanofluidic molecular charge-coupled device (CCD) for controlled DNA transport and separation. By leveraging the unique field-effect coupling in nanofluidic systems, the nanofluidic molecular CCD aims to store charged biomolecules such as DNAs in discrete regions in nanochannels and transfer and separate these biomolecules as a charge packet in a bucket brigade fashion. We developed a quantitative model to capture the impact of nanochannel surface charge, gating voltage and frequency, molecule diffusivity, and gating electrode geometry on the transport and separation efficiency. We studied the synergistic effects of these factors to guide the device design and optimize the DNA transport and separation in a nanofluidic CCD. The findings in this study provided insight into the rational design and implementation of the nanofluidic molecular CCD. 
        more » 
        « less   
        
    
                            - Award ID(s):
- 1710831
- PAR ID:
- 10326648
- Date Published:
- Journal Name:
- Nanotechnology
- Volume:
- 32
- Issue:
- 34
- ISSN:
- 0957-4484
- Page Range / eLocation ID:
- 345501
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
- 
            
- 
            Abstract Biological membrane channels mediate information exchange between cells and facilitate molecular recognition. While tuning the shape and function of membrane channels for precision molecular sensing via de-novo routes is complex, an even more significant challenge is interfacing membrane channels with electronic devices for signal readout, which results in low efficiency of information transfer - one of the major barriers to the continued development of high-performance bioelectronic devices. To this end, we integrate membrane spanning DNA nanopores with bioprotonic contacts to create programmable, modular, and efficient artificial ion-channel interfaces. Here we show that cholesterol modified DNA nanopores spontaneously and with remarkable affinity span the lipid bilayer formed over the planar bio-protonic electrode surface and mediate proton transport across the bilayer. Using the ability to easily modify DNA nanostructures, we illustrate that this bioprotonic device can be programmed for electronic recognition of biomolecular signals such as presence of Streptavidin and the cardiac biomarker B-type natriuretic peptide, without modifying the biomolecules. We anticipate this robust interface will allow facile electronic measurement and quantification of biomolecules in a multiplexed manner.more » « less
- 
            RNA oligonucleotides are crucial for a range of biological functions and in many biotechnological applications. Herein, we measured, for the first time, the conductance of individual double-stranded (ds)RNA molecules and compared it with the conductance of single DNA : RNA hybrids. The average conductance values are similar for both biomolecules, but the distribution of conductance values shows an order of magnitude higher variability for dsRNA, indicating higher molecular flexibility of dsRNA. Microsecond Molecular Dynamics simulations explain this difference and provide structural insights into the higher stability of DNA : RNA duplex with atomic level of detail. The rotations of 2′-OH groups of the ribose rings and the bases in RNA strands destabilize the duplex structure by weakening base stacking interactions, affecting charge transport, and making single-molecule conductance of dsRNA more variable (dynamic disorder). The results demonstrate that a powerful combination of state-of-the-art biomolecular electronics techniques and computational approaches can provide valuable insights into biomolecules’ biophysics with unprecedented spatial resolution.more » « less
- 
            Charge transport near the Dirac point (DP) was investigated in graphene using ferroelectric (FE) gating in the temperature range of 300 < T < 350 K. We observed that the conductivity (σ) near the DP had a positive temperature gradient that switched to a negative temperature gradient with increasing temperature. The switch to a negative temperature gradient shifted to higher temperatures and gradually weakened upon moving away from the DP. Impurity charge compensation via polarization of the FE together with a temperature-dependent graphene–impurity charge separation was proposed as being responsible for the non-monotonicity in σ(T). A self-consistent theory for graphene transport with impurity charge scattering and phonon scattering was used to analyze the results. Non-monotonic charge transport was also observed in the temperature dependence of the residual conductivity (σr). Theoretical analysis of both σ and σr revealed a temperature independent contribution of ∼1.16e2h that is probably inherent to pristine graphene.more » « less
- 
            null (Ed.)Understanding the influence of polymer molecular weight on the morphology, photophysics, and photovoltaic properties of polymer solar cells is central to further advances in the design, processing, performance and optimization of the materials and devices for large scale applications. We have synthesized six number-average molecular weight ( M n ) values (21–127 kDa) of biselenophene–naphthalenediimide copolymer ( PNDIBS ) via direct heteroarylation polymerization and used them to investigate the effects of the acceptor polymer molecular weight on the charge transport, blend photophysics, blend morphology, and photovoltaic properties of all-polymer solar cells (all-PSCs) based on PNDIBS and the donor polymer PBDB-T . The short-circuit current and power conversion efficiency (PCE) of the PBDB-T : PNDIBS blend devices were found to increase with increasing M n until reaching peaks at an optimal molecular weight of 55 kDa and then decreased with further increases in M n . The maximum PCE of 10.2% observed at the optimal M n value of 55 kDa coincided with optimal blend charge transport properties, blend photophysics, and blend morphology at this critical molecular weight. Compared to the bi-continuous network of ∼5.5–6.5 nm crystalline domains with predominantly face-on molecular orientations observed at 55 kDa, a relatively disordered microstructure with larger scale phase separation was evident at higher M n while more finely packed crystalline domains were seen at 21 kDa. The sensitivity of the device efficiency to the active layer thickness was found to also depend on the PNDIBS M n value. These results highlight the importance of tuning the molecular weight of the polymer components to optimize the morphology, charge transport, photophysics and efficiency of all-polymer solar cells. The results also provide new insights on structure–property relationships for a promising n-type semiconducting copolymer.more » « less
 An official website of the United States government
An official website of the United States government 
				
			 
					 
					
 
                                    